CN1530377A - Preparation method of poly alpha-olefin drag reducer for pipeline oil product - Google Patents
Preparation method of poly alpha-olefin drag reducer for pipeline oil product Download PDFInfo
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- CN1530377A CN1530377A CNA031197434A CN03119743A CN1530377A CN 1530377 A CN1530377 A CN 1530377A CN A031197434 A CNA031197434 A CN A031197434A CN 03119743 A CN03119743 A CN 03119743A CN 1530377 A CN1530377 A CN 1530377A
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- drag reduction
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- 229920013639 polyalphaolefin Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 title abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 239000011541 reaction mixture Substances 0.000 claims abstract description 23
- 230000009467 reduction Effects 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 150000002148 esters Chemical class 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims abstract description 4
- 229920000728 polyester Polymers 0.000 claims abstract description 4
- 229920000570 polyether Polymers 0.000 claims abstract description 4
- -1 polyoxy Polymers 0.000 claims description 30
- 239000012530 fluid Substances 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000012968 metallocene catalyst Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 15
- 239000003921 oil Substances 0.000 claims description 15
- 150000001336 alkenes Chemical class 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920000151 polyglycol Polymers 0.000 claims 1
- 239000010695 polyglycol Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 239000004711 α-olefin Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 239000004721 Polyphenylene oxide Substances 0.000 abstract 1
- 238000002955 isolation Methods 0.000 abstract 1
- 229920000098 polyolefin Polymers 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- 239000003426 co-catalyst Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 238000012662 bulk polymerization Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 6
- 239000004584 polyacrylic acid Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 description 1
- FIWYWGLEPWBBQU-UHFFFAOYSA-N 2-heptylphenol Chemical compound CCCCCCCC1=CC=CC=C1O FIWYWGLEPWBBQU-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229920005556 chlorobutyl Polymers 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- JJSGABFIILQOEY-UHFFFAOYSA-M diethylalumanylium;bromide Chemical compound CC[Al](Br)CC JJSGABFIILQOEY-UHFFFAOYSA-M 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000000937 inactivator Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- OYMJNIHGVDEDFX-UHFFFAOYSA-J molybdenum tetrachloride Chemical compound Cl[Mo](Cl)(Cl)Cl OYMJNIHGVDEDFX-UHFFFAOYSA-J 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- MTAYDNKNMILFOK-UHFFFAOYSA-K titanium(3+);tribromide Chemical compound Br[Ti](Br)Br MTAYDNKNMILFOK-UHFFFAOYSA-K 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- HUYLAMJIPCOVOM-UHFFFAOYSA-K triiodotitanium Chemical compound [Ti+3].[I-].[I-].[I-] HUYLAMJIPCOVOM-UHFFFAOYSA-K 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
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a slurry polymerization preparation method of poly alpha-olefin drag reducer for oil products in pipeline transportation. The method is characterized in that a polymerization monomer is added into a reaction container, a catalyst is added under the condition of air isolation and stirring, a polyester, polyether or ester ether copolymer reaction base solution which is oil-soluble and alpha-olefin polymer is insoluble is slowly added within 20 hours from the beginning of the reaction, and the reaction is carried out for 3-10 days at normal pressure or low pressure at the temperature of-50-20 ℃. The method has simple production equipment and production process and is easy to control; the polymer has high molecular weight, low viscosity of reaction mixture, good drag reduction effect and good standing stability, and can be directly used for oil transportation production without stirring.
Description
Relate to the field
The present invention relates to the composition and the tubing system field of macromolecular compound, is the preparation method who is used for the oil product through pipelines poly-alpha-olefin drag reduction agent.
Background technology
Flow ducted because friction resistance has limited fluid, cause the pipeline throughput rate to reduce or the energy expenditure increase, thus the flow improver of a small amount of high molecular polymer in product pipeline, usually will in fluid, be injected, to reduce the resistance to flow under the turbulent state.The flow improver first Application of producing from U.S. Kang Nuoke company in 1979 is since Alaska crude oil pipeline is achieved success, and mainly having developed two kinds of acquisitions is the synthetic method of monomeric frictional reducing polymer with alpha-olefin, ie in solution polymerization and mass polymerization.And it is still like this to this day.
Initial poly-alpha-olefin drag reduction agent is that the method by solution polymerization makes.Solution polymerization is that monomer and initiator are dissolved in polymerization in the appropriate solvent, when adopting this method to produce poly-alpha-olefin drag reduction agent, because the molecular weight and the content in polymerisate thereof of monomer conversion, frictional reducing polymer are very low, therefore cause the drag-reduction effect of flow improver relatively poor relatively; The product viscosity of solution polymerization simultaneously is high, even surpasses 50000 centipoises, therefore, brings very big difficulty for the injection of flow improver.
To the mid-90s in 20th century, developed and adopted mass polymerization to obtain the method for alpha-olefin frictional reducing polymer.Mass polymerization is meant and does not add other medium to have only this polymerization of carrying out of monomer under action of evocating.This method has improved the monomer conversion of polymerisate and the molecular weight of polymkeric substance greatly.But because the reaction heat that mass polymerization produces is high, therefore, when implementing polymerization, polymerization reactant must be divided in the less relatively reaction vessel, be placed on reaction under the low temperature environment then, operating process is very loaded down with trivial details; Simultaneously,, be injected into pipeline, must make its fluidify state through postprocessing working procedures because the mass polymerization product is the viscoelastic solid material.Postprocessing working procedures generally includes following two steps, at first be that visco-elasticity frictional reducing polymer with solid state is ground into the powder that possesses certain fineness under the condition of very low temperature, make in its mixture that is suspended in alcohol-water mixture or several alcohol by various chemical additives then, form the paste-like fluid, whole process is loaded down with trivial details and complicated, and production cost is high, can cause serious environmental to pollute (dust pollution) simultaneously; In addition, the paste-like flow improver product that so obtains leave standstill less stable, alpha-olefinic polymer is easy to separate from the mixture of alcohol-water mixture or alcohol, therefore, needs the stirring of appropriateness to use usually.
Thereafter several years, poly-alpha-olefin drag reduction agent is the preparation method improve to some extent again, as american energy and environment international corporation at China (application number 97194741.4) and the U.S. (U.S.Patent5,869,570) Shen Qing " composition of poly-alpha-olefin drag reduction agent and preparation method " patent disclosure in reaction mixture, add viscosity reducers, viscosity and dispersion location micella to reduce reaction mixture make poly-alpha olefins that more uniform molecular weight distribution be arranged.It is that transition-metal catalyst adds alkylaluminoxane that " preparation method of amorphous ultra-high molecular poly-alpha-olefin drag reduction agent " patent (application number 99108944.3) that the said firm applies in China then discloses its catalyst body, also can use simultaneously, also disclose in addition and in reaction mixture, added a kind of " inactivator " to obtain the amorphous ultra-high molecular weight polymkeric substance with dialkylaluminum halides or haloalkane.More than two technology still belong to solution polymerization or mass polymerization category, only polymeric better, more even.The Chinese patent " nonaqueous drag reducing suspensions " (97198835.8) of U.S. Conoco Inc application is that a kind of mass polymerization acquisition polymkeric substance carries out pulverize at low temperature again, then together form by stirring pulping with carrier such as alcohol, its product can be lower than to be preserved under-20 conditions and can directly inject in-service pipeline and use again.But its production process is still complicated, and control is also difficult.
Summary of the invention
The objective of the invention is to invent a kind of production process simple, be easy to control, relatively low, the less gel effect of reaction product viscosity, make the molecular weight of alpha-olefinic polymer higher, molecular weight distribution is more even, and then makes the preparation method of the slurry polymerization of the more obvious poly-alpha-olefin drag reduction agent of drag-reduction effect.
Overcome the deficiency of the existing two kinds of polymerization processs of poly-alpha-olefin drag reduction agent, the present invention proposes a kind of new polymerization process, i.e. slurry polymerization.This method is earlier polymerization single polymerization monomer-alpha-olefin to be added closed reaction vessel, at secluding air with there is under the condition of stirring catalyzer of interpolation react, within 20 hours of reaction beginning, slowly add a kind oil soluble and alpha-olefinic polymer is insoluble to reaction base fluid wherein while stirring, and under-50～20 ℃ of temperature normal pressure or low pressure reaction 3～10 days.Air during the reaction beginning in the reaction vessel must be removed totally, and concrete grammar can be used nitrogen purging.And the weight ratio of polymerization single polymerization monomer in reaction mixture is 10～60%, Primary Catalysts or the metallocene catalyst content in reaction mixture is 300～3000 moles of alkene/every mol catalyst, the mol ratio of co-catalyst and Primary Catalysts or metallocene catalyst is controlled in 25: 1 to 1: 1 scopes, and the weight ratio of base fluid in reaction mixture is 40～90%.In order to improve the stability that leaves standstill of polymerisate, also can be in entire reaction course adding weight ratio to reaction mixture is 0～20% liquid hydrocarbon material.This liquid hydrocarbon comprises that all can make the alpha-olefinic polymer dissolved substances, can select alkane, aromatic hydrocarbons, various processed oil and some ester class, as hexane, heptane, octane, hexanaphthene, benzene,toluene,xylene, diesel oil, kerosene, gasoline, petroleum naphtha, machine oil and the various Ester that meets the demands.The polymerization single polymerization monomer that the present invention selects for use comprises all alpha-olefins with 2～20 carbon atoms, and during actual polymerization, selected monomer can be wherein a kind of, also can be two or more mixture wherein.The catalyzer that the present invention selects for use is Z-N System Catalyst or metallocene catalyst commonly used.Co-catalyst mainly is an alkyl metal cpd in the Z-N System Catalyst, generally include aluminum alkyls, haloalkyl aluminium, alkyl magnesium, zinc alkyl(s) etc., as trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three hexyl aluminium, three isohexyl aluminium, a fluorine diethyl aluminum, aluminium diethyl monochloride, monobromo diethyl aluminum, an iodine diethyl aluminum, magnesium ethide, zinc ethyl etc.; Primary Catalysts mainly is a transistion metal compound, transition metal generally includes titanium, zirconium, vanadium, chromium, molybdenum etc., such as titanous chloride, titanium tribromide, titanium triiodide, titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, vanadium tetrachloride, zirconium tetrachloride, molybdenum tetrachloride, two chlorobutyl titaniums, a chlorine tributyl titanium etc.The preparation method of metallocene catalyst, suitable co-catalyst be at United States Patent (USP) 5,442, has a detailed description in 019 and 5,416,179, do not do at this and give unnecessary details.Two big class catalyzer owing to contain the existence of oxygen base fluid in the reaction mixture, select for use metallocene catalyst lower to its active influence, its better effects if for the present invention.As oil soluble and the reaction base fluid that alpha-olefinic polymer is insoluble to wherein mainly comprises polyester, polyethers or ester ether copolymer class material, as poly-unsaturated acid alkyl ester, alkylphenol polyoxy second (third) alkene ether, lipid acid polyoxy second (third) alkene ester, alkyl polyoxy second (third) alkene ether, Fatty Alcohol(C12-C14 and C12-C18) polyoxy second (third) alkene ether, alkylphenol polyoxyethylene polyoxypropylene ether, the fatty alcohol polyoxypropylene Soxylat A 25-7, alkyl polyoxyethylene polyoxypropylene ether, fatty acid polyglycol oxypropylene polyoxyethylene ester etc. are such as butyl polyacrylate, the own ester of polyacrylic acid, the polyacrylic acid monooctyl ester, the different monooctyl ester of polyacrylic acid, heptyl phenol polyoxy second (third) alkene ether, octyl phenol polyoxy second (third) alkene ether, polyoxyethylene nonyl phenyl second (third) alkene ether, lauric acid polyoxy second (third) alkene ester etc.
Indication slurry polymerization of the present invention is that polymkeric substance-monomer viscous particle is dispersed in the polymerization of carrying out in the base fluid with the small droplets shape.When stirring in the reaction process, under shear action, polymkeric substance-monomer viscous particle will be dispersed into drop in base fluid.Drop is stressed greatly also can be out of shape, and continues to be dispersed into small droplets.Be dissolved with initiator in polymkeric substance-monomer viscous particle, a small droplets just is equivalent to a unit of mass polymerization.Clearly, change polymer solid particles into from monomer, middle through polymkeric substance above-mentioned-monomer viscous particle stage.Exist certain interfacial tension between this viscous particle and the base fluid, interfacial tension will make drop try hard to keep spherical.Interfacial tension is big more, keeps the spheric ability strong more, and the drop of formation is also big more.On the contrary, interfacial tension is more little, and it is also more little to have formed drop.Too small drop also can be gathered into bigger drop.It is opposite to becoming to drip the function influence direction with interfacial tension to stir shearing force, under certain stirring intensity and interfacial tension, the drop that differs in size is by a series of dispersions and unification process, constitute certain transient equilibrium, reach certain average fineness at last, but size still has certain distribution, because the stirring intensity that the inside reactor each several part is subjected to is inhomogenous.For this reason, among the present invention, uniform stirring intensity is very important in interfacial tension between appropriate controlling polymers-monomer viscous particle and the base fluid and the reactor, so, should select suitable reaction base fluid and alr mode.
After stirring stopped, it is big that the polymkeric substance drop may be assembled change, and may separate from base fluid lentamente.Because alpha-olefinic polymer all dissolves in the liquid hydrocarbon material of carrying the front with the reaction base fluid, therefore add an amount of liquid hydrocarbon material, can increase the transient equilibrium between polymkeric substance drop and the base fluid greatly, thereby effectively the augmenting response product leaves standstill stability.
By above-mentioned preparation method, just can obtain poly-alpha-olefin drag reduction agent into paste-like liquid, the molecular weight of polymkeric substance is 10
6More than, product viscosity is lower than 3000 centipoises.
Concrete enforcement
Embodiment 1: the polymerization single polymerization monomer alpha-olefin selects for use 1-hexene, 1-octene and 1-decene by 1: 3: 5 mixed, and the weight ratio in reaction mixture is 30%; Catalyzer is selected metallocene catalyst and corresponding co-catalyst for use, the content of metallocene catalyst in reactant is 1000 moles of alkene/every mol catalyst, the mol ratio of co-catalyst and metallocene catalyst is 6: 1, base fluid is selected the own ester of polyacrylic acid for use, and the weight ratio in reaction mixture is 65%; Varsol is selected heptane for use, and the weight ratio in reaction mixture is 5%.Method is earlier polymerization single polymerization monomer to be added closed reaction vessel, at secluding air with have and add catalyzer under the agitation condition and react, slowly adds base fluid and liquid hydrocarbon in 12 hours of reaction beginning, and in-10～10 ℃ of temperature ranges synthesis under normal pressure 8 days.Making polymericular weight at last is 4.5 * 10
6, product viscosity is the poly-alpha-olefin drag reduction agent paste-like liquid of 2800 centipoises, just can directly transport to the production scene and use.
Embodiment 2: the polymerization single polymerization monomer alpha-olefin is selected the 1-octene for use, and the weight ratio in reaction mixture is 50%; Catalyzer is selected metallocene catalyst and corresponding co-catalyst for use, the content of metallocene catalyst in reactant is 2000 moles of alkene/every mol catalyst, the mol ratio of co-catalyst and metallocene catalyst is 20: 1, base fluid is selected polyoxyethylene nonylphenol ether for use, and the weight ratio in reaction mixture is 50%.Method is earlier polymerization single polymerization monomer to be added closed reaction vessel, at secluding air with have and add catalyzer under the agitation condition and react, slowly adds base fluid and liquid hydrocarbon in 5 hours of reaction beginning, and in-10～10 ℃ of temperature ranges synthesis under normal pressure 5 days.Making polymericular weight at last is 4.0 * 10
6, product viscosity is the poly-alpha-olefin drag reduction agent paste-like liquid of 2900 centipoises, just can directly transport to the production scene and use.
Embodiment 3: the polymerization single polymerization monomer alpha-olefin selects for use 1-octene and 1-laurylene by 4: 1 mixed, and the weight ratio in reaction mixture is 20%; Catalyzer is selected metallocene catalyst and corresponding co-catalyst for use, the content of metallocene catalyst in reactant is 500 moles of alkene/every mol catalyst, the mol ratio of co-catalyst and metallocene catalyst is 3: 1, base fluid is selected the different monooctyl ester of polyacrylic acid for use, and the weight ratio in reaction mixture is 60%; Varsol is selected heptane for use, and the weight ratio in reaction mixture is 20%.Method is earlier polymerization single polymerization monomer to be added closed reaction vessel, at secluding air with have and add catalyzer under the agitation condition and react, slowly adds base fluid and liquid hydrocarbon in 10 hours of reaction beginning, and in-10～10 ℃ of temperature ranges synthesis under normal pressure 10 days.Making polymericular weight at last is 5.4 * 10
6, product viscosity is the poly-alpha-olefin drag reduction agent paste-like liquid of 1700 centipoises, just can directly transport to the production scene and use.
Embodiment 4: the polymerization single polymerization monomer alpha-olefin selects for use 1-hexene and 1-laurylene by 1: 1 mixed, and the weight ratio in reaction mixture is 40%; Catalyzer is selected metallocene catalyst and corresponding co-catalyst for use, the content of metallocene catalyst in reactant is 800 moles of alkene/every mol catalyst, the mol ratio of co-catalyst and metallocene catalyst is 7: 1, base fluid is selected the different monooctyl ester of polyacrylic acid for use, and the weight ratio in reaction mixture is 58%; Varsol is selected heptane for use, and the weight ratio in reaction mixture is 2%.Method is earlier polymerization single polymerization monomer to be added closed reaction vessel, at secluding air with have and add catalyzer under the agitation condition and react, slowly adds base fluid and liquid hydrocarbon in 12 hours of reaction beginning, and in-10～10 ℃ of temperature ranges synthesis under normal pressure 7 days.Making polymericular weight at last is 6.0 * 10
6, product viscosity is the poly-alpha-olefin drag reduction agent paste-like liquid of 2200 centipoises, just can directly transport to the production scene and use.
As from the foregoing, preparation method's production process of this poly-alpha-olefin drag reduction agent slurry polymerization is simple, and be easy to control, production unit is a conventional equipment, and is also uncomplicated, and the reactive polymeric thing is because of being insoluble to selected base fluid, therefore reaction mixture viscosity is lower, and mixing and heat transfer are easier, less gel effect, can avoid local superheating, make the molecular weight of alpha-olefinic polymer higher by (10
6More than), molecular weight distribution is more even, thereby makes drag-reduction effect better.And product needn't do to handle in addition just can directly inject the oil pipeline of operation, simultaneously, product itself leave standstill stability better, need not before the use to stir, therefore, not only saved production cost, and the scene use of giving brings great convenience.
Claims (6)
1. the slurry polymerization preparation method of an oil product through pipelines poly-alpha-olefin drag reduction agent, it is characterized in that: earlier polymerization single polymerization monomer is added closed reaction vessel, at secluding air with there is under the stirring state catalyzer of interpolation react, and within 20 hours of reaction beginning, slowly add a kind oil soluble and alpha-olefinic polymer is insoluble to the reaction base fluid that accounts for weight ratio 40～90% in reaction mixture wherein, and under-50～20 ℃ of temperature normal pressure or low pressure reaction 3～10 days.
2. the preparation method of a kind of oil product through pipelines poly-alpha-olefin drag reduction agent according to claim 1 is characterized in that adding the liquid hydrocarbon material that accounts for reaction mixture weight ratio 0～20% in entire reaction course.
3. the preparation method of a kind of oil product through pipelines poly-alpha-olefin drag reduction agent according to claim 2 is characterized in that: the feature of described liquid hydrocarbon material is to select for use to make alpha-olefinic polymer dissolved alkane, aromatic hydrocarbons, various processed oil and Ester.
4. the preparation method of a kind of oil product through pipelines poly-alpha-olefin drag reduction agent according to claim 1 is characterized in that described oil soluble and reaction base fluid that alpha-olefinic polymer is insoluble to wherein comprises polyester, polyethers and ester ether copolymer class material.
5. the preparation method of a kind of oil product through pipelines poly-alpha-olefin drag reduction agent according to claim 4 is characterized in that described polyester, polyethers, ester ether copolymer reaction base fluid comprise poly-unsaturated acid alkyl ester, alkylphenol polyoxy second (third) alkene ether, fatty acid polyglycol second (third) alkene ester, alkyl polyoxy second (third) alkene ether, Fatty Alcohol(C12-C14 and C12-C18) polyoxy second (third) alkene ether, alkylphenol polyoxyethylene polyoxypropylene ether and fatty alcohol polyoxypropylene Soxylat A 25-7, alkyl polyoxyethylene polyoxypropylene ether and fatty acid polyglycol oxypropylene polyoxyethylene ester.
6. the preparation method of a kind of oil product through pipelines poly-alpha-olefin drag reduction agent according to claim 1 is characterized in that being preferred with the metallocene catalyst in two kinds of catalyzer of Z-N System Catalyst and metallocene catalyst.
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Cited By (10)
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| CN101065181B (en) * | 2004-12-17 | 2010-12-01 | 北方科技有限公司 | Process for polymerising olefins in the presence of an olefin polymerisation catalyst |
| CN101328397B (en) * | 2007-06-20 | 2011-04-20 | 中国石油天然气股份有限公司 | Electronic donor of crude oil pipeline drag reducer and preparation method thereof |
| CN102898554A (en) * | 2011-07-27 | 2013-01-30 | 中国石油化工股份有限公司 | Preparation method, product and application of particulate poly-alpha-olefin |
| CN103626892A (en) * | 2012-08-23 | 2014-03-12 | 中国石油天然气股份有限公司 | Preparation method of bimodal MWD poly alpha-olefin oil drag reducer |
| CN105179941A (en) * | 2015-07-14 | 2015-12-23 | 中国石油天然气集团公司 | Emulsion type crude oil viscosity-reduction drag reduction agent applied to high-wax-content pure oil pipe transportation |
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| CN101065181B (en) * | 2004-12-17 | 2010-12-01 | 北方科技有限公司 | Process for polymerising olefins in the presence of an olefin polymerisation catalyst |
| CN101328397B (en) * | 2007-06-20 | 2011-04-20 | 中国石油天然气股份有限公司 | Electronic donor of crude oil pipeline drag reducer and preparation method thereof |
| CN102898554B (en) * | 2011-07-27 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method, product and application of particulate poly-alpha-olefin |
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| TWI570232B (en) * | 2012-02-09 | 2017-02-11 | 貝特烴溶劑科技公司 | Defoaming systems and methods in hydrocarbon processes |
| US9556878B2 (en) | 2012-02-09 | 2017-01-31 | Bechtel Hydrocarbon Technology Solutions Inc. | Defoaming systems and methods in hydrocarbon processes |
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| TWI613289B (en) * | 2012-02-09 | 2018-02-01 | 貝特烴溶劑科技公司 | Defoaming systems and methods in hydrocarbon processes |
| CN103626892B (en) * | 2012-08-23 | 2016-04-06 | 中国石油天然气股份有限公司 | Preparation method of bimodal MWD poly alpha-olefin oil drag reducer |
| CN103626892A (en) * | 2012-08-23 | 2014-03-12 | 中国石油天然气股份有限公司 | Preparation method of bimodal MWD poly alpha-olefin oil drag reducer |
| CN105179941B (en) * | 2015-07-14 | 2018-06-26 | 中国石油天然气集团公司 | A kind of emulsion-type reducing crude oil viscosity drag reducer defeated applied to the pure oil pipe of high-content wax |
| CN105179941A (en) * | 2015-07-14 | 2015-12-23 | 中国石油天然气集团公司 | Emulsion type crude oil viscosity-reduction drag reduction agent applied to high-wax-content pure oil pipe transportation |
| CN106402660A (en) * | 2016-09-05 | 2017-02-15 | 路殿勋 | Preparation method for emulsion suspension system of poly-alpha-olefin oil drag reducer |
| 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 |
| CN109796551A (en) * | 2017-11-17 | 2019-05-24 | 中国石油化工股份有限公司 | Preparation method, drag reducing polymerization composition granule and the application of frictional reducing polymer |
| CN114456407A (en) * | 2020-11-09 | 2022-05-10 | 中国石油天然气集团有限公司 | Drag reducer and preparation method thereof |
| CN114456407B (en) * | 2020-11-09 | 2024-03-01 | 中国石油天然气集团有限公司 | Drag reducer preparation method and drag reducer |
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