CN114870851A - Synthetic method of 3,3, 5-trimethylcyclohexanol - Google Patents
Synthetic method of 3,3, 5-trimethylcyclohexanol Download PDFInfo
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- CN114870851A CN114870851A CN202210681273.1A CN202210681273A CN114870851A CN 114870851 A CN114870851 A CN 114870851A CN 202210681273 A CN202210681273 A CN 202210681273A CN 114870851 A CN114870851 A CN 114870851A
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- trimethylcyclohexanol
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- nickel
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- BRRVXFOKWJKTGG-UHFFFAOYSA-N 3,3,5-trimethylcyclohexanol Chemical compound CC1CC(O)CC(C)(C)C1 BRRVXFOKWJKTGG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000010189 synthetic method Methods 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910003296 Ni-Mo Inorganic materials 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 230000009467 reduction Effects 0.000 claims abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 13
- 239000007791 liquid phase Substances 0.000 claims abstract description 8
- 238000001308 synthesis method Methods 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 22
- 239000011701 zinc Substances 0.000 claims description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 15
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- 230000002194 synthesizing effect Effects 0.000 claims description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 12
- 239000011733 molybdenum Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 4
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 18
- 238000010924 continuous production Methods 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 48
- 239000000047 product Substances 0.000 description 15
- LDRWAWZXDDBHTG-UHFFFAOYSA-N 3,5,5-trimethylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CC(C)(C)C1 LDRWAWZXDDBHTG-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910000564 Raney nickel Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 229910009367 Zn M Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- -1 isophorol Chemical compound 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- ZGMQLPDXPUINCQ-UHFFFAOYSA-N 3,3,5-trimethylcyclohexan-1-amine Chemical compound CC1CC(N)CC(C)(C)C1 ZGMQLPDXPUINCQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RDULJYNFAQRRJO-UHFFFAOYSA-N [Ni]=O.[Mo]=O Chemical compound [Ni]=O.[Mo]=O RDULJYNFAQRRJO-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical compound O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 208000019553 vascular disease Diseases 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8873—Zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/175—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with simultaneous reduction of an oxo group
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- 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
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Abstract
The invention relates to a synthesis method of 3,3, 5-trimethylcyclohexanol, which adopts a fixed bed reactor, and has the reaction temperature of 140-180 ℃, the reaction pressure of 1.5-3.0 Mpa and the liquid phase volume airspeed of 0.5-2.5 h ‑1 And carrying out deep hydrogenation reduction by using a Zn-promoted Ni-Mo unsupported catalyst under the condition that the volume ratio of hydrogen to oil is 240: 1-720: 1 to obtain the 3,3, 5-trimethylcyclohexanol. Under the action of the catalyst, the conversion rate of raw materials is 100%, the selectivity of the product 3,3, 5-trimethylcyclohexanol is more than 99.70%, the cis-trans ratio reaches 6.7, and the efficient continuous production of the 3,3, 5-trimethylcyclohexanol is realized. The catalyst is simple to prepare, easy to operate, short in period, low in cost, environment-friendly and suitable for large-scale production and application.
Description
Technical Field
The invention belongs to the technical field of fine chemical synthesis, and particularly relates to a synthetic method of 3,3, 5-trimethylcyclohexanol.
Background
3,3, 5-trimethyl cyclohexanol, i.e. isophorol, is mainly obtained by deep hydrogenation of 1,1, 3-trimethyl cyclohexenone (alias: isophorone), and can be used for synthesizing isophorol ester drugs by carboxylic esterification, and can be used for treating vascular diseases. In addition, isophorol can also be aminated to synthesize 3,3, 5-trimethyl cyclohexylamine, which can be used for the synthesis of emulsifying agent, antistatic agent, latex coagulant, petroleum product additive, corrosion inhibitor, bactericide, pesticide, etc. Also, the synthesis of many new fragrances, plasticizers, lubricants, dicyans, diamines or alcohol intermediates do not depart from the role of isophorol. Therefore, the isophorol is a fine chemical product or a medical intermediate with very high application value.
The traditional preparation method of isophorol is to use Raney nickel as a catalyst and adopt a reaction kettle to carry out an intermittent production process. Isophorol has cis-trans isomers, and the cyclanoate mainly uses cis-isophorol as a raw material, so that isophorone has high conversion rate and cis-isophorol in a product has high selectivity. The cis-trans alcohol ratio obtained by using Raney nickel as a catalyst is about 7/3(2.3), the total content of the cis-trans alcohol and the cis-iso-versol is about 90%, and if cis-iso-versol with higher purity is obtained, post-treatment such as vacuum rectification is required, which leads to the increase of the product cost. Meanwhile, high-temperature calcination and treatment of a large amount of high-concentration sodium hydroxide solution are required in the preparation process of the Raney nickel catalyst, and the waste alkali liquor is easy to pollute the environment. In addition, in order to prevent the spontaneous combustion of the catalyst, the catalyst must be stored in an organic solvent such as ethanol.
The molecular structure of the raw material isophorone contains one C ═ C double bond and one C ═ O double bond, and the product isophorone is obtained by deep hydrogenation of the two. From the thermodynamic point of view, the bond energy of C ═ C bonds is 615kJ "mol -1 The bond energy of the C ═ O bond is 715kJ "mol -1 Thus, C ═ C double bonds are more easily hydrogenated than C ═ O double bonds, but since C ═ C and C ═ O double bonds in isophorone molecule form a conjugated system, C ═ O double bonds are also easily reduced, a competing hydrogenation reaction of C ═ C and C ═ O double bonds takes place, and the product is often a mixture of C ═ C or C ═ O double bonds and of a plurality of substances which are both saturated by hydrogenationThe catalyst is required to have more active sites and higher selectivity, the content of cis-isophorol in the product is improved, the generation of byproducts is reduced, and the post-treatment cost of the product is reduced, so that the isophorol synthesis process and the catalyst need to be innovated.
The non-supported deep hydrogenation catalyst developed by the applicant and the preparation method thereof are disclosed in the publication No. CN105363460A, the preparation method comprises the steps of adding a nickel source and a molybdenum source into deionized water at the temperature of 20-60 ℃, stirring and dissolving, adding an activating assistant component, dropwise adding an organic amine aqueous solution, and conducting crystallization at the temperature of 100 ℃ and 150 ℃ in a reaction kettle. When the non-supported catalyst prepared by the technical scheme is used for synthesizing 3,3, 5-trimethylcyclohexanol, the conversion rate of isophorone serving as a raw material is about 95%, the selectivity of the 3,3, 5-trimethylcyclohexanol can reach 94%, and the ratio of cis-trans-isophorol is 3-3.5. How to further improve the conversion rate of isophorone serving as a raw material, the selectivity of 3,3, 5-trimethylcyclohexanol and the ratio of cis-trans-isophorol and reduce the cost are considered, so that the applicant continues to research the catalyst synthesis process.
Disclosure of Invention
The invention aims to provide a method for synthesizing 3,3, 5-trimethylcyclohexanol, which utilizes a specific unsupported catalyst synthesized by the applicant and a specific catalyst using method to remarkably improve the conversion rate of isophorone, the selectivity of 3,3, 5-trimethylcyclohexanol and the ratio of cis-trans-isophorol, and solves the problem that the production cost is still high.
The technical scheme breaks through the traditional kettle type synthesis method of 3,3, 5-trimethyl cyclohexanol, adopts a novel fixed bed synthesis process and a Zn-promoted Ni-Mo unsupported catalyst, realizes the conversion rate of the raw material isophorone of 100%, ensures the selectivity of the product isophorone to be more than 99.70%, ensures the cis-trans isophorone ratio to reach 6.7, saves the product purification process, reduces the cost, and simultaneously realizes the continuous production of the target product.
In order to achieve the purpose, the method is realized by the following technical scheme:
a process for synthesizing 3,3, 5-trimethyl cyclohexanol by fixed-bed reactorThe reaction temperature is 140-180 ℃, the reaction pressure is 1.5-3.0 Mpa, and the liquid phase volume space velocity is 0.5-2.5 h -1 And carrying out deep hydrogenation reduction by using a Zn-promoted Ni-Mo unsupported catalyst under the condition that the volume ratio of hydrogen to oil is 240: 1-720: 1 to obtain the 3,3, 5-trimethylcyclohexanol.
Furthermore, the main active components of the Zn-promoted Ni-Mo unsupported catalyst are Ni and Mo metal elements, and the molar ratio of the Ni to the Mo element is 1.0-3.0: 1.
Further, the auxiliary active component of the Zn-promoted Ni-Mo unsupported catalyst is Zn.
Furthermore, the mass of the auxiliary agent Zn in the Zn-promoted Ni-Mo unsupported catalyst accounts for 3.0-6.0% of the total mass of Ni and Mo.
Further, the preparation method of the Zn-promoted Ni-Mo unsupported catalyst comprises the following steps:
(1) adding organic amine into deionized water at the temperature of 30-60 ℃, and stirring for dissolving;
(2) adding a nickel source, a molybdenum source and an auxiliary active component into the solution at the same time, and stirring for 0.5-1 h under heat preservation;
(3) and (3) introducing the mixed solution obtained in the step (2) into a reaction kettle, crystallizing for 6-10 hours at the temperature of 100-150 ℃ by a hydrothermal synthesis method, cooling to room temperature, filtering, and drying the obtained solid product for 24 hours at the temperature of 150-300 ℃ to obtain the target catalyst.
In the preparation process and the hydrolysis process of the Zn-promoted Ni-Mo unsupported catalyst, a nickel source, a molybdenum source and an auxiliary active component are added into deionized water simultaneously, the hydrolysis process of soluble metal salt is utilized, and the temperature and the time of hydrothermal synthesis are controlled by adding organic amine, so that the hydrolysis-polymerization rate of each metal component is further controlled, and each component is fully reacted with OH - Ions form transition state M-OH (M ═ Ni, Mo and Zn), the transition state M-OH is uniformly dispersed in the system, then the mutual combination of nickel, molybdenum and auxiliary active components is strengthened in the drying and roasting process, the uniform dispersion of nickel, molybdenum and auxiliary active metal atoms in the hole wall of the material is successfully realized, and the zinc promoted nickel-molybdenum deep addition with Ni-O-Mo-Zn-M or Ni-O-Zn-Mo-M skeleton structure is obtainedA hydrogen catalyst. The formation of Ni-O-Mo-Zn-M or Ni-O-Zn-Mo-M bonds not only can effectively enhance the thermal stability of the nickel oxide-molybdenum oxide material, but also can improve the catalytic activity of the material.
Further, the organic amine in the step (3) is ethanolamine or diethylamine, and the mass ratio of the organic amine to the total mass of the main active component, namely the nickel source and the molybdenum source, is 1: 5-1: 22.
Further, the ratio of the added substance of the deionized water to the total substance of the nickel source and the molybdenum source serving as the main active components in the step (3) is 18.5: 1.
Further, the nickel source is one of nickel acetate, nickel nitrate or basic nickel carbonate; the molybdenum source is one of ammonium heptamolybdate or ammonium tetramolybdate.
Furthermore, the precursor of the auxiliary active component zinc is zinc nitrate.
Further, the Zn-promoted Ni — Mo unsupported catalyst was treated as follows before use:
(11) performing extrusion forming, namely loading a catalyst with uniform particles and a volume of 20-40 meshes of 10ml into a constant-temperature section of a fixed bed reactor;
(12) reducing the catalyst under the hydrogen atmosphere by adopting the conditions of hydrogen flow of 80ml/min, temperature of 350 ℃, pressure of 1.0MPa and reduction time of 8 h;
(13) and after the reduction is finished, feeding is started when the temperature of the fixed bed reactor is reduced to 140-180 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adopts the fixed bed reactor, realizes the continuous production of the 3,3, 5-trimethylcyclohexanol, breaks through the tradition of kettle type batch production by adopting the Raney nickel catalyst, and greatly improves the production capacity and the economic benefit.
(2) The Zn-promoted Ni-Mo unsupported catalyst prepared by the invention adopts a hydrothermal synthesis method, simplifies the preparation process, shortens the preparation period, obtains a deep hydrogenation catalyst with more metal active sites, and further improves the hydrogenation activity of the catalyst.
(3) Zn is introduced as an auxiliary active component in the preparation process of the Ni-Mo non-supported catalyst prepared by the invention, so that the thermal stability and the carbon deposition resistance of the catalyst are improved, and the long-period operation of the catalyst is facilitated.
(4) Compared with the non-supported nickel-molybdenum multi-metal catalyst prepared by applying CN105363460A, the Zn-promoted Ni-Mo non-supported catalyst prepared by the technical scheme has the advantages that under the condition of the same reaction parameters, the conversion rate of raw material isophorone, the selectivity of product isophorol and the ratio of cis-trans isophorol are both obviously improved. Under the action of the non-supported nickel-molybdenum multi-metal catalyst, the conversion rate of the raw material isophorone is 100%, the average selectivity of the product isophorol is more than 99.70%, the ratio of cis-trans isophorol is up to 6.7, the product post-treatment is avoided, and the production cost is reduced.
Drawings
FIG. 1 shows the reaction results of Ni-Mo unsupported catalysts promoted with Zn. In the reaction process of 100h in the figure, the conversion rate of raw material isophorone is 100%, and the average selectivity of product 3,3, 5-trimethyl cyclic ethanol is more than 99.70%.
Detailed Description
The technical solutions of the present invention are described in detail by the following examples, which are only exemplary and can be used for explaining and explaining the technical solutions of the present invention, but not construed as limiting the technical solutions of the present invention.
In order to examine the products of the examples of the present application, gas chromatography was used, and the following examples were conducted under the following conditions: and (3) importing an Shimadzu wax chromatographic column, controlling the injection inlet temperature to be 250 ℃, the detector temperature to be 260 ℃, fully automatically controlling the flow of hydrogen and air, and controlling the flow of hydrogen and air to be 1: 10.
Embodiment mode 1
In a 10ml fixed bed reactor, synthesizing 3,3, 5-trimethylcyclohexanol by deeply hydrogenating isophorone by adopting Zn-promoted Ni-Mo unsupported catalyst at the reaction temperature of 140 ℃, the reaction pressure of 1.5MPa and the liquid phase space velocity of raw materials of 0.5h -1 The conversion rate of the raw material isophorone is 99.46%, 3,3, 5-trimethyl by gas chromatography analysis under the condition of hydrogen-oil volume ratio 240Average cyclohexanol selectivity was 99.78%, cis-trans isophorol ratio 5.8.
The preparation steps of the Ni-Mo unsupported catalyst promoted by Zn are as follows:
(1) 0.5g of ethanolamine is added into 60ml of deionized water under the condition of 30 ℃, and the mixture is stirred uniformly.
(2) 15.0g of basic nickel carbonate, 10.8g of ammonium heptamolybdate and 1.6g of zinc nitrate were added to the solution and stirred for 1 hour.
(3) Pouring the mixed solution into a reaction kettle, crystallizing at 150 ℃ for 6 hours, cooling, disassembling the kettle, filtering, drying at 120 ℃ for 12 hours, and roasting at 400 ℃ for 5 hours.
(4) And (3) carrying out extrusion forming on the roasted composite metal oxide powder, and loading the catalyst with uniform particles and the volume of 20-40 meshes of 10ml into a constant-temperature section of a fixed bed reactor.
(5) In the hydrogen atmosphere, the catalyst is reduced by adopting the conditions of hydrogen flow of 80ml/min, temperature of 350 ℃, pressure of 1.0MPa and reduction time of 8 h.
(6) After the reduction is finished, feeding is started when the temperature of the fixed bed reactor is reduced to 140 ℃.
Embodiment mode 2
In a 10ml fixed bed reactor, adopting Zn promoted Ni-Mo non-supported catalyst to carry out the deep hydrogenation of isophorone to synthesize 3,3, 5-trimethyl cyclohexanol, wherein the reaction temperature is 160 ℃, the reaction pressure is 2.0MPa, and the liquid phase volume airspeed of the raw material is 1.5h -1 And the volume ratio of hydrogen to oil is 240, the conversion rate of isophorone is 99.52 percent, the average selectivity of 3,3, 5-trimethylcyclohexanol is 99.09 percent, and the ratio of cis-trans-isophorol is 6.1.
The preparation steps of the Zn-promoted Ni-Mo unsupported catalyst are as follows:
(1) at 45 ℃, 1.5g of ethanolamine is added into 60ml of deionized water and stirred uniformly.
(2) To the solution, 33.6g of nickel acetate, 7.9g of ammonium heptamolybdate and 2.4g of zinc nitrate were added and stirred for 1.0 h.
(3) Pouring the mixed solution into a reaction kettle, crystallizing at 160 ℃ for 9 hours, cooling, disassembling the kettle, filtering, drying at 120 ℃ for 12 hours, and roasting at 400 ℃ for 5 hours.
(4) And (3) carrying out extrusion forming on the roasted composite metal oxide powder, and loading the catalyst with uniform particles and the volume of 20-40 meshes of 10ml into a constant-temperature section of a fixed bed reactor.
(5) In the hydrogen atmosphere, the catalyst is reduced by adopting the conditions of hydrogen flow of 80ml/min, temperature of 350 ℃, pressure of 1.0MPa and reduction time of 8 h.
(6) After the reduction is finished, feeding is started when the temperature of the fixed bed reactor is reduced to 160 ℃.
Embodiment 3
In a 10ml fixed bed reactor, synthesizing 3,3, 5-trimethyl cyclohexanol by deep hydrogenation of isophorone by adopting a zinc promoted Ni-Mo unsupported catalyst at the reaction temperature of 160 ℃, the reaction pressure of 2.0MPa and the liquid phase space velocity of the raw material of 1.5h -1 And under the condition of a hydrogen-oil volume ratio of 480, through gas chromatography analysis, the conversion rate of isophorone of a raw material is 99.81%, the average selectivity of 3,3, 5-trimethylcyclohexanol is 99.54%, and the ratio of cis-trans-isophorol is 6.3.
The preparation steps of the Ni-Mo unsupported catalyst promoted by Zn are as follows:
(1) at 60 ℃, 1.9g of ethanolamine is added into 60ml of deionized water and stirred uniformly.
(2) 26.2g of nickel nitrate, 14.1g of ammonium tetramolybdate and 3.2g of zinc nitrate were added to the solution and stirred for 1 hour.
(3) Pouring the mixed solution into a reaction kettle, crystallizing at 170 ℃ for 12 hours, cooling, removing the kettle, filtering, drying at 120 ℃ for 12 hours, and roasting at 400 ℃ for 5 hours.
(4) And (3) carrying out extrusion forming on the roasted composite metal oxide powder, and loading the catalyst with uniform particles and the volume of 20-40 meshes of 10ml into a constant-temperature section of a fixed bed reactor.
(5) Under the hydrogen atmosphere, the catalyst is reduced by adopting the conditions of hydrogen flow of 80ml/min, temperature of 350 ℃, pressure of 1.0MPa and reduction time of 8 h.
(6) After the reduction is finished, feeding is started when the temperature of the fixed bed reactor is reduced to 160 ℃.
Embodiment 4
In a 10ml fixed bed reactor, synthesizing 3,3, 5-trimethyl cyclohexanol by deep hydrogenation of isophorone with a zinc promoted Ni-Mo unsupported catalyst at 160 ℃, 2.5MPa and 1.5h of liquid phase space velocity of raw material -1 And under the condition of a hydrogen-oil volume ratio of 480, through gas chromatography analysis, the conversion rate of the raw material isophorone is 100%, the average selectivity of 3,3, 5-trimethylcyclohexanol is 99.76%, and the ratio of cis-trans-isophorol is 6.7.
The preparation steps of the Ni-Mo unsupported catalyst promoted by Zn are as follows:
(1) at 45 ℃, 1.1g of ethanolamine is added into 60ml of deionized water and stirred uniformly.
(2) 15.0g of basic nickel carbonate, 10.8g of ammonium heptamolybdate and 2.4g of zinc nitrate were added to the solution and stirred for 1.0 h.
(3) And pouring the mixed solution into a reaction kettle, crystallizing at 170 ℃ for 8 hours, cooling, removing the kettle, performing suction filtration, drying at 120 ℃ for 12 hours, and roasting at 400 ℃ for 5 hours.
(4) And (3) carrying out extrusion forming on the roasted composite metal oxide powder, and loading the catalyst with uniform particles, 20-40 meshes and 10ml into a constant-temperature section of the fixed bed reactor.
(5) In the hydrogen atmosphere, the catalyst is reduced by adopting the conditions of hydrogen flow of 80ml/min, temperature of 350 ℃, pressure of 1.0MPa and reduction time of 8 h.
(6) After the reduction is finished, feeding is started when the temperature of the fixed bed reactor is reduced to 160 ℃.
Embodiment 5
In a 10ml fixed bed reactor, adopting Zn promoted Ni-Mo non-supported catalyst to carry out the deep hydrogenation of isophorone to synthesize 3,3, 5-trimethyl cyclohexanol, wherein the reaction temperature is 180 ℃, the reaction pressure is 3.0MPa, and the liquid phase space velocity of the raw material is 2.5h -1 And the gas chromatography analysis shows that the conversion rate of the raw material isophorone is 99.31%, the average selectivity of 3,3, 5-trimethylcyclohexanol is 98.80%, and the ratio of cis-trans-isophorol is 5.7 under the condition that the volume ratio of hydrogen to oil is 720.
The preparation steps of the Ni-Mo unsupported catalyst promoted by Zn are as follows:
(1) at 50 ℃, 2.2g of ethanolamine is added into 60ml of deionized water and stirred uniformly.
(2) 39.2g of nickel nitrate, 7.9g of ammonium heptamolybdate and 2.7g of zinc nitrate were added to the solution and stirred for 1 hour.
(3) And pouring the mixed solution into a reaction kettle, crystallizing at 150 ℃ for 8 hours, cooling, removing the kettle, performing suction filtration, drying at 120 ℃ for 12 hours, and roasting at 400 ℃ for 5 hours.
(4) And (3) carrying out extrusion forming on the roasted composite metal oxide powder, and loading the catalyst with uniform particles and the volume of 20-40 meshes of 10ml into a constant-temperature section of a fixed bed reactor.
(5) In the hydrogen atmosphere, the catalyst is reduced by adopting the conditions of hydrogen flow of 80ml/min, temperature of 350 ℃, pressure of 1.0MPa and reduction time of 8 h.
(6) After the reduction is finished, feeding is started when the temperature of the fixed bed reactor is reduced to 180 ℃.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The method for synthesizing 3,3, 5-trimethylcyclohexanol is characterized by adopting a continuous fixed bed reactor, and performing reaction at the reaction temperature of 140-180 ℃, the reaction pressure of 1.5-3.0 Mpa and the liquid phase volume space velocity of 0.5-2.5 h -1 And carrying out deep hydrogenation reduction by using a Zn-promoted Ni-Mo unsupported catalyst under the condition that the volume ratio of hydrogen to oil is 240: 1-720: 1 to obtain the 3,3, 5-trimethylcyclohexanol.
2. The method for synthesizing 3,3, 5-trimethylcyclohexanol as recited in claim 1, wherein the main active components of the Zn-promoted Ni-Mo unsupported catalyst are Ni and Mo metal elements, and the molar ratio of Ni/Mo element is 1.0-3.0: 1.
3. 3,3, 5-trimethylcyclohexanol as recited in claim 1, characterized in that the co-active component of Zn-promoted Ni-Mo unsupported catalyst is Zn.
4. The method for synthesizing 3,3, 5-trimethylcyclohexanol as claimed in claim 1, wherein the Zn-promoted Ni-Mo unsupported catalyst contains Zn as assistant in 3.0-6.0% of the total mass of Ni and Mo.
5. Process for the synthesis of 3,3, 5-trimethylcyclohexanol according to any one of claims 1 to 4, characterised in that the process for the preparation of the Zn-promoted Ni-Mo unsupported catalyst comprises the following steps:
(1) adding organic amine into deionized water at the temperature of 30-60 ℃, and stirring for dissolving;
(2) adding a nickel source, a molybdenum source and an auxiliary active component into the solution at the same time, and stirring for 0.5-1 h under heat preservation;
(3) and (3) introducing the mixed solution obtained in the step (2) into a reaction kettle, crystallizing for 6-10 hours at 150-180 ℃ by a hydrothermal synthesis method, cooling to room temperature, filtering, drying the obtained solid product at 120 ℃ for 12 hours, and roasting at 400 ℃ for 5 hours to obtain the target catalyst.
6. The method for synthesizing 3,3, 5-trimethylcyclohexanol according to claim 5, wherein the organic amine in step (3) is ethanolamine or diethylamine, and the mass ratio of the organic amine to the total mass of the main active component, namely the nickel source and the molybdenum source, is 1:5 to 1: 22.
7. The method for synthesizing 3,3, 5-trimethylcyclohexanol as set forth in claim 5, wherein the ratio of the amount of substance added to deionized water to the total amount of substances of the main active components, namely the nickel source and the molybdenum source, is 18.5:1 in step (3).
8. The method for synthesizing 3,3, 5-trimethylcyclohexanol as recited in claim 5, wherein the nickel source is one of nickel acetate, nickel nitrate or basic nickel carbonate; the molybdenum source is one of ammonium heptamolybdate or ammonium tetramolybdate.
9. A process for the synthesis of 3,3, 5-trimethylcyclohexanol as claimed in claim 5, wherein the precursor of the co-active component zinc is zinc nitrate.
10. 3,3, 5-trimethylcyclohexanol synthesis method according to claim 1, characterized in that Zn-promoted Ni-Mo unsupported catalyst is treated before use as follows:
(11) performing extrusion forming, namely loading a catalyst with uniform particles and a volume of 20-40 meshes of 10ml into a constant-temperature section of a fixed bed reactor;
(12) reducing the catalyst under the hydrogen atmosphere by adopting the conditions of hydrogen flow of 80ml/min, temperature of 350 ℃, pressure of 1.0MPa and reduction time of 8 h;
(13) and after the reduction is finished, feeding is started when the temperature of the fixed bed reactor is reduced to 140-180 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1318130A1 (en) * | 2001-12-06 | 2003-06-11 | Haarmann & Reimer Gmbh | Process for the preparation of 3,3,5-trimethylcyclohexanol |
| CN105061176A (en) * | 2015-07-22 | 2015-11-18 | 黄河三角洲京博化工研究院有限公司 | Fixed-bed synthetic method for 3,3,5-trimethylcyclohexanone |
| CN105363460A (en) * | 2015-11-24 | 2016-03-02 | 黄河三角洲京博化工研究院有限公司 | Non-loaded type deep-hydrogenation catalyst and preparation method thereof |
| US20190344248A1 (en) * | 2016-09-23 | 2019-11-14 | Basf Se | Method for providing a fixed catalyst bed containing a doped structured shaped catalyst body |
| CN111732496A (en) * | 2020-07-30 | 2020-10-02 | 成都科特瑞兴科技有限公司 | System for producing 3,3, 5-trimethylcyclohexanol by hydrogenation of isophorone and use method thereof |
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- 2022-06-15 CN CN202210681273.1A patent/CN114870851A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1318130A1 (en) * | 2001-12-06 | 2003-06-11 | Haarmann & Reimer Gmbh | Process for the preparation of 3,3,5-trimethylcyclohexanol |
| CN105061176A (en) * | 2015-07-22 | 2015-11-18 | 黄河三角洲京博化工研究院有限公司 | Fixed-bed synthetic method for 3,3,5-trimethylcyclohexanone |
| CN105363460A (en) * | 2015-11-24 | 2016-03-02 | 黄河三角洲京博化工研究院有限公司 | Non-loaded type deep-hydrogenation catalyst and preparation method thereof |
| US20190344248A1 (en) * | 2016-09-23 | 2019-11-14 | Basf Se | Method for providing a fixed catalyst bed containing a doped structured shaped catalyst body |
| CN111732496A (en) * | 2020-07-30 | 2020-10-02 | 成都科特瑞兴科技有限公司 | System for producing 3,3, 5-trimethylcyclohexanol by hydrogenation of isophorone and use method thereof |
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