CN113941361A - Aromatization catalyst and preparation method and application thereof - Google Patents
Aromatization catalyst and preparation method and application thereof Download PDFInfo
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- CN113941361A CN113941361A CN202111251338.0A CN202111251338A CN113941361A CN 113941361 A CN113941361 A CN 113941361A CN 202111251338 A CN202111251338 A CN 202111251338A CN 113941361 A CN113941361 A CN 113941361A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 238000005899 aromatization reaction Methods 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 78
- 150000003624 transition metals Chemical class 0.000 claims abstract description 78
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 claims abstract description 56
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000004694 iodide salts Chemical class 0.000 claims abstract description 16
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002808 molecular sieve Substances 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011651 chromium Substances 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 7
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 238000004939 coking Methods 0.000 abstract description 5
- 238000003763 carbonization Methods 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000741 silica gel Substances 0.000 abstract 1
- 229910002027 silica gel Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000002815 homogeneous catalyst Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XQDNFAMOIPNVES-UHFFFAOYSA-N 3,5-Dimethoxyphenol Chemical compound COC1=CC(O)=CC(OC)=C1 XQDNFAMOIPNVES-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 230000017858 demethylation Effects 0.000 description 2
- 238000010520 demethylation reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000010731 rolling oil Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910021573 transition metal iodide Inorganic materials 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- SYTQFBVTZCYXOV-UHFFFAOYSA-N 3,5,5-trimethylcyclohex-2-en-1-one Chemical compound CC1=CC(=O)CC(C)(C)C1.CC1=CC(=O)CC(C)(C)C1 SYTQFBVTZCYXOV-UHFFFAOYSA-N 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an aromatization catalyst, a preparation method thereof and application thereof in the reaction of producing 3,5-dimethylphenol by isophorone aromatization, wherein the aromatization catalyst comprises a carrier, an active component and an auxiliary agent; the active component comprises MnO, MgO, other transition metals and oxides of other transition metals; the auxiliary agent comprises iodides of other transition metals; the other transition metal is selected from one or more of copper, nickel, chromium and titanium; the carrier is selected from one or more of molecular sieve, alumina and silica gel. The aromatization catalyst disclosed by the invention is applied to the reaction of producing 3,5-dimethylphenol by isophorone aromatization, can obviously reduce the temperature of isophorone aromatization reaction, simultaneously ensures higher conversion rate of isophorone, improves the selectivity of a target product 3,5-dimethylphenol and obviously reduces the phenomena of carbonization and coking.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to an aromatization catalyst, a preparation method thereof and application thereof in a reaction for producing 3,5-dimethylphenol by isophorone aromatization.
Background
The product is named 3,5-Dimethylphenol (MX) in the Chinese and 3, 5-dimethoxyphenol in the English. It is white needle crystal in appearance, and is dissolved in water and ethanol. The method is mainly used for producing pesticides, rubber accelerators, anti-aging agents, medicaments, spices, phenolic resin and the like. And the additive is also used as an additive of cold rolling oil for steel rolling, and can prolong the service life of the cold rolling oil. The toxicity of the product is classified as high toxicity, and toxic smoke is released when the product is burnt.
The current preparation methods of 3,5-dimethylphenol mainly comprise four methods: 1. the coal tar washing oil fraction extraction method has the advantages that the coal tar is cheap and easy to obtain, but the content of 3,5-dimethylphenol is low, the equipment cost is high, and the potential safety hazard is high. 2. The method is a traditional method for producing 3,5-dimethylphenol, has mature process but complex process, serious equipment corrosion and serious environmental pollution, and is gradually eliminated as people pay more and more attention to environmental protection. 3. The phenol alkylation method has simple process route but poor selectivity and can not meet industrial requirements. 4. The isophorone aromatization method has simple operation process, high yield and is economic and environment-friendly.
In the isophorone aromatization method, the reaction temperature of isophorone is high without catalyst, and the conversion rate is low, so the catalyst in the process has great influence on the yield and the selectivity.
The inventors have studied supported metal oxide catalysts and solid base catalysts. Studies on supported metal oxide catalysts have shown that 2% K is added2O auxiliary, Cr2O3Supported amount of Cr of 15%2O3-Al2O3The catalyst is reacted at the temperature of 550 ℃ and the space velocity of 1.5h-1The reaction conditions of (A) give better results; the conversion rate of isophorone reaches 71.2%, the selectivity of 3,5-dimethylphenol reaches 84.9%, and the yield reaches 60.5%. The research on the solid base catalyst obtains that the MgO calcined at 600 ℃ in the nitrogen atmosphere has the reaction temperature of 560 ℃ and the space velocity of 1.5h-1The reaction conditions of (A) give better results; the conversion rate of isophorone reaches 83.7%, the selectivity of 3,5-dimethylphenol reaches 85.6%, and the yield reaches 71.6%. (the 2005 master academic thesis of Tianjin university) the two catalysts have obvious disadvantages, namely that the solid catalyst is easy to deposit carbon under a high-temperature environment, the service life of the catalyst is short, and large-scale production is difficult to realize.
A process for the catalytic cleavage of isophorone using a homogeneous catalyst. The catalyst used in this process is an aliphatic or aromatic hydrocarbon substituted with a halogen atom. For example, chinese patent application publication No. CN101348421A discloses a method for preparing 3,5-dimethylphenol, which uses a pressurized gas-solid phase reaction experimental apparatus for north-american chemical production, uses methyl iodide as a homogeneous catalyst in a stainless steel tubular reactor, and achieves a conversion rate of isophorone of 100% and a selectivity of 3,5-dimethylphenol of 98% under reaction conditions of a catalyst amount of 1%, a reaction temperature of 550 ℃, and a reaction pressure of 2 atm.
When the homogeneous catalyst is used, the yield of the 3,5-dimethylphenol is obviously improved compared with that of a supported metal oxide catalyst and a solid base catalyst, but the homogeneous catalyst and a product are difficult to separate, so that the consumption is high, the product quality is reduced, and the cost is high.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses an aromatization catalyst which is applied to the reaction of 3,5, 5-trimethyl-2-cyclohexen-1-one (isophorone) aromatization to produce 3,5-dimethylphenol, can obviously reduce the temperature of isophorone aromatization reaction, simultaneously ensures that isophorone still has higher conversion rate at lower temperature, improves the selectivity of a target product 3,5-dimethylphenol and obviously reduces the phenomenon of carbonization and coking.
The specific technical scheme is as follows:
an aromatization catalyst comprising a carrier, an active component and an auxiliary agent;
the active component comprises MnO, MgO, other transition metals and oxides of other transition metals;
the auxiliary agent comprises iodides of other transition metals;
the other transition metal is selected from one or more of copper, nickel, chromium and titanium;
the carrier is selected from one or more of molecular sieve, alumina and silica sol.
The inventor finds in experiments that in the isophorone demethylation aromatization reaction, a metal element has adsorption effect on oxygen atoms on carbonyl groups to loosen C-O double bonds, C-H bonds on 6 positions are loosened due to electron interaction, and hydrogen atoms are adsorbed on the oxygen atoms in metal oxides; meanwhile, C-C bonds between carbon atoms on the 5-position and carbon atoms on the methyl group are loosened at high temperature, and the transition metal iodide can attack the C-C bonds, so that the methyl group falls off under mild conditions and forms methane molecules together with hydrogen atoms adsorbed on the catalyst. Under the conditions that the C-O double bond is weakened and the methyl and one hydrogen atom are dropped, the rest electrons interact to form a more stable C-OH structure and a benzene ring structure, and finally the 3,5-dimethylphenol is generated. The chemical equation of the reaction process is shown as the following formula:
in the process of producing 3,5-dimethylphenol by aromatizing isophorone, byproducts are mainly generated by high-temperature dehydration of isophorone, high-temperature decomposition, re-decomposition of decomposition products and decomposition reaction of the product 3,5-dimethylphenol at high temperature. In further experiments, the inventors have found that MnO, MgO, other transition metals and oxides of other transition metals are supported on the catalyst carrier as active components, and iodides of other transition metals are additionally added as auxiliaries. The specific catalyst combination has a promoting effect on the demethylation process, so that the reaction temperature is greatly reduced, and the coking phenomenon caused by high temperature is greatly reduced; meanwhile, the conversion rate of the substrate and the selectivity of the product are also obviously improved.
The aromatization catalyst disclosed by the invention mainly contains five components, MnO, MgO, other transition metals, oxides of other transition metals and iodides of other transition metals. Through a series of comparative experiments, it is found that if the iodides of other transition metals or other transition metals in the above five components are removed, or the iodides of other transition metals are replaced by corresponding chlorides, even if the reaction temperature can be reduced, the conversion rate of the substrate and the selectivity of the product are greatly reduced.
The selection of the other transition metal, the oxide of the other transition metal and the other transition metal in the iodide of the other transition metal are independent of each other and do not require to be completely identical, i.e. when the other transition metal is selected from copper, the oxide of the other transition metal may be selected from the oxides of nickel, chromium or titanium.
Preferably:
the molar ratio of MnO to MgO is 1: 1-5;
the MnO and the MgO account for 10-30% of the mass of the carrier;
the other transition metals account for 0.5-5.0% of the mass of the carrier;
the oxide of other transition metal accounts for 1-5% of the mass of the carrier;
the iodide of other transition metals accounts for 1-5% of the mass of the carrier.
Further preferably:
the other transition metal is selected from one or more of copper, nickel and chromium;
the iodide of the other transition metal is selected from cuprous iodide and/or nickel iodide.
Further preferably:
the mol ratio of MnO to MgO is 2-3: 5;
the MnO and the MgO account for 15-25% of the mass of the carrier;
the other transition metals account for 2.0-3.0% of the mass of the carrier;
the oxide of other transition metal accounts for 2-3% of the mass of the carrier;
the iodides of other transition metals account for 3-5% of the mass of the carrier;
the iodide of the other transition metal is selected from cuprous iodide.
The invention also discloses a preparation method of the aromatization catalyst, which comprises the following steps:
the method comprises the following steps: immersing the carrier into inorganic salt solution of other transition metals, introducing other transition metals, filtering and roasting in a reducing atmosphere to obtain the carrier loaded with other transition metals;
step two: soaking the carrier loaded with other transition metals prepared in the step one into alkali liquor for modification, filtering, washing and drying to obtain a catalyst carrier;
step three: and (3) mixing the catalyst carrier prepared in the step two with MnO, MgO, oxides of other transition metals and iodides of other transition metals, and roasting and tabletting to obtain the aromatization catalyst.
In the first step:
the carrier is selected from a ZSM-5 molecular sieve and/or a ZSM-11 molecular sieve, and is preferably a mixture of the ZSM-5 molecular sieve and the ZSM-11 molecular sieve, wherein the mass ratio of the ZSM-5 molecular sieve to the ZSM-11 molecular sieve is 5-10: 1;
the inorganic salt solutions of other transition metals all use water as a solvent, are all soluble salts, and can be selected from nitrate solutions, sulfate solutions, chloride solutions and the like of other transition metals.
Preferably, the concentration of the inorganic salt solution of the other transition metal is 10-30%.
The reducing atmosphere may be selected from hydrogen.
Since the neutral alkaline condition is more favorable for the isophorone cleavage reaction, while the modified carrier prepared in step one is acidic, the modified carrier is treated with alkali solution in order to neutralize its acidity.
In the second step:
the alkali liquor is selected from one or more of sodium carbonate aqueous solution, sodium hydroxide aqueous solution and ammonia water;
the concentration of the alkali liquor is 1-5 wt%, and the temperature is 50-80 ℃.
The time for immersing in the alkali liquor is 1-10 h, and the subsequent drying is carried out at 80-150 ℃.
In the third step:
the MnO and the MgO account for 10-30% of the mass of the catalyst carrier;
the oxide of other transition metal accounts for 1-5% of the mass of the catalyst carrier;
the iodides of other transition metals account for 1-5% of the mass of the catalyst carrier;
the roasting temperature is 350-550 ℃, and the roasting time is 5-10 hours.
Further preferably:
the other transition metal is selected from copper and/or nickel;
the iodide of the other transition metal is selected from cuprous iodide;
the mol ratio of MnO to MgO is 2-3: 5;
the MnO and MgO account for 15-25% of the mass of the carrier;
the other transition metals account for 2.0-3.0% of the mass of the carrier;
the oxide of other transition metal accounts for 2-3% of the mass of the carrier;
the iodides of other transition metals account for 3-5% of the mass of the carrier.
More preferably:
the MnO and MgO account for 20% of the mass of the carrier;
the other transition metal accounts for 2.5 percent of the mass of the carrier;
the oxide of other transition metal accounts for 2-3% of the mass of the carrier;
the iodides of other transition metals account for 3-5% of the mass of the carrier.
Application tests show that when the aromatization catalyst prepared by continuously optimized raw material types and compositions is used for the reaction of producing 3,5-dimethylphenol by isophorone aromatization, the reaction temperature can be greatly reduced, and meanwhile, higher catalytic activity is ensured. Tests show that the conversion rate of isophorone is up to 100%, the selectivity of 3,5-dimethylphenol is up to more than 96% at 300-340 ℃, and no scorch precipitate exists in the reaction liquid.
Preferably:
under the catalytic action of the aromatization catalyst, carrying out heterogeneous aromatization reaction on isophorone in a reactor to produce 3, 5-dimethylphenol;
the temperature of the heterogeneous aromatization reaction is 300-600 ℃, the pressure is 0.1-0.2 atm, and the mass space velocity of the raw material is 0.3-0.6 h-1。
The reactor is a fixed bed reactor, preferably a fixed bed reactor of DN8 mm.
The aromatization catalyst was used by packing 10cm of catalyst in a fixed bed reactor of DN8 mm.
In order to further improve the selectivity of the target product 3,5-dimethylphenol and significantly reduce the carbonization coking phenomenon, the temperature of the heterogeneous aromatization reaction is preferably 300-340 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses an aromatization catalyst, which comprises a carrier and five main components loaded on the carrier, wherein the five main components comprise MnO, MgO, other transition metals, oxides of other transition metals and iodides of other transition metals; the aromatization catalyst is applied to the reaction of producing 3,5-dimethylphenol by isophorone aromatization, can obviously reduce the temperature of isophorone aromatization reaction to 300 ℃; the conversion rate of isophorone and the selectivity of a target product 3,5-dimethylphenol are obviously improved, and the phenomena of carbonization and coking are obviously reduced.
Detailed Description
The present invention will be described in further detail below with reference to examples and comparative examples, but the embodiments of the present invention are not limited thereto.
Example 1
Preparation of aromatization catalyst a:
the method comprises the following steps: soaking a mixed molecular sieve composed of ZSM-5(25g, the grain size of 300nm) and ZSM-11(5g, the grain size of 300nm) in 25 wt% nickel nitrate water solution (water is used as a solvent as the following description if no special description exists) for 2h, filtering out the molecular sieve, carrying out vacuum drying at 80 ℃ for 30min, and then carrying out roasting at 400-600 ℃ for 2h in hydrogen atmosphere to obtain a modified molecular sieve with the nickel content of 2.5 wt%;
step two: soaking the modified molecular sieve in a 2 wt% sodium hydroxide aqueous solution (water is used as a solvent if no special description is given below) at 80 ℃ for 10h, modifying the molecular sieve again, filtering, washing, and drying at 100 ℃ to obtain a catalyst carrier;
step three: and (2) mixing the catalyst carrier prepared in the step two with a mixture of MnO and MgO which accounts for 20 wt% of the mass of the catalyst carrier (the molar ratio of MnO to MgO is 2:5), 2 wt% of nickel oxide and 3 wt% of cuprous iodide, and roasting at the high temperature of 500 ℃ for 10 hours to obtain the aromatization catalyst A with the granularity of 40-60 meshes.
Aromatization reaction: filling 100mm of aromatization catalyst A in a fixed bed reactor of DN8mm, and ensuring that the reaction temperature is 300 ℃, the reaction pressure is 1atm, and the mass space velocity of raw materials is 0.5h-1The raw material 3,5, 5-trimethyl-2-cyclohexen-1-one is pumped in under the condition of (1) to carry out aromatization reaction for two hours.
And (3) cooling the reaction gas, separating a liquid phase from the gas-liquid mixture through a gas-liquid separator, and carrying out chromatographic analysis on the liquid phase: the conversion rate of 3,5, 5-trimethyl-2-cyclohexen-1-one is 100%, the selectivity of 3,5-dimethylphenol is 96.4%, and no scorch precipitate exists in the reaction liquid.
Examples 2 to 5
According to the preparation method of example 1, the aromatization catalysts B to E were prepared by adjusting the type, concentration, loading time and loading amount of the inorganic salt solution of the transition metal in the first step, and the aromatization reaction was performed by adjusting the catalyst and reaction temperature according to the process conditions of the aromatization reaction in example 1. The results are shown in table 1 below.
TABLE 1
Examples 6 to 9
According to the preparation method of the embodiment 1, the aromatization catalysts F to I are prepared by adjusting the type and the addition amount of the transition metal iodide in the step three, and the aromatization reaction is carried out by adjusting the catalysts and the reaction temperature according to the technological conditions of the aromatization reaction in the embodiment 1. The results are shown in table 2 below.
TABLE 2
Comparative example 1
According to the preparation method of example 1, the aromatization catalyst J is prepared by adjusting the type, concentration, loading time and loading amount of the inorganic salt solution of the transition metal in the first step, and the aromatization reaction is performed by using the prepared aromatization catalyst J according to the technological conditions of the aromatization reaction in example 1. The results are shown in table 3 below.
TABLE 3
Comparative examples 2 to 5
According to the preparation method of the embodiment 1, the aromatization catalysts H-K are prepared by adjusting the types and the addition amount of the additives in the step three, and the aromatization reaction is carried out by using the prepared aromatization catalysts H-K according to the technological conditions of the aromatization reaction in the embodiment 1. The results are shown in Table 4 below.
TABLE 4
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods.
Claims (10)
1. An aromatization catalyst is characterized by comprising a carrier, an active component and an auxiliary agent;
the active component comprises MnO, MgO, other transition metals and oxides of other transition metals;
the auxiliary agent comprises iodides of other transition metals;
the other transition metal is selected from one or more of copper, nickel, chromium and titanium;
the carrier is selected from one or more of molecular sieve, alumina and silica sol.
2. The aromatization catalyst according to claim 1 characterized in that:
the molar ratio of MnO to MgO is 1: 1-5;
the MnO and the MgO account for 10-30% of the mass of the carrier;
the other transition metals account for 0.5-5.0% of the mass of the carrier;
the oxide of other transition metal accounts for 1-5% of the mass of the carrier;
the iodide of other transition metals accounts for 1-5% of the mass of the carrier.
3. The aromatization catalyst according to claim 1 characterized in that:
the other transition metal is selected from one or more of copper, nickel and chromium;
the iodide of the other transition metal is selected from cuprous iodide and/or nickel iodide.
4. The aromatization catalyst according to claim 3 characterized in that:
the mol ratio of MnO to MgO is 2-3: 5;
the MnO and the MgO account for 15-25% of the mass of the carrier;
the other transition metals account for 2.0-3.0% of the mass of the carrier;
the oxide of other transition metal accounts for 2-3% of the mass of the carrier;
the iodides of other transition metals account for 3-5% of the mass of the carrier.
5. A method of preparing an aromatization catalyst according to any one of claims 1 to 4 comprising:
the method comprises the following steps: immersing the carrier into inorganic salt solution of other transition metals, introducing other transition metals, filtering and roasting in a reducing atmosphere to obtain the carrier loaded with other transition metals;
step two: soaking the carrier loaded with other transition metals prepared in the step one into alkali liquor for modification, filtering, washing and drying to obtain a catalyst carrier;
step three: and (3) mixing the catalyst carrier prepared in the step two with MnO, MgO, oxides of other transition metals and iodides of other transition metals, and roasting and tabletting to obtain the aromatization catalyst.
6. The method of preparing an aromatization catalyst according to claim 5 wherein in step one:
the carrier is selected from a ZSM-5 molecular sieve and/or a ZSM-11 molecular sieve;
the concentration of the inorganic salt solution of other transition metals is 10-30 wt%;
the other transition metal loaded on the carrier is 0.5-5 wt% of the original carrier.
7. The method of preparing an aromatization catalyst according to claim 5 wherein in step two:
the alkali liquor is selected from one or more of sodium carbonate aqueous solution, sodium hydroxide aqueous solution and ammonia water;
the concentration of the alkali liquor is 1-5 wt%, and the temperature is 50-80 ℃.
8. The process for preparing an aromatization catalyst according to claim 5 characterized in that in step three:
the MnO and the MgO account for 10-30% of the mass of the catalyst carrier;
the oxide of other transition metal accounts for 1-5% of the mass of the catalyst carrier;
the iodides of other transition metals account for 1-5% of the mass of the catalyst carrier;
the roasting temperature is 350-550 ℃, and the roasting time is 5-10 hours;
the calcination is carried out in an inert atmosphere.
9. Use of an aromatization catalyst according to any one of claims 1 to 4 in the reaction of producing 3,5-dimethylphenol by the aromatization of isophorone, characterized in that:
under the catalytic action of the aromatization catalyst, carrying out heterogeneous aromatization reaction on isophorone in a reactor to produce 3, 5-dimethylphenol;
the temperature of the heterogeneous aromatization reaction is 300-600 ℃, the pressure is 0.1-0.2 atm, and the mass space velocity of the raw material is 0.3-0.6 h-1。
10. The use of the aromatization catalyst according to claim 9 in the reaction of isophorone aromatization to produce 3,5-dimethylphenol, wherein the temperature of the heterogeneous aromatization reaction is 300-340 ℃.
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| CN1583697A (en) * | 2004-06-15 | 2005-02-23 | 上海茂阳化工科技发展有限公司 | Preparing method for 3,5-dimethyl phenol |
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| US20140357820A1 (en) * | 2013-02-27 | 2014-12-04 | Materia, Inc. | Olefin metathesis catalyst compositions comprising at least two metal carbene olefin metathesis catalysts |
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