CN106927996A - A kind of method of producing cyclohexane by adding hydrogen in benzene - Google Patents
A kind of method of producing cyclohexane by adding hydrogen in benzene Download PDFInfo
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- CN106927996A CN106927996A CN201710158402.8A CN201710158402A CN106927996A CN 106927996 A CN106927996 A CN 106927996A CN 201710158402 A CN201710158402 A CN 201710158402A CN 106927996 A CN106927996 A CN 106927996A
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- Prior art keywords
- zinc oxide
- catalyst
- alumina
- zinc
- benzene
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 201
- 238000000034 method Methods 0.000 title claims abstract description 59
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 42
- 239000001257 hydrogen Substances 0.000 title claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 78
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910003445 palladium oxide Inorganic materials 0.000 claims abstract description 11
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910003446 platinum oxide Inorganic materials 0.000 claims abstract description 11
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 78
- 239000011701 zinc Substances 0.000 claims description 72
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 70
- 229910052725 zinc Inorganic materials 0.000 claims description 70
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 55
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 43
- 239000011591 potassium Substances 0.000 claims description 43
- 229910052700 potassium Inorganic materials 0.000 claims description 43
- 239000011787 zinc oxide Substances 0.000 claims description 39
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 38
- 239000011777 magnesium Substances 0.000 claims description 38
- 229910052749 magnesium Inorganic materials 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 35
- 230000008569 process Effects 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 33
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 30
- 229910001676 gahnite Inorganic materials 0.000 claims description 30
- 229910052782 aluminium Inorganic materials 0.000 claims description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000004411 aluminium Substances 0.000 claims description 23
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 20
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 230000004913 activation Effects 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 15
- 239000000395 magnesium oxide Substances 0.000 claims description 15
- 239000011574 phosphorus Substances 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 13
- 239000002671 adjuvant Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 238000004448 titration Methods 0.000 claims description 11
- 238000002803 maceration Methods 0.000 claims description 9
- 239000004323 potassium nitrate Substances 0.000 claims description 9
- 235000010333 potassium nitrate Nutrition 0.000 claims description 9
- 238000002474 experimental method Methods 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 241000219782 Sesbania Species 0.000 claims description 6
- 229910001593 boehmite Inorganic materials 0.000 claims description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 150000003751 zinc Chemical class 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000009938 salting Methods 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims 1
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000004584 polyacrylic acid Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- JODIJOMWCAXJJX-UHFFFAOYSA-N [O-2].[Al+3].[O-2].[Zn+2] Chemical compound [O-2].[Al+3].[O-2].[Zn+2] JODIJOMWCAXJJX-UHFFFAOYSA-N 0.000 abstract 1
- 230000007306 turnover Effects 0.000 abstract 1
- 229910052573 porcelain Inorganic materials 0.000 description 24
- 238000004458 analytical method Methods 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 11
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 238000012856 packing Methods 0.000 description 6
- -1 palladium nitrates Chemical class 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002872 contrast media Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 2
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QDWGRSGGOUPRJF-UHFFFAOYSA-N O.O.[O--].[Zn++] Chemical compound O.O.[O--].[Zn++] QDWGRSGGOUPRJF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- B01J35/615—
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a kind of method of producing cyclohexane by adding hydrogen in benzene, the composition of catalyst is with oxidation material gauge, including following component：The 99wt% of complex carrier 80 containing zinc oxide aluminum oxide, the 5wt% of active component platinum oxide 0.1, the 5wt% of active component palladium oxide 0.1；Catalyst benzene hydrogenation activity is high, and noble metal active component turnover rate is low, and service cycle is long.
Description
Technical field
The present invention relates to a kind of method of producing cyclohexane by adding hydrogen in benzene, more specifically using one kind containing zinc oxide-oxygen
It is the benzene hydrogenating catalyst of carrier to change aluminium composite material, for producing cyclohexane by adding hydrogen in benzene reaction.
Background technology
It is hexamethylene to produce one of primary raw material of caprolactam, except fractionation and methyl cyclopentane isomery system in raw gasoline
Obtain outer, mainly standby by prepared from benzene and hydrogen, accounting about 90% or so.Because caprolactam purposes is more and more wider, demand is continuously increased,
The production of its primary raw material hexamethylene is increasingly important.
The suspension bed that the production technology of preparing cyclohexane by hydrogenating benzene mainly has the fixed bed of gas-solid phase, gas-liquid-solid three-phase reacts
System, fixed bed gas-solid phase reaction system is widely used, mainly applicable nickel catalyst and Pt series catalysts.Domestic benzene hydrogenation life
Nickel catalyst, platinum group catalyst being used product device, nickel catalyst is domestic main production process, and platinum group catalyst is in state more
Outer application is more.Because Pt systems benzene hydrogenating catalyst has many advantages compared with nickel catalyst：Sulfur tolerance is good, after poisoning easily again
Raw, heat resistance is good, and industrial operation temperature is up to 200-400 DEG C, and liquid benzene air speed is bigger, industrial application long lifespan, thus application
There is greater advantage in large-scale caprolactam factory producing cyclohexane by benzene hydrogenation system.
Nickel catalyst is widely used, but the industrial applications of platinum group catalyst are less, therefore the present invention is mainly to provide
A kind of method of platinum group catalyst in producing cyclohexane by adding hydrogen in benzene.
The content of the invention
The invention provides a kind of method of producing cyclohexane by adding hydrogen in benzene, for refinery's benzene hydrogenation, specifically include as
Lower step：
Platinum palladium-based catalyst is seated in fixed bed reactors, catalyst activation treatment is carried out after airtight experiment is qualified,
Activation starts into benzene raw materials after terminating, and benzene hydrogenation is carried out under reaction process condition, and reactor product carries out benzene content analysis.
Catalyst of the present invention is that the platinum palladium base noble metal being carried on the complex carrier containing zinc oxide-alumina is urged
Agent.Composition is with oxidation material gauge, the complex carrier 80-99wt% containing zinc oxide-alumina, active component platinum oxide 0.1-
5wt%, active component palladium oxide 0.1-5wt%；
The preparation method of described catalyst, comprises the following steps：
The soluble-salt of platiniferous palladium is made into maceration extract, complex carrier of the dipping containing zinc oxide-alumina is dried, roasting
Obtain benzene hydrogenating catalyst；
The described complex carrier containing zinc oxide-alumina, including the zinc oxide containing gahnite, aluminum oxide, and add
Enter phosphorus, potassium and magnesium as adjuvant component, the composition of complex carrier is with oxidation material gauge：Zinc oxide content containing gahnite
It is 5.0-40.0wt%, alumina content is 60.0-95.0wt%, and the content of adjuvant component phosphorus, potassium and magnesium accounts for carrier quality
Percentage composition is respectively P2O50.2-1.2wt%, K2O 0.2-2.5wt%, MgO 2.0-5.5wt%, complex carrier specific surface
Product 200-300m2/g。
The described complex carrier containing zinc oxide-alumina, the method for being prepared by the following procedure is obtained：
Soluble salt solutions and zinc-containing solution containing aluminium are alternately titrated by non-constant pH, is prepared containing gahnite
Zinc oxide stratified material；Zinc oxide and boehmite containing gahnite are well mixed, sesbania powder, nitric acid is added
The acid solution containing Sodium Polyacrylate after acidification, and phosphoric acid, potassium nitrate and magnesium nitrate the aqueous solution, kneading, after shaping,
Dried process, calcination process is obtained containing zinc oxide-alumina composite carrier.
Fixed bed reactors of the present invention, are fixed bed adiabatic reactor or fixed bed isothermal reactor, preferably solid
Fixed bed adiabatic reactor.
Described benzene hydrogenation, its process conditions is：180-280 DEG C of reaction temperature, reaction pressure 1.0-5.0MPa,
Hydrogen/oil volume compares 300-700:1, volume space velocity 1.0-6.0h-1；
210-230 DEG C of preferable reaction temperature, reaction pressure 2.0-3.5MPa, hydrogen/oil volume compares 450-650:1, volume is empty
Fast 2.0-4.0h-1。
The composition of preferred catalyst is with oxidation material gauge, including following component：The complex carrier of zinc oxide-alumina
96-99.4wt%, active component platinum oxide 0.3-2.0wt%, active component palladium oxide 0.3-2.0wt%；
The described complex carrier containing zinc oxide-alumina, with oxidation material gauge：Zinc oxide containing gahnite contains
It is 10.0-35.0wt% to measure, and alumina content is 65.0-90.0wt%, and the content of adjuvant component phosphorus, potassium and magnesium accounts for carrier quality
Percentage composition be respectively P2O50.4-1.0wt%, K2O 0.2-2.5wt%, MgO 2.5-4.5wt%, complex carrier compare table
Area 200-300m2/g。
Drying of the present invention, roasting obtains catalyst, is dried 6 hours preferably at 120 DEG C, is roasted at 400-600 DEG C
Burn 6-8 hours.
The described zinc oxide stratified material prepared containing gahnite, is preferably prepared by the following preparation method：Will
Soluble Zn salting liquid is divided into 2-4 parts, under the conditions of 40-80 DEG C, and sodium metaaluminate and sodium carbonate are added in a zinc solution
Mixed solution containing aluminium, stops that mixed solution containing aluminium is added dropwise when pH value reaches 8.5-9.5；Be further continued for be added dropwise another zinc salt it is molten
Liquid；After zinc solution is dripped, continue that mixed solution containing aluminium is added dropwise, stop being added dropwise containing aluminium mixing when pH value reaches 8.5-9.5
Solution；To contain aluminium mixed solution according to the above method and replace titration with zinc solution, until zinc solution whole completion of dropping, finally
Mixed solution containing aluminium is once added dropwise, when pH value reaches 8.5-9.5, the alternating titration process of non-constant pH value terminates, control drop
Determine process to be completed in 1-6h；After 80-95 DEG C of aging 2-8h, cooling washing dries 4-10h to neutrality at 80-140 DEG C,
450-550 DEG C of roasting 4-10h, obtains the dispersed zinc oxide stratified material containing gahnite.
The soluble zinc salt is zinc nitrate or zinc chloride.
The acid solution containing Sodium Polyacrylate after described nitric acid acidification, is preferably prepared by the following preparation method：
Deionized water is heated to 30-90 DEG C, then nitric acid is dissolved into deionized water, add Sodium Polyacrylate, and dissolved
Entirely, the acid solution containing Sodium Polyacrylate is obtained.The addition of described Sodium Polyacrylate is preferably the 0.6- of boehmite
12.0wt%.The Sodium Polyacrylate of acidified treatment, its is uniformly dispersed more preferably, and zinc oxide, alumina powder mixing are more
Uniformly.
The addition of the sesbania powder is preferably the 0.2-7.0wt% of boehmite.
Described dried process, calcination process, preferably 110-150 DEG C dried process 4-8 hours, at 550 DEG C -700 DEG C roast
Burn treatment 4.5-8 hours.
The complex carrier containing zinc oxide-alumina obtained using preparation method of the present invention, can also using potassium and
Magnesium is modified to the complex carrier surface containing zinc oxide-alumina, and the concentration of potassium and magnesium is unsuitable too high, preferably configuration concentration
Carrier surface is sprayed less than the potassium nitrate and magnesium nitrate aqueous solution when preparing complex carrier, carrier is preferably carried out as follows
Surface is modified：Aqueous solution spray complex carrier containing zinc oxide-alumina of the configuration containing potassium nitrate and magnesium nitrate, through drying, roasting
Burning obtains used additives potassium and magnesium carries out the modified zinc oxide-alumina complex carrier in surface, and control zinc oxide-alumina is compound to be carried
Potassium oxide and content of magnesia are respectively in the range of 0.2-2.5wt% and 2.5-5.5wt% in body, and make carrier external oxidation
The content of potassium and magnesia is 1.1-1.2 times of internal oxidation potassium and content of magnesia.
Compared with prior art, the present invention has advantages below：
1st, the method for producing cyclohexane by adding hydrogen in benzene of the present invention, reaction condition is gentle, and benzene hydrogenation conversion ratio rate is high, hydrogenation
Catalyst has more preferable activity stability, and long period reactivity worth is excellent.
2nd, the zinc oxide containing gahnite of the invention is that alternately prepared by titration by non-constant pH, i.e., in non-constant pH
Prepared by the alternating titration of sodium carbonate liquor and zinc-containing solution under the conditions of value, containing aluminium, accordingly, it would be desirable to zinc-containing solution is divided into number
Part, the sodium carbonate liquor containing aluminium is strong alkali solution, and the strong acid weak base salting liquid containing zinc is acid solution, between aluminium zinc solution
Repeatedly alternately titration pH value is swung between soda acid, be conducive to aluminium zinc precursor thing can orderly accumulation be layer structure, through straight
Connect that low-temperature bake can be uniformly dispersed and specific surface area can be in 150-220m2The point containing zinc-aluminium regulated and controled between/g is brilliant
The zinc oxide material of stone, it is to avoid the precursor obtained using alkaline solution one step titration zinc-aluminium mixed solution needs high-temperature roasting
The problem of fixed zinc oxide, decreases hydrothermal treatment process.The material has larger specific surface area.
3rd, the present invention can also introduce phosphorus, potassium, magnesium and Sodium Polyacrylate, poly- third in zinc oxide-alumina complex carrier
Olefin(e) acid sodium can be repaired and improve catalytic inner pore passage structure, and diffusion effect is good in catalyst.The carrier is prepared into hydrogenation catalyst
Agent, such as benzene hydrogenating catalyst, are conducive to adjusting the acidity of catalyst, and catalytic inner pore passage structure is improved in finishing, is improved and is added
The stability of hydrogen catalyst.
4th, the present invention obtain containing zinc oxide-alumina composite carrier, after surface is through potassium and magnesium modification, make carrier table
The content of the concentration formation concentration difference of the potassium in face and the concentration of magnesium and carrier inside potassium and magnesium, carrier surface potassium and magnesium is higher than carrier
The molar content or mass content of the content of internal potassium and magnesium, i.e., outside potassium and magnesium can be the 1.1- of the content of internal potassium and magnesium
1.2 times, carrier surface is tended to equally distributed state, reduce the acidity of carrier surface, the carrier can be improved
The specific surface area of catalyst.Improvement to carrier surface should not use dipping method, and impregnated carrier surface can enter large quantity of moisture
Carrier, intensity is deteriorated, and does not reach the purpose for improving carrier surface Jie-macropore ratio.To complex carrier table by the way of spray
Face is modified, and is capable of the partial pore on effective peptization complex carrier surface, so advantageously reduces the micro- of complex carrier surface
Boring ratio example, improves complex carrier surface Jie-macropore ratio, and promotion complex carrier surface is produced in more active sites loads
The heart, effectively improves catalyst activity.
5th, through potassium and magnesium modification, the complex carrier containing zinc oxide-alumina can be made carrier surface of the present invention
To be used for benzene hydrogenation after the carrier loaded active component of hydrogenation catalyst.
Specific embodiment
It is further detailed to a kind of method of producing cyclohexane by adding hydrogen in benzene of the invention with comparative example by the following examples
Explanation.But these embodiments are not regarded as limiting of the invention.
Prepare primary raw material source used by catalyst：Reagent of the present invention is commercially available prod.
Embodiment 1
1.2kg zinc nitrates are dissolved in 6L water and are made into zinc-containing solution, by 0.24kg sodium metaaluminates and 0.30kg sodium carbonate
It is dissolved in 4L water and is made into containing aluminum solutions.Zinc-containing solution is divided into 3 parts, every part of 2L.2L zinc-containing solutions are taken, temperature keeps 80
DEG C, mixed solution containing aluminium to pH value is added dropwise thereto and reaches 9.0；Stop that mixed solution containing aluminium is added dropwise, then 2L zinc-containing solutions are added dropwise
To in hybrid system, continue dropwise addition mixed solution containing aluminium to pH value and reach 9.0；Mixed solution containing aluminium and zinc-containing solution alternately drip
Fixed, until zinc-containing solution is all added, last time is added dropwise mixed solution containing aluminium and reaches 9.0 to pH, and titration time amounts to 3h.
After 80 DEG C of aging 4h, cooling washing dries 3h to the mixture for arriving to neutrality in 135 DEG C of air atmospheres, in 500 DEG C of roastings
9h, obtains the dispersed zinc oxide stratified material containing gahnite, and in terms of oxide, the content of zinc oxide is 65%；
Specific surface area is 196m2/g。
Weigh phosphatase 11 .04g, potassium nitrate 1.03g respectively, magnesium nitrate 17.76g is dissolved completely in 60g distilled water to be made into and contains
Phosphorus, potassium, the aqueous solution of magnesium.6.0g Sodium Polyacrylates are dissolved in 70g distilled water, add the nitre that 3.8g mass concentrations are 65%
Acid.By 40g, zinc oxide and 164.3g boehmites ground and mixed containing gahnite are uniform, add 6.0g sesbania powders,
Sodium Polyacrylate acid solution, phosphorous, potassium, the aqueous solution of magnesium, kneading, after shaping, 125 DEG C of dried process 7 hours are roasted at 580 DEG C
Burn treatment and obtain within 7 hours the complex carrier containing zinc oxide-alumina.Complex carrier specific surface area 276m2/g.Complex carrier includes
Zinc oxide 25.0wt% containing gahnite, aluminum oxide is 70.4wt%, and adjuvant component phosphorus, potassium, content of magnesium are respectively P2O5
0.4wt%, K2O 1.2wt%, MgO 3.0wt%.
Take 1.14g chloroplatinic acids and 1.35g palladium nitrates be added in 30ml distilled water, add ammoniacal liquor adjust pH value after 3.0,
Diluted with deionized water again, be made into maceration extract and impregnate the spherical complex carrier 100g containing zinc oxide-alumina, the catalyst for obtaining
Precursor is calcined 6h after drying 6h at 120 DEG C at 500 DEG C, obtains the catalyst 1 of producing cyclohexane by adding hydrogen in benzene.Catalyst 1 is main
Composition：Platinum oxide 0.5wt%, palladium oxide 1.0t%, the complex carrier 98.5wt% containing zinc oxide-alumina.
By catalyst 1 and the small porcelain balls 1 of φ 1mm:It is fitted into 100ml fixed bed reactors after 1 mixing, filling order is φ
The small porcelain balls of 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight qualified
After start to use H2It is activated, activation condition pressure 2.0MPa, 120 DEG C of temperature, under conditions of hydrogen flowing quantity 400mL/min
Constant temperature 12h.Activation starts into benzene raw materials after terminating, and benzene hydrogenation is carried out under certain process conditions.
The process conditions of benzene hydrogenation are：220 DEG C of reaction temperature, reaction pressure 2.0MPa, hydrogen/oil volume compares 450, body
Product air speed 2.0h-1.Sampling analysis after reaction about 48h, and 1000h estimation of stabilitys are carried out, analysis result is shown in Table 1.
Comparative example 1
The zinc nitrate solution of amount same as Example 1, sodium metaaluminate and sodium carbonate liquor are well mixed by blending method, with reality
Apply that the zinc-aluminium mol ratio of example 1 is identical, similarity condition is aging, washing, dry, roasting obtains the oxide material containing zinc-aluminium.Zinc oxide
Content be 65%；Specific surface area is 141m2/g.Compared with comparative example 1, embodiment 1 is using pH swing methods zinc, the friendship of aluminum solutions
For titration, zinc-aluminium stratified material can be obtained, under the conditions of two kinds of material zinc-aluminium mol ratio identicals, embodiment 1 is containing zinc-aluminium point
The specific surface area of the zinc oxide stratified material of spar is higher.
Weigh phosphatase 11 .04g, potassium nitrate 1.03g respectively, magnesium nitrate 17.66g is dissolved completely in 60g distilled water to be made into and contains
Phosphorus, potassium, the aqueous solution of magnesium.6.0g Sodium Polyacrylates are dissolved in 70g distilled water, add the nitre that 3.8g mass concentrations are 65%
Acid.By 40g, oxide material and 164.3g boehmites ground and mixed containing zinc-aluminium are uniform, add 6.0g sesbania powders, gather
PAA acid solution, phosphorous, potassium, the aqueous solution of magnesium, kneading, after shaping, 125 DEG C of dried process 7 hours are calcined at 580 DEG C
Treatment obtains carrier in 7 hours.
Take 1.14g chloroplatinic acids and 1.35g palladium nitrates be added in 30ml distilled water, add ammoniacal liquor adjust pH value after 3.0,
Diluted with deionized water again, be made into maceration extract and impregnate the spherical complex carrier 100g containing zinc oxide-alumina, the catalyst for obtaining
Precursor is calcined 6h after drying 6h at 120 DEG C at 500 DEG C, obtains comparative catalyst 1.Comparative catalyst 1 mainly constitutes：Platinum oxide
0.5wt%, palladium oxide 1.0t%, the complex carrier 98.5wt% containing zinc oxide-alumina.
By comparative catalyst 1 and the small porcelain balls 1 of φ 1mm:It is fitted into 100ml fixed bed reactors after 1 mixing, filling order is
The small porcelain balls of φ 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight conjunction
Start to use H after lattice2It is activated, activation condition pressure 2.0MPa, 120 DEG C of temperature, the condition of hydrogen flowing quantity 400mL/min
Lower constant temperature 12h.Activation starts into benzene raw materials after terminating, and benzene hydrogenation is carried out under certain process conditions.
The process conditions of benzene hydrogenation are：220 DEG C of reaction temperature, reaction pressure 2.0MPa, hydrogen/oil volume compares 450, body
Product air speed 2.0h-1.Sampling analysis after reaction about 48h, and 1000h estimation of stabilitys are carried out, analysis result is shown in Table 1.
Embodiment 2
The preparation method and step of the complex carrier containing zinc oxide-alumina are prepared containing gahnite with embodiment 1
Zinc oxide, pH value is adjusted to 8.7.In terms of oxide, the content of zinc oxide is 70%；Specific surface area is 191m2/g。
Complex carrier includes the zinc oxide 30wt% containing gahnite, and aluminum oxide is 67wt%, adjuvant component phosphorus, potassium,
Content of magnesium is respectively P2O50.6wt%, K2O 0.8wt%, MgO 1.6wt%.
Except that after obtaining complex carrier, table is carried out to the complex carrier containing zinc oxide-alumina using potassium and magnesium
Face is modified, and detailed process comprises the following steps：Configuration, as maceration extract, weighs nitric acid respectively containing potassium nitrate and magnesium nitrate aqueous solution
Potassium, magnesium nitrate is dissolved completely in 30ml distilled water, then is diluted with deionized water, wiring solution-forming spray zinc oxide-alumina
Complex carrier so that the content of carrier outside potassium and magnesium is 1.1 times of the content of internal potassium and magnesium, is used through drying, roasting
Auxiliary agent potassium and magnesium carry out the zinc oxide-alumina complex carrier of surface modification.Complex carrier specific surface area 238m2/g。
Take 0.684g chloroplatinic acids and 1.62g palladium nitrates are added in 30ml distilled water, add ammoniacal liquor to adjust pH value 3.0
Afterwards, then with deionized water dilute, be made into maceration extract and impregnate the spherical complex carrier 100g containing zinc oxide-alumina, what is obtained urges
Agent precursor is calcined 6h after drying 6h at 120 DEG C at 500 DEG C, obtains the catalyst 2 of producing cyclohexane by adding hydrogen in benzene.Catalyst 2
Main composition：Platinum oxide 0.3wt%, palladium oxide 1.2t%, the complex carrier 98.5wt% containing zinc oxide-alumina.
By catalyst 1 and the small porcelain balls 1 of φ 1mm:It is fitted into 100ml fixed bed reactors after 1 mixing, filling order is φ
The small porcelain balls of 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight qualified
After start to use H2It is activated, activation condition pressure 2.0MPa, 120 DEG C of temperature, under conditions of hydrogen flowing quantity 400mL/min
Constant temperature 12h.Activation starts into benzene raw materials after terminating, and benzene hydrogenation is carried out under certain process conditions.
The process conditions of benzene hydrogenation are：230 DEG C of reaction temperature, reaction pressure 3.0MPa, hydrogen/oil volume compares 500, body
Product air speed 2.5h-1.Sampling analysis after reaction about 48h, and 1000h estimation of stabilitys are carried out, analysis result is shown in Table 1.
Embodiment 3
The preparation method and step of the complex carrier containing zinc oxide-alumina are with embodiment 1.Prepare containing gahnite
Zinc oxide, pH value is adjusted to 9.3.Zinc oxide containing gahnite, in terms of oxide, the content of zinc oxide is 63%；Compare table
Area is 214m2/g。
Complex carrier includes the zinc oxide 18.3wt% containing gahnite, and aluminum oxide is 77.5wt%, adjuvant component phosphorus,
Potassium, content of magnesium are respectively P2O50.9wt%, K2O 0.8wt%, MgO 3.5wt%.Complex carrier specific surface area 242m2/g。
Take 2.28g chloroplatinic acids and 1.62g palladium nitrates be added in 30ml distilled water, add ammoniacal liquor adjust pH value after 3.0,
Diluted with deionized water again, be made into maceration extract and impregnate the spherical complex carrier 100g containing zinc oxide-alumina, the catalyst for obtaining
Precursor is calcined 6h after drying 6h at 120 DEG C at 500 DEG C, obtains the catalyst 3 of producing cyclohexane by adding hydrogen in benzene.Catalyst 3 is main
Composition：Platinum oxide 1.0wt%, palladium oxide 1.2t%, the complex carrier 97.8wt% containing zinc oxide-alumina.
By catalyst 1 and the small porcelain balls 1 of φ 1mm:It is fitted into 100ml fixed bed reactors after 1 mixing, filling order is φ
The small porcelain balls of 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight qualified
After start to use H2It is activated, activation condition pressure 2.0MPa, 120 DEG C of temperature, under conditions of hydrogen flowing quantity 400mL/min
Constant temperature 12h.Activation starts into benzene raw materials after terminating, and benzene hydrogenation is carried out under certain process conditions.
The process conditions of benzene hydrogenation are：235 DEG C of reaction temperature, reaction pressure 2.5MPa, hydrogen/oil volume compares 550, body
Product air speed 3.0h-1.Sampling analysis after reaction about 48h, analysis result is shown in Table 1.
Embodiment 4
The preparation method and step of the complex carrier containing zinc oxide-alumina are prepared containing gahnite with embodiment 1
Zinc oxide, pH value is adjusted to 8.6.Zinc oxide containing gahnite, in terms of oxide, the content of zinc oxide is 75%；Compare table
Area is 213m2/g。
Complex carrier includes the zinc oxide 22.0wt% containing gahnite, and aluminum oxide is 72.5wt%, adjuvant component phosphorus,
Potassium, content of magnesium are respectively P2O51.1wt%, K2O 0.4wt%, MgO 4.0wt%.Complex carrier specific surface area 256m2/g。
Take 4.56g chloroplatinic acids and 0.81g palladium nitrates be added in 30ml distilled water, add ammoniacal liquor adjust pH value after 3.0,
Diluted with deionized water again, be made into maceration extract and impregnate the spherical complex carrier 100g containing zinc oxide-alumina, the catalyst for obtaining
Precursor is calcined 6h after drying 6h at 120 DEG C at 500 DEG C, obtains the catalyst 4 of producing cyclohexane by adding hydrogen in benzene.Catalyst 4 is main
Composition：Platinum oxide 2.0wt%, palladium oxide 0.6t%, the complex carrier 97.4wt% containing zinc oxide-alumina.
By catalyst 1 and the small porcelain balls 1 of φ 1mm:It is fitted into 100ml fixed bed reactors after 1 mixing, filling order is φ
The small porcelain balls of 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight qualified
After start to use H2It is activated, activation condition pressure 2.0MPa, 120 DEG C of temperature, under conditions of hydrogen flowing quantity 400mL/min
Constant temperature 12h.Activation starts into benzene raw materials after terminating, and benzene hydrogenation is carried out under certain process conditions.
The process conditions of benzene hydrogenation are：210 DEG C of reaction temperature, reaction pressure 2.5MPa, hydrogen/oil volume compares 450, body
Product air speed 2.0h-1.Sampling analysis after reaction about 48h, analysis result is shown in Table 1.
Embodiment 5
The preparation method and step of the complex carrier containing zinc oxide-alumina are prepared containing gahnite with embodiment 1
Zinc oxide, pH value is adjusted to 8.7.Zinc oxide containing gahnite, in terms of oxide, the content of zinc oxide is 67%；Compare table
Area is 191m2/g。
Complex carrier includes the zinc oxide 30wt% containing gahnite, and aluminum oxide is 66.6wt%, adjuvant component phosphorus,
Potassium, content of magnesium are respectively P2O50.6wt%, K2O 1.0wt%, MgO 1.8wt%.Complex carrier specific surface area 279m2/g。
Except that after obtaining complex carrier, table is carried out to the complex carrier containing zinc oxide-alumina using potassium and magnesium
Face is modified, and detailed process comprises the following steps：Configuration is containing potassium nitrate and magnesium nitrate aqueous solution as solution spraying zinc oxide-oxidation
Aluminium complex carrier so that the content of carrier outside potassium and magnesium is 1.2 times of the content of internal potassium and magnesium.Obtained through drying, roasting
Used additives potassium and magnesium carry out the zinc oxide-alumina complex carrier of surface modification.
Take 3.42g chloroplatinic acids and 0.81g palladium nitrates be added in 30ml distilled water, add ammoniacal liquor adjust pH value after 3.0,
Diluted with deionized water again, be made into maceration extract and impregnate the spherical complex carrier 100g containing zinc oxide-alumina, the catalyst for obtaining
Precursor is calcined 6h after drying 6h at 120 DEG C at 500 DEG C, obtains the catalyst 5 of producing cyclohexane by adding hydrogen in benzene.Catalyst 5 is main
Composition：Platinum oxide 1.5wt%, palladium oxide 0.6t%, the complex carrier 97.9wt% containing zinc oxide-alumina.
By catalyst 1 and the small porcelain balls 1 of φ 1mm:It is fitted into 100ml fixed bed reactors after 1 mixing, filling order is φ
The small porcelain balls of 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight qualified
After start to use H2It is activated, activation condition pressure 2.0MPa, 120 DEG C of temperature, under conditions of hydrogen flowing quantity 400mL/min
Constant temperature 12h.Activation starts into benzene raw materials after terminating, and benzene hydrogenation is carried out under certain process conditions.
The process conditions of benzene hydrogenation are：225 DEG C of reaction temperature, reaction pressure 2.5MPa, hydrogen/oil volume compares 600, body
Product air speed 4.0h-1.Sampling analysis after reaction about 48h, analysis result is shown in Table 1.
Evaluation result when table 1 is for reaction 48h, catalyst 1,2,5 and contrast medium carry out 1000h study on the stability results
For:Catalyst 1,2,5 is respectively 98.6%, 100%, 100% and 90.7% with the benzene removal efficiency of contrast medium.
The benzene hydrogenation activity that can be seen that catalyst 1,2,5 by table 1 and catalyst stability evaluating data is good, benzene it is de-
Except rate is high, catalyst 2 and the active component of catalyst 5 after surface modification are not easily runed off, and the activity stability of reaction is good.
The catalyst of table 1 and contrast medium reactor product property
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Knowing those skilled in the art can make various corresponding changes and deformation, but these corresponding changes and deformation according to the present invention
Protection scope of the present invention should all be belonged to.
Claims (10)
1. a kind of method of producing cyclohexane by adding hydrogen in benzene, it is characterised in that comprise the following steps：
Platinum palladium base noble metal catalyst is seated in fixed bed reactors, is carried out at activation of catalyst after airtight experiment is qualified
Reason, activation starts into benzene raw materials after terminating, and benzene hydrogenation is carried out under reaction process condition, and reactor product is analyzed；
Described catalyst active center is palladium and platinum, and catalyst carrier is the complex carrier containing zinc oxide-alumina, catalyst
Composition with oxidation material gauge, including following component：Complex carrier 80-99wt% containing zinc oxide-alumina, active component
Platinum oxide 0.1-5wt%, active component palladium oxide 0.1-5wt%；
The preparation method of described catalyst, comprises the following steps：
The soluble-salt of platinum and palladium is made into maceration extract, complex carrier of the dipping containing zinc oxide-alumina is dried, and roasting is obtained
Benzene hydrogenating catalyst；
The described complex carrier containing zinc oxide-alumina, including the zinc oxide containing gahnite, aluminum oxide, adjuvant component
Phosphorus, potassium and magnesium, the composition of complex carrier is with oxidation material gauge：Zinc oxide content containing gahnite is 5.0-
40.0wt%, alumina content is 60.0-95.0wt%, and the percentage that the content of adjuvant component phosphorus, potassium and magnesium accounts for carrier quality contains
Amount is respectively P2O50.2-1.2wt%, K2O 0.2-2.5wt%, MgO 2.0-5.5wt%, complex carrier specific surface area 200-
300m2/g；
The described complex carrier containing zinc oxide-alumina, the method for being prepared by the following procedure is obtained：
Soluble salt solutions and zinc-containing solution containing aluminium are alternately titrated by non-constant pH, the oxygen containing gahnite is prepared
Change zinc stratified material；Zinc oxide and boehmite containing gahnite are well mixed, sesbania powder, nitric acid acidifying is added
The acid solution containing Sodium Polyacrylate after treatment, and phosphoric acid, potassium nitrate and magnesium nitrate the aqueous solution, kneading, after shaping, dry
Treatment, calcination process is obtained containing zinc oxide-alumina composite carrier.
2. the method for a kind of producing cyclohexane by adding hydrogen in benzene according to claim 1, it is characterised in that：Described fixed bed is anti-
Device is answered, is fixed bed adiabatic reactor or fixed bed isothermal reactor.
3. the method for a kind of producing cyclohexane by adding hydrogen in benzene according to claim 1, it is characterised in that：Described benzene hydrogenation is anti-
Should, its process conditions is：180-280 DEG C of reaction temperature, reaction pressure 1.0-5.0MPa, hydrogen/oil volume compares 300-700:1, body
Product air speed 1.0-6.0h-1。
4. the method for a kind of producing cyclohexane by adding hydrogen in benzene according to claim 1, it is characterised in that：Described benzene hydrogenation is anti-
Should, its process conditions is：210-230 DEG C of reaction temperature, reaction pressure 2.0-3.5MPa, hydrogen/oil volume compares 450-650:1, body
Product air speed 2.0-4.0h-1。
5. the method for a kind of producing cyclohexane by adding hydrogen in benzene according to claim 1, it is characterised in that：
The composition of described catalyst is with oxidation material gauge, including following component：The complex carrier 96- of zinc oxide-alumina
99.4wt%, active component platinum oxide 0.3-2.0wt%, active component palladium oxide 0.3-2.0wt%；
The described complex carrier containing zinc oxide-alumina, including the zinc oxide containing gahnite, aluminum oxide, adjuvant component
Phosphorus, potassium and magnesium, the composition of complex carrier is with oxidation material gauge：Zinc oxide content containing gahnite is 10.0-
35.0wt%, alumina content is 65.0-90.0wt%, and the percentage that the content of adjuvant component phosphorus, potassium and magnesium accounts for carrier quality contains
Amount is respectively P2O50.4-1.0wt%, K2O 0.2-2.5wt%, MgO 2.5-4.5wt%, complex carrier specific surface area 200-
300m2/g。
6. the method for a kind of producing cyclohexane by adding hydrogen in benzene according to claim 1, it is characterised in that：Described preparing contains
The zinc oxide stratified material of gahnite, is to be prepared by the following preparation method：Soluble Zn salting liquid is divided into 2-4 parts,
Under the conditions of 40-80 DEG C, the mixed solution containing aluminium of sodium metaaluminate and sodium carbonate is added in a zinc solution, when pH value reaches
Stop that mixed solution containing aluminium is added dropwise during 8.5-9.5；It is further continued for that another zinc solution is added dropwise；After zinc solution is dripped, continue
Mixed solution containing aluminium is added dropwise, stops that mixed solution containing aluminium is added dropwise when pH value reaches 8.5-9.5；To contain aluminium according to the above method to mix
Solution replaces titration with zinc solution, until zinc solution whole completion of dropping, last time dropwise addition mixed solution containing aluminium, work as pH
When value reaches 8.5-9.5, the alternating titration process of non-constant pH value terminates, and control titration process is completed in 1-6h；In 80-95
After DEG C aging 2-8h, cooling washing dries 4-10h, 450-550 DEG C of roasting 4-10h at 80-140 DEG C to neutrality, is uniformly divided
The scattered zinc oxide stratified material containing gahnite；The soluble zinc salt is zinc nitrate or zinc chloride.
7. the method for a kind of producing cyclohexane by adding hydrogen in benzene according to claim 1, it is characterised in that：Described nitric acid acidifying
The acid solution containing Sodium Polyacrylate after treatment, is to be prepared by the following preparation method：Deionized water is heated to 30-90 DEG C,
Then nitric acid is dissolved into deionized water, adds Sodium Polyacrylate, and dissolve complete, obtain sour molten containing Sodium Polyacrylate
Liquid.
8. the method for a kind of producing cyclohexane by adding hydrogen in benzene according to claim 1, it is characterised in that：Described polyacrylic acid
The addition of sodium is the 0.6-12wt% of boehmite；The addition of the sesbania powder is the 0.2-7wt% of boehmite.
9. the method for a kind of producing cyclohexane by adding hydrogen in benzene according to claim 1, it is characterised in that：Described drying, roasting
Burning obtains catalyst, is dried 6 hours at 120 DEG C, and roasting obtains hydrogenation catalyst in 6-8 hours at 400-600 DEG C；Described
Dried process, calcination process, be 110-150 DEG C dried process 4-8 hours, calcination process 4.5-8 hours at 550 DEG C -700 DEG C.
10. the method for a kind of producing cyclohexane by adding hydrogen in benzene according to claim 1, it is characterised in that：It is described containing oxidation
The complex carrier of zinc-aluminum oxide, carries out surface modification, by such as using potassium and magnesium to the complex carrier containing zinc oxide-alumina
Lower step carries out carrier surface modification：Aqueous solution spray of the configuration containing potassium nitrate and magnesium nitrate is compound containing zinc oxide-alumina
Carrier, obtaining used additives potassium and magnesium through drying, roasting carries out the modified zinc oxide-alumina complex carrier in surface, control oxidation
Potassium oxide and content of magnesia be respectively in the range of 0.2-2.5wt% and 2.5-5.5wt% in zinc-alumina composite carrier,
And make the content of carrier external oxidation potassium and magnesia be 1.1-1.2 times of internal oxidation potassium and content of magnesia.
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