CN114524889B - Method and system for synthesizing T803 pour point depressant from coal-based olefin and T803 pour point depressant - Google Patents
Method and system for synthesizing T803 pour point depressant from coal-based olefin and T803 pour point depressant Download PDFInfo
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- CN114524889B CN114524889B CN202210012971.2A CN202210012971A CN114524889B CN 114524889 B CN114524889 B CN 114524889B CN 202210012971 A CN202210012971 A CN 202210012971A CN 114524889 B CN114524889 B CN 114524889B
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- 230000000994 depressogenic effect Effects 0.000 title claims abstract description 73
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 64
- 239000003245 coal Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 49
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- 238000004821 distillation Methods 0.000 claims abstract description 73
- 238000005886 esterification reaction Methods 0.000 claims abstract description 58
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- 238000005406 washing Methods 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000005520 cutting process Methods 0.000 claims abstract description 43
- 238000001914 filtration Methods 0.000 claims abstract description 34
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 32
- 239000004711 α-olefin Substances 0.000 claims abstract description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001301 oxygen Substances 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 29
- 238000001179 sorption measurement Methods 0.000 claims abstract description 25
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims description 67
- 239000003795 chemical substances by application Substances 0.000 claims description 40
- 238000007670 refining Methods 0.000 claims description 39
- 239000007795 chemical reaction product Substances 0.000 claims description 32
- 239000002954 polymerization reaction product Substances 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 25
- 239000003513 alkali Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 230000007935 neutral effect Effects 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 230000032050 esterification Effects 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 230000000704 physical effect Effects 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000010687 lubricating oil Substances 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000003921 oil Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 10
- 239000001993 wax Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 229920013639 polyalphaolefin Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000881 depressing effect Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
- C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M107/28—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Emergency Medicine (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of lubricating oil pour point depressants, in particular to a method and a system for synthesizing a T803 pour point depressant from coal-based olefins, and the T803 pour point depressant prepared by the method. The method comprises the following steps: cutting coal-based olefin by adopting secondary fraction to obtain C 7 ‑C 20 A fraction; the C is subjected to 7 ‑C 20 The fraction is refined by adsorption, and the C is removed 7 ‑C 20 Oxygenates in the fraction; c of the resulting deoxidised compound 7 ‑C 20 Sequentially carrying out polymerization reaction, esterification reaction, water washing, distillation and filtration on the fractions to obtain a T803 pour point depressant; wherein, based on the total weight of the coal-based olefin, the content of alpha-olefin in the coal-based olefin is 50-65wt%, the content of alkane is 30-45wt% and the content of oxygen-containing compound is 1-5wt%. The method effectively improves the yield of the T803 pour point depressant and reduces the production cost.
Description
Technical Field
The invention relates to the technical field of lubricating oil pour point depressants, in particular to a method and a system for synthesizing a T803 pour point depressant from coal-based olefins, and the T803 pour point depressant prepared by the method.
Background
The indirect coal liquefaction technology mainly uses fuel oil for producing diesel oil and naphtha, the price of the fuel oil product is deeply influenced by the price fluctuation of crude oil, the market competitiveness is against the market competition of the petroleum refining industry, and the economic benefit of enterprises is severely restricted. Therefore, the downstream industrial chain of the indirect coal liquefaction project is extended, the added value of products is improved, and the realization of diversification, refinement and high-end of the products is a necessary way for industrial development.
The pour point depressant is one of the indispensable additives in lubricating oil, and is a chemically synthesized high molecular organic compound, and the T803 pour point depressant (poly alpha-olefin pour point depressant) is prepared by polymerizing alpha-olefin serving as a raw material under the catalysis of a catalyst. T803 pour point depressant has wide adaptability to light base, intermediate base and paraffin base oil, can effectively lower the solidification point of oil products, and can improve the low-temperature performance of the oil products. Compared with other pour point depressants, the T803 pour point depressant has better fluidity, is convenient to store and transport and is applicable, and can be widely applied to various industrial oils and internal combustion engine oils.
T803 pour point depressant is one of lubricating oil pour point depressants, and is prepared from four raw materials at present: (1) ethylene oligomerized alpha-olefins; (2) cracking olefins with hard waxes (oil content below 3 wt.%; (3) soap wax (oil content 5-10 wt%) cracking olefins; (4) the oil under wax (oil content 10-30 wt%) cracks the olefins.
DE2316730 discloses a process for preparing a polyalphaolefin pour point depressant from C 5 -C 10 And C 16 -C 24 Of two-stage olefins, wherein C 5 -C 10 Alpha-olefins of 70-96mol% of the total feed, C 16 -C 24 The alpha-olefin accounts for 4-30mol%, the weight average molecular weight of the polymer is 5-100 ten thousand, and the number average molecular weight of the polymer is 400-1000000.
US3151181 discloses ethylene oligomerizationC of (2) 10 -C 18 Alpha-olefin copolymer with substituent C on main chain 10 -C 14 The polymer has a molecular weight of 650-1000000.
US5188724 discloses a polyalphaolefin pour point depressant comprising C 10 、C 14 、C 16 The three alpha-olefins are copolymerized, each monomer is not less than 10wt%, the average side chain carbon number is 10.5-12, the molecular weight is 15-54 ten thousand, and the problem of light oil condensation point is solved.
FR1564812 discloses that the polyalphaolefin pour point depressant is C obtained by cracking hard wax 7 -C 20 The olefin is copolymerized as a raw material and hexane is used as a solvent.
CN99109415.8 discloses a poly alpha-olefin pour point depressant and a preparation method thereof, C by using oil under wax as raw material for cracking 8 -C 18 C obtained by oligomerization of alpha-olefins with ethylene in an amount of 1 to 20mol% based on the total olefins 20 -C 24 The olefins are mixed to form a mixed olefin having an average carbon number of 13 to 17.5.
In the method, the olefin obtained by cracking the alpha-olefin and the hard wax which are oligomerized by ethylene needs to be added with a solvent in the polymerization process, the molecular weight is difficult to control, the problems of larger molecular weight and tackifying are outstanding, and the shearing stability is poor; c obtained by cracking soap wax 7 -C 20 When the olefin is used as a raw material to prepare the T803 pour point depressant, the molecular weight is regulated by higher hydrogen pressure, the molecular weight is still higher, the post-treatment is difficult, and the soap wax source is insufficient; t803 pour point depressant synthesized by using oil under wax and ethylene oligomerization olefin as raw materials has higher cost, and still can not solve the market demand for low-cost pour point depressant.
Disclosure of Invention
The invention aims to solve the problems that the existing T803 pour point depressant has larger molecular weight, large viscosity, poor shear stability and difficult control of molecular weight, and the raw material sources are insufficient, the solvent is required to be added, the environment-friendly requirement is difficult to be met, the energy consumption is high, the cost is high and the like in the preparation process of the T803 pour point depressant, and provides a method and a system for synthesizing the T803 pour point depressant from coal-based olefins, and the T803 pour point depressant prepared by the method. The method takes coal-based olefin as a raw material, does not need to add a solvent in the polymerization process, realizes the molecular weight adjustment of the T803 pour point depressant, effectively improves the yield of the T803 pour point depressant, and reduces the production cost.
To achieve the above object, a first aspect of the present invention provides a method for synthesizing a T803 pour point depressant from coal-based olefins, the method comprising:
cutting coal-based olefin by adopting secondary fraction to obtain C 7 -C 20 A fraction; the C is subjected to 7 -C 20 The fraction is refined by adsorption, and the C is removed 7 -C 20 Oxygenates in the fraction; c of the resulting deoxidised compound 7 -C 20 Sequentially carrying out polymerization reaction, esterification reaction, water washing, distillation and filtration on the fractions to obtain a T803 pour point depressant;
wherein, based on the total weight of the coal-based olefin, the content of alpha-olefin in the coal-based olefin is 50-65wt%, the content of alkane is 30-45wt% and the content of oxygen-containing compound is 1-5wt%.
Preferably, the method comprises the steps of:
(1) Cutting the coal-based olefin into a first fraction, and subjecting the obtained C 7 + Cutting the second fraction to obtain the C 7 -C 20 A fraction;
(2) The C is subjected to 7 -C 20 The fraction and the refining agent are subjected to the adsorption refining to obtain the C of the de-oxygenated compound 7 -C 20 A fraction;
(3) C of the deoxidising compound under an inert gas atmosphere 7 -C 20 Carrying out the polymerization reaction on the fraction, the catalyst and the molecular weight regulator to obtain a polymerization reaction product;
(4) Carrying out the esterification reaction on the polymerization reaction product and an esterifying agent to obtain an esterification reaction product;
(5) Washing the esterification reaction product, alkali liquor and water to be neutral to obtain a washing product;
(6) Carrying out the distillation on the water washing product to obtain a distillation product;
(7) And filtering the distillation product and the filter aid to obtain a filtered product serving as the T803 pour point depressant.
In a second aspect, the invention provides a T803 pour point depressant made by the method provided in the first aspect.
In a third aspect, the invention provides a system for synthesizing T803 pour point depressant from coal-based olefins, the system comprising: the device comprises a fraction cutting unit, an adsorption refining unit, a polymerization unit, an esterification unit, a water washing unit, a distillation unit and a filtering unit which are connected in sequence;
the fraction cutting unit is used for performing secondary fraction cutting on the coal-based olefin to obtain C 7 -C 20 A fraction;
the adsorption refining unit is used for refining the C 7 -C 20 Adsorption refining of the fraction and refining agent to obtain C with oxygen-containing compound removed 7 -C 20 A fraction;
the polymerization unit is used for removing C of the oxygen-containing compound 7 -C 20 Carrying out polymerization reaction on the fraction, the catalyst and the molecular weight regulator in an inert gas atmosphere to obtain a polymerization reaction product;
the esterification unit is used for carrying out esterification reaction on the polymerization reaction product and an esterifying agent to obtain an esterification reaction product;
the washing unit is used for washing the esterification reaction product, the alkali liquor and the water to be neutral to obtain a washing product;
the distillation unit is used for distilling the water washing product to obtain a distillation product;
the filtering unit is used for filtering the distillation product and the filter aid, and the obtained filtering product is used as a T803 pour point depressant.
Compared with the prior art, the invention has the following advantages:
(1) The method provided by the invention takes coal-based olefin as raw material, and mainly uses C in the coal-based olefin 7 -C 20 The alpha-olefin and alkane in the fraction are combined with the technical means of secondary fraction cutting, adsorption refining, polymerization reaction, esterification reaction, water washing, distillation and filtration to obtain the T803 pour point depressant; in particular, the reduction of T803 by the molecular weight regulator is achieved without the need for introducing other solvents during the polymerization processThe molecular weight of the coagulant is regulated, so that the yield of the T803 pour point depressant is effectively improved, and the production cost is reduced; meanwhile, the method simplifies the process flow and is convenient for industrial production;
(2) The T803 pour point depressant prepared by the method provided by the invention has the advantages of small molecular weight, low viscosity, strong shear stability, low impurity content (such as moisture, ash and the like) and the like.
Drawings
Fig. 1 is a schematic diagram of a system for synthesizing a T803 pour point depressant from coal-based olefins.
Description of the reference numerals
I-1, first distillation column I-2, second distillation column II, adsorption purification unit
III, polymerization unit IV, esterification unit V, washing unit
VI, distillation unit VII, filtration unit
1. Coal-based olefins 2, C 6 - Fraction 3, C 7 + Fractions and process for preparing the fractions
4、C 21 + Fraction 5, C 7 -C 20 Fraction 6 and refining agent
7. Oxygen-enriched compound stream 8, C of the deoxored compound 7 -C 20 Fractions and process for preparing the fractions
9. Catalyst 10, molecular weight regulator 11, and polymerization reaction product
12. Esterifying agent 13, esterification reaction product 14, alkali liquor
15. Water 16, waste liquid 17, water washing products
18. Unreacted component 19, distilled product 20, filter aid
21. Filter residue 22, filtered product 23 and T803 pour point depressant
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, unless otherwise specified, "first" and "second" do not denote any order of preference, nor do they denote any limitation of quantity or step, but rather are used to distinguish one quantity or step from another. For example, "first" and "second" of "first cut" and "second cut" are used only to distinguish that this is not the same cut; the "first" and "second" of the "first distillation column" and the "second distillation column" are merely used to distinguish that this is not the same distillation column.
The first aspect of the invention provides a method for synthesizing T803 pour point depressant from coal-based olefin, which comprises the following steps:
cutting coal-based olefin by adopting secondary fraction to obtain C 7 -C 20 A fraction; the C is subjected to 7 -C 20 The fraction is refined by adsorption, and the C is removed 7 -C 20 Oxygenates in the fraction; c of the resulting deoxidised compound 7 -C 20 Sequentially carrying out polymerization reaction, esterification reaction, water washing, distillation and filtration on the fractions to obtain a T803 pour point depressant;
wherein, based on the total weight of the coal-based olefin, the content of alpha-olefin in the coal-based olefin is 50-65wt%, the content of alkane is 30-45wt% and the content of oxygen-containing compound is 1-5wt%.
The inventors of the present invention studied and found that: compared with the prior art, the invention adopts the coal-based olefin as the raw material, and the coal-based olefin does not contain sulfur, nitrogen and other impurity components, i.e. desulfurization and denitrification treatment is not needed; the invention adopts C 7 -C 20 The fraction is polymerized without cutting, so that energy consumption is reduced, meanwhile, solvent is not required to be introduced in the polymerization process, the regulation and control of the molecular weight of the T803 pour point depressant are realized through a molecular weight regulator on the premise of meeting the environmental protection requirement, and the T803 pour point depressant with excellent performance is obtainedAnd (5) a coagulant.
In the present invention, the alpha-olefin content parameter, the alkane content parameter and the oxygenate content parameter are all measured by a gas chromatography method without special description.
In the present invention, the oxygen-containing compound includes, without being limited to, alcohols, aldehydes, ketones, esters, and the like, unless otherwise specified.
In the present invention, the kind of the coal-based olefin has a wide selection range, as long as the above parameter limitations are satisfied. Preferably, the distillation range of the coal-based olefin is 140-370 ℃; further preferably, the coal-based olefins include, but are not limited to, indirect coal liquefaction products.
In some embodiments of the invention, preferably, the method comprises the steps of:
(1) Cutting the coal-based olefin into a first fraction, and subjecting the obtained C 7 + Cutting the second fraction to obtain the C 7 -C 20 A fraction;
(2) The C is subjected to 7 -C 20 The fraction and the refining agent are subjected to the adsorption refining to obtain the C of the de-oxygenated compound 7 -C 20 A fraction;
(3) C of the deoxidising compound under an inert gas atmosphere 7 -C 20 Carrying out the polymerization reaction on the fraction, the catalyst and the molecular weight regulator to obtain a polymerization reaction product;
(4) Carrying out the esterification reaction on the polymerization reaction product and an esterifying agent to obtain an esterification reaction product;
(5) Washing the esterification reaction product, alkali liquor and water to be neutral to obtain a washing product;
(6) Carrying out the distillation on the water washing product to obtain a distillation product;
(7) And filtering the distillation product and the filter aid to obtain a filtered product serving as the T803 pour point depressant.
In the present invention, the first fraction cut is intended to fractional cut coal-based olefins to give C 6 - Fraction and C 7 + And (3) fraction. Preferably, in step (1), the conditions for cutting the first fraction include: the overhead temperature is 150-170 ℃, e.g., 150 ℃, 160 ℃, 162 ℃, 165 ℃, 170 ℃, and any value in the range consisting of any two values, preferably 160-165 ℃; the pressure is normal pressure.
In the present invention, the normal pressure is 0.1MPa unless otherwise specified.
In a specific embodiment of the invention, the first cut is carried out in an atmospheric distillation column and the overhead temperature of the atmospheric distillation column is 150-170 ℃, preferably 160-165 ℃.
In the present invention, the second fraction is cut to cut C 7 + Fractionating and cutting the fraction to obtain C 21 + Fraction and C 7 -C 20 And (3) fraction. Preferably, in step (1), the conditions for cutting the second fraction include: the temperature of the top of the tower is 315-330 ℃, preferably 320-330 ℃; the pressure is 0.01-0.1MPa, preferably 0.06-0.08MPa.
In one embodiment of the invention, the second cut is carried out in a reduced pressure distillation column having a top temperature of 249-263 ℃ (corresponding to a temperature of 315-330 ℃ for atmospheric distillation), preferably 254-263 ℃ (corresponding to a temperature of 320-330 ℃ for atmospheric distillation). The pressure is 0.01-0.1MPa, preferably 0.06-0.08MPa.
In some embodiments of the invention, preferably, based on said C 7 -C 20 Total amount of fractions, C 7 -C 20 In the fraction, C 7 -C 20 The hydrocarbon content is more than or equal to 90wt percent, preferably 92 to 95wt percent; the oxygenate content is 1-5wt%, preferably 3-5wt%.
In some embodiments of the invention, it is further preferred that based on said C 7 -C 20 Total amount of fractions, C 7 -C 20 The alpha-olefin content in the fraction is more than or equal to 60wt%, preferably 60-70wt%.
In one embodiment of the invention, based on the C 7 -C 20 Total amount of fractions C 7 -C 20 In the fraction, C 7 -C 17 The alpha-olefin content of (2) is 53-63wt%, preferably 53-60wt%; c (C) 18 -C 20 The alpha-olefin content of (2) is 7 to 17wt%, preferably 7 to 10wt%.
In the present invention, the refining agent is intended to remove the C 7 -C 20 Oxygenates in the fraction. Preferably, in step (2), the refining agent is selected from clay, silica gel, ZSM-5 molecular sieve, 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, and AlCl 3 At least one of them.
In some embodiments of the invention, preferably, the C 7 -C 20 The weight ratio of the fraction to the refining agent is 1:0.1-2, e.g., 1:0.1, 1:0.2, 1:0.3, 1:0.5, 1:1, 1:2, and any value in the range of any two values, preferably 1:0.2-0.5. The preferred weight ratio is adopted to be more beneficial to the removal of C 7 -C 20 And (3) oxygen-containing compounds in the fraction.
In some embodiments of the invention, preferably, C based on the said deoxidising compound 7 -C 20 Total amount of fractions, C of said deoxidised compounds 7 -C 20 The fraction contains less than or equal to 2000ppm, preferably less than or equal to 1000ppm of oxygen-containing compounds.
In the present invention, the polymerization reaction is intended to give a polyalphaolefin product of the target molecular weight. Preferably, in step (3), the polymerization conditions include: the temperature is 90-150deg.C, preferably 120-140deg.C, more preferably 125-135 deg.C; the time is 0.5 to 10 hours, preferably 1 to 5 hours, more preferably 2 to 4 hours.
In some embodiments of the invention, preferably, the oxygenate-free C 7 -C 20 The ratio of the fractions to the catalyst used was 100:0.1-0.5, e.g., 100:0.1, 100:0.2, 100:0.25, 100:0.3, 100:0.5, and any value in the range of any two values, preferably 100:0.2-0.3.
In some embodiments of the present invention, preferably, the catalyst is a Ziegler-Natta catalyst, and the Ziegler-Natta catalyst has the general formula [ AX ] n ]-[BY m ]Wherein A is selected from group IVBAt least one metal element in VB group, VIB group, VIIB group and VIII group, X is at least one of fluorine, chlorine, bromine and iodine, and n is a positive integer of 1-8; b is at least one metal element selected from group IA, group IIA and group IIIA, Y is at least one metal element selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, m is a positive integer of 1-3, for example TiCl 3 -Al(iC 4 H 9 ) 3 A catalyst.
In the present invention, the molecular weight regulator is intended to regulate the molecular weight of the T803 pour point depressant. Preferably, the molecular weight regulator is hydrogen.
In the present invention, the esterification reaction is intended to remove an acidic component in the polymerization reaction product and terminate the polymerization reaction. Preferably, in step (4), the esterification reaction conditions include: the temperature is 50-80deg.C, preferably 60-70deg.C; the time is 0.5-5h, preferably 1-3h.
In some embodiments of the invention, preferably, the weight ratio of the polymerization reaction product to the esterifying agent is 100:5-20, e.g., 100:5, 100:10, 100:12, 100:15, 100:20, and any value in the range of any two values, preferably 100:10-15.
In the present invention, the variety of the esterifying agent has a wide selection range. Preferably, the esterifying agent is an alcohol; further preferably, the esterifying agent is selected from at least one of ethylene glycol, glycerol, methanol, ethanol, propanol and isopropanol.
In the present invention, the water wash is intended to remove the residual esterifying agent and acidic substances in the esterification reaction product. Preferably, in step (5), the temperature of the water wash is from 80 to 100 ℃, e.g., 80 ℃, 85 ℃, 90 ℃, 95 ℃,100 ℃, and any value in the range of any two values, preferably from 85 to 95 ℃.
In some embodiments of the invention, preferably, the volume ratio of esterification reaction product, lye, and water is 1:0.1-0.5:0.1-1, preferably 1:0.2-0.5:0.5-1.
In some embodiments of the present invention, preferably, the pH of the lye is between 6 and 8, wherein the alkali in the lye includes, but is not limited to, sodium hydroxide, potassium hydroxide, calcium hydroxide, and the like.
In the present invention, the distillation is intended to remove unreacted components in the water-washed product. Preferably, in step (6), the conditions of the distillation include: the temperature is 160-200deg.C, preferably 180-190 deg.C; the pressure is normal pressure.
In the present invention, the filtration is intended to remove colored impurities and residual catalyst in the distilled product. Preferably, in step (7), the filtering conditions include: the temperature is 50-100deg.C, preferably 60-80deg.C; the pressure is 0-0.5MPa, preferably 0-0.1MPa.
In some embodiments of the invention, preferably, the filter aid is selected from activated clay and/or activated carbon.
According to a particularly preferred embodiment of the present invention, a process for synthesizing T803 pour point depressants from coal-based olefins, the process comprising:
(1) Cutting the coal-based olefin into a first fraction, and subjecting the obtained C 7 + Cutting the second fraction to obtain C 7 -C 20 A fraction;
(2) The C is subjected to 7 -C 20 The fraction and the refining agent are subjected to the adsorption refining to obtain the C of the de-oxygenated compound 7 -C 20 A fraction;
(3) C of the deoxidising compound under an inert gas atmosphere 7 -C 20 Carrying out the polymerization reaction on the fraction, the catalyst and the molecular weight regulator to obtain a polymerization reaction product;
(4) Carrying out the esterification reaction on the polymerization reaction product and an esterifying agent to obtain an esterification reaction product;
(5) Washing the esterification reaction product, alkali liquor and water to be neutral to obtain a washing product;
(6) Carrying out the distillation on the water washing product to obtain a distillation product;
(7) The distillation product and the filter aid are subjected to the filtration, and the obtained filtration product is used as the T803 pour point depressant;
wherein, based on the total weight of the coal-based olefin, the content of alpha-olefin in the coal-based olefin is 50-65wt%, the content of alkane is 30-45wt% and the content of oxygen-containing compound is 1-5wt%;
wherein based on the C 7 -C 20 Total amount of fractions C 7 -C 20 In the fraction, C 7 -C 17 The alpha-olefin content of (2) is 53-60wt%; c (C) 18 -C 20 The alpha-olefin content of (2) is 7-10wt%.
In a second aspect, the invention provides a T803 pour point depressant made by the method provided in the first aspect.
According to the present invention, preferably, the physical properties of the T803 pour point depressant satisfy: the average carbon number of the alkyl side chain is 11.15-14.61, preferably 12-14; weight average molecular weight of 5X 10 4 -2.5×10 5 g/mol, preferably 8X 10 4 -2×10 5 g/mol; the moisture is less than or equal to 0.02wt percent, preferably less than or equal to 0.01wt percent; ash content is less than or equal to 0.1wt percent, preferably less than or equal to 0.06wt percent; the shear stability index is 30-40%, preferably 32-38%; the kinematic viscosity at 100 ℃ is less than or equal to 1000mm 2 S, preferably 800-1000mm 2 S; the pour point is more than or equal to 17, preferably 17-20.
In the invention, the average carbon number parameter of the alkyl side chain is measured by gas chromatography without special description; the weight average molecular weight parameter is measured by gel permeation chromatography; the moisture parameter is measured by Karl Fischer micro moisture analysis; ash parameters are measured by GB/T508 analysis; the shear stability index is measured by an ultrasonic SH/T0505 method; the kinematic viscosity parameter at 100 ℃ is measured by using GB/T265; the pour point depressing parameter is measured using GB/T510.
In a third aspect, the invention provides a system for synthesizing T803 pour point depressant from coal-based olefins, the system comprising: the device comprises a fraction cutting unit, an adsorption refining unit, a polymerization unit, an esterification unit, a water washing unit, a distillation unit and a filtering unit which are connected in sequence;
the fraction cutting unit is used for performing secondary fraction cutting on the coal-based olefin to obtain C 7 -C 20 A fraction;
the adsorption refining unit is used for refining theC 7 -C 20 Adsorption refining of the fraction and refining agent to obtain C with oxygen-containing compound removed 7 -C 20 A fraction;
the polymerization unit is used for removing C of the oxygen-containing compound 7 -C 20 Carrying out polymerization reaction on the fraction, the catalyst and the molecular weight regulator in an inert gas atmosphere to obtain a polymerization reaction product;
the esterification unit is used for carrying out esterification reaction on the polymerization reaction product and an esterifying agent to obtain an esterification reaction product;
the washing unit is used for washing the esterification reaction product, the alkali liquor and the water to be neutral to obtain a washing product;
the distillation unit is used for distilling the water washing product to obtain a distillation product;
the filtering unit is used for filtering the distillation product and the filter aid, and the obtained filtering product is used as a T803 pour point depressant.
According to the present invention, preferably, the fraction cutting unit includes a first distillation column and a second distillation column connected in sequence; further preferably, the first distillation column is used for cutting the coal-based olefin into a first fraction to obtain C 7 + A fraction, said second distillation column being used to convert said C 7 + Cutting the second fraction to obtain the C 7 -C 20 And (3) fraction.
The schematic diagram of a system for synthesizing T803 pour point depressant from coal-based olefin is shown in figure 1, and as can be seen from figure 1, the system comprises: the device comprises a fraction cutting unit, an adsorption refining unit II, a polymerization unit III, an esterification unit IV, a washing unit V, a distillation unit VI and a filtering unit VII which are sequentially connected, wherein the fraction cutting unit comprises a first distillation tower I-1 and a second distillation tower I-2 which are sequentially connected;
wherein the first distillation column I-1 is used for cutting the first fraction of the coal-based olefin 1 to obtain C 6 - Fractions 2 and C 7 + Fraction 3; a second distillation column I-2 for converting C 7 + Cutting the second fraction to obtain C 7 -C 20 Fraction 5And C 21 + Fraction 4; the adsorption refining unit II is used for purifying C 7 -C 20 Adsorption refining of fraction 5 and refining agent 6 to obtain C with oxygen-containing compound removed 7 -C 20 Fraction 8 and oxygenate-rich stream 7; polymerization unit III C for the removal of oxygenates 7 -C 20 The fraction 8, the catalyst 9 and the molecular weight regulator 10 are subjected to polymerization reaction under the inert gas atmosphere to obtain a polymerization reaction product 11; the esterification unit IV is used for carrying out esterification reaction on the polymerization reaction product 11 and the esterifying agent 12 to obtain an esterification reaction product 13; the washing unit V is used for washing the esterification reaction product 13, the alkali liquor 14 and the water 15 to be neutral to obtain a washing product 17 and a waste liquor 16; distillation unit VI is used to distill the water-washed product 17 to obtain distilled product 19 and unreacted component 18; the filtration unit VII is used for filtering the distillation product 19 and the filter aid 20, and the obtained filtration product 22 is used as a T803 pour point depressant 23.
The present invention will be described in detail by examples.
The average carbon number parameter of the alkyl side chain is measured by adopting a gas chromatography;
the weight average molecular weight parameter is measured by gel permeation chromatography;
the moisture parameter is measured by Karl Fischer micro moisture analysis;
ash parameters are measured by GB/T508 analysis;
the shear stability index is measured by an ultrasonic SH/T0505 method;
the kinematic viscosity parameter at 100 ℃ is measured by using GB/T265;
the pour point depressing parameter is measured using GB/T510.
Physical properties of T803 pour point depressants S1-S6 and D1-D2 prepared in examples 1-6 and comparative examples 1-2 are shown in Table 2.
Example 1
(1) Coal-based olefin-1 (specific composition is listed in Table 1) was subjected to first cut (atmospheric distillation, overhead temperature 160 to 165 ℃ C.) and the resulting C was subjected to distillation 7 + Cutting the second fraction (vacuum distillation, tower top vacuum temperature of 249-254 deg.C and vacuum pressure of 0.08 MPa) to obtain C 7 -C 20 A fraction;
wherein based on C 7 -C 20 Total amount of fractions C 7 -C 20 In the fraction, C 7 -C 20 The hydrocarbon content was 95wt% and the oxygenate content was 4wt%; wherein C is 7 -C 17 Has an alpha-olefin content of 60wt%, C 8 -C 20 Is 7 wt.%;
(2) C is as described above 7 -C 20 Fractions and refiners (silica gel) at 1: adsorption refining at a weight ratio of 0.2 to obtain C with oxygen-containing compound removed 7 -C 20 A fraction;
wherein C based on a deoxidising compound 7 -C 20 Total amount of fractions, C with oxygenate removal 7 -C 20 The content of oxygen-containing compound in the fraction is 1000ppm;
(3) C of the above-mentioned oxygen-containing compound is removed under nitrogen atmosphere 7 -C 20 Fraction TiCl 3 -Al(iC 4 H 9 ) 3 The catalyst and hydrogen are polymerized for 3 hours at 130 ℃ to obtain a polymerization reaction product;
wherein, C of the deoxidising compound 7 -C 20 Fraction and TiCl 3 -Al(iC 4 H 9 ) 3 The weight ratio of the catalyst is 100:0.25;
(4) Esterifying the polymerization reaction product and an esterifying agent (ethylene glycol) for 3 hours at the temperature of 60 ℃ according to the weight ratio of 100:10 to obtain an esterification reaction product;
(5) Washing the esterification reaction product, alkali liquor (sodium hydroxide solution with pH of 7) and water to be neutral at the temperature of 90 ℃ to obtain a washing product;
wherein, the volume ratio of the esterification reaction product, alkali liquor and water is 1:0.3:1;
(6) Distilling the dial oil from the water washing product under the conditions of normal pressure and 185 ℃ to obtain a distilled product;
(7) The distillation product and the filter aid (activated carbon) were combined in a ratio of 1: the filtration was carried out at a weight ratio of 0.2 (temperature 80 ℃ C., pressure 0.05 MPa) and the resulting filtration product was used as T803 pour point depressant S1.
Example 2
(1) Coal-based olefin-1 (specific composition is listed in Table 1) was subjected to first cut (atmospheric distillation, overhead temperature 160 to 165 ℃ C.) and the resulting C was subjected to distillation 7 + Cutting the second fraction (vacuum distillation, overhead vacuum temperature of 254-258 deg.C, vacuum pressure of 0.08 MPa) to obtain C 7 -C 20 A fraction;
wherein based on C 7 -C 20 Total amount of fractions C 7 -C 20 In the fraction, C 7 -C 20 The hydrocarbon content was 90wt% and the oxygenate content was 4.2wt%; c (C) 7 -C 17 Is 56wt%, C 8 -C 20 Is 8 wt.%;
(2) C is as described above 7 -C 20 Fractions and refiners (ZSM-5 molecular sieves) were used at 1: adsorption refining at a weight ratio of 0.1 to obtain C containing oxygen-free compound 7 -C 20 A fraction;
wherein C based on a deoxidising compound 7 -C 20 Total amount of fractions, C with oxygenate removal 7 -C 20 The content of oxygen-containing compound in the fraction is 2000ppm;
(3) C of the above-mentioned oxygen-containing compound is removed under nitrogen atmosphere 7 -C 20 Fraction TiCl 3 -Al(iC 4 H 9 ) 3 Polymerizing the catalyst and hydrogen at 120 ℃ for 4 hours to obtain a polymerization reaction product;
wherein, C of the deoxidising compound 7 -C 20 Fraction and TiCl 3 -Al(iC 4 H 9 ) 3 The weight ratio of the catalyst is 100:0.2;
(4) Esterifying the polymerization reaction product and an esterifying agent (glycerol) at the weight ratio of 100:15 at 65 ℃ for 1h to obtain an esterification reaction product;
(5) Washing the esterification reaction product, alkali liquor (sodium hydroxide solution with pH of 6) and water to be neutral at 85 ℃ to obtain a washing product;
wherein, the volume ratio of the esterification reaction product, alkali liquor and water is 1:0.2:1;
(6) Distilling the dial oil from the water washing product under the conditions of normal pressure and 180 ℃ to obtain a distilled product;
(7) The distillation product and the filter aid (activated clay) were mixed in a ratio of 1: the filtration was carried out at a weight ratio of 0.2 (temperature: 75 ℃ C., pressure: 0.1 MPa), and the obtained filtration product was used as T803 pour point depressant S2.
Example 3
(1) Coal-based olefin-1 (specific composition is listed in Table 1) was subjected to first cut (atmospheric distillation, overhead temperature 160 to 165 ℃ C.) and the resulting C was subjected to distillation 7 + Cutting the second fraction (vacuum distillation, overhead vacuum temperature 258-263 deg.C, vacuum pressure 0.08 MPa) to obtain C 7 -C 20 A fraction;
wherein based on C 7 -C 20 Total amount of fractions C 7 -C 20 In the fraction, C 7 -C 20 A hydrocarbon content of 85wt% and an oxygenate content of 4.5wt%; c (C) 7 -C 17 The alpha-olefin content of (C) was 53% by weight 8 -C 20 Is 10 wt.%;
(2) C is as described above 7 -C 20 Distillate and refining agent (AlCl) 3 ) 1, the method comprises the following steps: adsorption refining at a weight ratio of 0.001 to obtain C containing oxygen-free compound 7 -C 20 A fraction;
wherein C based on a deoxidising compound 7 -C 20 Total amount of fractions, C with oxygenate removal 7 -C 20 The content of the oxygen-containing compound in the fraction is 2500ppm;
(3) C of the above-mentioned oxygen-containing compound is removed under nitrogen atmosphere 7 -C 20 Fraction TiCl 3 -Al(iC 4 H 9 ) 3 Polymerizing the catalyst and hydrogen at 125 ℃ for 4 hours to obtain a polymerization reaction product;
wherein, C of the deoxidising compound 7 -C 20 Fraction and TiCl 3 -Al(iC 4 H 9 ) 3 The weight ratio of the catalyst is 100:0.3;
(4) Esterifying the polymerization reaction product and an esterifying agent (isopropanol) at the weight ratio of 100:12 at 70 ℃ for 1h to obtain an esterification reaction product;
(5) Washing the esterification reaction product, alkali liquor (sodium hydroxide solution with concentration of 2 mol/L) and water to be neutral at 95 ℃ to obtain a washing product;
wherein, the volume ratio of the esterification reaction product, alkali liquor and water is 1:0.5:0.5;
(6) Distilling the dial oil from the water washing product under the conditions of normal pressure and 190 ℃ to obtain a distilled product;
(7) The distillation product and the filter aid (activated clay) were mixed in a ratio of 1: the filtration was carried out at a weight ratio of 0.2 (temperature 80 ℃ C., pressure 0 MPa) and the resulting filtration product was used as T803 pour point depressant S3.
Example 4
According to the method of example 1, except that in step (3), the above-mentioned oxygen-containing compound-removed C 7 -C 20 Fraction and TiCl 3 -Al(iC 4 H 9 ) 3 The weight ratio of the catalyst is replaced by 100:0.1, and the rest conditions are the same, so that the T803 pour point depressant S4 is obtained.
Example 5
The procedure of example 1 was followed except that in step (4), the weight ratio of the polymerization reaction product and the esterifying agent was replaced with 100:5, and the remaining conditions were the same, to obtain T803 pour point depressant S5.
Example 6
The procedure of example 1 was followed except that in step (5), the above-mentioned esterification reaction product, alkali liquor and water were replaced with a volume ratio of 1:0.6:1.5, and the remaining conditions were the same, to obtain T803 pour point depressant S6.
Comparative example 1
The procedure of example 1 was followed except that in step (1), coal-based olefin-1 was replaced with coal-based olefin-2 (specific composition is shown in Table 1), and the remaining conditions were the same, to obtain T803 pour point depressant D1.
Comparative example 2
The procedure of example 1 was followed except that in step (1), coal-based olefin-1 was replaced with refined soap wax (oil content: 5 wt%) and olefins C7 to C20 (alpha-olefin content: 70 wt%) were cracked, and the remaining conditions were the same, to obtain T803 pour point depressant D2.
TABLE 1
| Coal-based olefin-1 | Coal-based olefin-2 | |
| Distillation range, DEG C | 141.1-360.5 | - |
| Alpha-olefin content, wt% | 62.1 | 48 |
| Alkane content, wt% | 33.2 | 46.5 |
| Oxygen-containing compound content, wt% | 4.7 | 5.5 |
| Residual amount, wt% | 1.4 | - |
| Evaporation loss, wt% | 1.2 | - |
TABLE 2
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Yield% | 76 | 72 | 68 | 65 |
| Average number of carbon atoms in alkyl side chain | 13.5 | 12.1 | 12.6 | 11.5 |
| Weight average molecular weight, g/mol | 1.55×10 5 | 1.76×10 5 | 1.9×10 5 | 2.08×10 5 |
| The water content of the water-bearing agent,wt％ | 0.01 | 0.01 | 0.02 | 0.02 |
| ash, wt% | 0.06 | 0.08 | 0.08 | 0.08 |
| Shear stability index,% | 32 | 38 | 35 | 31 |
| Kinematic viscosity at 100 ℃ of mm 2 /s | 805 | 860 | 880 | 904 |
| Degree of pour point depression | 19.1 | 18.4 | 18.2 | 17.9 |
Continuous table 2
| Example 5 | Example 6 | Comparative example 1 | Comparative example 2 | |
| Yield% | 62 | 62 | 55 | 59 |
| Average number of carbon atoms in alkyl side chain | 14.23 | 14.09 | 15.23 | 11.03 |
| Weight average molecular weight, g/mol | 2.09×10 5 | 2.2×10 5 | 2.8×10 5 | 3.25×10 5 |
| Moisture, wt% | 0.02 | 0.02 | 0.1 | 0.08 |
| Ash, wt% | 0.09 | 0.09 | 0.38 | 0.15 |
| Shear stability index,% | 30.1 | 30.5 | 28 | 19 |
| Kinematic viscosity at 100 ℃ of mm 2 /s | 920 | 928 | 1450 | 1600 |
| Degree of pour point depression | 17.7 | 17.3 | 13 | 12 |
As can be seen from the results of tables 1-2, the T803 pour point depressant prepared by the method provided by the invention has higher yield and excellent pour point depressing effect compared with the comparative examples 1-2. In particular by limiting the C of the oxygenate removal 7 -C 20 The weight ratio of the fraction to the catalyst, the weight ratio of the polymerization reaction product to the esterifying agent, the volume ratio of the esterification reaction product to the alkali liquor and the water are in a preferred protection range, which is more beneficial to adjusting the performance parameters of the T803 pour point depressant.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (18)
1. A method for synthesizing T803 pour point depressant from coal-based olefin, which is characterized by comprising the following steps:
cutting coal-based olefin by adopting secondary fraction to obtain C 7 -C 20 A fraction; the C is subjected to 7 -C 20 The fraction is refined by adsorption, and the C is removed 7 -C 20 Oxygenates in the fraction; c of the resulting deoxidised compound 7 -C 20 Sequentially carrying out polymerization reaction, esterification reaction, water washing, distillation and filtration on the fractions to obtain a T803 pour point depressant;
wherein, based on the total weight of the coal-based olefin, the content of alpha-olefin in the coal-based olefin is 50-65wt%, the content of alkane is 30-45wt% and the content of oxygen-containing compound is 1-5wt%.
2. The method according to claim 1, characterized in that it comprises the steps of:
(1) Cutting the coal-based olefin into a first fraction, and subjecting the obtained C 7 + Cutting the second fraction to obtain the C 7 -C 20 A fraction;
(2) The C is subjected to 7 -C 20 The fraction and the refining agent are subjected to the adsorption refining to obtain the C of the de-oxygenated compound 7 -C 20 A fraction;
(3) C of the deoxidising compound under an inert gas atmosphere 7 -C 20 Carrying out the polymerization reaction on the fraction, the catalyst and the molecular weight regulator to obtain a polymerization reaction product;
(4) Carrying out the esterification reaction on the polymerization reaction product and an esterifying agent to obtain an esterification reaction product;
(5) Washing the esterification reaction product, alkali liquor and water to be neutral to obtain a washing product;
(6) Carrying out the distillation on the water washing product to obtain a distillation product;
(7) And filtering the distillation product and the filter aid to obtain a filtered product serving as the T803 pour point depressant.
3. The process of claim 2, wherein the coal-based olefin has a distillation range of 140-370 ℃;
and/or, in step (1), the conditions for cutting the first fraction include: the temperature of the tower top is 150-170 ℃; the pressure is normal pressure;
and/or the conditions for cutting the second fraction include: the temperature of the tower top is 315-330 ℃; the pressure is 0.01-0.1MPa;
and/or based on the C 7 -C 20 Total amount of fractions, C 7 -C 20 In the fraction, C 7 -C 20 The hydrocarbon content is more than or equal to 90wt%; the content of the oxygen-containing compound is 1-5wt%;
and/or based on the C 7 -C 20 Total amount of fractions, C 7 -C 20 In the fraction, the content of alpha-olefin is more than or equal to 60wt%;
and/or based on the C 7 -C 20 Total amount of fractions C 7 -C 20 In the fraction, C 7 -C 17 The alpha-olefin content of (2) is 53-63wt%; c (C) 18 -C 20 The alpha-olefin content of (2) is 7-17wt%.
4. A process according to claim 3, wherein the coal-based olefin is selected from the group consisting of coal indirect liquefaction products;
and/or, in step (1), the conditions for cutting the first fraction include: the temperature of the tower top is 160-165 ℃;
and/or the conditions for cutting the second fraction include: the temperature of the tower top is 320-330 ℃; the pressure is 0.06-0.08MPa;
and/or based on the C 7 -C 20 Total amount of fractions, C 7 -C 20 In the fraction, C 7 -C 20 The hydrocarbon content is 92-95wt%; the content of the oxygen-containing compound is 3-5wt%;
and/or based on the C 7 -C 20 Total amount of fractions, C 7 -C 20 The alpha-olefin content in the fraction is 60-70wt%;
and/or based on the C 7 -C 20 Total amount of fractions C 7 -C 20 In the fraction, C 7 -C 17 The alpha-olefin content of (2) is 53-60wt%; c (C) 18 -C 20 The alpha-olefin content of (2) is 7-10wt%.
5. The process of claim 2, wherein in step (2), the refining agent is selected from the group consisting of clay, silica gel, ZSM-5 molecular sieve, 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, and AlCl 3 At least one of (a) and (b);
and/or, the C 7 -C 20 The weight ratio of the fraction to the refining agent is 1:0.1-2;
and/or C based on said deoxidising compound 7 -C 20 Total amount of fractions, C of said deoxidised compounds 7 -C 20 In the fraction, the content of the oxygen-containing compound is less than or equal to 2000ppm.
6. The method of claim 5, wherein the C 7 -C 20 The weight ratio of the fraction to the refining agent is 1:0.2-0.5;
and/or C based on said deoxidising compound 7 -C 20 Total amount of fractions, C of said deoxidised compounds 7 -C 20 In the fraction, the content of the oxygen-containing compound is less than or equal to 1000ppm.
7. The method of claim 2, wherein in step (3), the polymerization conditions include: the temperature is 90-150 ℃; the time is 0.5-10h;
and/or C of the said de-oxygenated compounds 7 -C 20 The weight ratio of the fraction to the catalyst is 100:0.1-0.5;
and/or the catalyst is a Ziegler-Natta catalyst;
and/or the molecular weight regulator is hydrogen.
8. The method of claim 7, wherein in step (3), the polymerization conditions include: the temperature is 120-140 ℃; the time is 1-5h;
and/or C of the said de-oxygenated compounds 7 -C 20 The weight ratio of the fraction to the catalyst is 100:0.2-0.3.
9. The method of claim 7, wherein in step (3), the polymerization conditions include: the temperature is 125-135 ℃; the time is 2-4h.
10. The method according to any one of claims 2 to 9, wherein in step (4), the esterification reaction conditions include: the temperature is 50-80 ℃; the time is 0.5-5h;
and/or the weight ratio of the polymerization reaction product to the esterifying agent is 100:5-20 parts;
and/or, the esterifying agent is an alcohol;
and/or, in the step (5), the temperature of the water washing is 80-100 ℃;
and/or, the volume ratio of the esterification reaction product, alkali liquor and water is 1:0.1-0.5:0.1-1.
11. The method of claim 10, wherein in step (4), the esterification reaction conditions comprise: the temperature is 60-70 ℃; the time is 1-3h;
and/or the weight ratio of the polymerization reaction product to the esterifying agent is 100:10-15 parts;
and/or the esterifying agent is at least one selected from ethylene glycol, glycerol, methanol, ethanol, propanol and isopropanol;
and/or, in the step (5), the temperature of the water washing is 85-95 ℃;
and/or, the volume ratio of the esterification reaction product, alkali liquor and water is 1:0.2-0.5:0.5-1.
12. The method according to any one of claims 2 to 9, wherein in step (6), the conditions of the distillation include: the temperature is 160-200 ℃; the pressure is normal pressure;
and/or, in step (7), the filtering conditions include: the temperature is 50-100 ℃; the pressure is 0-0.5MPa;
and/or, the weight ratio of the distillation product to the filter aid is 1:0.1-1;
and/or the filter aid is selected from activated clay and/or activated carbon.
13. The method of claim 12, wherein in step (6), the conditions of distillation comprise: the temperature is 180-190 ℃;
and/or, in step (7), the filtering conditions include: the temperature is 60-80 ℃; the pressure is 0-0.1MPa;
and/or, the weight ratio of the distillation product to the filter aid is 1:0.2-0.5.
14. A T803 pour point depressant made by the method of any one of claims 1-13.
15. The T803 pour point depressant of claim 14, wherein the physical properties parameters of the T803 pour point depressant satisfy: the average carbon number of the alkyl side chain is 11.15-14.61; weight average molecular weight of 5X 10 4 -2.5×10 5 g/mol; the water content is less than or equal to 0.02wt%; ash content is less than or equal to 0.1wt%; the shear stability index is 30-40%; the kinematic viscosity at 100 ℃ is less than or equal to 1000mm 2 S; the pour point is more than or equal to 17.
16. The T803 pour point depressant of claim 14, wherein the physical properties parameters of the T803 pour point depressant satisfy: the average carbon number of the alkyl side chain is 12-14; weight average molecular weight of 8X 10 4 -2×10 5 g/mol; the water content is less than or equal to 0.01wt%; ash content is less than or equal to 0.06wt%; the shear stability index is 32-38%; the kinematic viscosity at 100 ℃ is 800-1000mm 2 S; the pour point depression is 17-20.
17. A system for synthesizing a T803 pour point depressant from a coal-based olefin, the system comprising: the device comprises a fraction cutting unit, an adsorption refining unit, a polymerization unit, an esterification unit, a water washing unit, a distillation unit and a filtering unit which are connected in sequence;
the fraction cutting unit is used for performing secondary fraction cutting on the coal-based olefin to obtain C 7 -C 20 A fraction;
the adsorption refining unit is used for refining the C 7 -C 20 Adsorption refining of the fraction and refining agent to obtain C with oxygen-containing compound removed 7 -C 20 A fraction;
the polymerization unit is used for removing C of the oxygen-containing compound 7 -C 20 Carrying out polymerization reaction on the fraction, the catalyst and the molecular weight regulator in an inert gas atmosphere to obtain a polymerization reaction product;
the esterification unit is used for carrying out esterification reaction on the polymerization reaction product and an esterifying agent to obtain an esterification reaction product;
the washing unit is used for washing the esterification reaction product, the alkali liquor and the water to be neutral to obtain a washing product;
the distillation unit is used for distilling the water washing product to obtain a distillation product;
the filtering unit is used for filtering the distillation product and the filter aid, and the obtained filtering product is used as a T803 pour point depressant.
18. The system of claim 17, wherein the fraction cutting unit comprises a first distillation column and a second distillation column connected in sequence;
the first distillation tower is used for cutting the first fraction of the coal-based olefin to obtain C 7 + A fraction;
the second distillation column is used for separating the C 7 + Cutting the second fraction to obtain the C 7 -C 20 And (3) fraction.
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