CN108404919B - Copper-carbon catalyst for synthesizing fatty alcohol by ester liquid-phase hydrogenation and preparation method thereof - Google Patents
Copper-carbon catalyst for synthesizing fatty alcohol by ester liquid-phase hydrogenation and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 34
- 150000002148 esters Chemical class 0.000 title claims abstract description 31
- 239000007791 liquid phase Substances 0.000 title claims abstract description 27
- 150000002191 fatty alcohols Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 title claims description 7
- 230000002194 synthesizing effect Effects 0.000 title claims description 7
- 239000013148 Cu-BTC MOF Substances 0.000 claims abstract description 37
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 claims abstract description 35
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000010949 copper Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011701 zinc Substances 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 28
- 238000002425 crystallisation Methods 0.000 claims description 25
- 230000008025 crystallization Effects 0.000 claims description 25
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 15
- 239000005639 Lauric acid Substances 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- 239000012018 catalyst precursor Substances 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 238000005259 measurement Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 229910052786 argon Inorganic materials 0.000 abstract description 2
- 239000012298 atmosphere Substances 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract 2
- 239000012752 auxiliary agent Substances 0.000 abstract 2
- 230000004913 activation Effects 0.000 abstract 1
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 239000003575 carbonaceous material Substances 0.000 abstract 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000010494 dissociation reaction Methods 0.000 abstract 1
- 230000005593 dissociations Effects 0.000 abstract 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- 239000011787 zinc oxide Substances 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 16
- 238000001291 vacuum drying Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 229940079593 drug Drugs 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000003599 detergent Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical group CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- -1 aluminum alcohol compound Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229940126589 solid medicine Drugs 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a carbon-coated copper-zinc catalyst for preparing fatty alcohol by ester liquid phase hydrogenation and a preparation method thereof. The carbon material is used as a carrier, copper is used as an active component, and zinc is used as a modification auxiliary agent. The mass percent of the active component copper is 30-50%, and the mass percent of the auxiliary agent zinc is 0-30%. The thermal decomposition atmosphere is nitrogen, argon or hydrogen. The invention adopts Cu-BTC as a precursor, thereby effectively limiting the agglomeration of copper species in the thermal decomposition process. The doping of the zinc oxide improves the dispersion of copper species in the catalyst on one hand, and enhances the dissociation activation capability of monovalent copper species on carbonyl on the other hand, thereby obviously improving the catalytic activity of the catalyst. The catalyst of the invention reacts for 24 hours under the reaction conditions of 230 ℃, 5MPa and 800rpm, the conversion rate of butyl butyrate is 96.7 percent, and the selectivity of n-butyl alcohol is close to 100 percent.
Description
Technical Field
The invention relates to a copper-carbon catalyst for synthesizing fatty alcohol by ester liquid-phase hydrogenation and a preparation method thereof.
Technical Field
Fatty alcohol (fattyyalchohol) is a worldwide, large-scale chemical. The fatty alcohol derivative obtained by reacting the hydroxyl functional group in the molecular structure of the fatty alcohol with other compounds has wide application and is mainly used as a raw material for producing detergents and surfactants. The market demand for fatty alcohols is largely influenced by the amount of product required downstream. In recent years, surfactant demand has steadily increased worldwide in 3% annual increments, with the asia-pacific region annual increments reaching even more than 4.7%. By 2016, the global demand for detergent alcohol reaches 272 million tons, with 64 million tons being reached in china alone. In addition, the annual average global demand for higher fatty alcohols is expected to remain at a 3.1% growth rate for the next 10 years. China is a large consumer of detergents and surfactants, and with further increase of the demand of domestic markets for surfactants, the demand of fatty alcohols is also increasing year by year. Therefore, the development of the fatty alcohol in China has wide market prospect.
The current methods for producing fatty alcohols are mainly the ziegler process, the oxo process and the high-pressure hydrogenation process. The ziegler process uses ethylene as raw material, and reacts with trialkyl aluminum to obtain aluminum alcohol compound through chain extension and oxidation, and then fatty alcohol is prepared through hydrolysis, neutralization and fractionation. The method was created by K Ziegler in 1954, and was first put into production by oil products of mainland America in 1962, and the product is straight-chain even carbon alcohol. The oxo-synthesis method is to synthesize aldehyde from olefin, carbon monoxide and hydrogen under the conditions of catalyst and pressurization, and the aldehyde is hydrogenated to obtain the fatty alcohol. The method was discovered by German chemist O.Roelen in 1938. The two processes both use ethylene as a raw material, but based on the current energy structure situation of rich coal, poor oil and less gas in China and the market situation of short supply and short demand of petroleum resources in recent years, a synthesis method using renewable natural animal and vegetable oil as a raw material, such as a high-pressure hydrogenation method, is developed, so that the demand of China on petroleum resources can be relieved, and the cost of the raw material is reduced. The high-pressure hydrogenation method is characterized in that raw material oil is converted into fatty acid through pretreatment and alcoholysis, and the fatty acid is directly hydrogenated or hydrogenated after esterification to prepare alcohol. The preparation of fatty alcohol by direct hydrogenation of fatty acid has high requirements on the material quality of equipment, so that the method which is commonly used in industry is to esterify the fatty acid into esters and then hydrogenate the fatty acid.
There are two main forms of ester hydrogenation: gas phase and liquid phase hydrogenation. The research on the hydrogenation of the gas-phase esters is more intensive, and the catalyst used is mainly a copper-based catalyst. Patent CN2014104289933 reports a copper-based catalyst for ester hydrogenation. The content of active component copper or its oxide is 10% -50%, and the adjuvant can be at least one element of lanthanide series in the periodic table of elements or its oxide, also can be at least one element of VIB group in the periodic table of elements or its oxide. The carrier is selected from one of silicon oxide, aluminum oxide or molecular sieve. The reactant is methyl acetate, the reaction temperature is 230 ℃, the reaction pressure is 3.0MPa, the hydrogen-ester ratio is 25:1, and the space velocity is 1.0h-1Under the conditions of (1), the conversion rate of methyl acetate>99% selectivity to ethanol>99 percent. Although the copper-based catalyst shows excellent reaction performance in gas-phase ester hydrogenation, the process is limited by high energy consumption of raw material gasification and large consumption of hydrogen. Compared with the prior art, the liquid-phase ester hydrogenation reaction is more economical and energy-saving, and the raw materials are widely available, so the method has a good application prospect.
Catalyst currently used for liquid-phase ester hydrogenation reactionMainly noble metal-based catalysts, such as Ru-based and Rh-based catalysts. Patent CN200610022483 discloses a method for preparing alcohol from carboxylic acid and its ester. The catalyst is a noble metal supported catalyst, and the metal active components comprise: one or two of Ru, Rh, Pt and Pa, and one of Cu, Fe, Sn, Zn, Ni, Co, etc. may be added to form double metal or multiple metal. The support being ZrO2. The reaction is a liquid phase reaction, and the carboxylic acid and ester thereof are C2-C20Carboxylic acids and esters thereof. The solvent is any one of water, methanol, ethanol, n-propanol, isopropanol, and n-hexane. The reaction temperature is within the range of 100-200 ℃, the reaction pressure is more than or equal to 1.0MPa, the stirring speed is 500-1000 rpm, and the reaction time is 6-24 h. The conversion rate of ester is 78.9-99.5%, and the selectivity of alcohol is 68.2-99.5%. Although the noble metal-based catalyst shows higher activity in the liquid-phase ester hydrogenation reaction, the problems of high price, poor alcohol selectivity and the like still exist.
At present, few reports about liquid-phase ester hydrogenation copper-based catalysts are provided. He et Al report a series of CuO/ZnO/Al2O3The catalyst is used for catalyzing ethyl stearate to prepare octadecanol through liquid phase hydrogenation, and the yield of the octadecanol is more than 98 percent under the reaction condition of 230 ℃ and 3.0Mpa (applied. Catal. A: general2013,452 and 88).
The results disclosed above show that copper-based catalysts exhibit good catalytic performance in ester hydrogenation reactions, but have less application in liquid-phase ester hydrogenation reactions. The carbon-coated copper-zinc catalyst synthesized by the method has good ester liquid phase hydrogenation catalytic performance.
Disclosure of Invention
The invention aims to provide a copper-carbon catalyst for synthesizing fatty alcohol by ester liquid-phase hydrogenation and a preparation method thereof, which can overcome the defects of the prior art, namely the problems of harsh reaction conditions, poor stability and the like existing in the existing liquid-phase ester hydrogenation reaction system. The novel carbon-coated copper-zinc catalyst provided by the invention has the outstanding characteristics of good catalytic performance and stability under mild reaction conditions.
The invention provides a carbon-coated copper-zinc catalyst for preparing fatty alcohol by ester liquid phase hydrogenation, which is a regular octahedral carbon carrier-coated copper and zinc component, wherein the mass content of copper is 30-50%, the mass content of zinc is 0-30%, and the balance is a carbon carrier.
The preparation method comprises the following steps: mixing n-butanol, lauric acid, copper nitrate and trimesic acid, crystallizing, separating to obtain Cu-BTC (BTC ═ benzene-1,3,5-tricarboxylic acid) precursor, and mixing with zinc nitrate to obtain Zn (NO)3)2Cu-BTC precursor, Cu-BTC precursor and Zn (NO)3)2And thermally decomposing the/Cu-BTC precursor in a tube furnace under the nitrogen atmosphere.
The preparation method of the carbon-coated copper-zinc catalyst for preparing fatty alcohol by ester liquid phase hydrogenation, which is provided by the invention, comprises the following steps:
(1) adding n-butanol into lauric acid, copper nitrate and trimesic acid, and uniformly stirring and mixing to obtain a solution A;
(2) transferring the solution A to a crystallization kettle, and placing the crystallization kettle in an oven at the temperature of 100-;
(3) cooling to room temperature after crystallization, centrifugally separating out blue solid, washing and drying to obtain a Cu-BTC precursor,
(4) adding ethanol into Cu-BTC and zinc nitrate, uniformly mixing, and continuously stirring for a period of time to obtain a solution B;
(5) rotary evaporating the solution B, and drying to obtain Zn (NO)3)2A Cu-BTC precursor;
(6) and (5) placing the catalyst precursor obtained in the step (3) and the step (5) in a tube furnace for thermal decomposition under the atmosphere of nitrogen, argon or hydrogen.
The ratio of the lauric acid in the solution A to the copper nitrate in the step (1) is 1: 1-20: 1. And (3) the crystallization time in the step (2) is 2-6 h.
The solution for washing the Cu-BTC in the step (3) is ethanol, and the drying condition is vacuum 50-80 ℃.
And (4) soaking the zinc nitrate for 5-30 h.
The thermal decomposition temperature in the step (6) is 350-500 ℃, and the thermal decomposition time is 2-10 h.
The method for preparing the n-butyl alcohol by applying the copper-carbon catalyst for synthesizing the fatty alcohol by ester liquid-phase hydrogenation to the butyl butyrate liquid-phase hydrogenation comprises the following steps:
(1) adding a certain amount of butyl butyrate, a solvent and a catalyst into a 100mL high-pressure reaction kettle for reaction. The reaction temperature is 180-220 ℃, the reaction pressure is 5-8 MPa, the stirring rotation speed is 800rad/min, and the reaction time is 6-18 h.
(2) And after the reaction is finished, naturally cooling to room temperature, separating the catalyst from the reaction product, adding a certain amount of internal standard substance, and analyzing the amount of reactants and products in the product.
The solvent is one of methanol, ethanol, water, cyclohexane and n-hexane.
The mass ratio of the butyl butyrate to the n-hexane is 5-10%.
In the present invention, the internal standard substance added to the product is n-propanol.
The copper-carbon catalyst for synthesizing fatty alcohol by ester liquid-phase hydrogenation provided by the invention overcomes the defects of the prior art, namely the problems of harsh reaction conditions, poor stability and the like existing in the existing liquid-phase ester hydrogenation reaction system. The most prominent characteristic is that under the mild reaction condition, the catalyst has good catalytic performance and stability. For example, the conversion rate of butyl butyrate can reach 96.7%, the selectivity of n-butyl alcohol is about 100%, and the catalyst is an excellent catalyst for preparing fatty alcohol by ester liquid phase hydrogenation.
Drawings
FIG. 1 is a TEM representation of coated copper and carbon coated copper zinc catalysts of the present invention [ (a) Cu @ C; (b) CuZn0.3@C]；
Detailed Description
The invention is further described by the following specific examples, which are not intended to limit the invention in any way.
Example 1: cu @ C-350-N2Catalyst No. 1
4.75g of lauric acid, 0.312g of Cu (NO)3)2·3H2O and 0.152g trimesic acid (BTC) were placed in a 250mL beaker, and 76mL of n-xylene was addedButanol, mixing evenly and stirring magnetically for 30min to completely dissolve the solid medicine. And transferring the mixed solution to a 200mL crystallization kettle, putting the crystallization kettle into a baking oven preheated to 140 ℃, and crystallizing for 4 hours. And cooling the crystallization kettle to room temperature, performing centrifugal separation, washing the solid matter with absolute ethyl alcohol for 3 times, and performing vacuum drying at 70 ℃ for 12 hours to obtain a blue Cu-BTC catalyst precursor.
Placing 1.2g of Cu-BTC in a tube furnace, heating to 350 ℃ at a heating rate of 2 ℃/min under a nitrogen atmosphere with a flow rate of 100mL/min, carrying out thermal decomposition for 2h, and naturally cooling to room temperature to obtain Cu @ C-350-N2And is marked as catalyst # 1.
Example 2: cu @ C-350-N2-H2Catalyst No. 2
4.75g of lauric acid, 0.312g of Cu (NO)3)2·3H2O and 0.152g trimesic acid (BTC) are placed in a 250mL beaker, 76mL n-butanol are added, mixed well and stirred magnetically for 30min to dissolve the solid drug completely. And transferring the mixed solution to a 200mL crystallization kettle, putting the crystallization kettle into a baking oven preheated to 140 ℃, and crystallizing for 4 hours. And cooling the crystallization kettle to room temperature, performing centrifugal separation, washing the solid matter with absolute ethyl alcohol for 3 times, and performing vacuum drying at 70 ℃ for 12 hours to obtain a blue Cu-BTC catalyst precursor.
Placing 1.2g of Cu-BTC in a tube furnace, heating to 350 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere with the flow rate of 100mL/min, carrying out thermal decomposition for 2h, and naturally cooling to room temperature. Switching nitrogen to H2Reducing the mixture for 2 hours at 350 ℃, and naturally cooling the mixture to room temperature to obtain Cu @ C-350-N2-H2And is marked as catalyst # 2.
Example 3: cu @ C-500-N2Catalyst No. 3
4.75g of lauric acid, 0.312g of Cu (NO)3)2·3H2O and 0.152g trimesic acid (BTC) are placed in a 250mL beaker, 76mL n-butanol are added, mixed well and stirred magnetically for 30min to dissolve the solid drug completely. And transferring the mixed solution to a 200mL crystallization kettle, putting the crystallization kettle into a baking oven preheated to 140 ℃, and crystallizing for 4 hours. Cooling the crystallization kettle to room temperature, centrifuging, washing the solid substance with anhydrous ethanol for 3 times, vacuum drying at 70 deg.C for 12 hr to obtain blue Cu-BTC catalystAnd (3) a reagent precursor.
Placing 1.2g of Cu-BTC in a tube furnace, heating to 500 ℃ at a heating rate of 2 ℃/min under a nitrogen atmosphere with a flow rate of 100mL/min, carrying out thermal decomposition for 2h, and naturally cooling to room temperature to obtain Cu @ C-500-N2And is marked as No. 3 catalyst.
Example 4: CuZn0.15@C-500-N2Catalyst No. 4
4.75g of lauric acid, 0.312g of Cu (NO)3)2·3H2O and 0.152g trimesic acid (BTC) are placed in a 250mL beaker, 76mL n-butanol are added, mixed well and stirred magnetically for 30min to dissolve the solid drug completely. And transferring the mixed solution to a 200mL crystallization kettle, putting the crystallization kettle into a baking oven preheated to 140 ℃, and crystallizing for 4 hours. And cooling the crystallization kettle to room temperature, performing centrifugal separation, washing the solid matter with absolute ethyl alcohol for 3 times, and performing vacuum drying at 70 ℃ for 12 hours to obtain a blue Cu-BTC catalyst precursor.
1g of Cu-BTC and 0.091gZn (NO)3)2In a 100mL flask, 50mL of ethanol was added, mixed well and stirred for 24 h. Rotary evaporating at 45 deg.C to dryness, and vacuum drying at 50 deg.C for 10 hr to obtain 0.15Zn (NO)3)2A Cu-BTC catalyst precursor.
Take 1g0.15Zn (NO)3)2Placing the/Cu-BTC in a tube furnace, heating to 500 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere with the flow rate of 100mL/min, carrying out thermal decomposition for 2h, and naturally cooling to room temperature to obtain CuZn0.15@C-500-N2And is marked as catalyst # 4.
Example 5: CuZn0.3@C-500-N2Catalyst No. 5
4.75g of lauric acid, 0.312g of Cu (NO)3)2·3H2O and 0.152g trimesic acid (BTC) are placed in a 250mL beaker, 76mL n-butanol are added, mixed well and stirred magnetically for 30min to dissolve the solid drug completely. And transferring the mixed solution to a 200mL crystallization kettle, putting the crystallization kettle into a baking oven preheated to 140 ℃, and crystallizing for 4 hours. And cooling the crystallization kettle to room temperature, performing centrifugal separation, washing the solid matter with absolute ethyl alcohol for 3 times, and performing vacuum drying at 70 ℃ for 12 hours to obtain a blue Cu-BTC catalyst precursor.
1g of Cu-BTC was takenAnd 0.182gZn (NO)3)2In a 100mL flask, 50mL of ethanol was added, mixed well and stirred for 24 h. Rotary evaporating at 45 deg.C to dryness, vacuum drying at 50 deg.C for 10 hr to obtain 0.3Zn (NO)3)2A Cu-BTC catalyst precursor.
Take 1g0.3Zn (NO)3)2Placing the/Cu-BTC in a tube furnace, heating to 500 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere with the flow rate of 100mL/min, carrying out thermal decomposition for 2h, and naturally cooling to room temperature to obtain CuZn0.3@C-500-N2And is marked as catalyst # 5.
Example 6: CuZn0.6@C-500-N2Catalyst No. 6
4.75g of lauric acid, 0.312g of Cu (NO)3)2·3H2O and 0.152g trimesic acid (BTC) are placed in a 250mL beaker, 76mL n-butanol are added, mixed well and stirred magnetically for 30min to dissolve the solid drug completely. And transferring the mixed solution to a 200mL crystallization kettle, putting the crystallization kettle into a baking oven preheated to 140 ℃, and crystallizing for 4 hours. And cooling the crystallization kettle to room temperature, performing centrifugal separation, washing the solid matter with absolute ethyl alcohol for 3 times, and performing vacuum drying at 70 ℃ for 12 hours to obtain a blue Cu-BTC catalyst precursor.
1g of Cu-BTC and 0.364gZn (NO)3)2In a 100mL flask, 50mL of ethanol was added, mixed well and stirred for 24 h. Rotary evaporating at 45 deg.C to dryness, vacuum drying at 50 deg.C for 10 hr to obtain 0.6Zn (NO)3)2A Cu-BTC catalyst precursor.
1g of 0.6Zn (NO) is taken3)2Placing the/Cu-BTC in a tube furnace, heating to 500 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere with the flow rate of 100mL/min, carrying out thermal decomposition for 2h, and naturally cooling to room temperature to obtain CuZn0.6@C-500-N2And is marked as catalyst # 6.
Comparative example 1: Cu/AC-350-N2Catalyst No. 7
Taking 0.5g of activated carbon carrier, adding 50g of 68% HNO3And 58.33gH2And O, stirring for 10 hours at room temperature, filtering, washing with a large amount of deionized water until the pH is approximately equal to 7.0, and drying for 12 hours at 100 ℃ to obtain the nitric acid treated AC carrier.
0.5g of the pretreated AC carrier and 0.7609g of copper nitrate are put into a 100mL pear-shaped bottle, 50mL of ethanol is added, stirring is carried out for 24h, rotary evaporation is carried out at 45 ℃ and evaporation is carried out to dryness, and vacuum drying is carried out at 50 ℃ for 10 h.
Placing 0.5g of the above solid in a tube furnace, heating to 350 deg.C at a heating rate of 2 deg.C/min under nitrogen atmosphere with flow rate of 100mL/min, calcining for 2h, and naturally cooling to room temperature to obtain Cu/AC-350-N2And is marked as catalyst # 7.
Comparative example 2: Cu/AC-350-N2-H2Catalyst No. 8
Taking 0.5g of activated carbon carrier, adding 50g of 68% HNO3And 58.33gH2And O, stirring for 10 hours at room temperature, filtering, washing with a large amount of deionized water until the pH is approximately equal to 7.0, and drying for 12 hours at 100 ℃ to obtain the nitric acid treated AC carrier.
0.5g of the pretreated AC carrier and 0.7609g of copper nitrate are put into a 100mL pear-shaped bottle, 50mL of ethanol is added, stirring is carried out for 24h, rotary evaporation is carried out at 45 ℃ and evaporation is carried out to dryness, and vacuum drying is carried out at 50 ℃ for 10 h.
Placing 0.5g of the solid in a tube furnace, heating to 350 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere with the flow rate of 100mL/min, roasting for 2h, and naturally cooling to room temperature. Switching nitrogen to H2Reducing at 350 ℃ for 2h, and naturally cooling to room temperature to obtain Cu/AC-350-N2-H2And is marked as catalyst # 8.
Example 7:
the catalytic performance of the catalyst in the reaction of preparing n-butyl alcohol by hydrogenating liquid-phase butyl butyrate is evaluated in a batch reactor. Wherein the loading amount of the catalyst is 0.3g, the mass ratio of butyl butyrate to n-hexane is 5%, the mass is 24g, and the reaction conditions are as follows: reacting at 200 ℃ under 8MPa at 800rad/min for 18 h. After the reaction is finished, naturally cooling to room temperature, separating the reacted solution from the catalyst by adopting an organic filter membrane of 0.22 mu m, adding an internal standard substance of n-propanol, and analyzing the product by adopting gas chromatography. The catalyst activity evaluation results are shown in table one.
Example 8:
the effect of reaction temperature and reaction time on the catalytic performance of the catalyst was examined using the # 2 catalyst. The reaction temperature was 230 ℃ and the reaction time was 24 hours, and other conditions were as in example 7. The catalyst activity results are shown in table one.
TABLE I evaluation results of catalysts
aThe reaction temperature is 230 ℃, and the reaction time is 24 h.
The present invention is not limited to the above embodiments, and various changes and modifications may be made by those skilled in the art without departing from the spirit of the present invention.
Claims (8)
1. An application method of a carbon-coated copper-zinc catalyst for preparing fatty alcohol by ester liquid phase hydrogenation is characterized in that: the catalyst is a carbon carrier with an octahedral structure and coats copper and zinc components, wherein the mass content of copper is 30-50%, the mass content of zinc is 0-30%, the mass content of zinc does not include 0, and the balance is the carbon carrier;
the preparation method comprises the following steps: mixing n-butanol, lauric acid, copper nitrate and trimesic acid, crystallizing, separating to obtain Cu-BTC precursor, and mixing with zinc nitrate to obtain Zn (NO)3)2Cu-BTC precursor, Cu-BTC precursor and Zn (NO)3)2the/Cu-BTC precursor is thermally decomposed in a tube furnace under the nitrogen atmosphere;
the preparation method comprises the following steps:
(1) adding n-butanol into lauric acid, copper nitrate and trimesic acid according to the measurement, and uniformly stirring and mixing to obtain a solution A;
(2) transferring the solution A to a crystallization kettle, and placing the crystallization kettle in an oven at the temperature of 100-;
(3) cooling to room temperature after crystallization, centrifugally separating out blue solid, washing and drying to obtain a Cu-BTC precursor;
(4) adding ethanol into Cu-BTC and zinc nitrate, uniformly mixing, and continuously stirring for a period of time to obtain a solution B;
(5) rotary evaporating the solution B, and drying to obtain Zn (NO)3)2A Cu-BTC precursor;
(6) putting the catalyst precursors obtained in the steps (3) and (5) into a tube furnace for thermal decomposition to obtain a liquid-phase ester hydrogenation catalyst;
the method for preparing the n-butyl alcohol by applying the copper-carbon catalyst for synthesizing the fatty alcohol by ester liquid-phase hydrogenation to the butyl butyrate liquid-phase hydrogenation comprises the following steps:
(1) adding butyl butyrate, a solvent and a catalyst into a high-pressure reaction kettle for reaction, wherein the reaction temperature is 180-220 ℃, the reaction pressure is 5-8 MPa, the stirring rotation speed is 800rad/min, and the reaction time is 6-18 h;
(2) and after the reaction is finished, naturally cooling to room temperature, separating the catalyst from the reaction product, adding a certain amount of internal standard substance, and analyzing the amount of reactants and products in the product.
2. The method of application according to claim 1, characterized in that: the ratio of lauric acid to copper nitrate in the solution A is 1: 1-20: 1.
3. The method of application according to claim 1, characterized in that: the solution for washing the Cu-BTC is ethanol, and the drying condition is vacuum 50-80 ℃.
4. The method of application according to claim 1, characterized in that: the dipping time of the zinc nitrate is 5-30 h.
5. The method of application according to claim 1, characterized in that: the Cu-BTC and Zn (NO)3)2The thermal decomposition temperature of the/Cu-BTC catalyst precursor is 350-500 ℃, and the thermal decomposition time is 2-10 h.
6. The method of application according to claim 1, characterized in that: the solvent is one of methanol, ethanol, water, cyclohexane and n-hexane.
7. The method of application according to claim 1, characterized in that: the mass ratio of the butyl butyrate to the n-hexane is 5-10%.
8. The method of application according to claim 1, characterized in that: the internal standard substance is n-propanol.
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