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Sulphonated asphalt is a additive in water based drilling muds that to improve performance, reduce costs, and increase drilling efficiency.
Asphasol or Sulphonated asphalt is commonly used as an additive in drilling muds for oil and gas wells. In drilling operations, the mud serves several important functions, including lubricating the drill bit, carrying cuttings to the surface, and maintaining pressure in the well to prevent blowouts.
The sulphonated asphalt is added to drilling muds because of its excellent emulsifying and wetting properties. It can help to stabilize the mud by preventing water from separating out, and it can also help to reduce the amount of fluid loss that occurs during drilling. This is important because fluid loss can lead to formation damage, decreased drilling efficiency, and even lost circulation events.
Sulfonated asphalt Or Asphasol is shale control additives that is used to inhibit the swelling and caving of shales caused by hydrous disintegration. Sulphonated asphalt is lost circulation additives and is used to plug a zone into which the drilling fluid is being lost, to prevent a complete loss of the drilling fluid is being lost, to prevent loss of the drilling fluid into the formation being drilled, and hence to prevent lost of drilling fluid circulation from the bottom of the drill hole to the top.
The sulfonated asphalt agents used to plug such a zone include inorganic chemical grouts or cement containing mixtures of silicates, metallic oxides, and limestone. Our drilling fluid is HTHP sodium sulfonated asphalt is very good shale control additives in the water-based mud.
Sulfonated Asphalt is sodium asphalt sulfonated made water-soluble by a unique sulfonation process. It is a versatile, total mud conditioner that stabilizes shale formations, significantly increases lubricity, lowers high-temperature high-pressure fluid loss (HTHP) water loss and enhances filter cake properties in both oil-based drilling fluids and water-based drilling fluids. Sulfonated asphalt product can be mixed in most water-based and all oil-based and synthetic muds.
Sulfonated asphalt additive is available in two different forms: Regular and Potassium enhanced. Potassium sulfonated asphalt additive is a specially prepared potassium salt of sulfonated asphalt. In addition to providing the same unique qualities as regular Sulfonated asphalt additive, it contributes water-soluble potassium ions at approximately 400ppm/lb of product carried in the mud system. This is beneficial in those areas that require the specific action of potassium to adequately minimize water induced clay swelling.
Sulfonated Asphalt is a proven extensively used drilling fluid additive with many fine properties. Oil asphalt is basal raw material. It appears brown in easy breakable pieces or fluidized powder. Its density is 0.98g/cm3. It’s partly water-soluble partly oil soluble for every kind of drilling fluid.The main consumer of sulfonated asphalt is the oil industry.
Sulfonated asphalt is a component of water- or oil-based drilling. As part of solutions, sulfonated asphalt performs several important functions:
sulphonated asphalt can also help to improve the rheological properties of drilling muds. It can increase the viscosity of the mud, which can improve hole cleaning and cuttings removal. It can also help to reduce the amount of torque and drag that is experienced during drilling, which can reduce wear and tear on drilling equipment and improve drilling efficiency.
HS code of Asphasol or Sulphonated Asphalt is 27149090 & 27150090.The CAS number is 68201-32-1 also EC number is 269-212-0
Sulphonated Asphalt is a water-soluble, high-performance additive that is made by treating Asphalt with concentrated sulfuric acid. This process produces a product that is highly reactive and has excellent binding properties.
Normal Packing of Asphasol is in PP bag 25kg or 50lb. Also based on customers’ requests can pack in jumbo bag 1000kg too.
The invention provides a kind of preparation method of sulfonated gilsonite, comprise the following steps: a, pitch and sulphonating agent are carried out sulfonation reaction, obtain intermediate product, the softening temperature < of described pitch 110 DEG C; B, described intermediate product and basic cpd are carried out neutralization reaction, obtain sulfonated gilsonite.Pitch lower for softening point temperature and sulphonating agent are carried out sulfonation reaction by the present invention, and the pitch that the amount of heat utilizing sulfonation reaction to release makes softening point temperature lower becomes liquid bitumen, and this liquid bitumen can compare sufficient sulfonation reaction with sulphonating agent.Compared with prior art, the present invention can prepare sulfonated gilsonite in organic solvent without the need to pitch being pulverized rear dissolving, saved a large amount of time of carrying out removing water treatment to organic solvent, therefore preparation method’s production efficiency of sulfonated gilsonite provided by the invention is higher.
A kind of preparation method of Sulfonated Gilsonite
The present invention relates to field of bitumen technology, particularly relate to a kind of preparation method of sulfonated gilsonite.
Sulfonated gilsonite is obtained through oversulfonate process by bitumen, and it is a kind of anionic superpolymer, and owing to containing a large amount of C-Cs and carbon-sulfide linkage in its molecular structure, bond energy is comparatively strong, and therefore sulfonated gilsonite has good high temperature resistance.Added to by sulfonated gilsonite in drilling fluid, can improve the oilness of drilling fluid and reduce drilling fluid filter loss at high temperature and pressure, therefore sulfonated gilsonite is that one has leak stopping, anti-collapse, lubrication, drag reduction, the multi-functional additive for drilling fluid such as high temperature resistant.Due to the property of sulfonated gilsonite, it is made to have a wide range of applications in drilling fluid field.
The technique of producing sulfonated gilsonite in prior art is generally first pulverized by pitch to be dissolved in organic solvent; In the bituminous solution obtained, add oleum again or pass into sulfur trioxide gas and carry out sulfonation reaction; Then in the reaction soln obtained, add basic cpd and carry out neutralization reaction; Finally the neutralized reaction product obtained is carried out oil reservoir separation, namely oven dry, pulverizing obtain sulfonated gilsonite.
As the application number Chinese patent discloses a kind of preparation method of sulfonated gilsonite, detailed process is, according to the composition of pitch, one or more pitch is selected to carry out in stable hydrocarbon composite, obtain composite pitch, the content of described composite pitch studies on asphaltene is 30% ~ 45%; Described composite pitch is placed in reactor, in described reactor, adds organic solvent, described composite pitch and organic solvent are stirred, obtain the bituminous solution that mass concentration is 15% ~ 30%; SO is passed in described bituminous solution 3carry out sulfonation reaction, the temperature controlling described sulfonation reaction is 20 DEG C ~ 40 DEG C, and the time of described sulfonation reaction is 40 minutes ~ 60 minutes; Described sulfonation reaction terminates to add alkaline solution in backward described reactor, makes the pH value of solution in described reactor reach 8 ~ 10; Adopt the solution in the dry described reactor of drum drying method, prepare sulfonated gilsonite.
Although the sulfonated gilsonite adopting aforesaid method to prepare has good high temperature resistance, filtrate-loss control, oilness and calcium fouling resistance, but preparation method’s production efficiency of this sulfonated gilsonite that prior art provides is lower, is unfavorable for the scale operation of sulfonated gilsonite.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of preparation method of sulfonated gilsonite, preparation method’s production efficiency of sulfonated gilsonite provided by the invention is higher, can be used for the scale operation of sulfonated gilsonite.
The invention provides a kind of preparation method of sulfonated gilsonite, comprise the following steps:
A, pitch and sulphonating agent are carried out sulfonation reaction, obtain intermediate product, the softening temperature < of described pitch 110 DEG C;
B, described intermediate product and basic cpd are carried out neutralization reaction, obtain sulfonated gilsonite.
Preferably, the mass ratio of described step a medium pitch and sulphonating agent is 1:(0.35 ~ 0.8).
Preferably, in described step a, the reaction times of sulfonation reaction is 10 minutes ~ 20 minutes.
Preferably, the softening temperature of described step a medium pitch is 50 DEG C ~ 90 DEG C.
Preferably, in described step a, the reaction raw materials of sulfonation reaction also comprises additive;
Described additive comprise in kerosene and diesel oil one or both.
Preferably, described step a is specially:
Pitch is mixed with additive, obtains mix products, the softening temperature < of described pitch 110 DEG C;
Described mix products and sulphonating agent are carried out sulfonation reaction, obtains intermediate product.
Preferably, the mass ratio of described pitch and additive is 1:(0.04 ~ 0.10).
Preferably, in described step b, the temperature of reaction of neutralization reaction is 100 DEG C ~ 180 DEG C;
In described step b, the reaction pressure of neutralization reaction is 80000Pa ~ 100000Pa.
Preferably, the mass ratio of the sulphonating agent in described step a and the basic cpd in described step b is (0.5 ~ 1.5): 1.
Preferably, the basic cpd in described step b is alkaline compound solution;
The mass concentration of described alkaline compound solution is 25% ~ 45%.
The invention provides a kind of preparation method of sulfonated gilsonite, comprise the following steps: a, pitch and sulphonating agent are carried out sulfonation reaction, obtain intermediate product, the softening temperature < of described pitch 110 DEG C; B, described intermediate product and basic cpd are carried out neutralization reaction, obtain sulfonated gilsonite.Pitch lower for softening point temperature and sulphonating agent are directly carried out sulfonation reaction by the present invention, the pitch that the amount of heat utilizing sulfonation reaction to release makes softening point temperature lower becomes liquid bitumen, and this liquid bitumen can compare sufficient sulfonation reaction with sulphonating agent.Compared with prior art, the present invention can make pitch carry out sufficient sulfonation reaction without the need to pitch being pulverized rear dissolving in organic solvent, prepares sulfonated gilsonite.The present invention has saved a large amount of time of carrying out removing water treatment to organic solvent in the process preparing sulfonated gilsonite, and therefore preparation method’s production efficiency of sulfonated gilsonite provided by the invention is higher.
In addition, pitch easily hardens, pulverize difficulty, and the present invention without the need to being pulverized by pitch, making preparation method’s technique of sulfonated gilsonite provided by the invention simple, further increasing the production efficiency of sulfonated gilsonite in the process preparing sulfonated gilsonite; And the present invention after preparing sulfonated gilsonite without the need to the organic solvent in sulfonated gilsonite is removed, avoid the loss of effective constituent in sulfonated gilsonite, the Performance comparision of sulfonated gilsonite that therefore the present invention obtains is stablized.
Experimental result shows, the high temperature and high pre ssure filtration of the sulfonated gilsonite that the present invention prepares is 6mL ~ 9.4mL, and relative expansion reduced rate is 40% ~ 55%, water solubles content is 73.9% ~ 90%, and pH value is 9 ~ 10.5, and moisture content is 4.3% ~ 8.9%, stable performance is qualified product; The production efficiency of the preparation method of sulfonated gilsonite provided by the invention is 0.003 hour/kilogram ~ 0.005 hour/kilogram, and production efficiency is higher; And preparation method’s production unit of sulfonated gilsonite provided by the invention is simple, do not need to use distillation plant and fractionation apparatus.
The invention provides a kind of preparation method of sulfonated gilsonite, comprise the following steps:
A, pitch and sulphonating agent are carried out sulfonation reaction, obtain intermediate product, the softening temperature < of described pitch 110 DEG C;
B, described intermediate product and basic cpd are carried out neutralization reaction, obtain sulfonated gilsonite.
Pitch lower for softening point temperature and sulphonating agent are directly carried out sulfonation reaction by the present invention, the pitch that the amount of heat utilizing sulfonation reaction to release makes softening point temperature lower becomes liquid bitumen, and this liquid bitumen can compare sufficient sulfonation reaction with sulphonating agent.Compared with prior art, the present invention can make pitch carry out sufficient sulfonation reaction without the need to pitch being pulverized rear dissolving in organic solvent, prepares sulfonated gilsonite; The present invention is in the process preparing sulfonated gilsonite, and saved a large amount of time of carrying out removing water treatment to organic solvent, therefore preparation method’s production efficiency of sulfonated gilsonite provided by the invention is higher.In addition, pitch easily hardens, pulverize difficulty, and the present invention without the need to being pulverized by pitch, making preparation method’s technique of sulfonated gilsonite provided by the invention simple, further increasing the production efficiency of sulfonated gilsonite in the process preparing sulfonated gilsonite; And the present invention to prepare after sulfonated gilsonite without the need to being removed by the organic solvent in sulfonated gilsonite, avoids the loss of effective constituent in sulfonated gilsonite, the Performance comparision of sulfonated gilsonite that therefore the present invention prepares is stablized.
Pitch and sulphonating agent are carried out sulfonation reaction by the present invention, obtain intermediate product, the softening temperature < of described pitch 110 DEG C; Preferably sulphonating agent is joined in pitch and carry out sulfonation reaction, obtain intermediate product.In the present invention, the mass ratio of described pitch and sulphonating agent is preferably 1:(0.35 ~ 0.8), be more preferably 1:(0.4 ~ 0.7), most preferably be 1:(0.5 ~ 0.6).In the present invention, the reaction times of described sulfonation reaction is preferably 10 minutes ~ 20 minutes, is more preferably 12 minutes ~ 18 minutes, most preferably is 14 minutes ~ 16 minutes, is the most preferably 15 minutes.In the present invention, the temperature of reaction of described sulfonation reaction is preferably 20 DEG C ~ 40 DEG C, is more preferably 22 DEG C ~ 30 DEG C, most preferably is 25 DEG C ~ 28 DEG C.The device of the present invention to described sulfonation reaction does not have special restriction, adopts the device preparing sulfonated gilsonite well known to those skilled in the art; Pitch and sulphonating agent are preferably carried out sulfonation reaction by the present invention in kneader, obtain intermediate product.
The kind of the present invention to described sulphonating agent does not have special restriction, adopts sulphonating agent well known to those skilled in the art; In the present invention, described sulphonating agent is preferably one or more in the vitriol oil, oleum, chlorsulfonic acid and sulphur trioxide, is more preferably one or both in oleum and sulphur trioxide, most preferably is oleum.In the present invention, in described oleum, the mass concentration of sulphur trioxide is preferably 25% ~ 45%, is more preferably 30% ~ 40%, most preferably is 32% ~ 38%, is the most preferably 35%.The source of the present invention to described sulphonating agent does not have special restriction, adopt the sulphonating agent of mentioned kind well known to those skilled in the art, described sulphonating agent both can be bought by market or obtain, and the preparation method of sulphonating agent well known to those skilled in the art also can be adopted to prepare.
Pitch lower for softening point temperature and sulphonating agent are directly carried out sulfonation reaction by the present invention, the pitch that the amount of heat utilizing sulfonation reaction to release makes softening point temperature lower becomes liquid bitumen, and this liquid bitumen can compare sufficient sulfonation reaction with sulphonating agent.Because the preparation method of sulfonated gilsonite provided by the invention can prepare sulfonated gilsonite in organic solvent without the need to pitch being pulverized rear dissolving, compared with prior art, the present invention carries out except water treatment organic solvent without the need to spending a large amount of time, and therefore preparation method’s production efficiency of sulfonated gilsonite provided by the invention is higher.In addition, the present invention, due to without the need to pulverizing pitch, making preparation method’s technique of sulfonated gilsonite provided by the invention simple, further increasing the production efficiency of sulfonated gilsonite; And the present invention is without the need to removing the organic solvent in the pitch after sulfonation, avoids the loss of effective constituent in sulfonated gilsonite, the Performance comparision of the sulfonated gilsonite that the present invention is prepared is stablized.
After obtaining intermediate product, described intermediate product and basic cpd are carried out neutralization reaction by the present invention, obtain sulfonated gilsonite; Preferably basic cpd is joined in described intermediate product and carry out neutralization reaction, obtain sulfonated gilsonite.In the present invention, the reaction times of described neutralization reaction is preferably 1 hour ~ 2 hours, is more preferably 1.2 hours ~ 1.8 hours, most preferably is 1.4 hours ~ 1.6 hours.In the present invention, the temperature of reaction of described neutralization reaction is preferably 100 DEG C ~ 180 DEG C, is more preferably 120 DEG C ~ 160 DEG C, most preferably is 130 DEG C ~ 150 DEG C.In the present invention, the reaction pressure of described neutralization reaction is preferably 80000Pa ~ 100000Pa, is more preferably 85000Pa ~ 95000Pa, most preferably is 87000Pa ~ 92000Pa.Described intermediate product and basic cpd are preferably carried out neutralization reaction by the present invention under the condition stirred, and obtain sulfonated gilsonite.
The present invention tests the production efficiency that aforesaid method prepares sulfonated gilsonite.In the present invention, described production efficiency is prepare every kilogram of sulfonated gilsonite time used.Test result is, the production efficiency that method provided by the invention prepares sulfonated gilsonite is 0.003 hour/kilogram ~ 0.005 hour/kilogram, and production efficiency is higher.The present invention tests high temperature and high pre ssure filtration, relative expansion reduced rate, water solubles content, the technical indicator such as pH value and moisture content of the sulfonated gilsonite obtained.
In the present invention, the measuring method of the high temperature and high pre ssure filtration of described sulfonated gilsonite is:
Measure 350mL distilled water, the drilling fluid test sodium bentonite of 14g is added in described distilled water, 24h is left standstill by being poured into by described mixture after the mixture high-speed stirring 20min obtained in maintenance tank, the evaluation soil of the feero-chromo-lignosulfonate and 7.0g that add 7.0g again in said mixture carries out the stirring at low speed of 30min, then by the stirring product mass percent obtained be 20% the NaOH aqueous solution regulate make its pH value be 10, then above-mentioned stirring product is carried out again the high-speed stirring of 20min, obtain base slurry.
The sulfonated gilsonite that 7.0g the present invention prepares is added in above-mentioned base slurry, the mixture obtained is carried out the stirring at low speed of 30min, it is the NaOH aqueous solution adjustment of 20% by the stirring product mass concentration obtained, its pH is made to be 10, by above-mentioned pH value be 10 stirring product first carry out the high-speed stirring of 20min, carry out the stirring at low speed of 1h again, obtain detecting liquid.According to the above-mentioned detection liquid of standard test of GB/T 16783.1-2006 ” industrial gas oil drilling fluid on-the-spot test part 1: water-base drilling fluid ” at 150 DEG C, high temperature and high pre ssure filtration under 3.45MPa.
In the present invention, the measuring method of described sulfonated gilsonite pH value is:
Take sulfonated gilsonite prepared by 2.0g the present invention, put it in the beaker of 300mL, in described beaker, add the distilled water of 200mL, carry out the stirring and dissolving of 30min, the solution glass stick obtained is dripped on pH test paper, reference standard color range reading.
In the present invention, the measuring method of described sulfonated gilsonite moisture content is:
Take the weighing bottle that sulfonated gilsonite prepared by 10g the present invention is placed in constant weight, weighing precision is accurate to 0.01g, and described weighing bottle is put into thermostatic drying chamber, dry 2h at 105 DEG C ± 3 DEG C, then put into moisture eliminator after being taken out by described weighing bottle and be cooled to 25 DEG C, claim its quality.The moisture content W of the sulfonated gilsonite prepared according to the formulae discovery the present invention shown in formula (I):
In formula (I):
W is moisture content, represents (%) with percentage ratio;
M 1for dry front weighing bottle adds the quality of sulfonated gilsonite prepared by the present invention, unit is gram (g);
M 2for weighing bottle after drying adds the quality of sulfonated gilsonite prepared by the present invention, unit is gram (g);
M 3for the quality of weighing bottle, unit is gram (g).
In the present invention, the testing method of the water solubles content of described sulfonated gilsonite is:
A paper roll be rolled into lens paper put into by the absorbent cotton getting 0.2g ~ 0.3g, and at 105 DEG C ± 2 DEG C, dry 2h for subsequent use;
Sulfonated gilsonite the present invention prepared crosses the sieve that sieve aperture is 0.45mm, the powdery sulfonated gilsonite obtained is dispersed in water, prepare powdery water-dispersion emulsified bitumen (SFT) sample, take the above-mentioned powdery water-dispersion emulsified bitumen sample of 0.5g, weighing precision is accurate to 0.0001g, described sample is put into above-mentioned paper roll Bao Yanhou to weigh, weighing data is designated as m 4; Paper roll after weighing is put into the sample cup of extractor, described sample cup to be hung in extractor below miniature prolong;
In above-mentioned extractor, inject the distilled water of 250mL ~ 300mL, described extractor is put into electric mantle and heats and keep boiling state, treat that the effluent liquid of described extractor is colourless, heating can be stopped.Take out the paper roll in above-mentioned sample cup, be placed in watch-glass, at described watch-glass being put into inherent 105 DEG C ± 2 DEG C of loft drier, carry out the drying of 4h, more dried paper roll is taken out from above-mentioned loft drier put into moisture eliminator, weigh after being cooled to 25 DEG C, weighing data is designated as m 5.
In the present invention, the measuring method of the relative expansion reduced rate of described sulfonated gilsonite is:
Take 10g drilling fluid calcium bentonite, it is stablized 5min aftershaping under 4MPa pressure, measures with NP-02 type shale expansion determinator the sulfonated gilsonite aqueous solution 8h shale expansion reading prepared of the present invention that distilled water 8h shale expansion reading and mass concentration are 3% respectively.Sulfonated gilsonite aqueous solution 8h shale expansion reading prepared by the present invention that described distilled water 8h shale expansion reading and described mass concentration are 3% by the present invention carries out twice replicate(determination), if the difference of the result of twice replicate(determination) is not more than 5%, then get its arithmetical av as measurement result.In the present invention, in above-mentioned distilled water 8h shale expansion reading mensuration process, after distilled water immersion experiment rock core 8h, rock core swell increment should be greater than 8.0mm, otherwise the wilkinite of the experiment rock core needing adjustment or replacing to use.The relative expansion reduced rate E of the sulfonated gilsonite prepared according to the formulae discovery the present invention shown in formula (III):
Test result is, the high temperature and high pre ssure filtration of sulfonated gilsonite prepared by the present invention is 6mL ~ 9.4mL, and relative expansion reduced rate is 40% ~ 55%, water solubles content is 73.9% ~ 90%, and pH value is 9 ~ 10.5, and moisture content is 4.3% ~ 8.9%, stable performance is qualified product.
The invention provides a kind of preparation method of sulfonated gilsonite, comprise the following steps: a, pitch and sulphonating agent are carried out sulfonation reaction, obtain intermediate product, the softening temperature < of described pitch 110 DEG C; B, described intermediate product and basic cpd are carried out neutralization reaction, obtain sulfonated gilsonite.Pitch lower for softening point temperature and sulphonating agent are directly carried out sulfonation reaction by the present invention, the pitch that the amount of heat utilizing sulfonation reaction to release makes softening point temperature lower becomes liquid bitumen, and this liquid bitumen can compare sufficient sulfonation reaction with sulphonating agent.Compared with prior art, the present invention can make pitch carry out sufficient sulfonation reaction without the need to pitch being pulverized rear dissolving in organic solvent, prepares sulfonated gilsonite; The present invention has saved a large amount of time of carrying out removing water treatment to organic solvent in the process preparing sulfonated gilsonite, and therefore preparation method’s production efficiency of sulfonated gilsonite provided by the invention is higher.
In addition, pitch easily hardens, pulverize difficulty, and the present invention without the need to being pulverized by pitch, making preparation method’s technique of sulfonated gilsonite provided by the invention simple, further increasing the production efficiency of sulfonated gilsonite in the process preparing sulfonated gilsonite; And the present invention removes without the need to the organic solvent in the sulfonated gilsonite that will prepare, avoids the loss of effective constituent in sulfonated gilsonite, the Performance comparision of sulfonated gilsonite that therefore the present invention obtains is stablized.
In order to understand the present invention further, below in conjunction with embodiment, the preparation method to sulfonated gilsonite provided by the invention is described in detail, but they can not be interpreted as limiting the scope of the present invention.
After preparing sulfonated gilsonite, the output of sulfonated gilsonite that the present invention prepares the sulfonated gilsonite time used according to embodiment 1 and obtains, calculate the production efficiency of sulfonated gilsonite, calculation result is, the production efficiency that the method that the embodiment of the present invention 1 provides prepares sulfonated gilsonite is 0.003 hour/kilogram, and production efficiency is higher.
The present invention tests high temperature and high pre ssure filtration, relative expansion reduced rate, water solubles content, the technical indicator such as pH value and moisture content of the sulfonated gilsonite that embodiment 1 obtains according to the method described in technique scheme, test result is as shown in table 1, and table 1 is the test result of the high temperature and high pressure filtration of the sulfonated gilsonite that the embodiment of the present invention and comparative example obtain, relative expansion reduced rate, water solubles content, pH value and moisture content.As shown in Table 1, the sulfonated gilsonite that the embodiment of the present invention 1 obtains is qualified product.
The test result of the high temperature and high pressure filtration of the sulfonated gilsonite that table 1 embodiment of the present invention and comparative example obtain, relative expansion reduced rate, water solubles content, pH value and moisture content
The invention provides a kind of preparation method of sulfonated gilsonite, comprise the following steps: a, pitch and sulphonating agent are carried out sulfonation reaction, obtain intermediate product, the softening temperature < of described pitch 110 DEG C; B, described intermediate product and basic cpd are carried out neutralization reaction, obtain sulfonated gilsonite.Pitch lower for softening point temperature and sulphonating agent are directly carried out sulfonation reaction by the present invention, the pitch that the amount of heat utilizing sulfonation reaction to release makes softening point temperature lower becomes liquid bitumen, and this liquid bitumen can compare sufficient sulfonation reaction with sulphonating agent.Compared with prior art, the present invention can make pitch carry out sufficient sulfonation reaction without the need to pitch being pulverized rear dissolving in organic solvent, prepares sulfonated gilsonite.The present invention has saved a large amount of time of carrying out removing water treatment to organic solvent in the process preparing sulfonated gilsonite, and therefore preparation method’s production efficiency of sulfonated gilsonite provided by the invention is higher.
In addition, pitch easily hardens, pulverize difficulty, and the present invention without the need to being pulverized by pitch, making preparation method’s technique of sulfonated gilsonite provided by the invention simple, further increasing the production efficiency of sulfonated gilsonite in the process preparing sulfonated gilsonite; And the present invention removes without the need to the organic solvent in the sulfonated gilsonite that will prepare, avoids the loss of effective constituent in sulfonated gilsonite, the Performance comparision of sulfonated gilsonite that therefore the present invention obtains is stablized.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
The invention discloses a kind of preparation method of sulfonated gilsonite/sodium alginate hybridized film, preparation including preparing sulfonated gilsonite dispersion liquid and film, the preparation process of wherein film is, is 2.5% by sodium alginate particle stirring 1h soluble in water according to mass fraction at 25 35 DEG C；Sulfonated gilsonite dispersion liquid is added dropwise in above-mentioned sodium alginatesoln, the mass ratio of sulfonated gilsonite and sodium alginate particle is 0.01~0.06:1,4h is stirred, obtained casting solution is filtered, is equably spun on after standing and defoaming on polyacrylonitrile ultrafiltration film, and dry at room temperature；Composite membrane is soaked in the calcium chloride solution that molar concentration is 0.2 0.5M and is crosslinked 10min, room temperature is dried as gained.Preparation process of the present invention is easy, and controllability is strong, cheap and easy to get using raw material, abundance, is applicable to liquid separation field.Obtained hybridized film is respectively provided with good ethanol/water separating property under different operating conditions.
Technical field
The present invention relates to a kind of preparation method of seperation film and application, predominantly sulfonated gilsonite/sodium alginate hybridized film and Preparation method and application, belong to new membrane technology isolation technics.
In recent years, global economy, which develops rapidly to live for people, creates many facilities, on the other side, is environmental problem Getting worse.The continuous consumption of the basic fossil fuel such as coal, oil, natural gas while environmental problem is brought also along with Reserves are reduced.The utilization of clean type new energy are particularly important.Alcohol fuel preparation is simple cheap, and combustion product cleaning is not easy Pollute, there is important development prospect.Ethanol dehydration prepares alcohol fuel and is referred to as important development problem.Currently used ethanol Dewatering includes chemical reaction conversion method, absorption, azeotropic distillation, vacuum distillation, UF membrane etc..Wherein membrane separation process has energy The advantages that low, easy to operate, equipment investment is small is consumed, is highly suitable for the production process of alcohol fuel.Based on dissolving-diffusion machine Reason, it is to prepare the target of high-performance ethanol dehydration film to improve the flux of film and separation factor.By being introduced in polymer matrix Hybrid organic-inorganic film prepared by inorganic component, can improve the network structure of polymer matrix, reduce the crystallinity of film, carry The free volume property of high film, increase the permeation flux of film.And the Preferential adsorption effect of the inorganic component and water introduced can be with Improve the separation factor of film.The mechanical stability of film and heat endurance also increase simultaneously.It is but inorganic in hybridized film at present The preparation process of filler is complicated, and it is high to prepare cost.And sulfonated gilsonite, as a kind of drilling fluid raw material, cheap and easy to get, source is wide It is general, it is with a wide range of applications, and the hybridized film of sulfonated gilsonite filling has no report for ethanol/water separation field.
It is an object of the invention to provide a kind of sulfonated gilsonite/sodium alginate hybridized film and preparation method and application.This sulphur Change pitch/sodium alginate hybridized film and utilize separating alcohol/water solution system, there is good separation effect at a temperature of adequate operation Fruit, preparation method is simple, and material is cheap and easy to get.
In order to solve the above-mentioned technical problem, a kind of sulfonated gilsonite/sodium alginate hybridized film proposed by the present invention, is by sulfonation Pitch and sodium alginate are according to mass ratio 0.01:1~0.06:It is the compound of 300nm~400nm that 1 spin coating, which forms separating layer thickness, Film；Wherein, the sulfonation degree of sulfonated gilsonite is 6%.
The preparation method of above-mentioned sulfonated gilsonite/sodium alginate hybridized film, comprises the following steps：
Step 1: it is that 3g/500~1000ml weighs the sulfonated gilsonite that sulfonation degree is 6% and is dissolved according to mass volume ratio In ionized water, the suspension of black is made in magnetic agitation 1h；First the suspension is filtered with the filter cloth of 500 mesh, then with 8000rpm centrifuges 5min, takes upper solution, and sulfonated gilsonite dispersion liquid is made；
It is 2.5% by sodium alginate particle stirring 1h soluble in water, shape according to mass fraction Step 2: at 25-35 DEG C Into sodium alginate soln；The sulfonated gilsonite dispersion liquid that step 1 obtains is added dropwise in above-mentioned sodium alginate soln, wherein, The mass ratio of sulfonated gilsonite and sodium alginate particle is 0.01~0.06:1,4h is stirred, obtains casting solution；By the casting solution mistake Filter, be equably spun on after standing and defoaming on the polyacrylonitrile ultrafiltration film that molecular cut off is 100,000, the process conditions of spin coating are： First with 500rpm spin coating 20s, then with 800rpm spin coatings 40s；Composite membrane is obtained, and is dried at room temperature；The composite membrane is soaked in The calcium chloride solution that molar concentration is 0.2-0.5M is crosslinked 10min, and room temperature is dried, and the separating layer thickness finally obtained is 300nm ~400nm composite membrane is sulfonated gilsonite/sodium alginate hybridized film.
Sulfonated gilsonite obtained above/sodium alginate hybridized film is used for separation water/ethanol (H2O/C2H5OH) mixed liquor Body, sulfonated gilsonite loading (the i.e. quality of sulfonated gilsonite and sodium alginate particle of experiment evaluation and test different quality containing at 76 DEG C Than for 0.01~0.06:1) film, permeation flux are 1117~1879g/m2H, H2O/C2H5OH separation factors 835~1903.
Compared with prior art, the beneficial effects of the invention are as follows：
Sulfonated gilsonite/sodium alginate hybridized film separation temperature easily reaches, and separating rate is fast, without using additive, divides From efficiency high, raw material is cheap and easy to get, can be recycled again for industrial sulfonated gilsonite, and formula is simple, easily operated.Separately Outside, long-term stable experiment as shown by data, the method, which prepares gained hybridized film, has more superior water resistance, mechanical stability and heat Stability, service life length, and the contained humidity suitable for separating alcohol solution under the conditions of high temperature low water content, show excellent Separating property.
Technical solution of the present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings, described is specific Only the present invention is explained for embodiment, is not intended to limit the invention.
A kind of sulfonated gilsonite/sodium alginate hybridized film proposed by the present invention, is according to matter by sulfonated gilsonite and sodium alginate Measure ratio 0.01:1~0.06:1 spin coating forms the composite membrane that separating layer thickness is 300nm~400nm；Wherein, the sulphur of sulfonated gilsonite Change degree is 6%.
A kind of drilling fluid sulfonated gilsonite and its preparation method and application
The present invention relates to drilling fluid sulfonated gilsonite field, a kind of drilling fluid sulfonated gilsonite and its preparation method and application is disclosed.This method includes：(1) it carries out asphalt stock and organic solvent to be mixed to get reaction raw materials, reaction raw materials and sulfonating agent is subjected to sulfonating reaction；(2) product for obtaining the sulfonating reaction carries out neutralization reaction, then is distilled and dried, and sulfonated gilsonite is obtained；Wherein, on the basis of the total weight of the asphalt stock, in the asphalt stock, content of ashes is 0.01~6.5 weight %, and the atomic ratio of hydrogen and carbon is (0.6~1.2) in the asphalt stock：1.The high water solubility of obtained sulfonated gilsonite, the high degree of dispersion in drilling fluid, lower production costs, and there is lower high temperature and high pressure filter loss.
The present invention relates to drilling fluid sulfonated gilsonite fields, and in particular, to a kind of drilling fluid sulfonated gilsonite and its system Preparation Method and application.
Sulfonated gilsonite is that under the action of sulfonating agent sulfonating reaction occurs for monocycle in pitch, bicyclic, condensed-nuclei aromatics, with sulphur Hydrogen atom on acidic group substituted aroma ring and the sulfonic acid pitch generated.Sulfonated gilsonite contains the water solubility of a large amount of electronegativity ion Component, these electronegative particles are attached to the positive charge edge of clay or shale by chemical action and mutually tie with positive charge It closes, prevents liquid from entering shale, reduce filter loss, inhibit clay swell and Shale Dispersion, to reduce the possibility of shale collapse Property, improve the stability of the borehole wall.The molten component of oil of sulfonated gilsonite provides appropriately sized particle, is conducive to wall building, can be covered on Rock surface, improvement of mud cake form Bao Erren, the filter cake that permeability is small and compressibility is strong, to reduce filter loss, and energy The lubricity for enhancing filter cake, reduces the torsion and towing tension of drilling tool, extends the service life of drilling tool.
The beginning of the sixties, U.S. Philips Corporation are raw material by processes systems such as sulfonation, neutralization and post-processings using petroleum residual oil Drilling fluid analog assistant.Asphalt paraffin is more, is difficult to be sulfonated, and the remaining sulfonating agent neutralization with alkali stage generates by-product Object sodium sulphate makes the drilling fluid prepared generate foam, very unfavorable to drilling well, and when well depth increases, well temperature and pressure increase Added-time, the sulfonated gilsonite lose its function.
This discloses a kind of Sulfonated asphalt used for high-temp and-pressure drilling liquid, drips containing coal tar sulfonate, petroleum Green sulfonate and the non-sulfonated part of coal tar and the non-sulfonated part of asphalt, sulfonated gilsonite contain 40~80% water-soluble objects Matter, 20~60% acetone soluble substances.Also disclosed preparation method includes：Coal tar and pitch are dissolved in solvent, sulphur is used Agent sulfonation, it is dry that finished product, coal tar contain 44~75% cyclic compounds with alkali neutralization；Pitch is asphalt, containing thick Cycle compound 30~60%；Reactant coal tar accounts for the 10~100% of coal tar and pitch weight sum；Solvent is liquid at room temperature Body alkane；Sulfonating agent is sulfur trioxide, oleum, the concentrated sulfuric acid, chlorosulfonic acid；Alkali is sodium hydroxide, potassium hydroxide；Sulfonation temperature 0~160 DEG C, preferably 10 DEG C；Sulfonating reaction time 10s~8h, preferably 2h；Neutralization temperature is room temperature to 150 DEG C, preferably 10 ~50 DEG C；10% pH value of solution is 3~12, preferably 8~10；Drying temperature is 70~150 DEG C, preferably 70~80 DEG C.Coal tar Contain a certain amount of oxygen-containing aromatic compound in oil, the progress of sulfonating reaction can be inhibited in sulfonation process, to need bigger The sulfonating agent of amount.
This discloses a kind of drilling fluid modified sulfonated gilsonite, including high temperature coal tar pitch and sulfonation medium temperature Coal tar pitch.Also disclosed preparation method includes：Medium temperature coal pitch, kerosene and oleum are mixed, obtained in sulfonation after reaction Warm coal tar pitch；The sulfonation medium temperature coal pitch is mixed with high temperature coal tar pitch, obtains drilling fluid modified sulfonated gilsonite. Its In, medium temperature coal pitch softening point is 75 DEG C~95 DEG C, and the softening point of high temperature coal tar pitch is 130~150 DEG C.In this method, ginseng It is only medium temperature coal pitch and kerosene with sulfonating reaction, utilizes the high temperature coal tar pitch to improve the high temperature and pressure drop of modified sulfonated gilsonite Filtration property.But the oil-soluble ingredients of high temperature coal tar pitch are less, cannot effectively enhance the lubricity of filter cake, to increase brill The torsion of tool reduces the service life of drilling tool.
It can be seen that the sulfonated gilsonite of prior art preparation is for the application in drilling fluid, there is also adverse effects.
The purpose of the invention is to improve the high temperature and pressure filtrate loss controllability of sulfonated gilsonite, a kind of drilling fluid use is provided Sulfonated gilsonite and its preparation method and application.
To achieve the goals above, the present invention provides a kind of method for preparing drilling fluid sulfonated Gilsonite, and this method includes： (1) it carries out asphalt stock and organic solvent to be mixed to get reaction raw materials, reaction raw materials and sulfonating agent is subjected to sulfonating reaction； (2) product for obtaining the sulfonating reaction and aqueousslkali carry out neutralization reaction, then by the product of the neutralization reaction through distilling And drying, obtain sulfonated Gilsonite；Wherein, on the basis of the total weight of the asphalt stock, content of ashes in the asphalt stock For 0.01~6.5 weight %, the atomic ratio of hydrogen and carbon is (0.6~1.2) in the asphalt stock：1.
The present invention also provides a kind of sulfonated Gilsonites as made from method of the invention.
The present invention also provides a kind of application of sulfonated Gilsonite of the invention in drilling fluid.
Through the above technical solutions, the present invention analyzes and limits the atomic ratio of the content of ashes in asphalt stock, hydrogen and carbon, To realize the suitable asphalt stock of selection, the asphalt stock containing coal directly-liquefied residue is preferably selected, sulfonated reaction can To obtain that the sulfonated Gilsonite of drilling fluid can be directly used as, it is not required to add other additives again.
It is 70 weight % or more, sodium sulfonate that the sulfonated Gilsonite that method provided by the invention is prepared, which has water solubles content, Base content be 10 weight % or more high water solubility, and be applied to drilling fluid when, according to Q/SH0043-2007 method measurement have 18ml high temperature and high pressure filter loss below.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
In the present invention, the product of the neutralization reaction is distilled, is to contain in the product for removing the neutralization reaction The water that some organic solvents and reaction generate.
The present invention also provides a kind of sulfonated Gilsonites as made from method of the invention.
It is water-soluble in the sulfonated Gilsonite on the basis of the total weight of the sulfonated Gilsonite in the case of, according to the invention it is preferred to Object content is 70 weight % or more, and sodium sulfonate group content is 10 weight % or more.
In the sulfonated Gilsonite that the present invention obtains, sodium sulfonate group content can have excellent more than 10 weight % High-temperature behavior.
The present invention also provides a kind of application of sulfonated Gilsonite of the invention in drilling fluid.
It can be following method that sulfonated Gilsonite of the invention, which is used for drilling fluid,：
In drilling process, by sulfonated Gilsonite of the invention according to additive amount be 1 weight of weight %~3 % and water-based drilling Liquid (such as+0.02 weight % resinae of weight %KOH+1~2.5 fluid loss additive of+0.25 weight % soda ash of 4 weight % bentonite+ + 5 weight of 1.5~2.5+3 weight % polymeric alcohol of weight % amine salt fluid loss additive+0.4 weight % coating agent of+0.4 weight % polyamine Amount % fluid lubricant+proper quantity of defoaming agent) it fills together into drilling well.Wherein, additive amount refers to that sulfonated Gilsonite dosage accounts for sulfonation The percentage composition of the sum of asphalt content and water-base drilling fluid dosage.
The present invention provides drilling fluid sealing agent low Poison sulfonated Gilsonite, high temperature and high pressure filter loss is 3.8 5.6ml/30min, water solubles content is water solubles content 79.4 87.6%, and sodium sulfonate group content 15.6 18.8%, the drilling fluid is prepared with sealing agent low Poison sulfonated Gilsonite by following methods：Silica white is dispersed in petroleum ether, chlorosulfonic acid, stirring to obtain sulfonating agent is slowly added；It will carry out being mixed to get reaction raw materials in low Poison pitch and solvent, reaction raw materials and sulfonating agent are subjected to 3 5h of sulfonating reaction；The product that sulfonating reaction is obtained is 89 with sodium hydrate aqueous solution progress neutralization reaction to pH, then the product of the neutralization reaction is obtained drilling fluid sealing agent low Poison sulfonated Gilsonite through distilling and drying；Solvent includes C6‑C12Sodium alkyl benzene sulfonate and petroleum ether.Drilling fluid of the present invention is high with sealing agent low Poison sulfonated Gilsonite water solubles content, and sulphonation rate is high, and drop high temperature and pressure filtration effect is good, and preparation method reaction condition is mild, is suitble to large-scale industrial production.
The invention belongs to petroleum drilling fluid additive agent fields, more particularly, to a kind of sealing agent low Poison sulfonation of drilling fluid Pitch.
Background technology
Drilling fluid is a kind of emulsifying pour depressor of good performance and drilling fluid additive with sealing agent low Poison sulfonated Gilsonite, Have the function of anti-collapse, lubrication and reduces high temperature and high pressure filter loss.Drilling fluid sealing agent low Poison sulfonated Gilsonite contains sulfonic acid Base, hydration is very strong, when being adsorbed on shale interface, the aquation dispersion of shale particle can be prevented to play the role of anti-collapse.Together When, part not soluble in water can fill pore throat again and plugging action is played in crack, and can be covered in shale interface, improve mud cake matter Amount.Drilling fluid also plays lubrication with sealing agent low Poison sulfonated Gilsonite in drilling fluid and reduces high temperature and high pressure filter loss, It is multi-functional organic additive for drilling fluid such as a kind of leak stopping, anti-collapse, lubrication, drag reduction, inhibition.
Domestic majority is used using oleum, sulfur trioxide, sodium sulfite or sodium hydrogensulfite as sulfonating agent at present It disposably feeds intake, reaction speed is controlled by adjusting mixing speed.The technique is there are sulfonation and hydrolyzes the positive mutual shadow of back reaction It rings, the shortcomings of reaction speed should not control, sulphonation rate is low, sulfonation is uneven.Obtained drilling fluid sealing agent low Poison sulphur Change pitch sodium sulfonate group and water solubles content is low, in the case where dosage is less, drop high temperature and high pressure filter loss effect is poor.
Application number：201410005382.7 providing a kind of preparation method of sulfonated Gilsonite, include the following steps：It a, will drip It is green to carry out sulfonating reaction with sulfonating agent, obtain intermediate product, 110 DEG C of the softening point ＜ of the pitch；B, by the intermediate product Neutralization reaction is carried out with alkali compounds, obtains sulfonated Gilsonite. The present invention by the lower pitch of softening point temperature and sulfonating agent into Row sulfonating reaction, the amount of heat released using sulfonating reaction makes the lower pitch of softening point temperature become liquid bitumen, this Liquid bitumen can be compared sufficient sulfonating reaction with sulfonating agent.This method is organic molten without being dissolved in after crushing pitch Sulfonated Gilsonite can be prepared in agent, saved the time largely carried out to organic solvent except water process.
The object of the present invention is to provide a kind of drilling fluid that sodium sulfonate group content is high sealing agent low Poison sulfonated Gilsonite, water Dissolubility is good, and the high temperature and pressure leak-off for the drilling fluid that 2% drilling fluid is obtained with sealing agent low Poison sulfonated Gilsonite is added in being starched to base Amount is 3.8-5.6ml/30min, well below prior art products.
The technical scheme is that：Drilling fluid is 3.8- with the high temperature and high pressure filter loss of sealing agent low Poison sulfonated Gilsonite 5.6ml/30min, water solubles content 79.4-87.6%, sodium sulfonate group content 15.6-18.8%, the drilling fluid block Agent low Poison sulfonated Gilsonite is prepared by following methods, is included the following steps：
1) silica white of 50 parts by weight is dispersed in 80 parts by weight petroleum ethers, 80-100 parts by weight is slowly added Chlorosulfonic acid is stirred to react 2-3 hours, obtains sulfonating agent；
2) it will carry out being mixed to get reaction raw materials in the low Poison pitch of 100 parts by weight and the solvent of 80-120 parts by weight, Reaction raw materials and the sulfonating agent of 150-200 parts by weight are subjected to sulfonating reaction 3-5h, controlling reaction temperature is 40- in reaction process 60 DEG C, stir speed (S.S.) 500rpm；
3) product for obtaining the sulfonating reaction and sodium hydrate aqueous solution progress neutralization reaction to pH are 8-9, then will The product of the neutralization reaction obtains drilling fluid sealing agent low Poison sulfonated Gilsonite through distilling and drying；
The solvent includes C6-C12Sodium alkyl benzene sulfonate 30-50 parts by weight, petroleum ether 50-100 parts by weight.
Drilling fluid is adopted new technology with sealing agent low Poison sulfonated Gilsonite and is prepared, and product fluorescence grade is reduced to 5 grades Hereinafter, not interfering survey well logging.
The drilling fluid is mild with the preparation method reaction condition of sealing agent low Poison sulfonated Gilsonite, high conversion rate, production effect Rate is high, is suitble to large-scale industrial production, and the water solubles content of prepared drilling fluid sealing agent low Poison sulfonated Gilsonite is high, It is good that high temperature and pressure filtration effect drops.
The present invention obtains suspension by colloidal silica dispersion to petroleum ether, and chlorosulfonic acid reaction is then added, obtains silica gel sulphur Acid.Silica gel sulfuric acid can be used for the aromatic ring in drilling fluid sealing agent low Poison sulfonated Gilsonite, and reaction condition is mild, reaction process In not will produce a large amount of waste water, environmental-friendly, and sulfonation effect is good, high conversion rate, obtained semi-annular jade pendant pitch sodium sulfonate group contains Amount is high.
Drilling fluid of the present invention is uniform with sealing agent low Poison sulfonated Gilsonite sulfonating reaction, and sulphonation rate is high, sodium sulfonate group content Height, water solubles content is high, and high temperature and high pressure filter loss is low, and dispersion effect is good in drilling fluid, and performance is stablized.
Product that the sulfonating reaction is obtained and sodium hydrate aqueous solution carry out neutralization reaction to pH be 8-9, then by institute The product of neutralization reaction is stated through distilling and drying, obtains drilling fluid sealing agent low Poison sulfonated Gilsonite.
After testing, drilling fluid is 3.9ml/30min with the high temperature and high pressure filter loss of sealing agent low Poison sulfonated Gilsonite, water-soluble Object content is 84.5%, sodium sulfonate group content 18.8%.
A kind of sulfonated Gilsonite produces drying unit
The invention provides a kind of sulfonated Gilsonite and produce drying unit, comprise expansion drying main frame, hot-blast stove, screw feeder, eliminator, bagroom and air-introduced machine; The present invention adopts expansion drying technology in sulfonated gilsonite production drying at home first, because of the temperature-sensitive character of sulfonated gilsonite, instantaneously complete drying, prevent material coking variable color, compared with former cylinder scraper plate drying unit, production capacity improves, and is 6 times of former separate unit cylinder scraper plate drying unit, reduces energy consumption about 50% simultaneously; And hot-blast stove is transformed, Mist heat recovering, improve the effective rate of utilization of the energy, achieve to regulate and control fast and effectively to flue-gas temperature, there is larger market economy benefit, be suitable for extensive use.
The invention belongs to technical field of chemical production equipment, relate to the production equipment of sulfonated Gilsonite, specifically refer to the drying unit in the production of a kind of sulfonated Gilsonite.
Background technology
Sulfonated Gilsonite is widely used in the fields such as geological prospecting, oil, coalfield, natural gas exploration and exploitation as Deal With Drilling Fluid additive, in drilling fluid, play lubrication and reduce high temperature and high pressure filtration, be multi-functional organic additive for drilling fluid such as a kind of leak stopping, anti-collapse, lubrication, drag reduction, suppression, can directly join in all kinds of drilling fluid system.Due to extensive use and significant effect of sulfonated Gilsonite, product presents the good momentum of development that supply falls short of demand; But in recent years because harmful competition at a low price appears in domestic market, some pseudo sulfonated asphalt and sulfonated Gilsonite compound product are flooded market, this type of substitute cost of production and selling price low, though the anti-collapse effect of shutoff of part can be played, but still there is very large gap in its performance indications, effect of field application, hinder the development and application of sulfonated Gilsonite to a certain extent compared with sulfonated Gilsonite.
At present, in the sulfonated Gilsonite technological process of production, the drying unit used is that two Rolling scratch boarddriers operate simultaneously, its drying capacity is only 1 ton/platform every day, the requirement and the water content of finished product also falls short of the target, also need carry out redrying further by roller drying machine, could be up to standard; This kind of drying unit takes time and effort, and the most important thing is the raising greatly constraining product yield, becomes the technical bottleneck place that sulfonated Gilsonite is enhanced production capacities, improved quality, reduces costs.Therefore expanding new sulfonated Gilsonite drying unit, improve production capacity, reduce costs, present great market prospects, is a technical problem urgently to be resolved hurrily.
For above-mentioned technical problem, the invention provides a kind of sulfonated Gilsonite and produce drying unit, effectively to enhance productivity, product quality, to reduce cost of production.
The present invention is achieved through the following technical solutions above-mentioned purpose:
A kind of sulfonated gilsonite produces drying unit, it is characterized in that, comprising:
Expansion drying main frame, described expansion drying main frame is provided with air inlet port, gas outlet and charging aperture, is provided with agitator in expansion drying main frame, and this agitator is electrically connected with motor;
Hot-blast stove, described hot-blast stove is provided with cold air inlet, hot-blast outlet and exhanst gas outlet, described exhanst gas outlet is connected with the air inlet port of described expansion drying main frame after being communicated with by pipeline with hot-blast outlet, described hot-blast stove is also provided with interim air intake passage, this interim air intake passage is closed along furnace wall and is arranged and be communicated with described exhanst gas outlet, and the passway of described interim air intake passage is provided with valve;
Feeder, described feeder is connected with the charging aperture of expansion drying main frame;
Eliminator, the import of described eliminator is connected with the gas outlet of expansion drying main frame, and separator bottom is provided with bleeder valve;
Bagroom, described bagroom is connected with the outlet of described eliminator, is provided with discharge valve bottom bagroom;
Air-introduced machine, described air-introduced machine is connected with described bagroom.
Described expansion drying main frame top is positioned at gas outlet lower position and is provided with clasfficiator.
Air distributor is provided with between described expansion drying main frame and hot-blast stove.
Described agitator is T-shaped cutter group.
The invention has the beneficial effects as follows:
1, expansion drying technology is adopted first in sulfonated Gilsonite production drying at home, because of the temperature-sensitive character of sulfonated Gilsonite, instantaneously complete drying, prevent material coking variable color, compared with former cylinder scraper plate drying unit, production capacity improves, and is 6 times of former separate unit cylinder scraper plate drying unit, reduces energy consumption about 50% simultaneously;
2, because sulfonated Gilsonite does not have particular/special requirement to impurity, improve hot-blast stove, former hot-blast stove fume is that exhausting is arranged outward, after improvement, the flue gas of outer row is passed into system and carries out waste heat recovery, reduces energy loss, improves production capacity;
3, because sulfonated Gilsonite is heat-sensitive substance, the condition of high temperature should not be in for a long time, by setting up interim air intake passage on hot-blast stove, energy is quick, Effective Regulation flue-gas temperature, reduce the pressure differential in stove, slow down burn rate, thus effectively ensure that the quality of product;
4, the agitator in expansion drying main frame is T-shaped cutter group, adopts spring steel material, not yielding, good crushing effect, and the more former mixing plant of this T-shaped cutter is slightly long, reduces the distance of stirrer paddle and wall, eliminate dead angle, material is not easily cohered on inwall, avoids the shutoff stall of agitator.
5, whole drying system is in negative pressure air-tight state, and dust does not leak, and substantially reduces dust pollution, both ensure that workers ‘ health additionally reduces the pollution to environment, high-efficiency environment friendly.
Expansion drying main frame, described expansion drying main frame is provided with air inlet port, gas outlet and charging aperture, is provided with agitator in expansion drying main frame, and this agitator is electrically connected with motor;
Hot-blast stove, described hot-blast stove is provided with cold air inlet, hot-blast outlet and exhanst gas outlet, described exhanst gas outlet is connected with the air inlet port of described expansion drying main frame after being communicated with by pipeline with hot-blast outlet, described hot-blast stove is also provided with interim air intake passage, this interim air intake passage is closed along furnace wall and is arranged and be communicated with described exhanst gas outlet, and the passway of described interim air intake passage is provided with valve;
Feeder, described feeder is connected with the charging aperture of expansion drying main frame;
Eliminator, the import of described eliminator is connected with the gas outlet of expansion drying main frame, and separator bottom is provided with bleeder valve;
Bagroom, described bagroom is connected with the outlet of described eliminator, is provided with discharge valve bottom bagroom;
Air-introduced machine, described air-introduced machine is connected with described bagroom.
The molten sulfonated Gilsonite of drilling fluid peracid
The invention discloses the process of the molten sulfonated Gilsonite of drilling fluid peracid：Light oil is added in a kettle, then add the pitch powder of lightweight weight of oil 40 50%, it is heated to 30 50 DEG C, first add the liquid sulphur trioxide for accounting for liquid sulphur trioxide total amount 60~70%, add shepardite micro mist, rosin and aluminum stearate, it is sufficiently stirred to obtain mixed solution, the sodium hydroxide solution of pitch weight 30 40% is added in mixed solution again, with alkali neutralization and adjust pH value, when the molten thing content of oil is less than 30%, again in reaction kettle addition liquid sulphur trioxide, light oil is recycled, is baked to and crushing obtains the molten sulfonated Gilsonite of peracid. The present invention can form thin and compact mud cake when boring and opening oil reservoir, and shielded layer is formed in the thin layer of rock of borehole, can effectively control the number of dropouts of drilling fluid, improve mud cake intensity, prevent rock stratum water suction from peeling off；On the other hand protection reservoir, makes reservoir permeability be restored and improve.
Description
The present invention relates to used in oil, natural gas probing with shale suppression, closure microcrack, prevent from collapsing Block, improve wellbore stability, lubrication drop frictional resistance, high temperature and pressure vena caval filter, raising mud cake quality, in oil base and water-base drilling fluid It can improve filter cake quality, improve mud property, across-the-board regulation drilling mud performance, can make in oil itself and water-base drilling fluid With, do not injure the polynary drilling fluid of oil-gas Layer.
Background technology
Drilling fluid is the circulation flushing medium used in drilling in oil, natural gas drilling process.Drilling fluid is drilling well Blood, also known as drilling fluid, its main function one are cooling and lubricating cleaning drill bits, improve drilling results and extend drill bit Service life, second, for blocking hole wall crack, protects hole wall, prevents hole wall collapse and wellbore liquid leaching loss.Widely use at present Drilling fluid be mud drilling liquid, it is primarily adapted for use in loose, cranny development, easy collapsing and breaking, water-swellable and the hole wall such as peels off Unstable formation.Mostly contain the asphalt drilling fluid of sulfonated processing most added with pitch, particularly in mud drilling liquid at present Excellent, it is both good cooling lubricant and to have the borehole wall stabilizer of good anti sloughing effectiveness in probing.
Drilling fluid is when for drilling oil reservoir, between the sulfonated Gilsonite and reservoir rock, reservoir fluid in outside fluid such as Fruit is incompatible, and will produce a series of physico effect, cause reservoir, particularly compact reservoir sensitiveness infringement and it is organic Thing, inorganic matter precipitation, although can form mud cake plugged zone during probing, block fracture pore, are not easy after the acidifying of later stage mud cake It is cracked and blocks, cause reservoir permeability to reduce, so that the geologic steering drilling to compactness oil-gas field development and horizontal well Have a negative impact.
Although sulfonated Gilsonite drilling fluid can form thin and compact mud cake faster when boring and opening oil reservoir at present, in borehole wall rock Shielded layer is formed in the thin layer of stone, to control the depth of invasion of the wastage of drilling fluid and solid phase particles, but in shielding plugging layer Sulfonated Gilsonite in oily molten material be not easy to be dissolved in oil well production, cause reservoir permeability to reduce, influence production of hydrocarbons.
The present invention adds a small amount of aluminum stearate in sulfonated Gilsonite, and its purpose is to prevent in sulfonated Gilsonite due to adding The problem of having entered rosin and having brought drilling fluid to blister.
The present invention can also add the 0.1-0.5% ethylenediamine tetraacetic methene sodium phosphates of pitch weight in sulfonated Gilsonite, with regard to energy Drilling fluid viscosity and shear force are effectively reduced, and stable conjugate is formed with metal ion, makes drilling fluid that there is stronger salt resistance Ability and temperature resistance.Do not allow containing chlorine in sulfonated Gilsonite of the present invention, be in order to prevent drill bit to corrode.
The present invention one is that to improve the oily molten thing content of sulfonated Gilsonite and acid by controlling liquid sulphur trioxide addition molten Rate, makes drilling fluid form thin and tough mud cake in drilling rock layer, can reach closure crack, protect hole wall, prevent filtrate It is lost in, and mud cake can be made to be acidified de-plugging after dissolving in oil well production, adequately protects reservoir, from make can reservoir permeability The purpose for being restored and improving, while by adding shepardite micro mist, rosin, aluminum stearate and ethylenediamine tetraacetic methene sodium phosphate The problem of to prevent viscosity, blistering and shear force caused by water solubles content reduces from raising.
The present invention can be made into the product of following different models；
1st, the molten sulfonated Gilsonite of conventional sodium-salt type peracid
2nd, the molten sulfonated Gilsonite of sylvite type peracid is strengthened
3rd, the molten sulfonated Gilsonite of liquid-type peracid
The wherein molten sulfonated Gilsonite of sylvite type peracid belongs to enhanced, is made of the special sylvite for using the molten sulfonated Gilsonite of peracid , in addition to possessing the molten sulfonated Gilsonite performance of conventional sodium-salt type peracid, it can also make drilling fluid provide substantial amounts of water-soluble potassium ion, For needing potassium ion processing to be used fully to suppress the occasion of clay water-swellable.And contain in the molten sulfonated Gilsonite of liquid-type peracid There is 40% or so effective ingredient, can be suspended in nontoxic system.
Drilling fluid of the present invention is that the sulfonated Gilsonite that a kind of water-soluble and oil-soluble has both produces with the molten sulfonated Gilsonite of peracid Product, are one of auxiliary agents that be able to need not lack in drilling fluid, it is not only cheap, but also has polynary performance.
A, quantitative light oil is first added in a kettle, then add lightweight weight of oil 40-50%, the drip that particle is 20-50 mesh Blue or green powder, being sufficiently stirred makes pitch be dispersed in light oil, obtains basic solution,
B, basic solution is heated to 30-50 DEG C, is then first slowly added to account for the liquid of liquid sulphur trioxide total amount 60~70% State sulfur trioxide, adds shepardite micro mist, rosin and aluminum stearate after being sufficiently stirred, the sulfur trioxide total amount is pitch emphasis The 50-70% of amount, the shepardite micro mist addition are the 5-10% of pitch weight, and rosin addition is the 2- of pitch weight 5%, aluminum stearate addition is the 1-3% of pitch weight, is sufficiently stirred to obtain mixed solution,
C, the sodium hydroxide solution of pitch weight 30-40% is slowly added in mixed solution, with alkali neutralization and adjusts pH value as 8 ~9.5, pitch sodium sulfonate solution is formed after carrying out sulfonation processing,
D, pitch sodium sulfonate solution is sampled into the molten thing content of detection oil and acid-soluble ratio, when the molten thing content of oil is low less than 30%, acid-soluble ratio Liquid sulphur trioxide is slowly added to until the molten thing content of oil is higher than 90% higher than 30%, acid-soluble ratio when 90%, then in reaction kettle Only,
E, fluid separation and solution distillation are carried out again, are recycled light oil, are obtained fix-bitumen sodium sulfonate, then be baked to and crush Obtain the molten sulfonated Gilsonite of peracid.
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