CN113831525B - Preparation method of nonionic fatty alcohol polyether for defoamer - Google Patents
Preparation method of nonionic fatty alcohol polyether for defoamer Download PDFInfo
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- CN113831525B CN113831525B CN202111207402.5A CN202111207402A CN113831525B CN 113831525 B CN113831525 B CN 113831525B CN 202111207402 A CN202111207402 A CN 202111207402A CN 113831525 B CN113831525 B CN 113831525B
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- Prior art keywords
- fatty alcohol
- catalyst
- reaction
- cerium
- alcohol polyether
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- 229920000570 polyether Polymers 0.000 title claims abstract description 53
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 50
- 150000002191 fatty alcohols Chemical class 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000013530 defoamer Substances 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 14
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 20
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000007792 addition Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 150000000703 Cerium Chemical class 0.000 claims description 7
- -1 zirconium ions Chemical class 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 150000003754 zirconium Chemical class 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- SMKFCFKIYPLYNY-UHFFFAOYSA-K cerium(3+);trichloride;hydrate Chemical compound O.Cl[Ce](Cl)Cl SMKFCFKIYPLYNY-UHFFFAOYSA-K 0.000 claims 1
- KQJQGYQIHVYKTF-UHFFFAOYSA-N cerium(3+);trinitrate;hydrate Chemical compound O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KQJQGYQIHVYKTF-UHFFFAOYSA-N 0.000 claims 1
- KKVSNHQGJGJMHA-UHFFFAOYSA-H cerium(3+);trisulfate;hydrate Chemical compound O.[Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KKVSNHQGJGJMHA-UHFFFAOYSA-H 0.000 claims 1
- ZICYSHJXIHXTOG-UHFFFAOYSA-N chloro hypochlorite zirconium hydrate Chemical compound O.[Zr].ClOCl ZICYSHJXIHXTOG-UHFFFAOYSA-N 0.000 claims 1
- XBMSSMOTGOJLBZ-UHFFFAOYSA-N zirconium(4+) tetranitrate hydrate Chemical compound O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XBMSSMOTGOJLBZ-UHFFFAOYSA-N 0.000 claims 1
- UXRMCZYAVOHQNB-UHFFFAOYSA-J zirconium(4+);disulfate;hydrate Chemical compound O.[Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O UXRMCZYAVOHQNB-UHFFFAOYSA-J 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 27
- 239000002585 base Substances 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 17
- 239000003513 alkali Substances 0.000 abstract description 8
- 238000007670 refining Methods 0.000 abstract description 8
- 150000001768 cations Chemical class 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000002910 solid waste Substances 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 description 20
- 239000007791 liquid phase Substances 0.000 description 11
- 238000001514 detection method Methods 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000007872 degassing Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 4
- 125000003158 alcohol group Chemical group 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZVHAANQOQZVVFD-UHFFFAOYSA-N 5-methylhexan-1-ol Chemical compound CC(C)CCCCO ZVHAANQOQZVVFD-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000007046 ethoxylation reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 1
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002173 cutting fluid Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000006200 ethylation reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- UUGLKVMAABOWLC-UHFFFAOYSA-N hexan-1-ol;oxirane Chemical compound C1CO1.CCCCCCO UUGLKVMAABOWLC-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/266—Metallic elements not covered by group C08G65/2648 - C08G65/2645, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Polyethers (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of nonionic fatty alcohol polyether for defoamer, which comprises the following steps: putting a catalyst and fatty alcohol into a reaction kettle, wherein the catalyst is cerium and zirconium composite metal oxide Ce x Zr 1‑x O 2 A solid base catalyst; dehydrating for 1-2 h; slowly adding the alkylene oxide after the temperature is raised to the reaction temperature, and continuously adding the alkylene oxide at the temperature and the reaction pressure lower than the atmospheric pressure until the reaction is finished; and (3) continuously preserving heat until the pressure is reduced to be stable and unchanged, and finally cooling and filtering to obtain the fatty alcohol polyether. The invention uses cerium and zirconium composite metal oxide Ce x Zr 1‑x O 2 The solid alkali is used as a catalyst to synthesize the fatty alcohol polyether, and the fatty alcohol polyether is mixed in a reaction system in a solid form, so that the fatty alcohol polyether can be filtered, recovered and reused, and solid waste is hardly generated; and secondly, the metal cations introduced in the system by dissolving the strong base catalyst are avoided, so that the secondary refining process of removing the strong base cations by post-treatment can be avoided, and considerable cost is saved.
Description
Technical Field
The invention relates to a preparation method of nonionic fatty alcohol polyether for a defoaming agent, belonging to the field of fine chemical engineering of synthetic surfactants.
Background
In the industrial production and manufacturing process, such as sewage treatment, textile printing and dyeing, biological fermentation, coating and filming, cutting fluid, lubricating oil, pesticide fertilizer, natural gas desulfurization and the like, if a large amount of foam exists, the gas-liquid interface area of the system is greatly increased, and the instability of the system is also increased. The result is not only inconvenient in operation, waste of equipment capacity, but also waste of raw materials, blocked production capacity, reduced product quality, economic loss and other series of problems. As such, defoaming and defoaming become indispensable technological means in certain production links.
Generally, the foam-reducing aim of the system is achieved by adding an antifoaming agent. The defoamer has lower surface tension and is easy to be adsorbed on the surface of the solution, so that the local surface tension of the surface of the solution is reduced and then the solution spreads locally. Displacing the molecules on the surface of the original liquid film after entering the bubble liquid film reduces the surface tension at the contact point lower than at other positions of the liquid film. Thus, the foam liquid film with higher surface tension generates shrinkage force to lead the liquid film with low surface tension to be pulled and stretched around to form a film with poor strength, the film is thinned slowly, and finally the rupture is eliminated.
Particularly, among a plurality of defoamers, the aliphatic alcohol polyether prepared by ring-opening polymerization of ethylene oxide and propylene oxide is the most important category of non-silicon defoamers, has the characteristics of no toxicity, no peculiar smell, no stimulation and easy biodegradation, and can show good defoaming, wetting, dispersing, emulsifying and decontaminating functions in aqueous solution. According to the application requirements, the fatty alcohol with a corresponding structure can be selected, the proportion and relative molecular mass of the hydrophilic epoxyethane chain unit and the hydrophobic epoxypropane chain unit can be regulated, and the characteristics of cloud point, water solubility, oil solubility and the like can be controlled, so that the defoaming effect of the water-phase system can be adapted to a wider water-phase system to the greatest extent.
The traditional preparation method of the aliphatic alcohol polyether adopts strong alkali as a catalyst, such as sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, metal potassium, sodium and the like, dissociates initiator aliphatic alcohol anions, then the initiator anions are added with ethylene oxide or propylene oxide to generate unitary addition initiator ether, and finally chain growth occurs to obtain the target aliphatic alcohol polyether product with corresponding molecular weight chain length. The catalyst is used for production, and can be dissolved in a reaction system, so that the pH value of the system is too high, and metal cations, especially potassium ions and sodium ions, are introduced. Therefore, in the method for producing the fatty alcohol polyether by using the strong base catalyst, a post-treatment process is often needed to be matched, the basic catalyst is neutralized by acid, metal ions are removed by using an adsorbent, a decoloring agent and the like, and finally, the finished product of the fatty alcohol polyether is obtained by filtering. Meanwhile, due to the reaction characteristic of the strong base catalyst, the speed of the chain initiation reaction is lower than that of the chain growth reaction, so that polyether chains are grown before all the initiator is not completely converted into the monobasic adduct, the initiator residues are left in the final product, the adduct number distribution is wide, and the product performance is limited. Nevertheless, since there are few catalysts developed to be comparable to those of the above, strong base catalysts have been mainly used in industry.
The reaction characteristics of the strong base catalyst determine the necessary post-treatment process, and in order to stabilize the product storage or meet the downstream application requirements, alkali metal ions introduced by the catalyst are usually removed for secondary refining, which not only prolongs the production period, but also greatly increases the production cost. In order to improve such disadvantages of the conventional strong base catalyst, to suppress the introduction of alkali metal ions from the source, to improve the quality of the finished aliphatic alcohol polyether and to obtain polyether with narrower molecular weight distribution, many reports have been made on the use of solid base as the catalyst.
Patent CN109369903a uses Zr oxide as a catalyst carrier, then adds a cocatalyst, and finally loads alkali metal, and the catalyst obtained by this composition can prepare aliphatic alcohol polyether with narrow distribution, low raw material residue and low PEG/PPG content. However, the catalyst carrier is loaded with alkali metal by an impregnation method, only one layer is formed on the surface, the catalyst activity can be reduced along with the use times, frequent supplementation is needed, and meanwhile, the reaction period of preparing fatty alcohol polyether by using the catalyst is not known.
The patent CN103846082B provides a mesoporous carbon supported composite metal oxide as an alkaline solid catalyst, has a two-dimensional hexagonal mesostructure, has the characteristics of large specific surface area and uniform pore size distribution, is used for catalyzing an ethoxylation reaction, and has the advantages of narrow product distribution, high reaction conversion rate, high selectivity, easiness in post-treatment and the like compared with the traditional ethoxylation catalyst alkali. However, it is known from the patent that this technique can only catalyze the ethoxylation reaction of lower alcohols having no more than 4 carbon atoms, and that the product is only a fatty alcohol monoether, and that the application range is narrow, and it is difficult to satisfy the breadth of fatty alcohol polyethers for defoamers.
It can be seen that with the continued depth of research, solid bases have gradually demonstrated their advantages in the field of polyether catalysis, avoiding the secondary refining process compared to strong base catalysis. The invention also adopts a solid catalyst and prepares the aliphatic alcohol polyether through proper process conditions.
Disclosure of Invention
In view of the prior art obstacles, the invention provides a method for preparing nonionic fatty alcohol polyether for defoamer. The method uses solid alkali as a catalyst, can be recycled, avoids using a strong alkali catalyst in a dissolving way, suppresses the introduction of metal ions in a system from the source, avoids secondary refining of fatty alcohol polyether, and shortens the process period; meanwhile, the aliphatic alcohol polyether with narrower distribution and low raw material residue can be obtained. The specific technical method comprises the following steps:
a preparation method of nonionic fatty alcohol polyether for defoamer comprises the following steps:
putting a catalyst and fatty alcohol into a reaction kettle, wherein the catalyst is cerium and zirconium composite metal oxide Ce x Zr 1-x O 2 A solid base catalyst;
dehydrating for 1-2 h;
slowly adding the alkylene oxide after the temperature is raised to the reaction temperature, and continuously adding the alkylene oxide at the temperature and the reaction pressure lower than the atmospheric pressure until the reaction is finished;
and (3) continuously preserving heat until the pressure is reduced to be stable and unchanged, and finally cooling and filtering to obtain the fatty alcohol polyether.
The catalyst Ce x Zr 1-x O 2 Wherein x is 0.6 to 0.9.
The fatty alcohol has the following general formula:
C n H 2n+1 -OH, wherein n represents a fatty alcohol carbon number of 4 to 18, and the fatty alcohol carbon chain may be straight-chain or branched. Further, the fatty alcohol used as the raw material may be one or a mixture of two or more of the above.
The fatty alcohol polyether has the following general formula:
C n H 2n+1 -O-(EO) a (PO) b h, wherein a+b is an integer or fraction of 3 to 20. The arrangement of the alkylene oxide is not particularly limited, and is related to the properties of the final desired product. The different alkylene oxides may be blocked, random, or a single alkylene oxide.
The alkylene oxide is ethylene oxide, propylene oxide, or a mixture of ethylene oxide and propylene oxide.
The reaction temperature is the control temperature in the reaction process, the reaction activity of the system is influenced by the fact that the temperature is too low, the reaction rate is too high, the heat release is severe, meanwhile, the serious side reaction is accompanied, and the proper temperature is 85-185 ℃.
The reaction pressure is influenced by the feeding speed and the reaction rate of the alkylene oxide, and when the feeding speed and the reaction rate are low, the pressure is high, otherwise, the pressure is low, and in order to achieve the reaction efficiency and the reaction safety, a large number of experiments prove that the pressure is more suitable at 0.0-0.4 Mpa.
The amount of the catalyst is mainly related to the reaction rate, the temperature is high, the reaction rate is high, the catalyst can be added little if the catalyst is fast, and otherwise, the catalyst needs to be added more if the catalyst is fast, and in order to simultaneously consider the reaction efficiency and the reaction safety, a large number of experiments prove that the mass of the catalyst is 0.1-2% of the mass of the aliphatic alcohol polyether.
The synthesis method of the catalyst is a common surfactant template method, and specifically comprises the following steps:
pouring a certain proportion of template agent into a beaker;
then 70ml of distilled water is measured and added into a beaker, after stirring for 30min at a certain water bath temperature, cerium salt and zirconium salt with a certain metering ratio are added, after continuously stirring for 10min, precipitator ammonia water is added dropwise, the pH value of the system is regulated to about 10, cerium ions and zirconium ions generate hydroxide precipitates, and stirring is continued for 3h;
then aging for 12 hours at room temperature, centrifuging, and washing the product with deionized water and absolute ethyl alcohol respectively until the washing liquid is neutral; finally, drying the obtained product in a drying oven at 100 ℃ for 12 hours, extruding the dried product into particles with 80-100 meshes, and placing the particles in a muffle furnace for high-temperature roasting for 3 hours to obtain a solid base catalyst;
further, in the preparation method of the catalyst, the surfactant used as the template agent can be cetyltrimethylammonium bromide, sodium dodecyl sulfate or a mixture of the two surfactants, and the addition amount is 1-10% of the total mass of the system.
Further, in the preparation method of the catalyst, the cerium salt may be cerium nitrate, cerium sulfate, cerium chloride and hydrates thereof or a mixture of the above cerium salts, and the zirconium salt may be zirconium nitrate, zirconium sulfate, zirconium chloride and hydrates thereof or a mixture of the above cerium salts.
Further, in the preparation method of the catalyst, the reaction temperature has a main influence on the external structure of the catalyst, and along with the improvement of the synthesis temperature, the specific surface area of the catalyst tends to be gradually increased. The water bath temperature is considered to be more proper at 50-70 ℃ through repeated consideration.
Further, in the preparation method of the catalyst, as the proportion of cerium and zirconium increases, the microscopic pore volume in a certain range slightly increases, and the pore diameter gradually increases, so that the large specific surface area is beneficial to the improvement of the activity and stability of the reaction. Thus at Ce x Zr 1-x O 2 Wherein, x is in the range of 0.6 to 0.9 to control the molar ratio of cerium salt and zirconium salt added in the preparation process.
Further, in the preparation method of the catalyst, the alkaline center of the surface of the cerium and zirconium composite metal oxide catalyst is subjected to H 2 O and other substances cover, so that the alkalinity is very weak, the catalytic activity is low, and after high-temperature roasting treatment, the surface covering can be removed, so that the alkaline sites are fully exposed, and the alkali strength is enhanced; meanwhile, the high-temperature roasting can remove the active agent template, form various pore channels in the oxide, and increase the inner surface area of the oxide, which is also beneficial to improving the catalytic activity. Through a large number of experiments, the roasting temperature is set at 600-800 ℃.
The invention can achieve the following expected outstanding effects through the technical method:
1. the invention uses cerium and zirconium composite metal oxide Ce x Zr 1-x O 2 Compared with the traditional strong alkali catalyst which needs to be dissolved into a system to react, the solid alkali is mixed in the reaction system in a solid form, can be filtered and recycled, and hardly generates solid waste; and secondly, the metal cations introduced in the system by dissolving the strong base catalyst are avoided, so that the secondary refining process of removing the strong base cations by post-treatment can be avoided, and considerable cost is saved.
2.Ce x Zr 1-x O 2 As rare earth metal oxide, the catalyst is used for synthesizing fatty alcohol polyether due to the alkaline characteristic, the reaction process is relatively stable, and the harsh conditions of high temperature and high pressure are not needed; secondly, the preparation process of the surfactant template method leads Ce to be x Zr 1-x O 2 The metal oxide has a high specific surface area and a porous microstructure, has high catalytic activity, can be suitable for ethylation reaction of high-carbon fatty alcohol compared with patent CN103846082B to obtain fatty alcohol polyether with narrow distribution (D is less than or equal to 1.1), and has low raw material residue (less than or equal to 1.0%).
3. Catalyst Ce used in the preparation of fatty alcohol polyethers by the process of the invention x Zr 1-x O 2 The synthesis method is simple, and the surfactant template enables Zr to be formed 4+ Completely enter CeO 2 In the crystal lattice, thereby forming a uniform cubic fluorite structure, crystallinity and machineThe mechanical strength is better. The specific surface area is large, and the pore volume is better, which is favorable for the adsorption, activation and reaction of reactant molecules in the pores, so that compared with the CN109369903A patent, the catalyst can achieve similar catalytic effect without loading other alkali metals.
Detailed Description
In the invention, the process period is obtained by counting the actual test time. The distribution of the fatty alcohol polyether is detected by GPC, the width of the distribution is expressed by the molecular weight distribution D (Ww/Wn), the raw material residue is detected by a liquid phase and GPC external standard curve, namely, the sample concentration is obtained by configuring samples with different concentrations, then fitting the sample concentration and the liquid phase or GPC signals into a standard curve, and the sample concentration is obtained by detecting the liquid phase signals of the samples.
The raw materials used in the invention can be prepared by adopting a method conventional in the art, and can also be commercially available products.
The invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention as claimed. Wherein examples 1-2 are catalysts for production and examples 3-8 are aliphatic alcohol polyethers produced using the catalysts produced in examples 1-2.
Example 1
Pouring 5.3g of cetyltrimethylammonium bromide into a beaker, then weighing 70ml of distilled water, adding into the beaker, stirring at the water bath temperature of 60 ℃ for 30min for dissolution, adding 0.012mol of cerium trichloride and 0.008mol of zirconium oxychloride, continuously stirring for 10min, then dripping precipitator ammonia water, regulating the pH value of the system to about 10, enabling cerium and zirconium ions to generate hydroxide precipitate, and continuously stirring for 3h. Then aging for 12 hours at room temperature, centrifuging, and washing the product with deionized water and absolute ethyl alcohol respectively until the washing liquid is neutral; finally, the obtained product is dried in a baking oven at 100 ℃ for 12 hours and then extruded into particles with 80 to 100 meshes, and the particles are placed in a muffle furnace for roasting at 700 ℃ for 3 hours to obtain the solid base catalyst Ce 0.6 Zr 0.4 O 2 。
Example 2
6.2g of sodium dodecyl sulfate was poured into a beaker, and then 70m was measured outAdding distilled water into a beaker, stirring at 65 ℃ for 30min for dissolution, adding 0.016mol of cerium nitrate hexahydrate and 0.004mol of zirconium nitrate pentahydrate, continuously stirring for 10min, then dripping precipitator ammonia water, regulating the pH value of the system to about 10, enabling cerium and zirconium ions to generate hydroxide precipitation, and continuously stirring for 3h. Then aging for 12 hours at room temperature, centrifuging, and washing the product with deionized water and absolute ethyl alcohol respectively until the washing liquid is neutral; finally, the obtained product is dried in a baking oven at 100 ℃ for 12 hours and then extruded into particles with 80 to 100 meshes, and the particles are placed in a muffle furnace for roasting at 750 ℃ for 3 hours, thus obtaining the solid base catalyst Ce 0.8 Zr 0.2 O 2 。
Example 3
21g of catalyst Ce 0.8 Zr 0.2 O 2 Adding 2.5L of polymerization reaction kettle, adding 204g of n-hexanol, heating, stirring, dehydrating for 1h at 100-105 ℃ and minus 0.096Mpa, then starting to add 1320g of ethylene oxide, keeping the reaction temperature at 130-135 ℃ and the reaction pressure at 0.15-0.20 MPa in the reaction control stage, continuing the reaction until the pressure drop is stable after the addition, finally reducing the degassing temperature to 60 ℃, and filtering to obtain the n-hexanol ethylene oxide polyether (designed molecular weight 762). This example was timed from the addition of the catalyst and the entire process cycle amounting to 8 hours and 15 minutes until the filtration gave the product. Molecular weight distribution d=1.05, isoheptanol residual 0.51% by GPC and liquid phase detection.
Example 4
5.8g of catalyst Ce 0.8 Zr 0.2 O 2 Adding 2.5L of polymerization reaction kettle, adding 232g of n-heptanol, heating, stirring, dehydrating for 1h at 105-110 ℃ and-0.096 Mpa, then continuously adding 528g of ethylene oxide, keeping the reaction temperature at 130-140 ℃ and the reaction pressure at 0.20-0.30 MPa in the reaction control stage, continuing the reaction until the pressure drop is stable after the ethylene oxide is added, finally cooling and degassing to 60 ℃, and filtering to obtain 757.3g of n-heptanol polyoxyethylene ether (with the designed molecular weight of 380). This example was timed from the addition of the catalyst and the total process cycle was 8 hours and 47 minutes until the filtration gave the product. Molecular weight distribution d=1.07, n-heptanol residual was 0.72% by GPC and liquid phase detection.
Example 5
7.9g of catalyst Ce 0.8 Zr 0.2 O 2 Adding 2.5L of a polymerization reaction kettle, adding 348g of isoheptanol, heating, starting stirring, dehydrating for 1.5h under the conditions of 100-110 ℃ and minus 0.096Mpa, then starting adding 484g of ethylene oxide, keeping the reaction temperature at 150-160 ℃ in a reaction control stage, keeping the reaction pressure at 0.20-0.25 MPa, continuing the reaction until the pressure drop is stable after the addition, cooling and degassing for 15min, continuously adding 174g of propylene oxide for reaction, keeping the reaction temperature at 120-125 ℃ in a reaction control stage, keeping the reaction pressure at 0.35-0.40 MPa, continuing the reaction until the pressure drop is stable after the addition, finally cooling and degassing to 60 ℃, and filtering to obtain the isoheptanol ethylene oxide propylene oxide block polyether (designed molecular weight 416). This example was timed from the addition of the catalyst and the entire process cycle amounting to 9 hours and 03 minutes until the filtration gave the product. Molecular weight distribution d=1.03, isoheptanol residual 0.68% by GPC and liquid phase detection.
Example 6
18.9g of catalyst Ce 0.6 Zr 0.4 O 2 2.5L of polymerization vessel was added followed by 195g C 12 -C 14 Alcohol, heating, stirring, dewatering for 1.5h at 115-125 deg.C and-0.096 Mpa, heating to 130 deg.C, continuously adding 823g of uniform mixture of ethylene oxide and 240g of propylene oxide, maintaining the reaction temperature at 130-135 deg.C and reaction pressure at 0.30-0.40 MPa, continuously reacting until pressure drop is stable, cooling and degassing to 60 deg.C, filtering to obtain C 12 -C 14 Alcohol ethylene oxide propylene oxide random polyether (design molecular weight 1258). This example was timed from the addition of the catalyst and the entire process cycle amounting to 9 hours and 33 minutes until the filtration gave the product. Molecular weight distribution d=1.08, c by GPC and liquid phase detection 12 -C 14 Alcohol residue 0.92%.
Example 7:
23g of catalyst Ce 0.6 Zr 0.4 O 2 2.5L of polymerization vessel was added followed by 330. 330g C 18 -C 16 Alcohol, heating up and stirring are started,dehydrating for 2h at 120-125 ℃ and-0.096 Mpa, then heating to 130 ℃ to continuously add 268g of uniform mixture of ethylene oxide and 691g of propylene oxide, keeping the reaction temperature at 135-140 ℃ and the reaction pressure at 0.35-0.40 MPa in the reaction control stage, continuing the reaction until the pressure drop is stable after the mixture is added, finally cooling and degassing to 60 ℃, and filtering to obtain C 18 ～C 16 Alcohol ethylene oxide propylene oxide random polyether (design molecular weight 1046). In this example, the time from the introduction of the catalyst into the polymerization reactor was counted and the total period of the whole operation was 8 hours and 29 minutes until the filtration was completed. Molecular weight distribution d=1.11, c by GPC and liquid phase detection 18 -C 16 Alcohol residue 0.97%. Since downstream products require this polyether K + The content is controlled within 20ppm, and the detection result of the inductively coupled plasma mass spectrometer is added to see K + The content was 2ppm, possibly from the raw material.
Example 8:
17.2g of catalyst Ce 0.6 Zr 0.4 O 2 Adding 2.5L of polymerization reaction kettle, adding 200g of isomeric tridecanol, heating, stirring, dewatering for 1h under 115-120 ℃ and-0.096 Mpa, then starting adding 880g of ethylene oxide, keeping the reaction temperature at 140-145 ℃ and the reaction pressure at 0.30-0.35 MPa in the reaction control stage, continuing the reaction until the pressure drop is stable after the addition, finally cooling, degassing to 60 ℃, and filtering to obtain the isomeric tridecanol ethylene oxide polyether (with the designed molecular weight of 1080). Molecular weight distribution d=1.06, isotridecyl alcohol residual 0.79% by GPC and liquid phase detection. In this example, the catalyst was fed into the polymerization reactor and was timed until the product was obtained by filtration, and the total process cycle was 8 hours and 15 minutes.
Comparative example 1:
only the catalyst of example 6 was changed to 6.3g NaOH, and the other experimental conditions were kept unchanged, and the reaction gave C 12 -C 14 Alcohol ethylene oxide propylene oxide random polyether (design molecular weight 1258). The comparative example was started from the time when the catalyst was charged into the polymerization reactor, and the total period of the whole operation was 8 hours and 43 minutes until the filtration was carried out to obtain a product. Molecular weight distribution d=1.19, c by GPC and liquid phase detection 12 -C 14 Alcohol residue 2.9%. As can be seen from comparative example 6, catalyst Ce 0.6 Zr 0.4 O 2 The use in fatty alcohol polyether synthesis provides effective control of the molecular weight distribution of the product and the residual amount of raw materials compared to the imposed catalyst.
Comparative example 2:
only the catalyst of example 7 was changed to 7.7g KOH, the other experimental conditions were kept unchanged, and the reaction gave C 18 -C 16 Crude alcohol ethylene oxide propylene oxide random polyether (design molecular weight 1046). Molecular weight distribution d=1.21, c by GPC and liquid phase detection 18 -C 16 Alcohol residue 1.8%. K in polyether due to downstream product application requirements + The ion is controlled within 10ppm, so the crude product needs further refining to remove K + Ions. The method comprises the steps of transferring the crude product into a four-neck flask, keeping the temperature at 70-75 ℃ in an oil bath, adding deionized water and phosphoric acid, neutralizing and stirring for 30min, adding an adsorbent and diatomite, stirring for 30min, heating to 110-115 ℃ and starting slow decompression and dehydration until the vacuum degree is reduced to minus 0.098MPa, continuing the process for 3h, keeping decompression and dehydration for 1h at the vacuum degree of minus 0.098MPa, and filtering to obtain the refined product. The comparative example was carried out in a total period of 13 hours and 45 minutes from the time when the catalyst was charged into the polymerization reactor to the time when the purified product was obtained by filtration, and the process period was too long. From the detection result of the inductively coupled plasma mass spectrometer, K is seen after refining + The content is 5ppm, which meets the application requirement of downstream products. As can be seen from comparative example 7, catalyst Ce 0.6 Zr 0.4 O 2 The use in the synthesis of the fatty alcohol polyether not only effectively controls the molecular weight distribution of the product and the residual quantity of raw materials, but also avoids the metal cations introduced by the dissolution of the strong base catalyst in the system, thereby avoiding the process of refining and removing the strong base cations, greatly shortening the production period and saving considerable cost.
The foregoing is a further detailed description of the proposed solution in connection with the preferred embodiments of the present invention, and it should not be construed that the invention is limited to the specific embodiments, but that several simple deductions or substitutions may be made by those skilled in the art to which the invention pertains without departing from the inventive concept, all shall be deemed to fall within the scope of the invention.
Claims (6)
1. The preparation method of the nonionic fatty alcohol polyether for the defoamer is characterized by comprising the following steps of:
s1, adding a catalyst and fatty alcohol into a reaction kettle, wherein the catalyst is cerium and zirconium composite metal oxide Ce x Zr 1-x O 2 A solid base catalyst;
s2, dehydrating;
s3, heating the mixture in the reaction kettle to a reaction temperature, slowly adding the alkylene oxide, and continuously adding the alkylene oxide at the temperature and a reaction pressure lower than the atmospheric pressure until the reaction is finished;
s4, continuously preserving heat until the pressure is reduced to be stable and unchanged;
s5, cooling and filtering to obtain fatty alcohol polyether;
the catalyst Ce x Zr 1-x O 2 Wherein x is 0.6 to 0.9;
in the S1, the fatty alcohol has the following general formula: c (C) n H 2n+1 -OH, wherein n represents the number of aliphatic alcohol carbon atoms of 4-18, the carbon chain of the aliphatic alcohol is straight chain or branched chain, and the aliphatic alcohol is one or more than two of the aliphatic alcohol;
the preparation method of the catalyst comprises the following steps: pouring the template agent into a beaker, adding distilled water into the beaker, stirring and dissolving at the water bath temperature of 50-70 ℃, adding cerium salt and zirconium salt, continuously stirring for 10 minutes, then dripping precipitator ammonia water, adjusting the pH value of the system to 10, enabling cerium and zirconium ions to generate hydroxide precipitate, and continuously stirring for 3 hours; aging at room temperature for 12 hours, centrifuging, and washing the product with deionized water and absolute ethyl alcohol until the washing liquid is neutral; drying the obtained product in a drying oven, extruding the dried product into particles, and roasting the particles at a high temperature to obtain a solid base catalyst;
the high-temperature roasting temperature is set at 600-800 ℃;
the surfactant of the template agent is cetyl trimethyl ammonium bromide, sodium dodecyl sulfate or a mixture of the two surfactants, and the addition amount of the surfactant is 1% -10% of the total mass of the system.
2. The method for producing nonionic fatty alcohol polyether for defoamer according to claim 1, wherein: the fatty alcohol polyether in S5 has the following general formula:
C n H 2n+1 -O-(EO) a (PO) b h, wherein a+b is an integer or fraction of 3 to 20.
3. The method for producing nonionic fatty alcohol polyether for defoamer according to claim 1, wherein: the alkylene oxide in S3 is a mixture of one or both of ethylene oxide and propylene oxide.
4. The method for producing nonionic fatty alcohol polyether for defoamer according to claim 1, wherein: the reaction temperature in the step S3 is 90-180 ℃; the reaction pressure in the step S3 is 0.0-0.4 Mpa.
5. The method for producing nonionic fatty alcohol polyether for defoamer according to claim 1, wherein: the mass of the catalyst in the step S1 is 0.1-2% of the mass of the aliphatic alcohol polyether to be prepared.
6. The method for producing nonionic fatty alcohol polyether for defoamer according to claim 1, wherein: the cerium salt is one of cerium nitrate, cerium sulfate and cerium chloride, or one of cerium nitrate hydrate, cerium sulfate hydrate and cerium chloride hydrate; the corresponding zirconium salt is one of zirconium nitrate, zirconium sulfate and zirconium oxychloride, or one of zirconium nitrate hydrate, zirconium sulfate hydrate and zirconium oxychloride hydrate.
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| CN109369903A (en) * | 2018-11-02 | 2019-02-22 | 浙江绿科安化学有限公司 | A kind of preparation method of aliphatic alcohol polyether |
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