CN116272989A - Serial maleic anhydride selective hydrogenation catalyst and its use method - Google Patents
Serial maleic anhydride selective hydrogenation catalyst and its use method Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 142
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 54
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052802 copper Inorganic materials 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000007787 solid Substances 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- OWXLRKWPEIAGAT-UHFFFAOYSA-N [Mg].[Cu] Chemical compound [Mg].[Cu] OWXLRKWPEIAGAT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011777 magnesium Substances 0.000 claims abstract description 10
- 239000006004 Quartz sand Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229920000742 Cotton Polymers 0.000 claims abstract description 5
- 238000011049 filling Methods 0.000 claims abstract description 5
- 239000010453 quartz Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 50
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 26
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 239000002808 molecular sieve Substances 0.000 claims description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 150000001879 copper Chemical class 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 238000011946 reduction process Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 9
- 239000002585 base Substances 0.000 description 19
- 239000003513 alkali Substances 0.000 description 13
- 150000002373 hemiacetals Chemical class 0.000 description 9
- UIUJIQZEACWQSV-UHFFFAOYSA-N succinic semialdehyde Chemical compound OC(=O)CCC=O UIUJIQZEACWQSV-UHFFFAOYSA-N 0.000 description 8
- 239000012752 auxiliary agent Substances 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000007806 chemical reaction intermediate Substances 0.000 description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- -1 hydrogen anhydride Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 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
- B01J23/72—Copper
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- 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
- B01J23/78—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 alkali- or alkaline earth metals
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/082—X-type faujasite
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7003—A-type
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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Abstract
The invention belongs to the technical field of chemical industry, and relates to a serial maleic anhydride selective hydrogenation catalyst and a use method thereof. The invention discloses a serial maleic anhydride selective hydrogenation catalyst, which consists of a metal catalyst and a solid base in serial with the mass ratio of (0.5-5): 1, wherein the metal catalyst comprises one or more of a copper-based catalyst and a copper-magnesium-based catalyst; the copper content in the copper-based catalyst is 10-50wt%; the Mg content in the copper magnesium-based catalyst is 3-20wt% and the copper content is 28-40wt%. The invention also discloses a use method of the serial maleic anhydride selective hydrogenation catalyst, which comprises the following steps: mixing a serial maleic anhydride selective hydrogenation catalyst and quartz sand, filling the mixture into the middle part of a reaction tube of a continuous fixed bed reaction device, and fixing the upper end and the lower end of a catalyst bed layer by quartz cotton; the particulate mixed catalyst is then reduced by hydrogen and then reduced to the reaction temperature for use.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and relates to a serial maleic anhydride selective hydrogenation catalyst and a use method thereof.
Background
Gamma-butyrolactone (GBL) is an important carbon four chemical intermediate and has wide application in fine chemical industry and medical intermediate. Selective hydrogenation of maleic anhydride is one of the most valuable routes to GBL production. According to the GBL reaction route of maleic anhydride hydrogenation, succinic anhydride (also called succinic anhydride) is hydrogenated to form an important intermediate hemiacetal, and this intermediate is often ignored in the whole maleic anhydride hydrogenation process. In this process, there is a dynamic equilibrium between the hemiacetal and its tautomer β -formylpropionic acid, but molecules with acyl and hydroxyl (or carboxyl) groups tend to form stable hemiacetals, so the equilibrium is biased towards hemiacetals, whereas β -formylpropionic acid has higher reactivity and is easily hydrogenated, so the conversion of β -formylpropionic acid to γ -butyrolactone has higher conversion and GBL selectivity.
In order to increase catalytic activity and GBL selectivity, there are a number of literature and patents reporting catalyst sites and modulation aids. Currently, copper-based catalysts are commonly used in industry in the production of gamma-butyrolactone, whether by hydrogenation of maleic anhydride to 1, 4-butanediol or by dehydrogenation of 1, 4-butanediol; for example, chinese patent application publication No. CN112742396A discloses a copper-based silicon-based composite catalyst containing a copper component, a silicon component and an auxiliary element, which is prepared by adopting a conventional precipitation method, wherein the copper component contains 2-50wt% of CuO and contains Na, K, cs, W, mn, re, ru, sn, sb, bi, la, ag, mn common auxiliary agents, mainly electronic auxiliary agents and metal oxides, and the action mechanism of the auxiliary agents on chemical equilibrium is not proposed. The precursor with hydrotalcite structure is prepared by introducing Mg source and using coprecipitation method, the catalyst has petal structure, and the sintering or agglomeration of the catalyst in high temperature process can be effectively prevented by coordination of active component Cu and other metals; the auxiliary Zn can be used for adjusting the acidity and alkalinity of the catalyst, and the catalyst dehydration can be inhibited due to the alkaline catalyst, so that the generation of byproducts tetrahydrofuran and butanol can be eliminated in the reaction of preparing gamma-butyrolactone by dehydration and dehydrogenation of 1, 4-butanediol; however, zn is a weak Lewis acid base, the improvement of the conversion rate is small, and the right shifting capability of the whole chemical balance is weak.
At present, cu-based catalysts, auxiliary agents, morphology or structure modulation forms are mainly concentrated for maleic anhydride selective hydrogenation catalysts. The system has important defects in combination with earlier-stage documents and patents: the maleic anhydride polyunsaturated bond selective hydrogenation network is urgently required to be refined, if a conversion hemiacetal catalyst can be introduced, the conversion rate of a reaction intermediate can be greatly improved, and further the maleic anhydride conversion rate and the GBL selectivity of a target product are improved. In conclusion, the preparation of the active component capable of improving the conversion of the intermediate has important significance for the selective hydrogenation of maleic anhydride.
Disclosure of Invention
The invention aims to solve the problems of the existing maleic anhydride selective hydrogenation catalyst, and provides a serial maleic anhydride selective hydrogenation catalyst which can greatly improve the conversion rate of a reaction intermediate, thereby improving the maleic anhydride conversion rate and the GBL selectivity of a target product.
The aim of the invention can be achieved by the following technical scheme:
a serial maleic anhydride selective hydrogenation catalyst consists of a metal catalyst and a solid base in serial with the mass ratio of (0.5-5) to 1,
the metal catalyst comprises one or more of a copper-based catalyst and a copper-magnesium-based catalyst;
the copper content in the copper-based catalyst is 10-50wt%;
the Mg content in the copper magnesium-based catalyst is 3-20wt% and the copper content is 28-40wt%.
The metal-based catalyst and the solid alkali in the serial maleic anhydride selective hydrogenation catalyst are formed by serial connection, wherein the metal-based catalyst has the function of selectively hydrogenating C=C double bonds and C=O double bonds; the solid base promotes the catalytic conversion of the reaction intermediate hemiacetal, which promotes the shift of the chemical equilibrium to the right.
Preferably, the copper-based catalyst has a copper content of 30 to 40wt%.
Preferably, the solid alkali is one or more of metal oxide, basic molecular sieve and supported solid alkali catalyst.
Further preferably, the metal oxide comprises one or more of MgO and CaO; the supported solid base comprises KF/Al 2 O 3 、K 2 O/Al 2 O 3 One or more of the following; the basic molecular sieve comprises one or more of 4A, 5A, 13X.
Preferably, the copper-based catalyst is prepared from copper salt through ammonia distillation, and the preparation method of the copper-based catalyst comprises the following steps: dropwise adding a dissolved copper salt solution into a mixed solution of ammonia water and alkaline silica sol, aging, placing in a constant-temperature water bath, heating to evaporate ammonia until the pH value of the solution reaches 7, standing, filtering, drying and roasting to obtain the copper-based catalyst.
Preferably, the preparation method of the copper magnesium-based catalyst comprises the following steps: dropwise adding a dissolved copper salt and magnesium salt mixed solution into a mixed solution of ammonia water and alkaline silica sol, aging, placing into a constant-temperature water bath, and heating and distilling ammonia until the pH value of the solution reaches 7; is prepared through standing, filtering, baking and roasting.
Preferably, the mass ratio of the ammonia water to the alkaline silica sol in the mixed solution is (1-3): 1, a step of; the mass ratio of the mixed solution to the copper salt solution is 1 (1.5-3).
Further preferably, concentrated ammonia water with the mass content of 20-30% is added in the preparation process of the copper-based catalyst and the copper-magnesium-based catalyst.
Preferably, the aging temperature is 85-95 ℃ and the aging time is 1-24 hours; the constant temperature water bath temperature is 45-60 ℃ and the time is 5-8 h.
Preferably, the temperature of the heating ammonia distillation process is 85-95 ℃.
Preferably, the temperature of the roasting process is 300-500 ℃ and the time is 3-24 hours.
Preferably, the metal catalyst and the solid base are mixed in the form of particles.
The invention also discloses a use method of the serial maleic anhydride selective hydrogenation catalyst, which comprises the following steps: mixing a serial maleic anhydride selective hydrogenation catalyst and quartz sand, filling the mixture into the middle part of a reaction tube of a continuous fixed bed reaction device, and fixing the upper end and the lower end of a catalyst bed layer by quartz cotton; the particulate mixed catalyst is then reduced by hydrogen and then reduced to the reaction temperature for use.
The serial maleic anhydride selective hydrogenation catalyst of the invention promotes the conversion of the hemiacetal to the beta-formylpropionic acid, promotes the chemical equilibrium to move rightwards, remarkably improves the selectivity of gamma-butyrolactone (GBL), and improves the yield of gamma-butyrolactone (GBL). And the mixed catalyst needs to be subjected to hydrogen reduction after filling in order to be used in the reaction process for preparing gamma-butyrolactone (GBL), because the maleic anhydride hydrogenation active component needs low-valence metal.
Preferably, the mass ratio of the serial maleic anhydride selective hydrogenation catalyst to the quartz sand is 1 (1-3).
Preferably, the hydrogen reduction process is carried out at a temperature of 280-350 ℃ for 5-7 hours.
Preferably, the filling process includes one or more of a physical mixing method, a powder mixing method, and a two-stage method.
Preferably, the particle size of the serial maleic anhydride selective hydrogenation catalyst is 20-40 meshes; the particle size of the quartz sand is 20-40 meshes.
Preferably, maleic anhydride is pumped by a high-pressure plunger pump in the continuous fixed bed reaction device, and hydrogen is input by a total hydrogen pipeline.
Preferably, after the use method of the serial maleic anhydride selective hydrogenation catalyst is adopted, the maleic anhydride conversion rate is 80-100%, and the gamma-butyrolactone (GBL) selectivity is 60-95%.
Compared with the prior art, the invention has the following beneficial effects:
1. the serial maleic anhydride selective hydrogenation catalyst consists of a metal-based catalyst and solid alkali, so that the chemical equilibrium right shift is promoted, and the gamma-butyrolactone selectivity is remarkably improved; the conversion rate of the hemiacetal converted beta-formylpropionic acid is promoted, the beta-formylpropionic acid is easy to hydrogenate, and the high-yield synthesis of the final product gamma-butyrolactone is realized through a dehydration step.
2. The metal-based catalyst in the serial maleic anhydride selective hydrogenation catalyst is prepared from copper salt through ammonia distillation, and an auxiliary agent is added in the process of heating and ammonia distillation to promote rapid conversion of intermediate products.
3. The serial maleic anhydride selective hydrogenation catalyst has the advantages of simple use method and easy operation, and is suitable for large-scale production.
Drawings
FIG. 1 is an XRD spectrum of a copper-based catalyst prepared in example 1 of the present invention.
FIG. 2 is a diagram showing the reaction path of the maleic anhydride hydrogenation to prepare gamma-butyrolactone according to the present invention.
FIG. 3 is an XRD pattern of the 5A solid base catalyst used in example 4 of the present invention.
FIG. 4 is an XRD pattern of the 13X solid base catalyst used in example 5 of the present invention.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention are further described, but the present invention is not limited to these examples.
The alkaline molecular sieve and the metal oxide adopted by the invention are all commercial materials;
the basic molecular sieves include 3A, 4A, 5A and 13X molecular sieves;
the metal oxide comprises MgO and CaO.
Example 1
Copper-based catalyst preparation:
copper-based catalyst (Cu-SiO) prepared by ammonia distillation method 2 )。
11.4g of Cu (NO) was weighed out 3 ) 2 ·3H 2 O, adding 22.8g of deionized water to prepare copper nitrate solution, adding 25% ammonia water, and adjusting the pH value to 11.0 to form copper ammonia solution. 13.6g of alkaline silica Sol (SiO) 2 Dropwise adding 30% by mass of silicon source into copper ammonia solution, stirring at room temperature for 4 hours, and then evaporating ammonia at 90 ℃; then aging for 12 hours at 90 ℃, filtering, washing, drying at 120 ℃ overnight, roasting at 350 ℃ for 6 hours, tabletting to 20-40 meshes, and ensuring that the Cu content is 30wt%.
Fig. 1 is an XRD spectrum of the prepared copper-based catalyst.
KF/Al 2 O 3 Preparation of solid base catalyst:
10g of KF is dissolved in 30mL of absolute ethanol, and carrier Al dried at 200 ℃ is added 2 O 3 (10g) Stirring at 60 ℃ for 3 hours, and removing the ethanol solvent; vacuum drying at 120deg.C, and calcining at 500deg.C in muffle furnace for 6 hr to obtain load type KF/Al 2 O 3 A solid base catalyst.
Synthesis of gamma-butyrolactone:
in the embodiment, a serial maleic anhydride selective hydrogenation catalyst is adopted for preparing gamma-butyrolactone, and relates to a use method of the serial maleic anhydride selective hydrogenation catalyst.
FIG. 2 is a diagram showing the reaction path of the maleic anhydride hydrogenation to prepare gamma-butyrolactone according to the present invention.
The using method specifically comprises the following steps: copper-based catalyst and solid base catalyst (KF/Al) 2 O 3 ) Mixing (30 meshes) and quartz sand (30 meshes), filling the mixture into the middle part of a reaction tube of a continuous fixed bed reaction device, and carrying out copper-based catalyst: the mass ratio of the solid base catalyst is 1:1, the mass ratio of the serial maleic anhydride selective hydrogenation catalyst to the quartz sand is 2:1, and the upper end and the lower end of the catalyst bed layer are fixed by quartz cotton. The mixed catalyst was then fed with hydrogen via the total hydrogen line at 300 cReducing for 6h, and then reducing to the reaction temperature; maleic anhydride is pumped by a high pressure plunger pump.
The gamma-butyrolactone is prepared by reaction at 240 ℃ under the conditions of 0.5MPa of pressure, 0.2 of airspeed and 80 of the hydrogen anhydride ratio, and the specific results are shown in table 1.
Example 2
The serial maleic anhydride selective hydrogenation catalyst of this embodiment is a copper-magnesium-based catalyst.
CuMg-SiO containing Mg auxiliary agent prepared by ammonia distillation method 2 A catalyst.
11.4g of Cu (NO) was weighed out 3 ) 2 ·3H 2 O and 2.6g of Mg (NO 3 ) 2 ·6H 2 O, adding 28g of deionized water to prepare copper nitrate solution, adding 25% ammonia water, and adjusting the pH value to 11.0 to form copper ammonia solution. 11.7g of alkaline silica sol (SiO 2 30% by mass) as a silicon source, is added dropwise to the copper ammonia solution, stirred at room temperature for 4 hours, subjected to ammonia distillation at 90 ℃, aged at 90 ℃ for 12 hours, filtered, washed and dried at 120 ℃ overnight, calcined at 350 ℃ for 6 hours, and tabletted to 20-40 mesh. The Mg content was 5wt% and the Cu content was 30wt%.
Synthesis of gamma-butyrolactone:
in the embodiment, a serial maleic anhydride selective hydrogenation catalyst is adopted for preparing gamma-butyrolactone, and relates to a use method of the serial maleic anhydride selective hydrogenation catalyst.
The method specifically comprises the following steps: cuMg-SiO 2 The catalyst (30 meshes), the solid base catalyst and quartz sand (30 meshes) are mixed and then filled into the middle part of a reaction tube of a continuous fixed bed reaction device, the mass ratio of the serial maleic anhydride selective hydrogenation catalyst to the quartz sand is 2:1, and the upper end and the lower end of a catalyst bed layer are fixed by quartz cotton. Then reducing the hydrogen input by the mixed catalyst through a total hydrogen pipeline at 300 ℃ for 6 hours, and then reducing the hydrogen to the reaction temperature; maleic anhydride is pumped by a high pressure plunger pump.
The gamma-butyrolactone is prepared by reaction at 240 ℃ under the conditions of 0.5MPa of pressure, 0.2 of airspeed and 80 of the hydrogen anhydride ratio, and the specific results are shown in table 1.
Example 3
Compared with the example 1, the difference is that the solid base is a 4A molecular sieve, and the mass ratio of the copper-based catalyst to the solid base catalyst in the serial maleic anhydride selective hydrogenation catalyst is 1:1.
Example 4
Compared with the example 1, the difference is that the solid alkali is a 5A molecular sieve, and the mass ratio of the copper-based catalyst to the solid alkali catalyst in the serial maleic anhydride selective hydrogenation catalyst is 1:1.
Figure 3 is an XRD spectrum of the 5A molecular sieve.
Example 5
Compared with the example 1, the difference is that the solid alkali is a 13X molecular sieve, and the mass ratio of the copper-based catalyst to the solid alkali catalyst in the serial maleic anhydride selective hydrogenation catalyst is 1:1.
Figure 4 is an XRD spectrum of 13X molecular sieve.
Example 6
In comparison with example 1, the difference is that the serial maleic anhydride selective hydrogenation catalyst is composed of a copper-based catalyst (Cu-SiO 2 ) The solid alkali MgO particles are mixed to form the magnesium alloy, so that the Mg content is 5 weight percent and the Cu content is 30 weight percent.
Example 7
In comparison with example 6, the difference is that the copper-based catalyst (Cu-SiO 2 ) The proportion of solid alkali MgO is such that the content of Mg is 7wt% and the content of Cu is 30wt%.
Example 8
In comparison with example 6, the difference is that the copper-based catalyst (Cu-SiO 2 ) The proportion of solid alkali MgO is such that the content of Mg is 25wt% and the content of Cu is 30wt%.
Example 9
Compared with example 1, the difference is that the serial maleic anhydride selective hydrogenation catalyst consists of Cu-SiO with the mass ratio of 1:0.5:0.5 2 Mixing MgO and 13A molecular sieve particles.
Comparative example 1
In comparison with example 1, the difference is that no solid base is added and the tandem maleic anhydride selective hydrogenation catalyst is only a copper-based catalyst.
Comparative example 2
Compared with example 1, the difference is that no solid alkali is added, and the serial maleic anhydride selective hydrogenation catalyst is only a copper-based catalyst; and the addition amount of copper salt is regulated to ensure that the Cu content in the copper-based catalyst is 40 weight percent.
Comparative example 3
The difference compared with example 1 is that the total mass of the copper-based catalyst and the solid base in the serial maleic anhydride selective hydrogenation catalyst is unchanged, and the mass ratio of the copper-based catalyst to the solid base is 0.4:1.
Comparative example 4
The difference compared with example 1 is that the total mass of the copper-based catalyst and the solid base in the serial maleic anhydride selective hydrogenation catalyst is unchanged, and the mass ratio of the copper-based catalyst to the solid base is 5.2:1.
TABLE 1 parameters of serial maleic anhydride selective hydrogenation catalysts and Table of Performance data for preparing gamma butyrolactone
In summary, the serial maleic anhydride selective hydrogenation catalyst provided by the invention consists of a copper-based catalyst and solid alkali, so that the chemical equilibrium right shift is promoted, and the gamma-butyrolactone selectivity is remarkably improved; the conversion rate of the hemiacetal converted beta-formylpropionic acid is promoted, the beta-formylpropionic acid is easy to hydrogenate, and the high-yield synthesis of the final product gamma-butyrolactone is realized through a dehydration step.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (10)
1. The serial maleic anhydride selective hydrogenation catalyst is characterized by comprising a metal catalyst and a solid base in serial, wherein the mass ratio of the metal catalyst to the solid base is (0.5-5): 1, and the metal catalyst comprises one or more of a copper-based catalyst and a copper-magnesium-based catalyst;
the copper content in the copper-based catalyst is 10-50wt%;
the Mg content in the copper magnesium-based catalyst is 3-20wt% and the copper content is 28-40wt%.
2. The tandem maleic anhydride selective hydrogenation catalyst according to claim 1, wherein said solid base is one or more of a metal oxide, a molecular sieve and a supported solid base catalyst.
3. The tandem maleic anhydride selective hydrogenation catalyst according to claim 1, wherein said copper-based catalyst is prepared from copper salts by ammonia distillation, said copper-based catalyst being prepared by a process comprising: dropwise adding dissolved copper salt into a mixed solution of ammonia water and alkaline silica sol, aging, placing into a constant-temperature water bath, heating to evaporate ammonia until the pH value of the solution reaches 7, standing, filtering, drying and roasting to obtain the copper-based catalyst.
4. The tandem maleic anhydride selective hydrogenation catalyst according to claim 1, wherein the preparation method of the copper-magnesium-based catalyst comprises the following steps: dropwise adding a dissolved copper salt and magnesium salt mixed solution into a mixed solution of ammonia water and alkaline silica sol, aging, placing into a constant-temperature water bath, and heating and distilling ammonia until the pH value of the solution reaches 7; is prepared through standing, filtering, baking and roasting.
5. The tandem maleic anhydride selective hydrogenation catalyst according to claim 3 or 4, wherein the aging temperature is 85-95 ℃ and the aging time is 1-24 hours; the constant temperature water bath temperature is 45-60 ℃ and the time is 5-8 h.
6. The tandem maleic anhydride selective hydrogenation catalyst according to claim 3 or 4, wherein the calcination process temperature is 300 to 500 ℃ for 3 to 24 hours.
7. The serial maleic anhydride selective hydrogenation catalyst according to claim 3 or 4, wherein the mass ratio of the ammonia water to the alkaline silica sol in the mixed solution is (1-3): 1.
8. a method for using a serial maleic anhydride selective hydrogenation catalyst, the method comprising: mixing serial maleic anhydride selective hydrogenation catalyst and quartz sand, filling the mixture into the middle part of a reaction tube of a continuous fixed bed reaction device, and fixing the upper end and the lower end of a catalyst bed layer by quartz cotton; the mixed catalyst is then reduced by hydrogen and then reduced to the reaction temperature for use.
9. The tandem maleic anhydride selective hydrogenation catalyst according to claim 8, wherein the hydrogen reduction process temperature is 280-350 ℃ for 5-7 hours.
10. The serial maleic anhydride selective hydrogenation catalyst according to claim 8, wherein after the serial maleic anhydride selective hydrogenation catalyst is used, the maleic anhydride conversion rate is 80-100% and the gamma-butyrolactone (GBL) selectivity is 60-95%.
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