CN116857564A - Oil drag reducer containing silicone oil and preparation method thereof - Google Patents
Oil drag reducer containing silicone oil and preparation method thereof Download PDFInfo
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- CN116857564A CN116857564A CN202310726431.5A CN202310726431A CN116857564A CN 116857564 A CN116857564 A CN 116857564A CN 202310726431 A CN202310726431 A CN 202310726431A CN 116857564 A CN116857564 A CN 116857564A
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- drag reducer
- oil
- silicone oil
- olefin
- poly alpha
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 83
- 229920002545 silicone oil Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 229920013639 polyalphaolefin Polymers 0.000 claims abstract description 72
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002981 blocking agent Substances 0.000 claims abstract description 17
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 16
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 27
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 19
- 239000004952 Polyamide Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 229920002647 polyamide Polymers 0.000 claims description 18
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 14
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 14
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 238000010008 shearing Methods 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 10
- CCDWGDHTPAJHOA-UHFFFAOYSA-N benzylsilicon Chemical compound [Si]CC1=CC=CC=C1 CCDWGDHTPAJHOA-UHFFFAOYSA-N 0.000 claims description 9
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 claims description 9
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- 229920000098 polyolefin Polymers 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 6
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 4
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- AGNTUZCMJBTHOG-UHFFFAOYSA-N 3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]propane-1,2-diol Chemical compound OCC(O)COCC(O)COCC(O)CO AGNTUZCMJBTHOG-UHFFFAOYSA-N 0.000 claims description 3
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 claims description 3
- 229940063655 aluminum stearate Drugs 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
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 235000019359 magnesium stearate Nutrition 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 47
- 230000009467 reduction Effects 0.000 abstract description 14
- 230000001965 increasing effect Effects 0.000 abstract description 7
- 239000010779 crude oil Substances 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 238000011156 evaluation Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 24
- 239000007787 solid Substances 0.000 description 23
- 239000000047 product Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 229940083037 simethicone Drugs 0.000 description 10
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 9
- 238000005054 agglomeration Methods 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000011161 development Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- -1 carbon chain amide Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940078456 calcium stearate Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229940057948 magnesium stearate Drugs 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 229940057977 zinc stearate Drugs 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
- F17D1/00—Pipe-line systems
- F17D1/08—Pipe-line systems for liquids or viscous products
- F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
- F17D1/17—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity by mixing with another liquid, i.e. diluting
Landscapes
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Public Health (AREA)
- Water Supply & Treatment (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Lubricants (AREA)
Abstract
The invention discloses a silicone oil-containing oil drag reducer and a preparation method thereof. The oil drag reducer comprises the following components: the poly alpha-olefin accounts for 15 to 35 percent of the total weight of the drag reducer slurry, the silicone oil accounts for 1 to 10 percent of the total weight of the drag reducer slurry, the anti-blocking agent accounts for 2 to 16 percent of the total weight of the drag reducer slurry, the alcohol ether dispersant accounts for 44 to 65 percent of the total weight of the drag reducer slurry, and the density regulator accounts for 3 to 20 percent of the total weight of the drag reducer slurry; the mass sum of the poly alpha-olefin, the silicone oil, the anti-blocking agent, the alcohol ether dispersant and the density regulator is 100 percent. The drag reducer has good stability, and does not delaminate or agglomerate in three months at normal temperature. The drag reduction rate of the crude oil drag reducer is evaluated by using the indoor loop evaluation device, so that a good drag reduction and transmission increasing effect can be achieved.
Description
Technical Field
The invention belongs to the technical field of drag reducers, and particularly relates to an oil drag reducer containing silicone oil and a preparation method thereof.
Background
The pipeline transportation is used as a main transportation mode of the finished oil and the crude oil, has the advantages of large transportation quantity, low cost, low energy consumption, long transportation distance, small influence by natural conditions and the like, but has the defects that the pipeline transportation has relatively poorer adjustability than that of highway, railway and marine transportation. How to reasonably regulate and control the pipe conveying amount of pipeline transportation is a relatively troublesome problem. In recent years, with the rapid increase of the demand of petroleum products, the petroleum transportation quantity is increased year by year, the development of an oil-gas pipe network system is rapid, and the improvement of the pipeline transportation quantity is urgent. At present, the total internal length of the oil and gas pipeline in China is 16.5 ten thousand kilometers, and the energy loss in the pipeline transportation process is huge due to the along-path friction resistance in the pipeline transportation process. In the past, people often adopt modes such as heating, adding middle pump station and add pipeline to improve oil delivery volume, but have a plurality of disadvantages such as high energy consumption, little operation elasticity, existence of potential safety hazard etc..
The oil drag reducer is a chemical additive applied to oil pipeline transportation, and can greatly reduce the friction resistance of the oil under the condition of unchanged oil delivery, thereby reducing the delivery pressure of a pipeline; the throughput of the pipeline can be increased without changing the pipeline operating pressure. Compared with the traditional method, the delivery of crude oil can be rapidly increased by adding a trace amount of oil drag reducer into an oil delivery pipeline, and the method has adjustability and becomes a large interest in drag reduction and delivery of oil. The drag reducer is a chemical auxiliary agent which can reduce the fluid conveying pressure by adding a small amount, is mostly a water-soluble or oil-soluble high polymer, and has the advantages of low investment, convenient filling, energy saving, consumption reduction and the like. Since 1979 when oil-soluble drag reducers were first used in crude oil delivery pipelines, the development of drag reducers was extremely rapid. The friction resistance of a pipeline system can be reduced by utilizing the drag reducer, the transmission and consumption are increased, the investment is saved, and the method has important practical significance for accelerating the development of petrochemical industry.
At present, the drag reduction polymer with better drag reduction effect is a poly alpha-olefin which is a nonpolar polymer and can be quickly dissolved in oil, and the drag reduction polymer is in a comb-shaped structure in oil flow, so that the flow resistance of the oil in a turbulent flow state can be effectively reduced; however, the production conditions are difficult to control, and strict anhydrous and anaerobic conditions are required. Generally, the higher the molecular weight of the poly-alpha-olefin, the higher the drag reduction rate of the drag reducer, and the better the relief of the flow resistance of the oil product.
The molecular weight of poly alpha-olefin used in industry is up to millions or even tens of millions, and the poly alpha-olefin is viscoelastic solid at normal temperature and can not be normally injected without treatment. For convenience in use, poly-alpha-olefins are usually processed into powder particles for use, but there are still some problems, such as agglomeration, adhesion, delamination, etc., when stored for a certain time at normal temperature, which are unfavorable for transportation, use and storage.
The production technology of the oil drag reducer has two key points: (1) synthesis of ultra-high molecular weight polyalphaolefins; (2) post-treatment process. Wherein the post-treatment process includes composition investigation of the drag reducer.
Chinese patent CN101544766a relates to a method for preparing a suspension of poly-alpha-olefin drag reducer, which comprises poly-alpha-olefin, long carbon chain amide and solvent, and suspending stabilizer, thickener, dispersant and surfactant are added to stabilize the suspension system. Firstly, long carbon chain amide, surfactant and solvent need to be emulsified for several hours at 40-50 ℃, and then crushed poly alpha-olefin, surfactant, thickener, suspending agent and the like are added to prepare the drag reducer. The drag reducer prepared by the method can be stable for 24 months at normal temperature, but components except the poly alpha-olefin cannot be emulsified at low temperature, otherwise, the drag reducer prepared by adding the poly alpha-olefin is easy to layer.
Chinese patent CN105218720a discloses a solution in-situ synthesis method of composite drag reducer, which is prepared from nano-SiO-containing solution 2 The polyolefin is prepared by dissolving n-heptane or diesel oil, has better shearing resistance, but is inconvenient to store and use.
The existing suspension liquid system technology of the oil drag reducer has certain defects, and the problems of precipitation, sedimentation, agglomeration, layering and the like of active ingredients can be unavoidable in the industrial production process. The reasons for this are, on the one hand, the inability to control the molecular weight distribution of the polyalphaolefins very well and, on the other hand, the inadequate level of work-up technology or the inadequate formulation.
Disclosure of Invention
The invention aims to: the invention aims to overcome the defects of the prior art and provides a silicon oil-containing oil drag reducer. The oil drag reducer solves the problem of insufficient stability commonly existing in the existing drag reducer under the condition of ensuring good drag reduction rate.
The technical scheme is as follows: the aim of the invention is achieved by the following technical scheme:
the invention provides a silicone oil-containing oil drag reducer, which comprises the following components: 15-35 wt% of poly alpha-olefin, 1-10 wt% of silicone oil, 2-16 wt% of anti-blocking agent, 44-65 wt% of alcohol ether dispersant and 3-20 wt% of density regulator; wherein, the mass sum of the poly alpha-olefin, the silicone oil, the anti-blocking agent, the alcohol ether dispersant and the density regulator is 100 percent.
The invention has the advantages that as the silicone oil is contained, the invention can play a role in preventing the secondary agglomeration of poly alpha-olefin; the existence of the silicone oil enables the solid anti-blocking agent to be easily wrapped on the surface of the poly alpha-olefin, which is beneficial to the stability of the drag reducer product.
Preferably, the molecular weight of the polyalphaolefin is 600 to 1000 tens of thousands.
Further preferably, the molecular weight of the polyalphaolefin is 800 to 1000 tens of thousands. The higher the molecular weight is, the better the drag reduction effect of the poly alpha-olefin is, and the molecular weight of the poly alpha-olefin in China is generally below 500 ten thousand at present.
Preferably, the viscosity of the silicone oil at 25 ℃ is 5-200 cst. Silicone oils as reaction solvents, too high a viscosity, which is detrimental to the dispersion of the polyolefin product, can cause increased poly-alpha-olefin particles; the larger the particles are, the poorer the solubility of the poly-alpha-olefin in the oil product, and in order to reduce the particles of the poly-alpha-olefin, the post-treatment is generally required by a low-temperature freezing and crushing method, and the generated poly-alpha-olefin particles are large and inconvenient for the post-treatment.
Further preferably, the silicone oil is selected from one of phenyl methyl silicone oil or dimethyl silicone oil.
Preferably, the anti-blocking agent is selected from one or more of sodium dodecyl benzene sulfonate, calcium stearate, zinc stearate, magnesium stearate, aluminum stearate, talcum powder, ethylene bis stearamide or polyamide wax. The anti-blocking agent can be wrapped on the surface of the polyolefin particles to play a certain role in isolation, so as to prevent the polyolefin particles from further agglomerating. The sodium dodecyl benzene sulfonate, the calcium stearate, the zinc stearate, the magnesium stearate, the aluminum stearate, the talcum powder, the ethylene bis stearamide and the polyamide wax all have polar bonds, and repulsive force exists between particles after the particles are wrapped on the surface of the poly alpha-olefin, so that the anti-adhesion effect is achieved.
Further preferably, the anti-blocking agent is selected from one or more of talc, ethylene bis stearamide or polyamide wax.
Preferably, the alcohol ether dispersant is selected from one or more of isobutanol, n-amyl alcohol, tertiary amyl alcohol, n-hexyl alcohol, n-octyl alcohol, isooctyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether or diethylene glycol monobutyl ether.
Further preferably, the alcohol ether dispersant is one or more selected from n-amyl alcohol, n-octyl alcohol, isooctyl alcohol, diethylene glycol monomethyl ether, diethylene glycol diethyl ether and diethylene glycol monobutyl ether.
Preferably, in the alcohol ether dispersant, the mass ratio of alcohol to ether is 40-55: 1 to 8.
Preferably, the density regulator is one or more selected from glycerol, diglycerol, triglycerol, N-dimethylformamide or dioxane.
Further, the density regulator is selected from one or more of diglycerol, triglycerol or N, N-dimethylformamide.
The invention also provides a preparation method of the oil drag reducer, which comprises the following steps:
(1) After the polymerization reaction is completed, utilizing a centrifugal solid-liquid separator to carry out solid-liquid separation, filtering polyolefin suspended in silicone oil,
(2) Mixing the filter cake, namely poly alpha-olefin, with an anti-blocking agent, and fully mixing the two by utilizing a pushing three-blade stirring and dispersing device; sequentially adding a metered alcohol ether dispersing agent and a density regulator into the mixture, and carrying out uniform dispersion for 1.5 hours by a high-speed shearing machine at the temperature of 0-10 ℃ to obtain uniform and stable white slurry, namely the drag reducer.
Preferably, the amount of residual silicone oil in the polyalphaolefin is from 3 to 21% of the total weight of polyalphaolefin.
When the additive amount of the drag reducer for oil products is 20ppm, the friction reducer has the increasing and outputting rate of not less than 50 percent.
The beneficial effects are that:
the drag reducer for oil products of the invention mainly comprises poly alpha-olefin with ultra-high molecular weight, silicone oil, anti-blocking agent, alcohol ether dispersant and density regulator. The poly alpha-olefin is mainly used for drag reduction, the silicone oil can play a certain role in isolation, and the probability of poly alpha-olefin particle agglomeration is reduced; the anti-blocking agent can further avoid the agglomeration of poly alpha-olefin particles; the alcohol ether substance can play a certain role in dispersing, but the density of the alcohol ether dispersing agent is less than that of poly alpha-olefin, so that the product stability is improved by using a density regulator, and layering is avoided. The silicone oil, the alcohol ether dispersant and the density regulator form a mutual-soluble system, the anti-blocking agent powder and the poly alpha-olefin are suspended in the solution, and the components are synergistic, so that the stability of the drag reducer is improved, the phenomenon of layering, caking or agglomeration easily occurring in the use and storage processes of the drag reducer is avoided, and the filling of the drag reducer product is facilitated. The drag reducer product has the advantages of good stability, low production cost, simple preparation method, environmental protection and the like.
Detailed Description
The technical scheme of the present invention is described in detail below through specific examples, but the scope of the present invention is not limited to the examples.
The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase through regular channels, with no manufacturer noted.
The experimental methods in the following examples are conventional methods unless otherwise specified. The test materials used in the examples described below, unless otherwise specified, are all commercially available products.
The polyalphaolefins in the examples were synthesized using a company-independent development process: the method is characterized in that n-olefin with carbon chain length in a range of C3-C22, preferably C6-C14, is selected as a polymerization monomer, a supported high-activity Ziegler-Natta catalyst containing a special internal electron donor is utilized to cooperate with alkyl aluminum such as triethyl aluminum, triisobutyl aluminum or diethyl aluminum chloride and external electron donor organosiloxane such as diisopropyl dimethoxy silane, diphenyl dimethoxy silane or dimethoxy dicyclopentyl siloxane to form a high-efficiency catalytic system, olefin monomer polymerization is catalyzed, and alpha-olefin polymer is synthesized at low temperature and normal pressure. The small poly alpha-olefin particles generated in the reaction are suspended in inert silicone oil, and the white loose poly alpha-olefin containing silicone oil is obtained through filtering after the reaction is completed.
After the polymerization reaction is completed, solid-liquid separation is performed by using a centrifugal solid-liquid separator, and the polyolefin suspended in the silicone oil is filtered. In the embodiment of the invention, the silicone oil is remained in the loose poly-alpha-olefin, the silicone oil, the poly-alpha-olefin and the anti-blocking agent are still in a solid state.
Because the particle size of the adopted catalyst is small, the average particle size of the obtained poly-alpha-olefin is less than 500 mu m, and the weight average molecular weight is more than 600 ten thousand. The poly-alpha-olefin involved in the preparation of the drag reducer is not limited to poly-alpha-olefin synthesized by adopting the autonomous development process of the company; polyalphaolefins meeting the above conditions can be used in the preparation of the drag reducing agent of the present invention.
The polyamide wax referred to in the examples is from Shanghai suitable coating industry under the trade designation T-6650.
Example 1
The silicon oil-containing drag reducer comprises the following components in percentage by mass:
phenyl methyl silicone oil (5 cst): 4.2%;
polyalphaolefins (weight average molecular weight 607 ten thousand, particle size 400 μm): 15.8%;
talc powder: 2.0%;
n-amyl alcohol: 6.0%;
n-octanol: 46.0%;
diethylene glycol monobutyl ether: 8.0%;
glycerol: 9.0%;
n, N-dimethylformamide: 9.0%.
The preparation method comprises the following steps:
according to the mass percentage of the components, 40.0g of loose poly alpha-olefin solid (phenyl methyl silicone oil content is 21%) is weighed into a 500ml beaker, 4.0g of talcum powder is weighed and added into the beaker, and the loose poly alpha-olefin solid and the phenyl methyl silicone oil are fully mixed by using a pushing three-blade stirring and dispersing device; 12.0g of n-amyl alcohol, 92.0g of n-octyl alcohol, 16.0g of diethylene glycol monobutyl ether, 18.0g of glycerol and 18.0g of N, N-dimethylformamide are weighed and added into the solid, and the uniform dispersion is carried out for 1.5 hours by a high-speed shearing machine at the temperature of 0-10 ℃ to obtain uniform and stable drag reducer slurry. The materials are not agglomerated or layered within three months.
Example 2
The silicon oil-containing drag reducer comprises the following components in percentage by mass:
simethicone (10 cst): 1.4%;
poly alpha-olefins (weight average molecular weight 820 ten thousand, particle size 490 μm): 34.8%;
polyamide wax powder: 8.0%;
ethylene bis stearamide: 7.8%;
n-amyl alcohol: 3.0%;
isooctanol: 39.0%;
diethylene glycol monobutyl ether: 2.0%;
triglycerin: 4.0%.
The preparation method comprises the following steps:
according to the mass percentage of the components, 71.0g of loose poly alpha-olefin solid (the content of the simethicone is 4.0 percent) is weighed into a 500ml beaker, 15.7g of polyamide wax powder and 15.3g of ethylene bis stearamide are weighed and added into the beaker, and the two materials are fully mixed by utilizing a pushing three-blade stirring and dispersing device; 5.9g of n-amyl alcohol, 76.5g of isooctanol, 3.9g of diethylene glycol monobutyl ether and 7.8g of triglycerin are weighed and added into the solid, and the mixture is subjected to homogenizing and dispersing for 1.5 hours by a high-speed shearing machine at the temperature of 0-10 ℃ to obtain uniform and stable drag reducer slurry. The materials are not agglomerated or layered within three months.
Example 3
The silicon oil-containing drag reducer comprises the following components in percentage by mass:
simethicone (50 cst): 5.0%;
poly alpha-olefins (weight average molecular weight 785 ten thousand, particle size 380 μm): 26.0%;
talc powder: 8.0%;
isobutanol: 7.0%;
isooctanol: 45.0%;
diethylene glycol monoethyl ether: 2.0%;
triglycerin: 7.0%.
The preparation method comprises the following steps:
according to the mass percentage of the components, weighing 75g of loose poly alpha-olefin solid (the content of the simethicone is 16 percent) into a 500ml beaker, then weighing 19.4g of talcum powder, adding the talcum powder into the beaker, and fully mixing the two by utilizing a pushing three-blade stirring and dispersing device; 16.9g of isobutanol, 108.9g of isooctanol, 4.8g of diethylene glycol monoethyl ether and 16.9g of triglycerin are weighed and added into the solid, and the solid is subjected to homogenizing and dispersing for 1.5 hours by a high-speed shearing machine at the temperature of 0-10 ℃ to obtain uniform and stable drag reducer slurry. The materials are not agglomerated or layered within three months.
Example 4
The silicon oil-containing drag reducer comprises the following components in percentage by mass:
simethicone (150 cst): 5.0%;
polyalphaolefins (weight average molecular weight 830 ten thousand, particle size 350 μm): 26.5%;
talc powder: 3.5%;
polyamide wax: 3.5%;
tertiary amyl alcohol: 5.0%;
isooctanol: 44.5%;
diethylene glycol monomethyl ether: 3.0%;
diglycerol: 9.0%.
The preparation method comprises the following steps:
according to the mass percentage of the components, 72g of loose poly alpha-olefin solid (the content of the simethicone is 16%) is weighed into a 500ml beaker, 8.0g of talcum powder and 8.0g of polyamide wax are weighed and added, and the two materials are fully mixed by utilizing a pushing three-blade stirring and dispersing device; 11.4g of tertiary amyl alcohol, 101.7g of isooctyl alcohol, 6.9g of diethylene glycol monomethyl ether and 20.6g of diglycerol are weighed and added into the solid, and the mixture is subjected to homogenizing and dispersing for 1.5 hours by a high-speed shearing machine at the temperature of 0-10 ℃ to obtain uniform and stable drag reducer slurry. The materials are not agglomerated or layered within three months.
Example 5
The silicon oil-containing drag reducer comprises the following components in percentage by mass:
simethicone (200 cst): 5.3%;
poly alpha-olefins (weight average molecular weight 811 ten thousand, particle size 420 μm): 25.7%;
polyamide wax powder: 6.0%;
tertiary amyl alcohol: 6.0%;
isooctanol: 48.0%;
diethylene glycol monobutyl ether: 3.0%;
triglycerin: 6.0%.
The preparation method comprises the following steps:
according to the mass percentage of the components, 81g of loose poly alpha-olefin solid (the content of the simethicone is 17%) is weighed into a 500ml beaker, 15.7g of polyamide wax powder is weighed and added, and the two are fully mixed by utilizing a pushing three-blade stirring and dispersing device; 15.7g of tertiary amyl alcohol, 125.4g of isooctyl alcohol, 7.8g of diethylene glycol monomethyl ether and 15.7g of triglycerin are weighed and added into the solid, and the mixture is subjected to homogenizing and dispersing for 1.5 hours by a high-speed shearing machine at the temperature of 0-10 ℃ to obtain uniform and stable drag reducer slurry. The materials are not agglomerated or layered within three months.
Example 6
The silicon oil-containing drag reducer comprises the following components in percentage by mass:
phenyl methyl silicone oil (200 cst): 3.0%;
poly alpha-olefins (weight average molecular weight 809 ten thousand, particle size 430 μm): 25.0%;
10.0% of polyamide wax powder;
tertiary amyl alcohol: 6.0%;
isooctanol: 48.0%;
diethylene glycol monobutyl ether: 2.0%;
triglycerin: 6.0%.
The preparation method comprises the following steps:
according to the mass percentage of the components, 91g of loose poly alpha-olefin solid (the phenyl methyl silicone oil content is 11%) is weighed into a 500ml beaker, 32.5g of polyamide wax powder is weighed and added, and the two are fully mixed by utilizing a pushing three-blade stirring and dispersing device; 19.5g of tertiary amyl alcohol, 156.0g of isooctyl alcohol, 6.5g of diethylene glycol monomethyl ether and 19.5g of triglycerin are weighed and added into the solid, and the mixture is subjected to homogenizing and dispersing for 1.5 hours by a high-speed shearing machine at the temperature of 0-10 ℃ to obtain uniform and stable drag reducer slurry. The materials are not agglomerated or layered within three months.
Example 7
The silicon oil-containing drag reducer comprises the following components in percentage by mass:
phenyl methyl silicone oil (5 cst): 6.1%;
poly alpha-olefins (weight average molecular weight 910 ten thousand, particle size 320 μm): 28.0%;
polyamide wax powder: 5.0%;
tertiary amyl alcohol: 5.0%;
isooctanol: 47.0%;
diethylene glycol monobutyl ether: 3.0%;
triglycerin: 5.9%.
The preparation method comprises the following steps:
according to the mass percentage of the components, weighing 95g of loose poly alpha-olefin solid (phenyl methyl silicone oil content is 18%) into a 500ml beaker, then weighing 13.9g of polyamide wax powder, adding the polyamide wax powder into the beaker, and fully mixing the two by utilizing a pushing three-blade stirring and dispersing device; 13.9g of tertiary amyl alcohol, 130.9g of isooctyl alcohol, 8.4g of diethylene glycol monobutyl ether and 16.4g of triglycerin are weighed and added into the solid, and the mixture is subjected to homogenizing and dispersing for 1.5 hours by a high-speed shearing machine at the temperature of 0-10 ℃ to obtain uniform and stable drag reducer slurry. The materials are not agglomerated or layered within three months.
Comparative example 1
The silicon oil-containing drag reducer comprises the following components in percentage by mass:
poly alpha-olefins (weight average molecular weight 780 ten thousand, particle size 370 μm): 25.4%;
polyamide wax powder: 5.0%;
tertiary amyl alcohol: 5.0%;
isooctanol: 51.0%;
diethylene glycol monobutyl ether: 7.0%;
triglycerin: 6.6%.
The preparation method comprises the following steps:
according to the mass percentage of each component, 100g of poly alpha-olefin solid without silicone oil is weighed in a 500ml beaker, 19.7g of polyamide wax powder is weighed and added, and the two are fully mixed by utilizing a pushing three-blade stirring and dispersing device; 19.7g of tertiary amyl alcohol, 200.8g of isooctyl alcohol, 27.6g of diethylene glycol monobutyl ether and 26.0g of triglycerin are weighed and added into the solid, and the mixture is subjected to homogenizing and dispersing for 1.5 hours by a high-speed shearing machine at the temperature of 0-10 ℃ to obtain uniform and stable drag reducer slurry. Layering occurs within a week, and poly alpha-olefin agglomeration occurs.
Comparative example 2
The silicon oil-containing drag reducer comprises the following components in percentage by mass:
simethicone (5 cst): 5.9%;
poly alpha-olefins (weight average molecular weight 815 ten thousand, particle size 390 μm): 25.0%;
tertiary amyl alcohol: 7.4%;
isooctanol: 46.5%;
diethylene glycol monobutyl ether: 8.5%;
triglycerin: 6.7%.
The preparation method comprises the following steps:
according to the mass percentage of the components, 98g of loose poly alpha-olefin solid (the content of the simethicone is 19%) is weighed in a 500ml beaker, and is dispersed into small particles by utilizing a pushing three-blade stirring dispersion device; 23.5g of tertiary amyl alcohol, 147.5g of isooctyl alcohol, 27.0g of diethylene glycol monomethyl ether and 21.2g of triglycerin are weighed and added into the solid, and the mixture is subjected to homogenizing and dispersing for 1.5 hours by a high-speed shearing machine at the temperature of 0-10 ℃ to obtain uniform and stable drag reducer slurry. Layering is carried out within three days, and poly alpha-olefin agglomeration phenomenon occurs.
The indoor loop effect test standard and method are as follows:
the drag reduction effect of the drag reducer for oil products prepared in the above examples and comparative examples was evaluated and compared with commercially available drag reducers at an additive level of 20ppm by reference to the standard "indoor test method for drag reduction effect of oil pipeline drag reducer SY/T6578-2009", and the results are shown in table 1:
commercially available inlet drag reducers: beijing Jin Dingke (agency), crude oil drag reducer brand SIL643
Commercially available drag reducing agents: jiangyin Hua Heng auxiliary agent Co., ltd, crude oil drag reducer brand HH-33
The standard for evaluating the stability at normal temperature is that the stability is not layered and is not agglomerated.
Table 1 drag reducing effect and stability of drag reducing agent
The drag reducer products produced by examples 1-7 above were tested for the following characteristics:
1. the flash point is more than or equal to 50 ℃;
2. placing for 3 months at normal temperature, the drag reducer product is not layered and is not agglomerated;
3. the drag reducer product has good fluidity without obvious reduction after being placed for 1 to 2 days at the temperature of-45 ℃; has no strong pungent smell.
As described above, although the present invention has been shown and described with reference to certain preferred embodiments, it is not to be construed as limiting the invention itself. Various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A silicone oil-containing drag reducer comprising: 15-35 wt% of poly alpha-olefin, 1-10 wt% of silicone oil, 2-16 wt% of anti-blocking agent, 44-65 wt% of alcohol ether dispersant and 3-20 wt% of density regulator; the mass sum of the poly alpha-olefin, the silicone oil, the anti-blocking agent, the alcohol ether dispersant and the density regulator is 100 percent.
2. The oil drag reducer of claim 1, wherein the polyalphaolefin has a molecular weight of 600 to 1000 tens of thousands.
3. The oil drag reducer of claim 1, wherein the silicone oil has a viscosity of 5 to 200cst at 25 ℃.
4. The oil drag reducer of claim 3 wherein said silicone oil is selected from one of phenyl methyl silicone oil or dimethyl silicone oil.
5. The oil drag reducer of claim 1, wherein the anti-blocking agent is selected from one or more of sodium dodecylbenzene sulfonate, calcium stearate, zinc stearate, magnesium stearate, aluminum stearate, talc, ethylene bis stearamide, or polyamide wax.
6. The oil drag reducer of claim 1, wherein the alcohol ether dispersant is selected from one or more of isobutanol, n-pentanol, t-pentanol, n-hexanol, n-octanol, isooctanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, or diethylene glycol monobutyl ether.
7. The oil drag reducer of claim 6, wherein the mass ratio of alcohol to ether in the alcohol ether dispersant is 40-55: 1 to 8.
8. The oil drag reducer of claim 1, wherein the density modifier is selected from one or more of glycerol, diglycerol, triglycerol, N-dimethylformamide, and dioxane.
9. The method of producing an oil drag reducer according to any one of claims 1-8, comprising the steps of:
(1) After the polymerization reaction is completed, utilizing a centrifugal solid-liquid separator to carry out solid-liquid separation, filtering polyolefin suspended in silicone oil,
(2) Mixing the filter cake, namely poly alpha-olefin, with an anti-blocking agent, and fully mixing the two by utilizing a pushing three-blade stirring and dispersing device; sequentially adding a metered alcohol ether dispersing agent and a density regulator into the mixture, and carrying out uniform dispersion for 1.5 hours by a high-speed shearing machine at the temperature of 0-10 ℃ to obtain uniform and stable white slurry, namely the drag reducer.
10. The method of claim 9, wherein the amount of residual silicone oil in the polyalphaolefin is 3 to 21% of the total weight of the polyalphaolefin.
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