CN114471524B - Catalyst for preparing 1, 3-butadiene, regenerated catalyst and preparation method - Google Patents
Catalyst for preparing 1, 3-butadiene, regenerated catalyst and preparation method Download PDFInfo
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- CN114471524B CN114471524B CN202011147900.0A CN202011147900A CN114471524B CN 114471524 B CN114471524 B CN 114471524B CN 202011147900 A CN202011147900 A CN 202011147900A CN 114471524 B CN114471524 B CN 114471524B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 44
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 31
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910001936 tantalum oxide Inorganic materials 0.000 claims abstract description 29
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001868 water Inorganic materials 0.000 claims abstract description 10
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 64
- 229910052715 tantalum Inorganic materials 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 44
- 239000002243 precursor Substances 0.000 claims description 36
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 33
- 229910052726 zirconium Inorganic materials 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 17
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 150000004703 alkoxides Chemical class 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000007787 solid Substances 0.000 description 22
- 229910052681 coesite Inorganic materials 0.000 description 20
- 229910052906 cristobalite Inorganic materials 0.000 description 20
- 229910052682 stishovite Inorganic materials 0.000 description 20
- 229910052905 tridymite Inorganic materials 0.000 description 20
- 230000008929 regeneration Effects 0.000 description 15
- 238000011069 regeneration method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001914 filtration Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 2
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- UHHKSVZZTYJVEG-UHFFFAOYSA-N oxepane Chemical compound C1CCCOCC1 UHHKSVZZTYJVEG-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- HSXKFDGTKKAEHL-UHFFFAOYSA-N tantalum(v) ethoxide Chemical group [Ta+5].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-] HSXKFDGTKKAEHL-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B01J37/0201—Impregnation
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Abstract
The invention provides a catalyst for preparing 1, 3-butadiene, a regenerated catalyst and a preparation method thereof. The catalyst for preparing 1, 3-butadiene provided by the invention comprises a mesoporous silica carrier, and zirconium oxide and tantalum oxide loaded on the mesoporous silica carrier, wherein the molar ratio of zirconium atoms in the zirconium oxide to tantalum atoms in the tantalum oxide is 1:1-3:1. The catalyst or regenerated catalyst is used for preparing butadiene by ethanol in a two-step method, and is converted into butadiene by feeding an ethanol-acetaldehyde-water mixed solution, so that the catalyst or regenerated catalyst has remarkable performance advantages in the aspects of catalytic activity and selectivity.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst for preparing 1, 3-butadiene, a regenerated catalyst and a preparation method thereof.
Background
1, 3-Butadiene is widely used in the chemical industry, butadiene being the main raw material for synthetic Styrene Butadiene Rubber (SBR), polybutadiene rubber (BR), neoprene and nitrile rubber. The largest used for styrene-butadiene rubber is, in turn, polybutadiene rubber (mainly butadiene rubber). Butadiene is also used in the production of styrene-butadiene latex, ABS resins, adiponitrile, etc., which is a raw material for the production of nylon 66. At present, a byproduct C4 fraction produced in ethylene by steam cracking is a main source of butadiene, and about 97% of devices worldwide adopt a cracking C4 mixture extraction process. However, in recent years, the price of petroleum has increased, and the global lightening of steam cracking raw materials has an influence on the yield of butadiene, and development of alternative methods for producing butadiene has become important.
The method for preparing butadiene from ethanol mainly comprises two production methods of a one-step method and a two-step method: the one-step method is to separately feed ethanol and produce butadiene in one step; the two-step process first dehydrogenates ethanol to acetaldehyde in one reactor and then converts the mixture of ethanol and acetaldehyde as a feedstock to butadiene in another reactor. The complete reaction path for preparing butadiene from ethanol is as follows: (1) Firstly, performing anaerobic dehydrogenation on a part of ethanol to generate acetaldehyde; (2) Two molecules of acetaldehyde are subjected to aldol condensation reaction to generate 3-hydroxybutyraldehyde; (3) subsequent dehydration of 3-hydroxybutyraldehyde to 2-butenal; (4) Reacting 2-butenal with ethanol to generate MPVO intermolecular hydrogen transfer reaction, converting into 2-butenol, and dehydrogenating ethanol to generate acetaldehyde again; (5) finally, 2-butenol is dehydrated to form butadiene.
(1)CH3CH2OH→CH3CHO+H2
(2)2CH3CHO→CH3-CHOH-CH2-CHO
(3)CH3-CHOH-CH2-CHO→CH3-CH＝CH-CHO+H2O
(4)CH3-CH＝CH-CHO+CH3CH2OH→CH3-CH＝CH-CH2OH+CH3CHO
(5)CH3-CH＝CH-CH2OH→CH2＝CH-CH＝CH2
In the reaction process, various side reactions exist, particularly, ethanol is dehydrated to generate ethylene, diethyl ether and aldehyde to generate more than five-carbon heavy components, and other reactions (such as cracking, hydrogenation, cyclization, diels-Alder reaction and the like) can also occur.
The united states corporation of carbide (PEP Report 35E// On-Purpose Butadiene production, ihs Markit, california, 2012) uses a 2% ta 2O5/SiO2 catalyst to obtain butadiene selectivity 63% in a two-step process at a temperature of 325-350 ℃ and a catalyst life of 120 hours, the catalyst regeneration process uses air containing nitric acid to bake at 400 ℃ and requires nitric acid to assist in oxidizing the carbon deposit, and if the catalyst is directly regenerated by baking at 500 ℃ without using nitric acid, the catalyst cannot recover the original activity. Similarly, dumeignil et al (Green chem.,2018, 20:3203-3209) used ZnTa-TUD-1 catalyst, and after 60 hours of continuous reaction, butadiene selectivity was reduced from 73% to less than 60%, catalyst activity was restored after calcination and regeneration, but after 15 hours was reduced to the pre-regeneration activity level, and authors hypothesize that the structure or properties of the calcined catalyst surface species was altered.
For tantalum system catalysts, butadiene selectivity is higher, but the regeneration conditions are harsh.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an original method, which is characterized in that tantalum oxide and zirconium oxide are compounded to avoid aggregation and growth of tantalum oxide particles in the high-temperature regeneration process, so that the acidity of tantalum oxide is reduced, and the regeneration activity and the service life of a catalyst are influenced.
The invention provides a catalyst for preparing 1, 3-butadiene, which comprises a mesoporous silica carrier, and zirconium oxide and tantalum oxide loaded on the mesoporous silica carrier, wherein the mol ratio of zirconium atoms in the zirconium oxide to tantalum atoms in the tantalum oxide is 0.5-3.5:1.
According to some embodiments of the invention, the molar ratio of zirconium atoms in the zirconia to tantalum atoms in the tantalum oxide is from 1:1 to 3:1.
According to some embodiments of the invention, the molar ratio of zirconium atoms in the zirconia to tantalum atoms in the tantalum oxide is 0.6:1, 1.2:1, 1.8:1, 2.4:1, 3:2:1, and any value therebetween.
According to some embodiments of the invention, the zirconia is 1% -5% by mass of the mesoporous silica support, which may be, for example, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% and any value therebetween.
According to some embodiments of the invention, the mesoporous silica support is selected from amorphous mesoporous silica having different pore sizes, i.e. amorphous mesoporous silica having disordered pores.
According to some embodiments of the invention, the mesoporous silica support has a specific surface area of 300m 2/g-700m2/g.
According to some embodiments of the invention, the mesoporous silica support has an average pore size of 4nm or more.
In a second aspect, the present invention provides a method for preparing a catalyst for preparing 1, 3-butadiene, comprising the steps of:
S1: dipping a mesoporous silica carrier in a zirconium precursor solution, drying and roasting to obtain a zirconia-loaded mesoporous silica carrier;
s2: and (3) dipping the mesoporous silica carrier loaded with the zirconia into a precursor solution of tantalum, and drying and roasting to obtain the catalyst loaded with the zirconia and the tantalum oxide.
According to some embodiments of the invention, the precursor solution of zirconium is selected from an inorganic salt solution of zirconium and/or an alkoxide solution of zirconium.
According to some embodiments of the invention, the precursor solution of zirconium is selected from a solution of zirconium n-propoxide in n-hexane.
According to some embodiments of the invention, the precursor solution of zirconium is selected from a cyclohexane solution of zirconium n-propoxide.
According to some embodiments of the invention, the precursor solution of tantalum is selected from an inorganic salt solution of tantalum and/or an alkoxide solution of tantalum.
According to some embodiments of the invention, the tantalum precursor solution is selected from the group consisting of tantalum pentachloride in n-hexane.
According to some embodiments of the invention, the tantalum precursor solution is selected from a cyclohexane solution of tantalum pentachloride.
According to some embodiments of the invention, the molar ratio of zirconium atoms in the zirconia to tantalum atoms in the tantalum oxide is 0.5-3.5:1.
According to some embodiments of the invention, the molar ratio of zirconium atoms in the zirconia to tantalum atoms in the tantalum oxide is 0.6:1, 1.2:1, 1.8:1, 2.4:1, 3:2:1, and any value therebetween.
According to some embodiments of the invention, in the catalyst, the molar ratio of zirconium atoms in the zirconia to tantalum atoms in the tantalum oxide is from 1:1 to 3:1.
According to some embodiments of the invention, the zirconia is 1% -5% by mass of the mesoporous silica support, which may be, for example, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% and any value therebetween.
According to some embodiments of the invention, the mesoporous silica support is amorphous mesoporous silica having different pore sizes.
According to some embodiments of the invention, the mesoporous silica support has a specific surface area of 300m 2/g-700m2/g.
According to some embodiments of the invention, the mesoporous silica support has an average pore size of 4nm or more.
According to some embodiments of the invention, in S1, the drying is performed at a temperature of 50-120 ℃ for a time of 10-48 hours.
According to some specific embodiments of the invention, in S1, the drying comprises drying in a vacuum oven at 50-80 ℃ for 1-12 hours, and then keeping the temperature in a forced air drying oven for 12-24 hours, wherein the drying temperature is 100-120 ℃.
According to some embodiments of the invention, in S1, the calcination is performed at a temperature of 500-650 ℃ for a time of 3-6 hours.
According to some embodiments of the invention, in S2, the drying is performed at a temperature of 50-120 ℃ for a time of 10-48 hours.
According to some specific embodiments of the invention, in S2, the drying comprises drying in a vacuum oven at 50-80 ℃ for 1-12 hours, and then keeping the temperature in a forced air drying oven for 12-24 hours, wherein the drying temperature is 100-120 ℃.
According to some embodiments of the invention, in S2, the firing temperature is 500-650 ℃ for 3-6 hours.
According to some embodiments of the invention, in S1 and/or S2, the firing is performed in a muffle furnace.
According to the invention, the preparation process of the catalyst comprises the following steps:
① Dissolving an elemental zirconium precursor in n-hexane to obtain a zirconium precursor solution, wherein the elemental zirconium precursor is selected from zirconium n-propoxide and zirconium isopropoxide;
② Adding a silicon dioxide carrier into a zirconium precursor solution, heating and refluxing for 4-12h at 69 ℃, filtering, pouring the filtered solid into deionized water, stirring for 1-2h, filtering, drying the obtained solid in a drying oven at 80 ℃, and roasting in a muffle furnace at 550 ℃ for 3-6h;
③ Dissolving a precursor of elemental tantalum in n-hexane to obtain a precursor solution of tantalum, wherein the precursor of elemental tantalum is selected from tantalum pentaethoxide and tantalum pentachloride;
④ Adding the solid obtained in the step ② into a tantalum precursor solution, heating and refluxing for 4-12h at 69 ℃, filtering, pouring the filtered solid into deionized water, stirring for 1-2h, filtering, drying the obtained solid in a drying oven at 80 ℃, and roasting in a muffle furnace at 500-550 ℃.
A third aspect of the present invention provides a regenerated catalyst for producing 1, 3-butadiene by calcining the catalyst according to the first aspect or the catalyst obtained by the production method according to the second aspect in an oxygen-containing gas.
According to some embodiments of the invention, the firing temperature is 500-600 ℃.
According to a preferred embodiment of the invention, the calcination temperature is 540-560 ℃, for example 550 ℃.
According to some embodiments of the invention, the firing time is from 5 to 20 hours.
According to a preferred embodiment of the invention, the calcination temperature is 10-15h, for example 12h.
According to some embodiments of the invention, the average particle size of the zirconia and/or tantalum oxide in the regenerated catalyst is 0.1-0.3nm.
According to the present invention, in the regenerated catalyst, the metal oxide is highly dispersed. The inventor creatively discovers that by compounding tantalum oxide with zirconium oxide, the aggregation and growth of tantalum oxide particles in the high-temperature regeneration process can be avoided, so that the acidity of tantalum oxide is reduced, and the regeneration activity and the service life of a catalyst are influenced. The catalyst can maintain good activity compared with fresh catalyst after being regenerated at 550 ℃.
In a fourth aspect, the present invention provides a process for the conversion of ethanol to produce 1, 3-butadiene comprising contacting a mixed solution comprising ethanol, acetaldehyde and water with a catalyst selected from the group consisting of the catalyst according to the first aspect or the catalyst obtained according to the process of production according to the second aspect, or the regenerated catalyst according to the third aspect.
According to some embodiments of the invention, the molar ratio of ethanol to acetaldehyde in the mixed solution is from 2:1 to 5:1.
According to a preferred embodiment of the invention, the molar ratio of ethanol to acetaldehyde in the mixed solution is between 2.5:1 and 4:1.
According to some embodiments of the invention, the water content in the mixed solution is 5wt% to 50wt% based on the total weight of the mixed solution.
According to a preferred embodiment of the present invention, the content of water in the mixed solution is 8wt% to 30wt% based on the total weight of the mixed solution.
According to some embodiments of the invention, the contacting conditions include: the space velocity of the mixed solution is 0.5h -1-5h-1, and the temperature is 300-400 ℃.
According to a preferred embodiment of the present invention, the contacting conditions include: the space velocity of the mixed solution is 0.8h -1-3h-1; the temperature is 320-350 ℃.
According to some embodiments of the invention, the pressure of the contacting is atmospheric pressure.
According to some embodiments of the invention, the method is performed in a fixed bed.
The catalyst or regenerated catalyst is used for preparing butadiene by ethanol in a two-step method, and the butadiene is converted into butadiene by feeding an ethanol-acetaldehyde-water mixed solution, so that obvious performance advantages are generated in the aspects of catalytic activity and selectivity.
Drawings
FIG. 1 is a STEM-HAADF characterization image of a 2% Ta 2O5/2.73％ZrO2/SiO2 catalyst prepared according to example 1 of the invention after regeneration.
FIG. 2 is a graph showing the particle size distribution of oxide after regeneration of 2% Ta 2O5/2.73％ZrO2/SiO2 catalyst prepared according to example 1 of the invention.
FIG. 3 is a STEM-HAADF characterization image of a 2% Ta 2O5/SiO2 catalyst prepared according to example 2 of the invention after regeneration.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In the invention, the following components are added:
[ example 1]
4.558G of zirconium n-propoxide (70 wt% of zirconium n-propoxide solution) is dissolved in 150mL of normal hexane to obtain zirconium precursor solution, 30g of silicon dioxide carrier is added into the zirconium precursor solution, heating reflux is carried out at 69 ℃ for 6h, then filtration is carried out, the filtered solid is poured into 150mL of deionized water, stirring is carried out for 1h, filtration is carried out again, the obtained solid is dried at 80 ℃ in a drying oven, then the obtained solid is placed in a muffle furnace for roasting at 550 ℃ for 3h, and Zr content is analyzed by an ICP-AES test, thus obtaining 2.73% ZrO 2/SiO2 catalyst;
1.45g of tantalum pentachloride is dissolved in 150mL of normal hexane to obtain a tantalum precursor solution, 30g of ZrO 2/SiO2 solid obtained above is added into the tantalum precursor solution, heating reflux is carried out for 6h at 69 ℃, then filtration is carried out, the filtered solid is poured into 150mL of deionized water, stirring is carried out for 1h, the obtained solid is filtered again, dried at 80 ℃ in a drying box, then the obtained solid is placed in a muffle furnace for roasting at 500 ℃ for 3h, and the Ta content is analyzed through an ICP-AES test, so that a 2% Ta 2O5/2.73％ZrO2/SiO2 catalyst is obtained, wherein the atomic mole ratio of zirconium to tantalum is 2.4:1.
[ Example 2]
The same preparation as in example 1 was carried out, except that the amounts of zirconium n-propoxide and tantalum pentachloride were changed, to prepare a 0.73% Ta 2O5/1.0％ZrO2/SiO2 catalyst, in which the atomic molar ratio of zirconium to tantalum was 2.4:1.
[ Example 3]
The same procedure as in example 1 was followed except that the amounts of zirconium n-propoxide and tantalum pentachloride were varied to produce a 3.7% Ta 2O5/5.0％ZrO2/SiO2 catalyst, wherein the atomic molar ratio of zirconium to tantalum was 2.4:1.
[ Example 4]
The same procedure as in example 1 was followed except that the amounts of zirconium n-propoxide and tantalum pentachloride were varied to produce a 7.4% Ta 2O5/10.0％ZrO2/SiO2 catalyst, wherein the atomic molar ratio of zirconium to tantalum was 2.4:1.
[ Example 5]
The same procedure as in example 1 was followed except that the amounts of zirconium n-propoxide and tantalum pentachloride were varied to produce 1% Ta 2O5/3.73％ZrO2/SiO2 with an atomic molar ratio of zirconium to tantalum of 6.7:1.
[ Example 6]
The same procedure as in example 1 was followed except that the amounts of zirconium n-propoxide and tantalum pentachloride were varied to produce 1.7% Ta 2O5/3.03％ZrO2/SiO2 with an atomic molar ratio of zirconium to tantalum of 3.2:1.
[ Example 7]
The same preparation as in example 1 was carried out, except that the amounts of zirconium n-propoxide and tantalum pentachloride were changed to prepare 3% Ta 2O5/1.73％ZrO2/SiO2, the atomic molar ratio of zirconium to tantalum being 1:1.
[ Example 8]
The same procedure as in example 1 was followed except that the amounts of zirconium n-propoxide and tantalum pentachloride were varied to produce 3.5% Ta 2O5/1.23％ZrO2/SiO2 with an atomic molar ratio of zirconium to tantalum of 0.6:1.
Comparative example 1
4.558G of zirconium n-propoxide (70 wt% zirconium n-propoxide solution) was dissolved in 150mL of n-hexane to obtain a zirconium precursor solution, 30g of silica carrier was added to the zirconium precursor solution, heated at 69 ℃ and refluxed for 6 hours, then filtered, the filtered solid was poured into 150mL of deionized water, and stirred for 1 hour, and then filtered, and the obtained solid was dried at 80 ℃ in a drying oven, and then placed in a muffle furnace to be baked at 550 ℃ for 3 hours, and analyzed for Zr content by ICP-AES test to obtain 2.73% zro 2/SiO2 catalyst.
Comparative example 2
1.45G of tantalum pentachloride is dissolved in 150mL of normal hexane to obtain a tantalum precursor solution, 30g of silicon dioxide carrier is added into the tantalum precursor solution, heating reflux is carried out at 69 ℃ for 6h, then filtration is carried out, the filtered solid is poured into 150mL of deionized water, stirring is carried out for 1h, filtration is carried out again, the obtained solid is dried at 80 ℃ in a drying oven, then the obtained solid is placed in a muffle furnace for roasting at 500 ℃ for 3h, and the Ta content is analyzed by an ICP-AES test, so that 2% Ta 2O5/SiO2 is obtained.
[ Comparative example 3]
The procedure for the preparation of the catalyst was the same as in example 1, except that the loading of tantalum element was carried out first and then the loading of zirconium element was carried out, to obtain a 2.73% ZrO 2/2％Ta2O5/SiO2 catalyst.
[ Comparative example 4]
7.897G of zirconium n-propoxide (70 wt% zirconium n-propoxide solution) was dissolved in 260mL of n-hexane to obtain a zirconium precursor solution, 30g of silica carrier was added to the zirconium precursor solution, heated at 69 ℃ and refluxed for 6 hours, then filtered, the filtered solid was poured into 150mL of deionized water, and stirred for 1 hour, and then filtered, and the obtained solid was dried at 80 ℃ in a drying oven, and then placed in a muffle furnace for roasting at 550 ℃ for 3 hours, and analyzed for Zr content by ICP-AES test to obtain 4.73% ZrO 2/SiO2 catalyst.
Comparative example 5
3.43G of tantalum pentachloride is dissolved in 350mL of normal hexane to obtain a tantalum precursor solution, 30g of silicon dioxide carrier is added into the tantalum precursor solution, heating reflux is carried out at 69 ℃ for 6h, then filtration is carried out, the filtered solid is poured into 150mL of deionized water, stirring is carried out for 1h, filtration is carried out again, the obtained solid is dried at 80 ℃ in a drying oven, then the obtained solid is placed in a muffle furnace for roasting at 500 ℃ for 3h, and the Ta content is analyzed by an ICP-AES test, so that 4.73% Ta 2O5/SiO2 is obtained.
Catalytic activity test method
In the above examples, the reactor used for the catalyst activity test was a fixed bed reactor. The temperature of the reactor was controlled using a tube furnace with three heating zones, and liquid feed was performed using a double plunger pump. The product formed during the reaction remains in the gas phase and is analyzed on-line using agilent 7890A gas chromatography. Specific operating conditions are described in the examples below.
In the catalyst activity test, the molar ratio of ethanol to acetaldehyde of the feed was 3.5:1, the water content was 20wt%, the reaction temperature was 325℃and the pressure was normal, the flow rate of the feed was 2g/g of WHSV of catalyst/h based on the total mass of ethanol and acetaldehyde. The total conversion of ethanol and acetaldehyde and the carbon selectivity of butadiene were measured under this process condition.
The catalyst regeneration conditions were: regeneration temperature 550 ℃, air flow rate 50mL/min, lasting 12h.
TABLE 1
As can be seen from Table 1, the conversion rate of the fresh catalyst of comparative example 1 was 26% for 15 hours compared with that of comparative example 1, and the conversion rate was only 21% after regeneration at 550℃and the activity was lowered because the roasting temperature was too high to destroy the acid site of L-acid of the active component; the activity of the regenerated catalyst of example 1 was almost completely recovered. As shown in fig. 1 and 2, STEM-HAADF characterization pictures of the regenerated catalysts of comparative example 1 and comparative example 1 show that the particle size of the regenerated catalyst oxide of example 1 is distributed in small particles, and the particle size is 0.1-0.3nm; and the regenerated catalyst of the comparative example 1 has large tantalum oxide particles, and the tantalum oxide particles are aggregated and grow up. This shows that in example 1, by compounding tantalum oxide with zirconium oxide, the aggregation and growth of tantalum oxide particles during high temperature regeneration are avoided, and the L acid site of the active component is maintained.
Example 1 compared to comparative example 2, the butadiene selectivity of the 2.73% ZrO 2/SiO2 catalyst was only 63%, indicating that ZrO 2 itself was not highly selective for butadiene, and the loading of Ta 2O5 increased the butadiene selectivity.
Example 1 compared with comparative example 3, the catalyst of comparative example 3 was loaded with tantalum element first and then zirconium element, and the selectivity of butadiene was much lower than that of example 1.
It should be noted that the above-described embodiments are only for explaining the present invention and do not limit the present invention in any way. The invention has been described with reference to exemplary embodiments, but rather should be construed as being limited to the words which have been used herein are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined within the scope of the appended claims, and the invention may be modified without departing from the spirit and scope of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (16)
1. A catalyst for preparing 1, 3-butadiene, comprising a mesoporous silica carrier, and zirconium oxide and tantalum oxide loaded on the mesoporous silica carrier, wherein the mol ratio of zirconium atoms in the zirconium oxide to tantalum atoms in the tantalum oxide is 0.5-3.5:1; the mass of the zirconia is 1% -5% of the mass of the mesoporous silica carrier;
The preparation method of the catalyst for preparing 1, 3-butadiene comprises the following steps:
S1: dipping a mesoporous silica carrier in a zirconium precursor solution, drying and roasting to obtain a zirconia-loaded mesoporous silica carrier;
s2: and (3) dipping the mesoporous silica carrier loaded with the zirconia into a precursor solution of tantalum, and drying and roasting to obtain the catalyst loaded with the zirconia and the tantalum oxide.
2. The catalyst of claim 1, wherein the molar ratio of zirconium atoms in the zirconia to tantalum atoms in the tantalum oxide is from 1:1 to 3:1.
3. The catalyst of claim 1 wherein the mesoporous silica support is selected from amorphous mesoporous silica having different pore sizes.
4. The catalyst according to claim 3, wherein the mesoporous silica support has a specific surface area of 300m 2/g-700m2/g and an average pore diameter of 4nm or more.
5. A method for preparing a catalyst for preparing 1, 3-butadiene, comprising the steps of:
S1: dipping a mesoporous silica carrier in a zirconium precursor solution, drying and roasting to obtain a zirconia-loaded mesoporous silica carrier;
s2: and (3) dipping the mesoporous silica carrier loaded with the zirconia into a precursor solution of tantalum, and drying and roasting to obtain the catalyst loaded with the zirconia and the tantalum oxide.
6. The method according to claim 5, wherein the zirconium precursor solution is selected from an inorganic salt solution of zirconium and/or an alkoxide solution of zirconium; and/or the tantalum precursor solution is selected from an inorganic salt solution of tantalum and/or an alkoxide solution of tantalum.
7. The method of claim 6, wherein the zirconium precursor solution is selected from the group consisting of n-hexane or cyclohexane solutions of zirconium n-propoxide; and/or the tantalum precursor solution is selected from a solution of tantalum pentachloride in n-hexane or cyclohexane.
8. The production method according to any one of claims 5 to 7, wherein in the catalyst, a molar ratio of zirconium atoms in zirconia to tantalum atoms in tantalum oxide is 0.5 to 3.5:1; and/or the mass of the zirconia is 1% -5% of the mass of the mesoporous silica carrier.
9. The method according to claim 8, wherein a molar ratio of zirconium atoms in the zirconium oxide to tantalum atoms in the tantalum oxide in the catalyst is 1:1 to 3:1.
10. Regenerated catalyst for the preparation of 1, 3-butadiene, obtained by calcination of the catalyst according to any one of claims 1 to 4 or of the catalyst obtained by the preparation process according to any one of claims 5 to 9 in an oxygen-containing gas.
11. The regenerated catalyst according to claim 10 wherein the calcination temperature is 500-600 ℃; and/or the roasting time is 5-20h.
12. The regenerated catalyst according to claim 11 wherein the calcination temperature is 540-560 ℃; and/or the roasting time is 10-15h.
13. The regenerated catalyst according to any one of claims 10 to 12, characterized in that in the regenerated catalyst the average particle size of the zirconia and/or tantalum oxide is 0.1-0.3nm.
14. A process for the preparation of 1, 3-butadiene by conversion of ethanol, comprising contacting a mixed solution comprising ethanol, acetaldehyde and water with a catalyst selected from the group consisting of the catalyst according to any one of claims 1 to 4 or the catalyst obtained by the preparation process according to any one of claims 5 to 9 or the regenerated catalyst according to any one of claims 10 to 13.
15. The method according to claim 14, wherein the molar ratio of ethanol to acetaldehyde in the mixed solution is 2:1 to 5:1; and/or
In the mixed solution, the content of water is 5-50 wt% based on the total weight of the mixed solution; and/or
The conditions of the contacting include: the space velocity of the mixed solution is 0.5h -1-5h-1; the temperature is 300-400 ℃.
16. The method of claim 15, wherein the molar ratio of ethanol to acetaldehyde in the mixed solution is from 2.5:1 to 4:1; and/or
In the mixed solution, the content of water is 8-30wt% based on the total weight of the mixed solution; and/or
The conditions of the contacting include: the space velocity of the mixed solution is 0.8h -1-3h-1; the temperature is 320-350 ℃.
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| KR20140047329A (en) * | 2012-10-12 | 2014-04-22 | 한국화학연구원 | Tantala-based complex metal oxide supported on silica-based catalysts for the production of 1,3-butadiene from ethanol and production method of 1,3-butadiene using thereof |
| CN107921414A (en) * | 2015-07-13 | 2018-04-17 | Ifp 新能源公司 | For ethanol to be converted into the catalyst based on the tantalum being deposited on silica of butadiene |
| CN110237859A (en) * | 2018-03-07 | 2019-09-17 | 中国石油化工股份有限公司 | The preparation method of catalyst and its preparation method and application and 1,3- butadiene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20110117953A (en) * | 2010-04-22 | 2011-10-28 | 금호석유화학 주식회사 | Nano-silica based catalysts for the production of 1,3-butadiene and production method of 1,3-butadiene thereof |
| KR20140047329A (en) * | 2012-10-12 | 2014-04-22 | 한국화학연구원 | Tantala-based complex metal oxide supported on silica-based catalysts for the production of 1,3-butadiene from ethanol and production method of 1,3-butadiene using thereof |
| CN107921414A (en) * | 2015-07-13 | 2018-04-17 | Ifp 新能源公司 | For ethanol to be converted into the catalyst based on the tantalum being deposited on silica of butadiene |
| CN110237859A (en) * | 2018-03-07 | 2019-09-17 | 中国石油化工股份有限公司 | The preparation method of catalyst and its preparation method and application and 1,3- butadiene |
Non-Patent Citations (1)
| Title |
|---|
| 王文兴.工业催化.化学工业出版社,1978,第95-96页. * |
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