CN117046479A - Catalyst for preparing gamma-butyrolactone by dehydrogenation of 1, 4-butanediol, preparation method and application thereof - Google Patents
Catalyst for preparing gamma-butyrolactone by dehydrogenation of 1, 4-butanediol, preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title claims abstract description 66
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000006356 dehydrogenation reaction Methods 0.000 title claims description 25
- 238000002360 preparation method Methods 0.000 title abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 36
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 36
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 24
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 52
- 239000000725 suspension Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 24
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 24
- 239000002270 dispersing agent Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 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 claims description 13
- 239000010949 copper Substances 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 11
- 239000011701 zinc Chemical class 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 229910052725 zinc Chemical class 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007853 buffer solution Substances 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229960004063 propylene glycol Drugs 0.000 claims description 3
- 235000013772 propylene glycol Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 8
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 229910001701 hydrotalcite Inorganic materials 0.000 description 5
- 229960001545 hydrotalcite Drugs 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000005751 Copper oxide Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 229910017813 Cu—Cr Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910003120 Zn-Ce Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical compound [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- 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
-
- 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
Abstract
The application belongs to the technical field of catalysis, and particularly discloses a catalyst for preparing gamma-butyrolactone by dehydrogenating 1, 4-butanediol, and a preparation method and application thereof. The catalyst consists of active components of CuO, an auxiliary agent of ZnO, ca and a carrier of oxidized graphene/gamma-Al 2 O 3 The composition of @ montmorillonite; the active component CuO accounts for 20-30% by weight, the auxiliary agent ZnO accounts for 1.5-10%, the auxiliary agent Ca accounts for 0-3%, and the carrier is graphene oxide/gamma-Al 2 O 3 57-78.5% of @ montmorillonite; the graphene oxide/gamma-Al 2 O 3 The @ montmorillonite carrier is prepared by taking graphene oxide and pseudo-boehmite as precursor substances. The catalyst has low CuO content, does not contain Cr, and is nontoxic and pollution-free; the raw material components are easy to obtain, and the cost is low; high activity.
Description
Technical Field
The application belongs to the technical field of catalysis, and particularly relates to a catalyst for preparing gamma-butyrolactone by dehydrogenating 1, 4-butanediol, and a preparation method and application thereof.
Background
PVP has excellent solubility, low toxicity, film forming property, chemical stability, physiological inertia, adhesive capability and the like, and is widely used in the fields of medical and medical treatment and health, cosmetics, foods, beverages, brewing, papermaking, textile printing and dyeing, new materials, suspension, emulsion polymerization dispersion stabilizers and the like. In 2021, the application ratio of PVP products in the new energy field is improved to 10% under the influence of the new energy field. The PVP application field is continuously expanded, and the development of PVP industry is promoted. Experts predict a global PVP demand of 20.2 ten thousand tons in 2025.
The synthesis process of PVP includes acetylene process and gamma-butyrolactone process. The gamma-butyrolactone method has lower yield and is more suitable for small and medium-sized enterprises. The gamma-butyrolactone method refers to a method of producing target monomer NVP by reacting gamma-butyrolactone with ethanolamine to produce hydroxyethyl pyrrolidone (NHP), and then dehydrating the NHP directly or indirectly in the presence of a dehydration catalyst. The production process involves the problems of harmful substance absorption, complicated process and difficult control, and the common equipment has low utilization rate and low NVP yield compared with an acetylene method. The acetylene method is mature and is the main production process at present. Acetylene method takes acetylene, formaldehyde and the like as initial raw materials, firstly synthesizes 1, 4-Butanediol (BDO), and finally obtains PVP monomer NVP through reactions such as catalytic dehydrogenation, ammonolysis, alkyne addition and the like. Acetylene is the earliest and relatively well established method of synthesizing NVP. The technology for producing NVP by acetylene method has the main advantages of mature technology, cheap and easily available raw materials, suitability for large-scale industrial production and the like.
An important step in the acetylene process is the catalytic dehydrogenation of 1, 4-butanediol to form gamma-butyrolactone. For catalytic reactions, it is well known that the performance of the catalyst is not sufficient. The common catalyst system for preparing gamma-butyrolactone by a1, 4-butanediol dehydrogenation method comprises the following steps: there are Cu-Cr-based catalysts, cu-Zn-based catalysts, and the above catalysts modified by using an alkali metal or alkaline earth metal such as K, la as an auxiliary agent. Among them, the Cu-Cr series catalyst is the earliest catalyst, and has the advantages of long service life and good stability, but the Cr has strong toxicity and large pollution. In recent years, cu-Zn catalysts have received increasing attention.
Chinese patent CN103044367a discloses a catalyst for preparing gamma-butyrolactone by dehydrogenating 1, 4-butanediol, first preparing Cu-Zn-A1 mixed oxide by coprecipitation method, then loading K or Li auxiliary agent. The copper oxide mass percentage of the catalyst is 37-52%, the conversion rate of 1, 4-butanediol reaches 98%, and the selectivity of gamma-butyrolactone reaches 99%. CN1562473A adopts an alkaline precipitant precipitation method to prepare the Cu-Zn-Ce catalyst, wherein the copper oxide accounts for 48-55% of the total mass, the conversion rate of 1, 4-butanediol can reach 98%, and the selectivity of gamma-butyrolactone is close to 95%. The preparation method of the Cu-Zn catalyst is complex, and the copper oxide content is high. The high content of copper oxide is easy to cause active metal Cu agglomeration, thereby bringing about the problems of low yield of target products and the like.
Therefore, a catalyst for preparing gamma-butyrolactone by dehydrogenating 1, 4-butanediol, which has the advantages of simple preparation mode, high activity, low content of active components, no toxicity and no pollution, needs to be developed.
Disclosure of Invention
Aiming at the defects of the prior art, the application provides a catalyst for preparing gamma-butyrolactone by catalyzing the dehydrogenation of 1, 4-butanediol, and a preparation method and application thereof, wherein the preparation process is environment-friendly and nontoxic, and has good catalytic activity.
The application is realized by the following technical scheme:
a catalyst for preparing gamma-butyrolactone by dehydrogenating 1, 4-butanediol is characterized by comprising active components of CuO, an auxiliary agent of ZnO, ca and a carrier of graphene oxide/gamma-Al 2 O 3 The composition of @ montmorillonite; the active component CuO accounts for 20 to 30 percent, the auxiliary agent ZnO accounts for 1.5 to 10 percent, the auxiliary agent Ca accounts for 0 to 3 percent, and the carrier is graphene oxide/gamma-Al 2 O 3 57 to 78.5 percent of@montmorillonite;
the graphene oxide/gamma-Al 2 O 3 The @ montmorillonite carrier is prepared by taking graphene oxide and pseudo-boehmite as precursor substances.
The application adopts gamma-Al 2 O 3 And montmorillonite as basic matrix material to prepare composite material capable of improving stability of carrier and active component and adsorbing site of active component, on one hand, gamma-Al 2 O 3 Can start upThe effect of the column support montmorillonite is supported, and the gamma-Al is improved while the adsorption site of the carrier is improved 2 O 3 Binding strength with montmorillonite; on the other hand, the montmorillonite can increase the adsorption effect on metal ions, and the montmorillonite can regulate and control gamma-Al 2 O 3 Is beneficial to the catalysis of the carrier.
Ca can be added with gamma-Al 2 O 3 The CaAl-LDH hydrotalcite precursor with a layered structure is formed, active metals can be simultaneously introduced into the hydrotalcite laminate by the CaA1-LDH hydrotalcite precursor, so that the active metals are uniformly and tightly arranged on the hydrotalcite laminate, the proportion of metal cations can be modulated to a certain extent, and the composite metal oxide is formed by later roasting. The uniform dispersion of the active metal can improve the activity of the catalyst. The formation of the composite metal oxide can improve the alkalinity of the hydrotalcite material to a certain extent, namely the alkalinity of the final catalyst material is improved, so that the catalyst material is particularly suitable for alcohol dehydrogenation reaction.
And then graphene oxide is carried out on the matrix material to form a graphene oxide carrier, and graphene oxide contains hydroxyl oxygen, carboxyl oxygen, epoxy oxygen and aldehyde oxygen which provide coordination capability, so that the graphene oxide can be better adsorbed with active metals such as Cu, zn and the like to form adsorption between chemical bonds, and further the bond strength between the graphene oxide and metal ions is improved. The presence of Ca also acts as a promoter.
In turn, the pseudo-boehmite can also use montmorillonite and graphene oxide as templates, so that the uniform dispersibility of the pseudo-boehmite on the montmorillonite and the graphene oxide is improved, the agglomeration of the pseudo-boehmite is avoided, and the adsorptivity of the pseudo-boehmite on active components is improved, so that the catalytic activity of the catalyst is improved.
The preparation method of the catalyst for preparing gamma-butyrolactone by dehydrogenating 1, 4-butanediol comprises the following steps:
s1, dissolving pseudo-boehmite and montmorillonite in a dispersing agent, and then adding the dispersing agent into a mechanochemical reactor to react to obtain a first suspension;
s2, adding CaO into deionized water, and performing ultrasonic treatment to form a second suspension of calcium hydroxide;
s3, ultrasonically dispersing graphene oxide in distilled water, dropwise adding the first suspension and the second suspension, and continuing to ultrasonically until the color of the suspensions is uniform to obtain a third suspension; adding alkali liquor for coprecipitation to prepare a solution containing solid suspended matters, and marking the solution as a fourth solution;
s4, dissolving soluble salts of copper and zinc in water, adding an alkaline buffer solution to control the solution to be alkaline, and preparing a solution containing solid suspended matters, namely a fifth solution;
s5, adding the fourth solution into the fifth solution, stirring, mixing and aging, then washing with deionized water to be neutral, and drying to obtain a precursor with a hydrotalcite structure;
s6, roasting the precursor with the hydrotalcite structure in air atmosphere at 300-500 ℃ for 2-6 hours, so as to prepare the catalyst;
preferably, in the step, the mass ratio of the pseudo-boehmite, the montmorillonite, the dispersing agent and the graphene oxide is l-1.5: l-1.2: 8-10: 0.002-0.005.
Further, the dispersing agent used in the step S1 is an ethylene glycol aqueous solution;
preferably, the volume ratio of glycol to water in the glycol aqueous solution is 3:1.
Further, the alkali liquor used in the step S3 is one of ammonia water, sodium bicarbonate, sodium hydroxide and ammonium carbonate;
preferably, the pH of the fourth solution is controlled to 9-11.
Further, at least one of nitrate, acetate and basic carbonate is used as the soluble salts of copper and zinc in the step S4, and preferably nitrate is used.
Further, the alkaline buffer solution in the step S4 is a mixed solution of sodium hydroxide and sodium carbonate;
preferably, the pH of the fifth solution is controlled to be 8-10.
Further, the powder obtained by roasting in the step S6 is formed into a cylinder with the diameter of 3-5 mm by tabletting, and a tablet press with the punch pressure of 70-120 kN is used for tabletting.
Further, the catalyst is used in alcohol selective dehydrogenation reaction.
Further, the alcohol substance is one of ethanol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 2-propanediol, cyclohexanol and isopropanol; in the selective dehydrogenation reaction of the alcohols, the reaction temperature is 210-280 ℃, the reaction pressure is 0.1-2.0 Bar, and the reaction pressure is gauge pressure.
The beneficial effects of the application are as follows:
1. the catalyst of the application has the advantages that the required active component CuO content is low, and the active component is not easy to agglomerate in the use process; the catalyst does not contain Cr, and is nontoxic and pollution-free; the raw material components are easy to obtain, and the cost is low; the obtained catalyst has high activity.
2. The catalyst is mainly prepared by adopting ultrasonic cavitation and coprecipitation methods, the preparation method is simple, the used raw materials are simple and easy to obtain, the cost is saved, and the catalyst is suitable for popularization and use.
3. The catalyst of the application can be used in selective dehydrogenation reactions of ethanol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 2-propanediol, cyclohexanol and isopropanol.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below. 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.
The application provides a catalyst for preparing gamma-butyrolactone by dehydrogenating 1, 4-butanediol, which comprises active components of CuO, an auxiliary agent of ZnO, ca and a carrier of graphene oxide/gamma-Al 2 O 3 The composition of @ montmorillonite; the active component CuO accounts for 20 to 30 percent, the auxiliary agent ZnO accounts for 1.5 to 10 percent, the auxiliary agent Ca accounts for 0 to 3 percent, and the carrier is graphene oxide/gamma-Al 2O 3 57 to 78.5 percent of@montmorillonite;
the graphene oxide/gamma-Al 2 O 3 Support of @ montmorillonite with graphene oxide, pseudo-thinThe boehmite is used as a precursor material for preparation.
The application provides a preparation method of a catalyst for preparing gamma-butyrolactone by dehydrogenating 1, 4-butanediol, which comprises the following steps:
s1, dissolving pseudo-boehmite and montmorillonite in a dispersing agent, and then adding the dispersing agent into a mechanochemical reactor to react to obtain a first suspension;
s2, adding CaO into deionized water, and performing ultrasonic treatment to form a second suspension of calcium hydroxide;
s3, ultrasonically dispersing graphene oxide in distilled water, dropwise adding the first suspension and the second suspension, and continuing to ultrasonically until the color of the suspensions is uniform to obtain a third suspension; adding alkali liquor for coprecipitation to prepare a solution containing solid suspended matters, and marking the solution as a fourth solution;
s4, dissolving soluble salts of copper and zinc in water, adding an alkaline buffer solution to control the solution to be alkaline, and preparing a solution containing solid suspended matters, namely a fifth solution;
s5, adding the fourth solution into the fifth solution, stirring, mixing and aging, then washing with deionized water to be neutral, and drying to obtain a precursor with a hydrotalcite structure;
s6, roasting the precursor with the hydrotalcite structure in air atmosphere at 300-500 ℃ for 2-6 hours, so as to prepare the catalyst;
in the steps, the mass ratio of the pseudo-boehmite to the montmorillonite to the dispersing agent to the graphene oxide is 1-1.5:1-1.2:8-10:0.002-0.005.
In the application, the dispersing agent is glycol aqueous solution, and the volume ratio of glycol to water in the glycol aqueous solution is 3:1.
In the application, in S1, the operation parameters of the mechanochemical reactor are that the time is 1.5 h-3 h, and the temperature is 80-100 ℃. Preferably, in the step S1, half of pseudo-boehmite and montmorillonite are dissolved in the full part of dispersing agent, uniformly stirred in a mechanical reactor, reacted, and then the rest half of pseudo-boehmite and montmorillonite are added, and stirred and reacted to obtain the first suspension.
In the application, in S2, the ultrasonic temperature is 60-80 ℃, and the ultrasonic time is 0.2-0.5 h.
In the application, in S3, the ultrasonic temperature is 60-80 ℃ and the ultrasonic time is 1-2 h.
In the application, the alkali liquor used in the step S3 is one of ammonia water, sodium bicarbonate, sodium hydroxide and ammonium carbonate; preferably, the pH of the fourth solution is controlled to 9-11.
In the present application, at least one of nitrate, acetate and basic carbonate is used as the soluble salts of copper and zinc in step S4, and nitrate is preferably used. The alkaline buffer solution in the step S4 is a mixed solution of sodium hydroxide and sodium carbonate; preferably, the pH of the fifth solution is controlled to be 8-10.
In the application, the powder obtained by roasting in the step S6 is formed into a cylinder with the diameter of 3-5 mm by tabletting, and a tablet press with the punch pressure of 70-120 kN is used for tabletting.
In order to more clearly show the technical scheme and the technical effects, the catalyst for catalyzing alcohol dehydrogenation, the preparation method and the application thereof are described in detail in the following by using specific embodiments.
Example 1
The preparation method of the catalyst for catalyzing alcohol dehydrogenation specifically comprises the following steps:
s1, dissolving half of pseudo-boehmite and montmorillonite in a full part of dispersing agent, adding the dispersing agent into a mechanochemical reactor, stirring and reacting, and adding the other half of pseudo-boehmite and montmorillonite for reacting to obtain a first suspension; wherein the mass ratio of the pseudo-boehmite to the montmorillonite to the dispersing agent to the graphene oxide is 1:1:8:0.002; the dispersing agent is glycol aqueous solution, and the volume ratio of glycol to water in the glycol aqueous solution is 3:1, a step of; the operation parameters of the mechanochemical reactor are that the time is 1.5 hours, and the temperature is 80 ℃;
s2, adding 0g of CaO into deionized water, and performing ultrasonic treatment at 60 ℃ for 0.2h to form a second suspension of calcium hydroxide;
s3, dispersing 1.57g of graphene oxide in distilled water by ultrasonic for 1h at 60 ℃, dropwise adding the first suspension and the second suspension, and continuing ultrasonic until the color of the suspensions is uniform to obtain a third suspension; then adding ammonia water for coprecipitation to prepare a solution containing solid suspended matters, and marking the solution as a fourth solution; the pH value of the fourth solution is controlled to be 9.4-9.5;
s4, dissolving 47g of copper nitrate and 3.5g of zinc nitrate in water, and adding a mixed solution of sodium hydroxide and sodium carbonate to control the solution to be alkaline to prepare a solution containing solid suspended matters, namely a fifth solution; the pH value of the fifth solution is controlled to be 8.2-8.3;
s5, adding the fourth solution into the fifth solution, stirring, mixing, aging for 3-4 hours, then flushing with deionized water to be neutral, and drying a filter cake at 100-130 ℃ to obtain a precursor with a hydrotalcite structure;
s6, grinding the precursor with the hydrotalcite structure, roasting for 2 hours at 300 ℃ in an air atmosphere, naturally cooling, adding a small amount of graphite powder, and tabletting to form a cylindrical catalyst with phi of 5 multiplied by 3-4 mm by adopting a single punch tablet press (produced by Guozhong) under the action of a punch with the pressure of 110KN, thereby preparing the catalyst for catalyzing alcohol dehydrogenation. The content of each component in the catalyst is 78.5wt% of carrier, 20wt% of CuO, 1.5wt% of ZnO and 0 of Ca.
Example 2
The difference between this example and example 1 is that the mass ratio of pseudo-boehmite, montmorillonite, dispersant, and graphene oxide is 1.5:1.2:10:0.005.
Example 3
The difference between this example and example 1 is that the mass ratio of pseudo-boehmite, montmorillonite, dispersant, and graphene oxide is 1.2:1.2:9:0.003.
Example 4
This embodiment differs from embodiment 1 in that: the operation parameters of the mechanochemical reactor in the step S are that the time is 3 hours, and the temperature is 100 ℃; in the step S2, the ultrasonic temperature is 80 ℃, and the ultrasonic time is 0.5h; in the step S3, the ultrasonic temperature is 80 ℃ and the ultrasonic time is 2 hours; in the step S6, the roasting temperature is 500 ℃ and the roasting time is 6 hours.
Example 5
This embodiment differs from embodiment 1 in that: the operation parameters of the mechanochemical reactor in the step S1 are that the time is 2 hours, and the temperature is 90 ℃; in the step S2, the ultrasonic temperature is 70 ℃, and the ultrasonic time is 0.35h; in the step S3, the ultrasonic temperature is 70 ℃, and the ultrasonic time is 1.5h; in the step S6, the roasting temperature is 400 ℃ and the roasting time is 4.5 hours.
Example 6
The difference between this example and example 1 is that in the preparation of the catalyst, the alkali solution used in step S3 is sodium bicarbonate, and the pH of the fourth solution is controlled to be 9.6-9.7; the soluble salts of copper and zinc in the step S4 are copper acetate and zinc acetate, and the pH value of the fifth solution is controlled to be 8.6-8.7.
Example 7
The difference between this example and example 1 is that in the preparation of the catalyst, the alkali solution used in step S3 is sodium hydroxide, and the pH of the fourth solution is controlled to be 10.4-10.5; the soluble salts of copper and zinc in the step S4 are basic copper carbonate and basic zinc carbonate, and the pH value of the fifth solution is controlled to be 9.2-9.3.
Example 8
The difference between this example and example 1 is that in the preparation of the catalyst, the alkali solution used in step S3 is ammonium carbonate, and the pH of the fourth solution is controlled to be 10.6-10.7; the soluble salts of copper and zinc in the step S4 are copper nitrate and zinc nitrate, and the pH value of the fifth solution is controlled to be 9.5-9.6.
Example 9
This example differs from example 1 in that in the preparation of the catalyst, 7g of CaO was added in step S2, 70.5g of copper nitrate was added in step S4, and 23.34g of zinc nitrate was added. The content of each component in the obtained catalyst was 57wt% of carrier, 30wt% of CuO, 10wt% of ZnO and 3wt% of Ca.
Example 10
This example differs from example 1 in that in the preparation of the catalyst, 3.5g of CaO was added in step S2, 35g of copper nitrate was added in step S4, and 11.67g of zinc nitrate was added. The content of each component in the obtained catalyst was 67wt% of carrier, 25wt% of CuO, 6wt% of ZnO and 2wt% of Ca.
Example 11
This example differs from example 1 in that in the preparation of the catalyst, 0.5g of CaO was added in step S2. The content of each component in the obtained catalyst was 77wt% of carrier, 21wt% of CuO, 1.65wt% of ZnO and 0.35wt% of Ca.
Example 12
This example differs from example 1 in that in the preparation of the catalyst, 3.5g of CaO was added in step S2. The content of each component in the obtained catalyst was 74wt% of the carrier, 22wt% of CuO, 2.15wt% of ZnO and 1.85wt% of Ca.
Comparative example 1
The catalyst prepared by the preparation method of the application, wherein the carrier is gamma-Al 2 O 3 CuO is an active component, znO is an auxiliary agent, wherein gamma-Al 2 O 3 78.5wt% of CuO 20wt% and 1.5wt% of ZnO.
Comparative example 2
The difference between this example and example 1 is that the mass ratio of pseudo boehmite, montmorillonite, dispersant, graphene oxide is 0.8: 1.2:10:0.005.
Comparative example 3
The difference between this example and example 1 is that the mass ratio of pseudo boehmite, montmorillonite, dispersant, graphene oxide is 1.7: 1:8:0.002.
Comparative example 4
This example differs from example 1 in that pseudo-boehmite was not added during the preparation of the catalyst.
Comparative example 5
This example differs from example 1 in that no montmorillonite was added during the preparation of the catalyst.
Comparative example 6
The present example differs from example 1 in that graphene oxide was not added during the preparation of the catalyst.
Comparative example 7
The difference between this example and example 1 is that in step S1 in the preparation process of the catalyst, all pseudo-boehmite and montmorillonite are dissolved in the whole dispersant, and the mixture is stirred uniformly in a mechanical reactor to react to obtain a first suspension.
The parameters for the catalyst preparation in examples 1-12 are shown in Table 1 below.
Table 1 catalyst preparation parameters in examples 1-12
The parameters of the components of the products prepared in examples 1, 9, 10, 11 and 12 are shown in Table 2.
Table 2, examples 1, 9, 10, 11, 12, parameters of the respective components of the products obtained
| Sample of | Carrier body | CuO | ZnO | Ca |
| Example 1 | 78.5wt％ | 20wt％ | 1.5wt％ | 0 |
| Example 9 | 57wt％ | 30wt％ | 10wt％ | 3wt％ |
| Example 10 | 67wt％ | 25wt％ | 6wt％ | 2wt％ |
| Example 11 | 77wt％ | 21wt％ | 1.65wt％ | 0.35wt％ |
| Example 12 | 74wt％ | 22wt％ | 2.15wt％ | 1.85wt％ |
Application example 1
The catalyst for catalyzing alcohol dehydrogenation prepared in the embodiment 1 of the application is used for alcohol dehydrogenation reaction.
The catalyst for catalyzing alcohol dehydrogenation prepared in the embodiment 1 of the application is firstly reduced by adopting a mixed gas of hydrogen and nitrogen (the hydrogen content is 5 vol%) before being used for feeding in alcohol dehydrogenation reaction, and is reduced at normal pressure, the maximum temperature is 270 ℃, so that the catalyst after hydrogen reduction is obtained.
The ethanol dehydrogenation reaction is carried out in a fixed bed reactor, 2g of the catalyst after hydrogen reduction is filled in the reactor, nitrogen is adopted as accompanying gas under the condition of the reaction temperature of 260 ℃ and normal pressure, the mol ratio of the nitrogen to the ethanol is 8:1, and the Liquid Hourly Space Velocity (LHSV) is 0.8 g.gcat -1 ·h -1 After the reaction was stabilized, the reaction raw materials and the products were analyzed by online chromatography, and the reaction results at 12, 48, 96 and 120 hours after the feeding were respectively tested, so that the experimental results shown in the following table 3 could be obtained; in Table 3, the conversion of the application example 1 is the conversion of ethanol into other substancesThe selectivity of the application example 1 is the selectivity of the target product acetaldehyde product.
Application examples 2 to 20
The catalysts for catalyzing the dehydrogenation of alcohols prepared in examples 1 to 12 and comparative examples 1 to 7 according to the present application were used for the dehydrogenation reaction of 1, 4-butanediol, respectively.
Specifically, the catalyst after hydrogen reduction is obtained by first adopting a mixed gas of hydrogen and nitrogen (the hydrogen content is 5 vol%) to carry out reduction before feeding for the dehydrogenation reaction of 1, 4-butanediol and carrying out normal pressure reduction at the maximum temperature of 260 ℃.
The 1, 4-butanediol dehydrogenation reaction is carried out in a fixed bed reactor, 2g of the catalyst after hydrogen reduction is filled in the reactor, hydrogen is adopted as accompanying gas under the condition that the reaction temperature is 240 ℃ and normal pressure, the molar ratio of the hydrogen to the 1, 4-butanediol is 8:1 so as to adjust the gas phase concentration of the 1, 4-butanediol, and the Liquid Hourly Space Velocity (LHSV) is 2.7 g.gcat based on butanediol -1 ·h -1 After the reaction is stable, the reaction raw materials and products are condensed and then are subjected to offline chromatographic analysis, and the reaction results of 12 hours, 48 hours, 96 hours and 120 hours after feeding are respectively tested, so that the experimental results shown in the following table 3 can be obtained; in Table 3, the conversion of 1, 4-butanediol to other substances was shown in the application examples 2 to 20, and the selectivity of the application examples 2 to 20 was shown to be the selectivity of the target gamma-butyrolactone product.
TABLE 3 Table 3
From the experimental results in table 3, it can be seen that: the experimental data of the example group are higher than the experimental results of the comparative example group, the conversion rate and the selectivity have no obvious change within 12 hours to 120 hours, which shows that the catalyst has good stability, enters a steady state within 48 hours under the condition of 6 times of the conventional production airspeed of the gamma-butyrolactone prepared by 1, 4-butanediol, and the reaction result has no change within 120 hours.
As can be seen from the comparison of the example group with comparative example 1, the composition was superior to conventional gamma-Al 2 O 3 In comparison, adoptThe catalyst carrier of the application has better technical effect. Example groups the technical effect of using the components of the present application and the catalyst support within the defined range is better than that of comparative examples 2 to 7. The catalyst of the present application (low Cu component) has higher 1, 4-butanediol conversion and gamma-butyrolactone selectivity than the Cu-Zn-Al catalysts reported in the prior art by China petrochemical Co., ltd (patent No. CN103044367B, examples 3-6 and comparative example 1). From the comparison of example 1 and examples 11 and 12, it can be seen that the addition of CaO has an accelerating effect on the conversion and selectivity of the catalyst.
Claims (9)
1. A catalyst for preparing gamma-butyrolactone by dehydrogenating 1, 4-butanediol is characterized by comprising active components of CuO, an auxiliary agent of ZnO, ca and a carrier of graphene oxide/gamma-Al 2 O 3 The composition of @ montmorillonite; the active component CuO accounts for 20-30% by weight, the auxiliary agent ZnO accounts for 1.5-10%, the auxiliary agent Ca accounts for 0-3%, and the carrier is graphene oxide/gamma-Al 2 O 3 57-78.5% of @ montmorillonite;
the graphene oxide/gamma-Al 2 O 3 The @ montmorillonite carrier is prepared by taking graphene oxide and pseudo-boehmite as precursor substances.
2. The method for preparing the catalyst for preparing gamma-butyrolactone by dehydrogenating 1, 4-butanediol according to claim 1, comprising the following steps:
s1, dissolving pseudo-boehmite and montmorillonite in a dispersing agent, and then adding the dispersing agent into a mechanochemical reactor to react to obtain a first suspension;
s2, adding CaO into deionized water, and performing ultrasonic treatment to form a second suspension of calcium hydroxide;
s3, ultrasonically dispersing graphene oxide in distilled water, dropwise adding the first suspension and the second suspension, and continuing to ultrasonically until the color of the suspensions is uniform to obtain a third suspension; adding alkali liquor for coprecipitation to prepare a solution containing solid suspended matters, and marking the solution as a fourth solution;
s4, dissolving soluble salts of copper and zinc in water, adding an alkaline buffer solution to control the solution to be alkaline, and preparing a solution containing solid suspended matters, namely a fifth solution;
s5, adding the fourth solution into the fifth solution, stirring, mixing and aging, then washing with deionized water to be neutral, and drying to obtain a precursor with a hydrotalcite structure;
s6, roasting the precursor with the hydrotalcite structure in air atmosphere at 300-500 ℃ for 2-6 hours, so as to prepare the catalyst;
preferably, in the steps, the mass ratio of the pseudo-boehmite to the montmorillonite to the dispersing agent to the graphene oxide is 1-1.5:1-1.2:8-10: 0.002-0.005.
3. The method for preparing a catalyst for preparing gamma-butyrolactone by dehydrogenating 1, 4-butanediol according to claim 2, wherein the dispersant used in the step S1 is an aqueous ethylene glycol solution;
preferably, the volume ratio of glycol to water in the glycol aqueous solution is 3:1.
4. The method for preparing a catalyst for preparing gamma-butyrolactone by dehydrogenating 1, 4-butanediol according to claim 2, wherein the alkali liquor used in the step S3 is one of ammonia water, sodium bicarbonate, sodium hydroxide and ammonium carbonate;
preferably, the pH value of the fourth solution is controlled to be 9-11.
5. The method for preparing a catalyst for preparing gamma-butyrolactone by dehydrogenating 1, 4-butanediol according to claim 2, wherein the soluble salts of copper and zinc in step S4 are at least one of nitrate, acetate and basic carbonate, preferably nitrate.
6. The method for preparing a catalyst for preparing gamma-butyrolactone by dehydrogenating 1, 4-butanediol according to claim 2, wherein the alkaline buffer solution in the step S4 is a mixed solution of sodium hydroxide and sodium carbonate;
preferably, the pH value of the fifth solution is controlled to be 8-10.
7. The method for preparing a catalyst for the production of gamma-butyrolactone by dehydrogenation of 1, 4-butanediol according to claim 2, wherein the powder obtained by calcination in the step S6 is tabletted into a cylinder having a diameter of 3 to 5mm, and the tableting is performed using a tablet press having a punch pressure of 70 to 120 kN.
8. Use of a catalyst according to claim 1 or a catalyst obtainable by a process according to any one of claims 2 to 5, in a selective dehydrogenation of an alcohol.
9. The use of the catalyst according to claim 8, wherein the alcohol is one of ethanol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 2-propanediol, cyclohexanol, and isopropanol; in the selective dehydrogenation reaction of the alcohols, the reaction temperature is 210-280 ℃, the reaction pressure is 0.1-2.0 Bar, and the reaction pressure is gauge pressure.
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