CN112371130A - Dehydrogenation catalyst and preparation method thereof - Google Patents
Dehydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN112371130A CN112371130A CN202011253758.8A CN202011253758A CN112371130A CN 112371130 A CN112371130 A CN 112371130A CN 202011253758 A CN202011253758 A CN 202011253758A CN 112371130 A CN112371130 A CN 112371130A
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- butanediol
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- 239000003054 catalyst Substances 0.000 title claims abstract description 160
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 96
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims abstract description 94
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 14
- 238000000975 co-precipitation Methods 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 10
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 10
- 238000001354 calcination Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 230000003993 interaction Effects 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910017518 Cu Zn Inorganic materials 0.000 description 3
- 229910017752 Cu-Zn Inorganic materials 0.000 description 3
- 229910017943 Cu—Zn Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910017813 Cu—Cr Inorganic materials 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- FYNVARJNCVQAAI-UHFFFAOYSA-N 5-hydroxyoxolan-2-one Chemical compound OC1CCC(=O)O1 FYNVARJNCVQAAI-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Furan Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalysts, and discloses a dehydrogenation catalyst and a preparation method thereof. The dehydrogenation catalyst consists of CuO, ZnO and ZrO2The molar ratio of the raw materials is 5: (1-5): (0.5-4). The preparation method of the dehydrogenation catalyst comprises the following specific steps: 1) dissolving soluble salts of Cu, Zn and Zr in water according to the proportion of Cu, Zn and Zr in the dehydrogenation catalyst to obtain a mixed solution; 2) mixing the mixed solution with a precipitant solution, then carrying out coprecipitation, and after the coprecipitation reaction is finished, sequentially carrying out aging, filtering and washing treatment to obtain a precipitate; 3) and drying the precipitate, and roasting at 300-400 ℃ for 3-5 h to obtain the dehydrogenation catalyst. The dehydrogenation catalyst has large specific surface area and high catalytic activity, can specifically catalyze the dehydrogenation of 1, 4-butanediol to prepare the gamma-butyrolactone, has high conversion rate to the 1, 4-butanediol, and selects the gamma-butyrolactoneThe selectivity is high.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a dehydrogenation catalyst and a preparation method thereof.
Background
The gamma-butyrolactone is also called 4-hydroxy-butyrolactone, the structure of the gamma-butyrolactone is a compound containing five-membered heterocycle, and the gamma-butyrolactone is a colorless liquid, has the smell similar to acetone, and has the characteristics of high boiling point and high dissolving capacity. The catalyst has the advantages of good reaction performance, high conductivity, good stability and safe use. Gamma-butyrolactone is an important organic solvent and is widely used in many fields such as petroleum industry, medicine, synthetic fiber, synthetic resin, pesticide, etc. As an important fine chemical and organic chemical raw material, the method is mainly used for synthesizing products such as pyrrolidone, N-methyl pyrrolidone, vinyl pyrrolidone and the like.
The methods for synthesizing gamma-butyrolactone include a furfural method, a maleic anhydride hydrogenation method, and a 1, 4-butanediol dehydrogenation method, according to the classification of synthesis raw materials. The byproducts of the 1, 4-butanediol dehydrogenation method are mainly Tetrahydrofuran (THF) and a small amount of Butanol (BOL), the components are simple, the product is easy to separate, the quality of the synthesized gamma-butyrolactone is good, and the high requirements of pharmaceutical raw materials and battery electrolyte on the quality of the gamma-butyrolactone can be met, so the 1, 4-butanediol dehydrogenation method is a main method for synthesizing the gamma-butyrolactone.
At present, the main catalyst for preparing gamma-butyrolactone by adopting a 1, 4-butanediol dehydrogenation method at home and abroad is a copper-chromium (Cu-Cr) catalyst. The Cu-Cr-based catalyst also has problems of low yield of γ -butyrolactone, Cr contamination, etc., and thus, in recent years, as people pay more and more attention to environmental protection, the Cu-Zn-based catalyst, which has been used as a hydrogenation catalyst, has also become another research focus of the 1, 4-butanediol dehydrogenation catalyst, and has received more and more attention. However, the conventional Cu-Zn-based catalyst has disadvantages of a low specific surface area, a low catalytic activity, a low selectivity, a poor stability, and the like, as compared with a Cr-containing catalyst.
Disclosure of Invention
In view of the problems and deficiencies of the prior art, it is an object of the present invention to provide a dehydrogenation catalyst and a method for preparing the same.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows:
the invention firstly provides a dehydrogenation catalyst which is prepared from CuO, ZnO and ZrO2Composition of CuO, ZnO and ZrO2In a molar ratio of 5: (1-5): (0.5 to 4).
According to the above dehydrogenation catalyst, preferably, CuO, ZnO and ZrO are contained in the dehydrogenation catalyst2In a molar ratio of 5:4: 1.
The invention also provides a preparation method of the dehydrogenation catalyst, which comprises the following steps:
(1) dissolving soluble salts of Cu, Zn and Zr in water according to the molar ratio of Cu, Zn and Zr in the dehydrogenation catalyst to obtain a mixed solution;
(2) mixing the mixed solution prepared in the step (1) with a precipitant solution, then carrying out coprecipitation, and after the coprecipitation reaction is finished, sequentially carrying out aging, filtering and washing treatment to obtain a precipitate;
(3) and drying the precipitate, and roasting at 300-400 ℃ for 3-5 h to obtain the dehydrogenation catalyst.
According to the above production method, preferably, the soluble salts of Cu, Zn and Zr in step (1) are nitrates of Cu, Zn and Zr.
According to the preparation method, the precipitating agent is preferably NaOH or Na2CO3、NaHCO3、NH4HCO3And ammonia water.
According to the preparation method, preferably, the reaction temperature of the coprecipitation reaction is 65-85 ℃, and the pH value of the reaction system is 7.0-7.5.
According to the above preparation method, preferably, the aging treatment is specifically performed by: and standing the reaction mixture after the coprecipitation reaction at 65-85 ℃ for 20-50 min, and then standing at room temperature for 15-20 h.
The invention also provides an application of the dehydrogenation catalyst, namely the dehydrogenation catalyst can be used for catalyzing 1, 4-butanediol dehydrogenation to prepare gamma-butyrolactone.
According to the above application, preferably, the dehydrogenation catalyst catalyzes the reaction of dehydrogenation of 1, 4-butanediol to prepare gamma-butyrolactoneThe conditions are as follows: the reaction pressure is 0.07-0.08MPa, the reaction temperature is 200-240 ℃, and the liquid feeding airspeed is 1.0-2.5 h-1，H2The molar ratio of the 1, 4-butanediol to the 1, 4-butanediol is (5-10): 1. more preferably, H2The molar ratio of the 1, 4-butanediol to the 1, 4-butanediol is (6-8): 1.
the catalytic mechanism of the dehydrogenation catalyst of the present invention is as follows:
in the dehydrogenation catalyst, Zn exists in a ZnO form, and the existence of ZnO is beneficial to the adsorption and desorption of hydrogen on the surface of the catalyst, so that ZnO has certain dehydrogenation activity on alcohols and is beneficial to the generation of dehydrogenation reaction of the alcohols. Zr in catalyst as ZrO2Form exists of, ZrO2The Cu-Zn catalyst carrier exists in an amorphous state and can provide a larger specific surface area for the Cu-Zn-Zr catalyst; and with ZrO2Addition of ZnO and ZrO2The CuO can interact with Cu, and the hydrogenation capability of the CuO subjected to the strong interaction after reduction is stronger than that of free CuO; furthermore, ZnO and ZrO in the catalyst2The existence of the catalyst can reduce the acidity of the catalyst, inhibit the occurrence of dehydration side reaction, greatly improve the selectivity of gamma-butyrolactone, reduce the generation of by-product tetrahydrofuran and improve the yield of gamma-butyrolactone.
Compared with the prior art, the invention has the following positive beneficial effects:
(1) the invention researches CuO, ZnO and ZrO in the catalyst2The prepared dehydrogenation catalyst has large specific surface area and high catalytic activity, can specifically catalyze 1, 4-butanediol to prepare the gamma-butyrolactone through dehydrogenation, has high conversion rate of the 1, 4-butanediol (the maximum conversion rate reaches 99.6 percent), has high selectivity to the gamma-butyrolactone, has the maximum yield of the gamma-butyrolactone reaching 99.1 percent, and greatly improves the yield of the gamma-butyrolactone.
(2) The dehydrogenation catalyst has low catalytic reaction temperature, can reduce the reaction temperature of the dehydrogenation reaction of the 1, 4-butanediol, and is energy-saving and environment-friendly; moreover, the dehydrogenation catalyst disclosed by the invention does not contain Cr, and is environment-friendly and pollution-free.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited thereto.
Catalyst composition discussion experiment
In order to discuss the influence of the composition of the catalyst components on the catalytic performance of the prepared dehydrogenation catalyst, the invention carries out experiments of examples 1 to 3, and three catalysts with different compositions are respectively prepared; then, three catalysts are used for catalyzing 1, 4-butanediol to dehydrogenate to prepare gamma-butyrolactone. Specific contents of examples 1 to 3 are as follows.
Example 1:
a dehydrogenation catalyst is prepared from CuO, ZnO and ZrO2Composition of CuO, ZnO and ZrO2In a molar ratio of 5:4: 1.
the preparation method of the dehydrogenation catalyst comprises the following steps:
(1) weighing copper nitrate, zinc nitrate and zirconium nitrate according to the molar ratio of Cu, Zn and Zr in the dehydrogenation catalyst, and dissolving the copper nitrate, the zinc nitrate and the zirconium nitrate in 1000ml of water to obtain a mixed solution of the copper nitrate, the zinc nitrate and the zirconium nitrate; the concentration of copper nitrate in the mixed solution was 0.81 mol/L.
(2) Synchronously dripping the mixed solution prepared in the step (1) and 1L of 1mol/L sodium carbonate solution into a reaction container with a certain amount of distilled water, carrying out coprecipitation reaction at a constant temperature of 70 ℃ in a water area, stirring in the reaction process, controlling the pH of a reaction system to be 7.0-7.5, and stopping stirring after the dripping of the mixed solution is finished; standing the reaction mixture at 70 ℃ for 30min, and standing at room temperature for 20 h; the reaction mixture after standing was then filtered to obtain a precipitate.
(3) And drying the precipitate, and roasting at 350 ℃ for 4h to obtain the dehydrogenation catalyst.
The specific surface area analysis of the dehydrogenation catalyst is carried out by adopting a BET method, and the specific operation is as follows: high-purity helium is used as carrier gas, degassing pretreatment is carried out for 10 hours at 250 ℃, nitrogen adsorption is carried out in a liquid nitrogen cold trap, and the specific surface area of a sample is measured. The flow rate is as follows: n is a radical of230mL/min, bridge flow: 100 mA. Using X-ray diffraction of D/max-2500 type manufactured by Nippon chemical Co., LtdThe analyzer performs the catalyst surface phase determination. The powder sample was placed in an analyzer, a Cu K α graphite monochromator, a Cu target, a tube voltage of 40kV, a tube current of 100mA, a scanning range of 2 θ ═ 5 to 80 °, a scanning speed of 2 °/min, and the measured specific surface area was shown in table 1.
Example 2:
a dehydrogenation catalyst comprised of CuO and ZnO, the molar ratio of CuO to ZnO being 5: 4.
the preparation of the above catalyst was carried out in the same manner as in example 1.
Example 3:
a dehydrogenation catalyst consisting of CuO and ZrO2Composition of CuO and ZrO2In a molar ratio of 5: 1.
the preparation of the above catalyst was carried out in the same manner as in example 1.
The three catalysts prepared in the examples 1 to 3 are respectively used for catalyzing 1, 4-butanediol to dehydrogenate to prepare gamma-butyrolactone, and the specific conditions of the catalytic reaction are as follows: the reaction pressure is 0.07MPa, and the reaction temperature is 220 ℃; the liquid feeding airspeed is 2.0h-1；H2The molar ratio of 1, 4-butanediol to 5: 1; the amount of catalyst used was 20ml (volume of catalyst treated feed per unit volume of time). Meanwhile, the conversion of BDO (1, 4-butanediol) and the yield of γ -butyrolactone (yield ═ γ -butyrolactone formation (mol)/1, 4-butanediol starting amount (mol) × 100%) of the catalytic reaction were calculated, and the specific results are shown in table 1.
TABLE 1 Effect of catalyst ingredient composition on dehydrogenation catalyst Performance
As can be seen from table 1, the catalyst prepared in example 1 has the largest specific surface area, and when the catalyst is used to catalyze dehydrogenation of 1, 4-butanediol to prepare gamma-butyrolactone, the conversion of BDO is the highest, and the yield of gamma-butyrolactone is also the highest. This is because ZnO in the catalyst can react with the carrier ZrO2The existence of interaction is beneficial to the dispersion of each component in the catalyst, thereby obtaining the catalyst with high specific surface areaThe catalyst has high catalytic efficiency and good selectivity when used for catalysis. The specific surface area of the catalyst prepared in example 3 was determined to be the smallest. Therefore, the composition of the catalyst components is preferably CuO, ZnO and ZrO2A combination of three components.
Investigation experiment of ZnO content in catalyst
In order to discuss the influence of the ZnO content in the catalyst on the catalytic performance of the prepared dehydrogenation catalyst, the invention carries out experiments of examples 4 to 9, and five different catalysts are respectively prepared; then, five catalysts are used for catalyzing 1, 4-butanediol to dehydrogenate to prepare gamma-butyrolactone. Specific contents of examples 4 to 9 are as follows.
Example 4:
a dehydrogenation catalyst is prepared from CuO, ZnO and ZrO2Composition of CuO, ZnO and ZrO2In a molar ratio of 5: 0.5: 1.
the above dehydrogenation catalyst was prepared in the same manner as in example 1.
Example 5:
the content of example 5 is substantially the same as that of example 4, except that: CuO, ZnO and ZrO in dehydrogenation catalyst2In a molar ratio of 5: 1: 1.
example 6:
the contents of example 6 are substantially the same as those of example 4, except that: CuO, ZnO and ZrO in dehydrogenation catalyst2In a molar ratio of 5: 2: 1.
example 7:
the content of example 7 is substantially the same as that of example 4, except that: CuO, ZnO and ZrO in dehydrogenation catalyst2In a molar ratio of 5: 3: 1.
example 8:
the content of example 8 is substantially the same as example 4, except that: CuO, ZnO and ZrO in dehydrogenation catalyst2In a molar ratio of 5: 5: 1.
example 9:
example 9 is substantially the same as example 4 except that: CuO in the dehydrogenation catalyst,ZnO and ZrO2In a molar ratio of 5: 6: 1.
the five catalysts prepared in examples 4 to 9 are respectively used for catalyzing 1, 4-butanediol to dehydrogenate to prepare gamma-butyrolactone, and the specific conditions of the catalytic reaction are as follows: the reaction pressure is 0.07MPa, and the reaction temperature is 220 ℃; the liquid feeding airspeed is 2.0h-1；H2The molar ratio of 1, 4-butanediol to 5: 1; the amount of catalyst used was 20ml (volume of catalyst treated feed per unit volume of time). Meanwhile, the conversion rate of BDO (1, 4-butanediol) and the yield of gamma-butyrolactone in the catalytic reaction were calculated, and the specific results are shown in Table 2.
TABLE 2 influence of ZnO content on dehydrogenation catalyst Performance
As can be seen from Table 2, the specific surface area of the catalyst gradually increased with the increase of the ZnO content in the catalyst, when CuO: ZnO: ZrO were added to the catalyst2When the molar ratio of the catalyst to the mixed solution is 5:4:1, the specific surface area of the catalyst reaches the maximum, when the catalyst is used for catalyzing 1, 4-butanediol dehydrogenation to prepare gamma-butyrolactone, the BDO conversion rate is highest, and the yield of the gamma-butyrolactone also reaches the maximum; when the amount of ZnO in the catalyst is further increased, the specific surface area of the catalyst is rather reduced, and when the catalyst is used for catalyzing dehydrogenation of 1, 4-butanediol to prepare gamma-butyrolactone, the BDO conversion rate is also reduced, and the yield of the gamma-butyrolactone is also reduced. This is because ZnO is present together with the carrier ZrO2The existing interaction is beneficial to the dispersion of each component in the catalyst, so that the specific surface area of the catalyst is increased, and therefore, the specific surface area of the catalyst is gradually increased and the catalytic efficiency is gradually improved along with the increase of the ZnO content in the catalyst; however, when the ZnO content in the catalyst is too high, the interaction between ZnO and Cu reduces the ZrO content between Cu and the carrier2Resulting in a decrease in the specific surface area of the prepared catalyst, which in turn causes a decrease in the catalytic efficiency and selectivity of the catalyst.
ZrO in (III) catalyst2Content discussion experiment
To investigate ZrO in the catalyst2Content controlInfluence of catalytic performance of the prepared dehydrogenation catalyst, experiments of examples 10 to 14 are carried out, and five different catalysts are respectively prepared; then, five catalysts are used for catalyzing 1, 4-butanediol to dehydrogenate to prepare gamma-butyrolactone. Specific contents of examples 10 to 14 are as follows.
Example 10:
a dehydrogenation catalyst is prepared from CuO, ZnO and ZrO2Composition of CuO, ZnO and ZrO2In a molar ratio of 5:4: 0.5.
the above dehydrogenation catalyst was prepared in the same manner as in example 1.
Example 11:
example 11 is substantially the same as example 10 except that: CuO, ZnO and ZrO in dehydrogenation catalyst2In a molar ratio of 5:4: 2.
example 12:
the contents of example 12 are substantially the same as those of example 10, except that: CuO, ZnO and ZrO in dehydrogenation catalyst2In a molar ratio of 5:4: 3.
example 13:
the contents of example 13 are substantially the same as those of example 10, except that: CuO, ZnO and ZrO in dehydrogenation catalyst2In a molar ratio of 5:4: 4.
example 14:
example 14 is substantially the same as example 10 except that: CuO, ZnO and ZrO in dehydrogenation catalyst2In a molar ratio of 5:4: 5.
the five catalysts prepared in examples 10 to 14 are respectively used for catalyzing 1, 4-butanediol to dehydrogenate to prepare gamma-butyrolactone, and the specific conditions of the catalytic reaction are as follows: the reaction pressure is 0.07MPa, and the reaction temperature is 220 ℃; the liquid feeding airspeed is 2.0h-1；H2The molar ratio of 1, 4-butanediol to 5: 1; the amount of catalyst used was 20ml (volume of catalyst treated feed per unit volume of time). Meanwhile, the conversion of BDO (1, 4-butanediol) and the yield of γ -butyrolactone (yield ═ amount of γ -butyrolactone produced (mol)/starting 1, 4-butanediol of the catalytic reaction were calculatedAmount (mol). times.100%), yield purity of gamma-butyrolactone, see table 3 for specific results.
TABLE 3 ZrO2Effect of content on dehydrogenation catalyst Performance
As can be seen from Table 3, ZrO supported on the carrier2Adding the auxiliary agent ZnO and the carrier ZrO2The existing interaction is beneficial to the dispersion of each component in the catalyst, the specific surface area of the catalyst is gradually increased, and the catalytic efficiency is gradually improved; but with ZrO in the catalyst system2Further increase in the content, higher ZrO2The interaction with CuO reduces the interaction between CuO and the auxiliary ZnO, so the specific surface area, the conversion rate and the selectivity of the catalyst also tend to be reduced. Therefore, the specific surface area, BDO conversion and gamma-butyrolactone yield of the catalyst are comprehensively considered, and CuO, ZnO and ZrO in the dehydrogenation catalyst2Preferably 5:4: 1.
(IV) roasting temperature discussion experiment
In order to discuss the influence of the roasting temperature on the catalytic performance of the prepared dehydrogenation catalyst in the preparation process of the catalyst, experiments of examples 15 to 19 are carried out, and six different catalysts are respectively prepared; then, six catalysts are used for catalyzing 1, 4-butanediol to dehydrogenate to prepare gamma-butyrolactone. Specific contents of examples 15 to 19 are as follows.
Example 15:
a dehydrogenation catalyst is prepared from CuO, ZnO and ZrO2Composition of CuO, ZnO and ZrO2In a molar ratio of 5:4: 1.
The preparation method of the dehydrogenation catalyst comprises the following steps:
(1) dissolving copper nitrate, zinc nitrate and zirconium nitrate in water according to the proportion of Cu, Zn and Zr in the dehydrogenation catalyst to obtain a mixed solution of the copper nitrate, the zinc nitrate and the zirconium nitrate;
(2) synchronously dripping the mixed solution prepared in the step (1) and 1mol/L sodium carbonate solution into a reaction container with a certain amount of distilled water, carrying out coprecipitation reaction at a constant temperature of 70 ℃ in a water area, stirring in the reaction process, controlling the pH of a reaction system to be 7.0-7.5, and stopping stirring after the dripping of the mixed solution is finished; standing the reaction mixture at 70 ℃ for 30min, and standing at room temperature for 20 h; then filtering the reaction mixture after standing to obtain a precipitate;
(3) and drying the precipitate, and roasting at 200 ℃ for 4h to obtain the dehydrogenation catalyst.
Example 16:
example 16 is substantially the same as example 15 except that: in the preparation method of the dehydrogenation catalyst, the precipitate is dried in the step (3) and then roasted at 250 ℃ for 4 hours.
Example 17:
example 17 is substantially the same as example 15 except that: in the preparation method of the dehydrogenation catalyst, the precipitate is dried in the step (3) and then roasted at 300 ℃ for 4 hours.
Example 18:
example 18 is substantially the same as example 15 except that: in the preparation method of the dehydrogenation catalyst, the precipitate is dried in the step (3) and then roasted at 400 ℃ for 4 hours.
Example 19:
example 19 is substantially the same as example 15 except that: in the preparation method of the dehydrogenation catalyst, the precipitate is dried in the step (3) and then roasted at 450 ℃ for 4 hours.
The catalysts prepared in examples 15 to 19 are respectively used for catalyzing dehydrogenation of 1, 4-butanediol to prepare gamma-butyrolactone, and the specific conditions of the catalytic reaction are as follows: the reaction pressure is 0.07MPa, and the reaction temperature is 220 ℃; the liquid feeding airspeed is 2.0h-1；H2The molar ratio of 1, 4-butanediol to 5: 1; the amount of catalyst used was 20ml (volume of catalyst treated feed per unit volume of time). At the same time, the meterThe conversion of BDO (1, 4-butanediol) of the catalytic reaction, the yield of γ -butyrolactone (yield ═ amount of γ -butyrolactone produced (mol)/initial amount of 1, 4-butanediol (mol) × 100%), and the yield purity of γ -butyrolactone were calculated, and the specific results are shown in table 4.
TABLE 4 Effect of calcination temperature on dehydrogenation catalyst Performance
As can be seen from Table 4, the specific surface area of the catalyst gradually increases with the increase of the calcination temperature, and when the calcination temperature is 350 ℃, the specific surface area of the catalyst reaches the maximum and the catalytic efficiency also reaches the maximum; when the calcination temperature is further increased, the specific surface area of the catalyst is rather decreased, and the catalytic efficiency is gradually decreased. This is because, as the calcination temperature increases, the pore diameter of the catalyst gradually increases, and the specific surface area of the catalyst increases, thereby improving the catalytic efficiency; however, when the calcination temperature exceeds 350 ℃, the too high calcination temperature may cause the chemical bond of the catalyst to be destroyed, which may cause the collapse of the metal structure of the catalyst, the destruction of the catalyst structure, and the reduction of the catalytic performance of the catalyst. When the calcination temperature is 350 ℃, the specific surface area of the prepared catalyst reaches a maximum of 80.1m2And/g, when the catalyst is used for catalyzing 1, 4-butanediol dehydrogenation to prepare the gamma-butyrolactone, the BDO conversion rate can reach 99.6 percent, and the yield of the gamma-butyrolactone also reaches the highest 99.5. Therefore, the calcination temperature is preferably 300-400 deg.C, and most preferably 350 deg.C, taking the specific surface area, BDO conversion and gamma-butyrolactone yield of the catalyst into consideration.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the present invention, but rather as the following description is intended to cover all modifications, equivalents and improvements falling within the spirit and scope of the present invention.
Claims (9)
1. A dehydrogenation catalyst comprising CuO, ZnO and ZrO2Composition of CuO, ZnO and ZrO2In a molar ratio of 5: (1～5）：（0.5～4）。
2. The dehydrogenation catalyst of claim 1 wherein the dehydrogenation catalyst comprises CuO, ZnO, and ZrO2In a molar ratio of 5:4: 1.
3. A method of preparing a dehydrogenation catalyst comprising the steps of:
(1) dissolving soluble salts of Cu, Zn and Zr in water in a molar ratio of Cu, Zn and Zr in the dehydrogenation catalyst according to claim 1 or 2 to obtain a mixed solution;
(2) mixing the mixed solution prepared in the step (1) with a precipitant solution, then carrying out coprecipitation, and after the coprecipitation reaction is finished, sequentially carrying out aging, filtering and washing treatment to obtain a precipitate;
(3) and drying the precipitate, and roasting at 300-400 ℃ for 3-5 h to obtain the dehydrogenation catalyst.
4. The production method according to claim 3, wherein the soluble salts of Cu, Zn and Zr in the step (1) are nitrates of Cu, Zn and Zr.
5. The method according to claim 4, wherein the precipitant is NaOH or Na2CO3、NaHCO3、NH4HCO3And ammonia water.
6. The preparation method according to claim 5, wherein the reaction temperature of the coprecipitation reaction is 65 to 85 ℃, and the pH of the reaction system is 7.0 to 7.5.
7. The preparation method according to claim 6, characterized in that the aging treatment is carried out by the following specific operations: and standing the reaction mixture after the coprecipitation reaction at 65-85 ℃ for 20-50 min, and then standing at room temperature for 15-20 h.
8. Use of the dehydrogenation catalyst of claim 1 for catalyzing the dehydrogenation of 1, 4-butanediol to produce gamma-butyrolactone.
9. The use of claim 8, wherein the dehydrogenation catalyst is used for catalyzing the dehydrogenation of 1, 4-butanediol to prepare gamma-butyrolactone under the following reaction conditions: the reaction pressure is 0.07-0.08MPa, the reaction temperature is 200-240 ℃, and the liquid feeding airspeed is 1.0-2.5 h-1，H2The molar ratio of the 1, 4-butanediol to the 1, 4-butanediol is (5-10): 1.
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| CN117443407A (en) * | 2023-09-25 | 2024-01-26 | 重庆中润新材料股份有限公司 | Copper rare earth-based LDHs dehydrogenation catalyst and preparation method and application thereof |
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| US20040242917A1 (en) * | 1999-03-08 | 2004-12-02 | Chisso Corporation | Catalyst for ester production and process for producing ester |
| CN1850328A (en) * | 2006-05-18 | 2006-10-25 | 复旦大学 | High-selectivity catalyst for preparing 1,4-butanediol and its preparing method |
| CN103769110A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for dehydrogenating 1,4-butanediol to prepare gramma-butyrolactone and its preparation method and application |
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| US20040242917A1 (en) * | 1999-03-08 | 2004-12-02 | Chisso Corporation | Catalyst for ester production and process for producing ester |
| CN1850328A (en) * | 2006-05-18 | 2006-10-25 | 复旦大学 | High-selectivity catalyst for preparing 1,4-butanediol and its preparing method |
| CN103769110A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for dehydrogenating 1,4-butanediol to prepare gramma-butyrolactone and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117443407A (en) * | 2023-09-25 | 2024-01-26 | 重庆中润新材料股份有限公司 | Copper rare earth-based LDHs dehydrogenation catalyst and preparation method and application thereof |
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