CN103012641A - Preparation method of organic-silicon-containing drag reducer for oil product delivery - Google Patents
Preparation method of organic-silicon-containing drag reducer for oil product delivery Download PDFInfo
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- CN103012641A CN103012641A CN2012105943991A CN201210594399A CN103012641A CN 103012641 A CN103012641 A CN 103012641A CN 2012105943991 A CN2012105943991 A CN 2012105943991A CN 201210594399 A CN201210594399 A CN 201210594399A CN 103012641 A CN103012641 A CN 103012641A
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- 238000002360 preparation method Methods 0.000 title claims description 6
- 239000003638 chemical reducing agent Substances 0.000 title abstract 4
- 239000003921 oil Substances 0.000 title description 17
- 229910052710 silicon Inorganic materials 0.000 title 1
- 239000010703 silicon Substances 0.000 title 1
- 239000004711 α-olefin Substances 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000009467 reduction Effects 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 230000008014 freezing Effects 0.000 claims description 10
- 238000007710 freezing Methods 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 9
- 229910000077 silane Inorganic materials 0.000 claims description 9
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 3
- 235000010292 orthophenyl phenol Nutrition 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- 230000008719 thickening Effects 0.000 claims description 3
- WGRZHLPEQDVPET-UHFFFAOYSA-N 2-methoxyethoxysilane Chemical compound COCCO[SiH3] WGRZHLPEQDVPET-UHFFFAOYSA-N 0.000 claims description 2
- FASUFOTUSHAIHG-UHFFFAOYSA-N 3-methoxyprop-1-ene Chemical compound COCC=C FASUFOTUSHAIHG-UHFFFAOYSA-N 0.000 claims description 2
- AGUIILSGLFUTKG-UHFFFAOYSA-N CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] Chemical compound CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] AGUIILSGLFUTKG-UHFFFAOYSA-N 0.000 claims description 2
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- MJINPUKGRATQAC-UHFFFAOYSA-N triethoxy(prop-1-enyl)silane Chemical compound CCO[Si](OCC)(OCC)C=CC MJINPUKGRATQAC-UHFFFAOYSA-N 0.000 claims description 2
- OWUTVCVPEOXXHD-UHFFFAOYSA-N trimethoxy(prop-1-enyl)silane Chemical compound CO[Si](OC)(OC)C=CC OWUTVCVPEOXXHD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 38
- 238000012545 processing Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 11
- 229920001577 copolymer Polymers 0.000 abstract description 6
- 229920013639 polyalphaolefin Polymers 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000013461 design Methods 0.000 abstract description 2
- 230000015271 coagulation Effects 0.000 abstract 1
- 238000005345 coagulation Methods 0.000 abstract 1
- 238000001879 gelation Methods 0.000 abstract 1
- 229920001296 polysiloxane Polymers 0.000 abstract 1
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 abstract 1
- 239000002283 diesel fuel Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 5
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000011158 quantitative evaluation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- -1 vinylsiloxane group Chemical group 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
一种含有机硅的油品输送减阻剂的制备方法，其特征是将重量百分数为90％-99％的碳数为C8-C18的α-烯烃与重量百分数为1％-10％的活性乙烯基硅烷为共聚原料，加入Ziegler-Natta催化剂进行聚合得到减阻共聚物，将其低温粉碎加工成120目以下减阻共聚物细粉末，加入水、表面活性剂和其它助剂调配形成稳定的减阻剂悬浮液产品。本发明的优点是从α-烯烃减阻聚合物分子结构设计入手，将少量活性乙烯基有机硅基团共聚引入聚α-烯烃减阻聚合物分子中，共聚合成非晶态、油溶性好、脆化温度高、减阻率高和抗剪切的减阻聚合物，从而解决现有减阻剂低温粉碎加工成本高、贮存过程中容易凝聚结胶和不耐剪切的问题。A method for preparing a silicone-containing drag reducer for oil transportation, which is characterized in that 90%-99% by weight of α-olefins with carbon numbers of C8-C18 and 1%-10% by weight of active Vinyl silane is used as the raw material for copolymerization, and Ziegler-Natta catalyst is added to carry out polymerization to obtain drag-reducing copolymer, which is pulverized at low temperature and processed into fine powder of drag-reducing copolymer below 120 mesh, and added with water, surfactant and other additives to form a stable Drag reducer suspension product. The advantage of the present invention is that starting from the molecular structure design of the α-olefin drag-reducing polymer, a small amount of active vinyl organosilicon groups are copolymerized and introduced into the poly-α-olefin drag-reducing polymer molecules, and the copolymerization becomes amorphous, oil-soluble, A drag-reducing polymer with high embrittlement temperature, high drag-reduction rate and shear resistance, thereby solving the problems of high low-temperature pulverization and processing costs, easy coagulation and gelation during storage, and shear resistance of existing drag-reducers.
Description
Technical field
The present invention relates to a kind of oil product and carry the preparation method of flow improver, particularly the copolymerization of vinylsiloxane group is introduced in the alpha-olefin anti-drag polymer molecule, copolymerization non-crystalline state, good, the easy grinding and processing of oil soluble, drag reducing efficiency height and shear-stable oil product are carried the method for flow improver, belong to petrochemical industry.
Background technology
Flow improver is a kind of chemical additive that is widely used in crude oil, products pipeline conveying, trace adds in the mobile oil product of Turbulent Flow can make turbulent flow be converted into laminar flow, greatly reduce the friction resistance of piping system, enlarge rapidly and economically the oil pipeline flow and reduce the transferpump energy consumption, improve the safety coefficient of oil pipeline operation.The market development of flow improver both at home and abroad is very fast, has been applied to marine and land hundreds of bar oil pipeline, and the pipeline that not only greatly improves oil product increases Movement Capabilities, and economic benefit is very considerable.China reaches more than 50% the interdependency of imported crude oil, and a large amount of flow improvers of long-distance transportation through pipeline consumption of imported crude oil need constantly to enlarge the flow improver industrial scale and reduce the flow improver production cost.
The significant flow improver of drag-reduction effect is molecular weight at 3,000,000-3,000 ten thousand long carbochain alpha-olefinic polymer (C in the industry practical application
6-C
18).Industrially usually first alpha-olefin mass polymerization under Z-N (Ziegler-Natta) catalyst action is made frictional reducing polymer, then frictional reducing polymer low temperature under the liquid nitrogen freezing condition is ground into the frictional reducing polymer particulate about 0.5mm, the aqueous solution that again its adding is contained dispersion agent and stablizer mixes and makes low viscous drag-reduction polymer suspension.
The flow improver need of production carries out under the severe condition such as anhydrous, anaerobic and low temperature, only has at present 3-5 company to carry flow improver by the suitability for industrialized production oil product both at home and abroad.Existing flow improver product Main Problems one is that production cost is high, limits to a certain extent its widespread use; The 2nd, drag reduction agent suspension condenses gum deposit easily in storage process, and product weak point storage period and quality are stable not; The 3rd, anti-shear performance is poor, needs segmentation to add in long distance is carried and replenishes the flow improver that consumes.
For the too high problem of flow improver production cost, can start with from reducing the several respects such as raw materials cost and reduction grinding and processing cost.Usually longer carbochain alpha-olefin and vinylbenzene relative low price, Chinese patent CN102504057 (2012-06-20) and US Patent No. 2003/0069330 (2003-04-10) openly will be than short carbon chain alpha-olefin or vinylbenzene and long carbochain alpha-olefin mixings copolymerization to reduce raw materials cost and improvement product performance.Need to consume a large amount of liquid nitrogen freezing agent during the frictional reducing polymer pulverize at low temperature, the grinding and processing cost accounts for more than 50% of flow improver total production cost, adopts Cryogenic air freezing to reduce the grinding and processing cost when Chinese patent CN101386665 (2009-03-18) is disclosed in the frictional reducing polymer grinding and processing.Condense easily the gum deposit problem for drag reduction agent suspension, the open solution of mixing separant or coating the frictional reducing polymer particulate that adopts of Chinese patent CN101544766 (2009-09-30) and Chinese patent CN101418077 (2009-04-29).For solving anti-shearing and solubility problem, US Patent No. 2007/0021531 (2007-01-25) patent disclosure is mixed use with the flow improver of different grain size and different methods preparation.But prior art is failed fundamentally to solve flow improver and is produced the expensive and undesirable problem of quality product.
Summary of the invention
The objective of the invention is to start with from the alpha-olefin anti-drag polymer Molecular Structure Design, a small amount of active ethylene group organosilicon radical copolymerization is introduced in the alpha-olefin anti-drag polymer molecule, the copolymerization non-crystalline state, oil soluble is good, embrittlement temperature is high, drag reducing efficiency is high and the shear-stable frictional reducing polymer, and existing flow improver pulverize at low temperature tooling cost is high to solve, easily cohesion gum deposit and not shear-stable problem in the storage process.
Thinking of the present invention is based on the mutual relationship between frictional reducing polymer molecular structure, pulverize at low temperature processing characteristics, product resistance reducing performance and the anti-shear performance of summing up in the long-term flow improver research and development.A small amount of low-molecular-weight flexible organosilicon radical is introduced in the poly-alpha olefins frictional reducing polymer molecule by copolyreaction, be expected to improve the frictional reducing polymer over-all properties.
Experiment finds that the α-octene polymer than short carbon chain is oil soluble and the good gel of resistance reducing performance, and shortcoming is the pulverize at low temperature processing difficulties, and the liquid nitrogen consumption is very big in the pulverize at low temperature process, and drag reduction agent suspension condenses gum deposit easily.
The α of longer carbochain-laurylene polymkeric substance is oil soluble and the relatively poor hardened resin of resistance reducing performance, the poor major cause of its resistance reducing performance is to form to finish the crystalline state polymer molecule in polymerization process, the crystal form polymkeric substance is swelling in oil product, can not dissolve the formation polymers soln.
The alpha-olefin copolymer of different carbon chain lengths can form random copolymers, alternating copolymer and segmented copolymer, and performance of copolymer depends on multipolymer raw material properties and composition to a great extent.Desirable frictional reducing polymer should be random copolymers on molecular structure, and the host molecule structure should show as stiff molecule mainly by the longer carbochain alpha-olefin molecular composition of rigidity on the macroscopic view, is conducive to pulverize at low temperature processing; Some node of frictional reducing polymer molecular structure should by flexibility than the short carbon chain molecular composition, thereby improve its anti-shear performance, become the point of penetration of polymer molecule dissolving on the microcosmic, be conducive to improve its oil soluble.With vinyl organosilicon group and alpha-olefin copolymer, make the easier formation random copolymers of alpha-olefin, the α of the long carbochain of improvement-laurylene structure adaptability performance.
The alpha-olefin that adopts in the invention process is industrial raw material, need not further to dewater pre-treatment before the use.Because active ethylene group silane is not only as polymer raw among the present invention, and the while is as the dewatering agent of alpha-olefin raw material, a small amount of moisture in the alpha-olefin can be removed with the active ethylene group silane reaction, thereby simplifies polymerization process condition and stablized polymer performance.
Thinking of the present invention is verified in great many of experiments, and the technical scheme that the present invention takes is:
(1) be that the carbon number of 90%-99% is that the alpha-olefin of C8-C18 and active ethylene group silane mixture that weight percentage is 1%-10% are packed in the polymerization bottle with weight percentage, it is freezing to below-5 ℃ that refrigerator-freezer is put in sealing; Adoptable active ethylene group silane comprises vinyltrimethoxy silane, vinyltriethoxysilane, vinyl silane triisopropoxide, vinyl three (2-methoxy ethoxy) silane, vinyltriacetoxy silane, vinyl-dimethyl oxygen ylmethyl silane, propenyl Trimethoxy silane, propenyl triethoxyl silane etc.
(2) add the Ziegler-Natta catalyst initiated polymerization with syringe in polymerization bottle, the catalyzer add-on is alpha-olefin by weight: titanous chloride: aluminium diethyl monochloride=1500: 1: 3;
(3) after polyreaction is proceeding to reaction soln viscosity under the vibration and reaches catalyzer and no longer sink, make it-10 ℃ of-15 ℃ of lower standing and reacting 24 hours, at room temperature continue reaction more than 48 hours, become elastomerics or hardened resin shape fully by gel to multipolymer;
(4) from polymerization bottle, take out the drag reduction multipolymer, add the liquid nitrogen freezing agent, and in the presence of calcium stearate and methylene radical distearyl acid amides dispersion agent, with Lowtemperaturepulverizer it is crushed to below 120 orders, sieving separating dispersion agent and thick multipolymer obtain drag reduction multipolymer fine powder;
(5) be that 0.2% thickening material carboxymethyl cellulose and weight percentage are that 0.3% tensio-active agent sodium laurylsulfonate is dissolved in the distilled water with weight percentage, add again weight percentage and be 20% frostproofer propylene glycol and weight percentage and be 0.1% sanitas orthoxenol;
(6) the drag reduction multipolymer pulverized is added the above aqueous solution, the drag reduction agent suspension product that the rear formation that stirs is stable take weight percentage as 40%.
Flow improver pulverize at low temperature processing characteristics adopt with polymkeric substance in Lowtemperaturepulverizer, be crushed to below 120 orders the ratio evaluation of the liquid nitrogen weight that consumes and frictional reducing polymer weight.
To the drag reducing polymerization matter sample below 120 orders, dissolving formation weight percentage is the average evaluation of 0.1% polymers soln to the employing of flow improver solubility property in 0# diesel oil under normal temperature and stirring with pulverize at low temperature.
Resistance reducing performance adopts drag reducing efficiency to carry out quantitative evaluation, sets up a cover flow improver circuit evaluating apparatus.Measure in the 0# diesel oil and add 10 * 10
-6Before and after the flow improver, the pressure reduction at pressure at two ends sensor place during by diameter 12mm stainless steel pipes is calculated as follows the drag reducing efficiency of flow improver.
Δ P in the formula
0-pipe ends frictional resistance pressure drop during with flow improver, Pa
Δ P
DRPipe ends frictional resistance pressure drop after the-adding flow improver, Pa
The flow improver anti-shear performance adopts will contain 10 * 10
-6The 0# diesel oil of flow improver is used impeller pump circulation shear 10 minutes, measures its drag reducing efficiency again, by the Assessment of Changes of drag reducing efficiency before and after shearing.
The drag reduction agent suspension estimation of stability adopts the standby drag reduction agent suspension product of observed and recorded new system to keep good fluidity, does not condense the time fate of gum deposit.
The present invention has simplified alpha-olefine polymerizing technique, and makes the character generation material alterations of poly-alpha olefins frictional reducing polymer, and beneficial effect is embodied in:
(1) drag reduction multipolymer brittle temperature of the present invention is high, and grinding and processing is easy, liquid nitrogen consumption and cost;
(2) the present invention contains organosilyl drag reduction copolymer oil dissolubility enhancing and drag reducing efficiency raising;
(3) the present invention contains organosilyl flow improver anti-shear performance and package stability raising.
Embodiment
Embodiment 1
With 10.0g polymerization-grade TiCl
3Add in the new distilled 100ml hexane solvent and make Primary Catalysts suspension; Aluminium diethyl monochloride 50ml added in the new distilled 150ml hexane solvent make promotor solution.
In polymerization bottle, add the α-octene of weight percent 95% and 5% vinyltriethoxysilane and be total to 500g as polymer raw, freezing to below-5 ℃ in refrigerator-freezer.Draw titanium trichloride catalyst and aluminium diethyl monochloride promotor with syringe, make its admixture activation 30 seconds, adding fills in the polymerization bottle of alpha-olefin again, shakes up.The weight ratio that catalyzer adds is alpha-olefin: titanous chloride: aluminium diethyl monochloride=1500: 1: 3.After alkene mixture prepolymerization to reaction soln viscosity reaches catalyzer and no longer sinks ,-10 ℃ of-15 ℃ of lower standing and reacting 24 hours, then it is continued to react at normal temperatures more than 48 hours, become elastomerics or hardened resin shape by gel fully to multipolymer.From polymerization bottle, take out the drag reduction multipolymer, add the liquid nitrogen freezing agent, in the presence of calcium stearate and methylene radical distearyl acid amides dispersion agent, with Lowtemperaturepulverizer it is crushed to below 120 orders, sieving separating dispersion agent and thick multipolymer, obtain drag reduction multipolymer fine powder, consume the approximately liquid nitrogen freezing agent of its 8 times of weight.Take by weighing 1g drag reduction multipolymer fine powder, normal temperature and stirring are lower to add in the 1000m10# diesel oil, and the drag reduction multipolymer all dissolves in 10 minutes, and forms the colloidal solution of thickness.With the drag reduction multipolymer with effective concentration 10 * 10
-6Add in the 0# diesel oil, carry out the resistance reducing performance evaluation under 25 ℃ of temperature, drag reducing efficiency is 52.4%.After 10 minutes, drag reducing efficiency becomes 30.8% with the impeller pump circulation shear.Be that 0.2% thickening material carboxymethyl cellulose and weight percent are that 0.3% tensio-active agent sodium laurylsulfonate is dissolved in the distilled water with weight percent, add again weight percent and be 20% frostproofer propylene glycol and weight percent and be 0.1% sanitas orthoxenol.The drag reduction copolymer powder is added the above aqueous solution take weight percent as 40%, and the stable drag reduction agent suspension finished product of the rear formation solid content 40% that stirs is stored at normal temperatures and is still kept good fluidity more than 300 days, cohesion gum deposit phenomenon occurs.
Embodiment 2
In polymerization bottle, add the α-octene, α-laurylene of 75% of weight percent 20% and 5% vinyltriethoxysilane altogether 500g test according to embodiment 1 same process condition as polymer raw, the frictional reducing polymer experimental evaluation the results are shown in Table 1.Frictional reducing polymer pulverize at low temperature processing consumes the liquid nitrogen of about 5 times of weight, in 0# diesel oil 10 * 10
-6Drag reducing efficiency 42.2% under the concentration, drag reducing efficiency 31.4% after shearing, and drag reduction agent suspension was stablized more than 300 days.
Embodiment 3
In polymerization bottle, add the α-laurylene of weight percent 20% and 5% vinyltriethoxysilane and be total to 500g as polymer raw.Test according to embodiment 1 same process condition, the frictional reducing polymer experimental evaluation the results are shown in Table 1.Frictional reducing polymer pulverize at low temperature processing consumes the liquid nitrogen of about 5 times of weight, in 0# diesel oil 10 * 10
-6Drag reducing efficiency 54.6% under the concentration, drag reducing efficiency 36.8% after shearing, and drag reduction agent suspension was stablized more than 300 days.
Reference examples 1-3
Adding respectively α-octene, α-laurylene, weight fraction 20% α-octene and 80% α-laurylene in polymerization bottle is polymer raw, do not add the organosilicon component and carry out control experiment, carry out polyreaction according to embodiment 1 same process condition, the frictional reducing polymer experimental evaluation the results are shown in Table 1.The drag reducing efficiency, anti-shear performance and the drag reduction agent suspension stability that do not contain organosilyl poly-alpha-olefin drag reduction agent are starkly lower than and contain the organosilicon poly-alpha-olefin drag reduction agent.
Table 1 organosilicon is on the impact of drag reducing polymerization physical performance
Claims (2)
1. an oil product is carried the preparation method of flow improver, it is characterized in that with carbon number being that the alpha-olefin of C8-C18 or its mixture and active ethylene group silane are the copolymerization raw material, the adding Ziegler-Natta catalyst carries out polymerization and obtains the drag reduction multipolymer, mainly may further comprise the steps:
(1) be that the carbon number of 90%-99% is that the alpha-olefin of C8-C18 or its mixture and weight percentage are that the active ethylene group silane mixture of 1%-10% is packed in the polymerization bottle with weight percentage, it is freezing to below-5 ℃ that refrigerator-freezer is put in sealing;
(2) add the Ziegler-Natta catalyst initiated polymerization with syringe in polymerization bottle, the catalyzer add-on is alpha-olefin by weight: titanous chloride: aluminium diethyl monochloride=1500: 1: 3;
(3) after polyreaction is proceeding to reaction soln viscosity under the vibration and reaches catalyzer and no longer sink, make it-10 ℃ of-15 ℃ of lower standing and reacting 24 hours, at room temperature continue reaction more than 48 hours, become elastomerics or hardened resin shape fully by gel to multipolymer;
(4) from polymerization bottle, take out the drag reduction multipolymer, add the liquid nitrogen freezing agent, and in the presence of calcium stearate and methylene radical distearyl acid amides dispersion agent, with Lowtemperaturepulverizer it is crushed to below 120 orders, sieving separating dispersion agent and thick multipolymer obtain drag reduction multipolymer fine powder;
(5) be that 0.2% thickening material carboxymethyl cellulose and weight percentage are that 0.3% tensio-active agent sodium laurylsulfonate is dissolved in the distilled water with weight percentage, add again weight percentage and be 20% frostproofer propylene glycol and weight percentage and be 0.1% sanitas orthoxenol, the drag reduction multipolymer pulverized is added in the aqueous solution drag reduction agent suspension product that the rear formation that stirs is stable take weight percentage as 40%.
2. described oil product is carried the preparation method of flow improver according to claim 1, it is characterized in that described active ethylene group silane is vinyltrimethoxy silane, vinyltriethoxysilane, vinyl silane triisopropoxide, vinyl three (2-methoxy ethoxy) silane, vinyltriacetoxy silane, vinyl-dimethyl oxygen ylmethyl silane, propenyl Trimethoxy silane, propenyl triethoxyl silane.
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| CN104214515A (en) * | 2014-09-14 | 2014-12-17 | 天津市职业大学 | Microencapsulated crude oil transportation drag reducer slurry and preparation method thereof |
| CN107266632A (en) * | 2017-08-05 | 2017-10-20 | 天津鸿波石油设备有限公司 | Polymer drag reducing agent and preparation method thereof, application |
| CN107353375A (en) * | 2015-09-11 | 2017-11-17 | 刘玉友 | Composite anti-drag agent solution in-situ synthetic method |
| CN109593153A (en) * | 2018-12-19 | 2019-04-09 | 沈阳宏城精细化工科技有限公司 | A kind of preparation method of modified poly alpha olefin |
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| CN102746520A (en) * | 2012-06-15 | 2012-10-24 | 中国石油化工股份有限公司 | Post-treatment and preparation method for polyolefin drag reducing agent used for oil based crude oil |
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| CN104214515A (en) * | 2014-09-14 | 2014-12-17 | 天津市职业大学 | Microencapsulated crude oil transportation drag reducer slurry and preparation method thereof |
| CN107353375A (en) * | 2015-09-11 | 2017-11-17 | 刘玉友 | Composite anti-drag agent solution in-situ synthetic method |
| CN107353375B (en) * | 2015-09-11 | 2019-07-19 | 山东科兴化工有限责任公司 | Composite anti-drag agent solution in-situ synthetic method |
| CN107266632A (en) * | 2017-08-05 | 2017-10-20 | 天津鸿波石油设备有限公司 | Polymer drag reducing agent and preparation method thereof, application |
| CN107266632B (en) * | 2017-08-05 | 2019-05-28 | 李馥波 | Polymer drag reducing agent and preparation method thereof, application |
| CN109593153A (en) * | 2018-12-19 | 2019-04-09 | 沈阳宏城精细化工科技有限公司 | A kind of preparation method of modified poly alpha olefin |
| CN109593153B (en) * | 2018-12-19 | 2021-05-28 | 沈阳宏城精细化工科技有限公司 | A kind of preparation method of modified polyalpha-olefin |
| CN115917208A (en) * | 2020-05-18 | 2023-04-04 | 虹膜科技有限公司 | Preparation method of anti-turbulence additive |
| CN118812761A (en) * | 2024-06-24 | 2024-10-22 | 西安三环石油管材科技有限公司 | Maleimide/α-olefin multipolymer, maleimide/α-olefin multipolymer oil-soluble drag reducer, and preparation method and application thereof |
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