CN115138363A - Catalyst for preparing benzofuran-2 (3H) -ketone by catalytic dehydrogenation and preparation method thereof - Google Patents
Catalyst for preparing benzofuran-2 (3H) -ketone by catalytic dehydrogenation and preparation method thereof Download PDFInfo
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- CN115138363A CN115138363A CN202110338460.5A CN202110338460A CN115138363A CN 115138363 A CN115138363 A CN 115138363A CN 202110338460 A CN202110338460 A CN 202110338460A CN 115138363 A CN115138363 A CN 115138363A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 6
- -1 7,7a-dihydro-2 (6H) -benzofuran ketone Chemical class 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 11
- 239000012018 catalyst precursor Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000001308 synthesis method Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 4
- 239000007789 gas Substances 0.000 claims 4
- 229910052786 argon Inorganic materials 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 2
- 241000219793 Trifolium Species 0.000 claims 1
- 230000004913 activation Effects 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 2
- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical compound C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 description 11
- LREIXJCOBQFJME-UHFFFAOYSA-N O=C1OC(CCC=C2)C2=C1 Chemical compound O=C1OC(CCC=C2)C2=C1 LREIXJCOBQFJME-UHFFFAOYSA-N 0.000 description 11
- 238000011068 loading method Methods 0.000 description 11
- CCVYRRGZDBSHFU-UHFFFAOYSA-N (2-hydroxyphenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC=C1O CCVYRRGZDBSHFU-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000002791 soaking Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 3
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- DWXSYDKEWORWBT-UHFFFAOYSA-N 2-(2-bromophenyl)acetic acid Chemical group OC(=O)CC1=CC=CC=C1Br DWXSYDKEWORWBT-UHFFFAOYSA-N 0.000 description 2
- IUJAAIZKRJJZGQ-UHFFFAOYSA-N 2-(2-chlorophenyl)acetic acid Chemical group OC(=O)CC1=CC=CC=C1Cl IUJAAIZKRJJZGQ-UHFFFAOYSA-N 0.000 description 2
- IUHXGZHKSYYDIL-UHFFFAOYSA-N 2-(2-iodophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC=C1I IUHXGZHKSYYDIL-UHFFFAOYSA-N 0.000 description 2
- JECYUBVRTQDVAT-UHFFFAOYSA-N 2-acetylphenol Chemical compound CC(=O)C1=CC=CC=C1O JECYUBVRTQDVAT-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 1
- GOCCREQJUBABAL-UHFFFAOYSA-N 2,2-dihydroxyacetic acid Chemical compound OC(O)C(O)=O GOCCREQJUBABAL-UHFFFAOYSA-N 0.000 description 1
- RNHTVJLYWNCKPE-UHFFFAOYSA-N 2,2-dihydroxyacetic acid oxaldehydic acid Chemical compound C(=O)C(=O)O.C(C(=O)O)(O)O RNHTVJLYWNCKPE-UHFFFAOYSA-N 0.000 description 1
- DGCOXJUMRBMOSM-UHFFFAOYSA-N 2-(2-oxocyclohexylidene)acetic acid Chemical class OC(=O)C=C1CCCCC1=O DGCOXJUMRBMOSM-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 1
- 239000005730 Azoxystrobin Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 1
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 1
- 102100021392 Cationic amino acid transporter 4 Human genes 0.000 description 1
- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 1
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 1
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 1
- LYIUZCUOSFQWGI-UHFFFAOYSA-N O1C=CC2=C1C=CC=C2.O2C(CC1=C2C=CC=C1)=O Chemical compound O1C=CC2=C1C=CC=C2.O2C(CC1=C2C=CC=C1)=O LYIUZCUOSFQWGI-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 108091006231 SLC7A2 Proteins 0.000 description 1
- 108091006230 SLC7A3 Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- WFDXOXNFNRHQEC-GHRIWEEISA-N azoxystrobin Chemical compound CO\C=C(\C(=O)OC)C1=CC=CC=C1OC1=CC(OC=2C(=CC=CC=2)C#N)=NC=N1 WFDXOXNFNRHQEC-GHRIWEEISA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 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
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000000457 gamma-lactone group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- 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
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans 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 carbon atoms of the hetero ring
- C07D307/83—Oxygen atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for preparing benzofuran-2 (3H) -ketone by catalytic dehydrogenation and a preparation method thereof, and mainly solves the problem of poor stability of the catalyst in the prior art. The invention relates to a catalyst for preparing benzofuran-2 (3H) -ketone by catalytic dehydrogenation of 7,7a-dihydro-2 (6H) -benzofuran ketone, which comprises a carrier, an active component and a cocatalyst; the active component is metal Pd, and the Pd content in the catalyst is 0.2-1.0 wt%; the cocatalyst is selected from at least one of alkali metal or alkaline earth metal, and the content of the cocatalyst is 0.1-0.5 wt%; the carrier is the technology of rare earth element La or Ce modified alumina, the technical problem is well solved, and the method can be used for the reaction for producing benzofuran-2 (3H) -ketone.
Description
Technical Field
The invention belongs to the technical field of fine chemical production, and particularly relates to a catalyst for preparing benzofuran-2 (3H) -one by catalytic dehydrogenation of 7,7a-dihydro-2 (6H) -benzofuranone and a preparation method thereof.
Background
Benzofuran-2 (3H) -one, 2-Coumaranone, another name benzofuran-2-Coumaranone, formula C 8 H 6 O 2 The pure product is light yellow or brown yellow powder, the melting point is 49-51 ℃, the boiling point is 248-250 ℃, and the relative density is 1.22. The application is as follows: the benzofuran-2 (3H) -one has good physiological activity, can be used for synthesizing medicines, pesticides and novel antioxidants, is also a key intermediate for synthesizing bactericide azoxystrobin, and has the characteristics of high efficiency, low toxicity, broad spectrum and the like.
At present, the synthesis method is mainly adopted at home and abroad and comprises the following steps: (1) Taking o-hydroxyphenylacetic acid as a raw material and p-toluenesulfonic acid as a catalyst, and dehydrating to obtain benzofuran-2 (3H) -one (world patent WO 92/08703); (2) O-chloro, o-bromo or o-iodo phenylacetic acid is used as a raw material, and is jected to high temperature, high pressure and strong alkali reaction to be acidized to form o-hydroxyphenylacetic acid, and then benzofuran-2 (3H) -one is obtained under the microwave-enhanced condition (Chinese patent CN 201210393538.4); (3) Taking o-hydroxyacetophenone as a raw material, obtaining thioacetamide under the action of morphiline, hydrolyzing to obtain o-hydroxyphenylacetic acid, and then performing intramolecular esterification under the catalysis of toluenesulfonic acid to obtain benzofuran-2 (3H) -one (Chinese patent CN 201911340181.1). In the methods, the reaction process adopts strong corrosive liquid acid, so that the equipment investment is large, the acid dissolved in the product needs to be treated by a large amount of water, and the environment is greatly polluted; in addition, the traditional synthesis method takes o-chlorophenylacetic acid, o-bromophenylacetic acid or o-iodophenylacetic acid as starting raw materials, and the o-hydroxyphenylacetic acid is prepared by high-temperature high-pressure reaction, acidification and solvent extraction, then a dehydration catalyst is added, and the benzofuran-2 (3H) -ketone is obtained by high-temperature treatment and recrystallization. The preparation of o-hydroxyphenylacetic acid has long route, harsh reaction conditions and low yield, and increases the production cost.
Taking dihydroxyacetic acid (glyoxylic acid) and cyclohexanone as raw materials, preparing 7,7a-dihydro-2 (6H) -benzofuranone through esterification and condensation, and then obtaining the benzofuranone-2 (3H) -ketone through catalytic dehydrogenation. The raw materials of the route are cheap and easy to obtain, the operation is simple, and the method has practical application value. Since the condensation reaction is easier to proceed andeasy to control, catalytic dehydrogenation becomes the key of the process. Chinese patent CN 9510710.X discloses a method for preparing benzofuran-2 (3H) -ketone from glyoxylic acid and cyclohexanone. First, glyoxylic acid and cyclohexanone are reacted to form a mixture of (2-oxo-cyclohexylidene) acetic acids (including different stereoisomers and gamma-lactone forms), followed by dehydrogenation to yield benzofuran-2 (3H) -ones. Chinese patent CN 97114606.3 discloses a process for the production of pure 2-oxocyclohexylidene acetic acid enol lactone compound (7,7a-dihydro-2 (6H) -benzofuranone) in high yield from dihydroxyacetic acid and cyclohexanone in pure acetic acid medium, followed by Pd/Al at 250 deg.C 2 O 3 A method for synthesizing benzofuran-2 (3H) -ketone under the action of a dehydrogenation catalyst has the defects of poor catalyst stability, easy inactivation and the like. How to improve the stability of the catalyst is an important technical problem to be solved.
Disclosure of Invention
The technical problem to be solved by the invention is the problem of catalyst stability in the prior art, and the catalyst for catalytic dehydrogenation is provided, is used for the reaction of preparing benzofuran-2 (3H) -ketone from 7,7a-dihydro-2 (6H) -benzofuranone, and has the characteristic of high stability.
The second technical problem to be solved by the present invention is a method for preparing a catalyst corresponding to the first technical problem.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a catalyst for preparing benzofuran-2 (3H) -ketone by catalytic dehydrogenation comprises a carrier, an active component and a cocatalyst; the active component is metal Pd, and the Pd content in the catalyst is 0.2-1.0 wt%; the cocatalyst is selected from at least one of alkali metal and alkaline earth metal, and the content of the cocatalyst is 0.1-0.5 wt% calculated by metal elements; the carrier is rare earth element La or Ce modified alumina, and the La or Ce content is 1-20 wt%.
In the above technical scheme, the alumina is spherical, cylindrical or clover-shaped.
In the technical scheme, the specific surface area of the alumina is 50-300 m 2 The pore volume is 0.5-2.0 ml/g, and the pore diameter is 3-50 nm.
In the technical scheme, compared with the common alumina, the La or Ce rare earth oxide coated on the surface of the alumina carrier can obviously improve the stability of the catalyst.
In the technical scheme, the cocatalyst contains alkali metal or alkaline earth metal, and has a promoting effect on the stability of the catalyst.
In order to solve the second technical problem, the catalyst preparation method of the invention comprises the following steps:
(1) Vacuumizing the alumina carrier at 80-120 ℃ for 1-4 h, and then cooling to room temperature;
(2) Preparing soluble La or Ce salt into solution, putting the alumina in the step (1) into the La or Ce salt water solution for dipping for 2-4 hours, drying, roasting for 2-10 hours at 800-1000 ℃, and cooling to room temperature to obtain a catalyst precursor I;
(3) Dipping the aqueous solution of soluble alkali metal or alkaline earth metal salt in the catalyst precursor I for 2-4 hours, drying, and roasting at 300-500 ℃ for 2-10 hours to obtain a catalyst precursor II;
(4) And fully mixing the soluble Pd salt aqueous solution with the catalyst precursor II, drying, and roasting at 300-500 ℃ for 2-10 hours to obtain the catalyst.
In the above technical scheme, the rare earth element La or Ce compound is selected from one of nitrate, acetate or chloride.
In the above technical solution, the alkali metal is selected from Li, na and K or the alkaline earth metal is selected from one of Mg, ca and Ba.
In the above technical solution, the Pd-containing compound is selected from one of palladium nitrate, palladium acetate, chloropalladic acid and salts thereof.
In the prior art, the single metal Pd is loaded on alumina for dehydrogenation reaction, so that high catalytic activity can be obtained at the initial stage of the reaction, but the catalyst is easy to deposit carbon and inactivate, and the activity is rapidly reduced; the technical key point of the invention is that the provided catalyst carrier is alumina coated with rare earth oxide on the surface, and one of alkali metal or alkaline earth metal is added, so that the inactivation of the catalyst can be obviously inhibited, and the catalyst can keep higher reaction activity and selectivity. The catalyst of the invention has better technical effect in the reaction of preparing benzofuran-2 (3H) -ketone by dehydrogenating 7,7a-dihydro-2 (6H) -benzofuranone.
The invention mainly solves the problem of poor catalyst stability in the prior art. The carrier is the technology of rare earth element La or Ce modified alumina, the technical problem is well solved, and the method can be used for the reaction for producing benzofuran-2 (3H) -ketone.
Drawings
FIG. 1 Experimental results of the conversion rate of example 1, comparative example 1 and comparative example 2 in the reaction for 20 hours;
FIG. 2 Experimental results on selectivity of example 1, comparative example 1 and comparative example 2 in the case where the reaction was carried out for 20 hours.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof.
Example 1
The raw material of the catalyst carrier is spherical alumina with the specific surface area of 185m 2 Per g, pore volume of 0.78ml/g, pore diameter of 12.5nm 2 O content less than 0.1wt%, fe 2 O 3 The mass content is less than 0.02 percent. Before use, the mixture is vacuumized at 100 ℃ for 2 hours and then cooled to room temperature, and the temperature is recorded as A.
0.317g of La (NO) was weighed 3 ) 3 ·6H 2 And adding 10ml of deionized water into the O to fully dissolve the O, putting 10g of the A into the solution for soaking, naturally drying in the shade, drying at 120 ℃ for 12h, and roasting at 800 ℃ for 6h to obtain the B.
Weighing 0.019g of KCl, adding 10ml of deionized water, fully dissolving, putting the B into the solution, soaking, naturally drying in the shade, drying at 120 ℃ for 12h, and roasting at 400 ℃ for 4h to obtain the C.
Weighing 0.254g of Pd 2wt% to obtain 2 PdCl 4 Adding 10ml deionized water into the aqueous solution to fully dissolveSoaking C in the solution, naturally drying in the shade, drying at 120 deg.C for 12h, and calcining at 400 deg.C for 4h to obtain a final product with a mass content of 0.5% Pd-0.1% 2 O 3 The catalyst, catalyst number CAT-1. The catalytic activity and selectivity of the catalyst for dehydrogenation reaction can be changed with time as shown in figure 1 and figure 2.
Example 2 Pd/Al supported on Pd 0.5wt%, K0.2 wt% and La 5.0wt% was prepared in the same manner as in example 1 2 O 3 The catalyst, catalyst number CAT-2.
Example 3 Pd/Al supported on Pd 0.5wt%, K0.3 wt% and La 10.0wt% was prepared in the same manner as in example 1 2 O 3 The catalyst, catalyst number CAT-3.
Example 4 Pd/Al supported at 0.5wt%, K supported at 0.4wt% and La supported at 15.0wt% was prepared in the same manner as in example 1 2 O 3 The catalyst, catalyst number CAT-4.
Example 5 Pd/Al supported on Pd 0.5wt%, K0.5 wt% and La 20.0wt% was prepared in the same manner as in example 1 2 O 3 The catalyst, catalyst number CAT-5.
Example 6
With gamma-Al 2 O 3 As a carrier, the carrier is vacuumized for 2 hours at 100 ℃ and then cooled to room temperature, and the carrier is marked as A. Weighing 1.641g Ce (NO) 3 ) 3 ·6H 2 And adding 10ml of deionized water into the O to be fully dissolved, putting 10g of the A into the solution to be soaked, naturally drying in the shade, drying at 120 ℃ for 12h, and roasting at 800 ℃ for 6h to obtain the B.
0.089g MgCl was weighed 2 ·6H 2 And adding 10ml of deionized water into the O for full dissolution, soaking the B in the solution, naturally drying in the shade, drying at 120 ℃ for 12h, and roasting at 400 ℃ for 4h to obtain the C.
Weighing 0.265g of Pd 2wt% and 2 PdCl 4 adding 10ml deionized water into the aqueous solution, dissolving, soaking C in the solution, naturally drying in the shade, drying at 120 deg.C for 12h, and calcining at 400 deg.C for 4h to obtain the final product with a content of 0.5% Pd-0.1% Ce/Al 2 O 3 The catalyst, catalyst number CAT-6.
Example 7 in the same manner as in example 6, pd/Al was prepared with a Pd loading of 0.5wt%, a Mg loading of 0.5wt%, and a Ce loading of 5.0wt% 2 O 3 The catalyst, catalyst number CAT-7. Example 8 in the same manner as in example 6, pd/Al supported at 0.2wt% in Pd, 0.1wt% in Ca and 10.0wt% in Ce was prepared using calcium chloride in place of magnesium chloride hexahydrate 2 O 3 The catalyst, catalyst number CAT-8.
Example 9 in the same manner as in example 6, by using barium chloride in place of magnesium chloride hexahydrate, pd/Al was prepared with a Pd loading of 1.0wt%, a Ba loading of 0.5wt%, and a Ce loading of 15.0wt% 2 O 3 The catalyst, catalyst number CAT-9.
Example 10 in the same manner as in example 6, pd/Al having a Pd loading of 0.5wt%, a K loading of 0.1wt% and a Ce loading of 10.0wt% was prepared by using potassium chloride in place of magnesium chloride hexahydrate 2 O 3 The catalyst, catalyst number CAT-10.
Example 11
The catalysts obtained in examples 1 to 10 were evaluated in a trickle bed reactor for their performance in the catalytic dehydrogenation of 7,7a-dihydro-2 (6H) -benzofuranone to benzofuran-2 (3H) -one.
The evaluation method comprises the following steps: the reaction tube is a 316L stainless steel tube with the inner diameter of 9mm, the loading amount of the catalyst is 4ml, and a proper amount of inert quartz sand is filled in the upper part and the lower part of a catalyst bed layer of the reactor. And (3) catalyst reduction: normal pressure, 250 ℃, pure hydrogen and space velocity of 1000h -1 Reducing for 4 hours; then the temperature is reduced to 160 ℃, the atmospheric pressure is kept, and the hourly space velocity of 7,7a-dihydro-2 (6H) -benzofuranone liquid is 2.0H -1 ,N 2 Airspeed of 2000h -1 7,7a-dihydro-2 (6H) -benzofuranone was pumped into the reactor for dehydrogenation.
The product was analyzed by Agilent 7890 gas chromatography using an HP-5 capillary column, FID detector. The conversion rate of the raw materials and the selectivity of the product were calculated according to the area normalization method, and the experimental results are shown in table 1.
Comparative example 1
With gamma-Al 2 O 3 As a carrier, the carrier is vacuumized for 2 hours at 100 ℃, and then cooled to room temperature, and the carrier is marked as A.
Weighing 0.251g of Pd 2wt% to obtain 2 PdCl 4 Adding 10ml deionized water into the water solution, dissolving, soaking 10g A in the solution, naturally drying in the shade, drying at 120 deg.C for 12h, and calcining at 400 deg.C for 4h to obtain the final product with a content of 0.5% Pd/Al 2 O 3 A catalyst. The reaction temperature is 160 ℃, the reaction pressure is normal, and the hourly space velocity of the raw material of 7,7a-dihydro-2 (6H) -benzofuranone liquid is 2.0H -1 ,N 2 Airspeed 2500h -1 The process is carried out as follows. The catalytic activity and selectivity of the catalyst for dehydrogenation reaction can be changed with time as shown in figure 1 and figure 2.
TABLE 1 dehydrogenation performance of different catalysts
It can be seen from table 1 that the conversion of 7,7a-dihydro-2 (6H) -benzofuranone, or the selectivity of benzofuran-2 (3H) -one, or both the conversion of 7,7a-dihydro-2 (6H) -benzofuranone and the selectivity of benzofuran-2 (3H) -one can be improved by using the alumina coated with the rare earth oxide as a carrier and then loading the carrier with an auxiliary agent and the active metal Pd.
Fig. 1 and 2 show the results of evaluating the reactivity and selectivity of the catalysts of example 1 and comparative example 1 with time, respectively. The reaction is carried out at the temperature of 160 ℃, the normal pressure and the liquid hourly space velocity of 2.0h -1 ,N 2 Airspeed 2500h -1 Under the condition of the reaction. It can be seen that the catalyst of example 1 maintains higher reactivity, selectivity and longer stability; the catalyst of comparative example 1, on the other hand, rapidly decreased in activity during the dehydrogenation reaction, indicating that the catalyst surface was easily coked up, resulting in rapid deactivation of the catalyst.
The invention uses rare earth oxide to modify the surface of the alumina carrier, and adds a proper amount of alkali metal or alkaline earth metal, which can improve the stability of the dehydrogenation catalyst.
Claims (10)
1. A catalyst, which is characterized in that the catalyst comprises a carrier, an active component and a cocatalyst; the active component is metal Pd, and the Pd content in the catalyst is 0.1-2.0 wt% (preferably 0.2-1.0 wt%); the cocatalyst is selected from at least one or more than two of alkali metal and alkaline earth metal, and the content of the cocatalyst in the catalyst is 0.05-1.0 wt% (preferably 0.1-0.5 wt%) calculated by metal elements; the carrier is alumina modified by La and/or Ce in rare earth elements, and the La and/or Ce content in the carrier is 0.5-30 wt% (preferably 1-20 wt%).
2. The catalyst of claim 1, wherein the alumina is in the shape of one or more of a sphere, a cylinder, or a clover.
3. The catalyst according to claim 1, wherein the alumina has a pore volume of 0.5 to 2.0ml/g and a specific surface area of 50 to 300m 2 The pore diameter is 3-50 nm.
4. A method for preparing the catalyst of any of claims 1-3, comprising the steps of:
(1) Vacuumizing the alumina carrier at 80-120 ℃ for 1-4 h, and then cooling to room temperature;
(2) Preparing soluble La and/or Ce salt into solution, putting the alumina obtained in the step (1) into La and/or Ce salt aqueous solution for dipping for 2-4 hours, drying, roasting for 2-10 hours at 800-1000 ℃, and cooling to room temperature to obtain a catalyst precursor I;
(3) Dipping the catalyst precursor I by adopting one or more than two aqueous solutions of soluble alkali metal or alkaline earth metal salts for 2 to 4 hours, drying, and roasting at the temperature of between 300 and 500 ℃ for 2 to 10 hours to obtain a catalyst precursor II;
(4) And fully mixing the soluble Pd salt aqueous solution with the catalyst precursor II, drying, and roasting at 300-500 ℃ for 2-10 hours to obtain the catalyst.
5. The method according to claim 4, wherein the rare earth element La and/or Ce compound is selected from one or more of nitrate, acetate and chloride thereof.
6. A production method according to claim 4, wherein the promoter is one or more of an alkali metal selected from Li, na and K or an alkaline earth metal selected from Mg, ca and Ba.
7. The method according to claim 4, wherein the Pd-containing compound is selected from the group consisting of palladium nitrate, palladium acetate, chloropalladic acid, and salts thereof.
8. A synthesis method for preparing benzofuran-2 (3H) -ketone by catalytic dehydrogenation, which takes 7,7a-dihydro-2 (6H) -benzofuran ketone as a raw material, and obtains the benzofuran-2 (3H) -ketone by reacting in the presence of the catalyst of any one of claims 1 to 3 or the catalyst prepared by the preparation method of any one of claims 4 to 6.
9. The synthesis method according to claim 8, wherein the reaction temperature is 100-200 ℃ and the hourly space velocity of the raw material liquid is 0.5-5.0 h -1 (preferably 1.0 to 4.0 hours) -1 ) The space velocity of inert atmosphere gas (the inert atmosphere gas is one or two of nitrogen or argon) is 1000 to 5000h -1 (preferably 2000 to 4000 h) -1 ) And the dehydrogenation reaction is carried out under the condition that the reaction pressure is normal pressure.
10. The method as claimed in any one of claims 8 to 9, wherein the catalyst is activated before use, and the activation is reduced in an atmosphere containing hydrogen, wherein the hydrogen content is more than or equal to 10% by volume (in the atmosphere containing other atmosphere gas than hydrogen, one or two of nitrogen or argon), the reduction temperature is 150-300 ℃ (preferably 180-260 ℃), and the gas space velocity is 500-2000 h -1 (preferably 800 to 1500 h) -1 ) The reduction time is 2 to 10 hours (preferably 4 to 8 hours).
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