CN116474794A - Preparation method and application of dual-function molded framework cobalt catalyst - Google Patents
Preparation method and application of dual-function molded framework cobalt catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 239000010941 cobalt Substances 0.000 title claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 32
- 239000000956 alloy Substances 0.000 claims abstract description 32
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 28
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 238000005576 amination reaction Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 27
- 238000001994 activation Methods 0.000 claims description 15
- 230000004913 activation Effects 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 229910020639 Co-Al Inorganic materials 0.000 claims description 8
- 229910020675 Co—Al Inorganic materials 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 8
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- OITMBHSFQBJCFN-UHFFFAOYSA-N 2,5,5-trimethylcyclohexan-1-one Chemical compound CC1CCC(C)(C)CC1=O OITMBHSFQBJCFN-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 244000275012 Sesbania cannabina Species 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 33
- JJDFVIDVSCYKDS-UHFFFAOYSA-N 1,3,3-trimethyl-5-oxocyclohexane-1-carbonitrile Chemical compound CC1(C)CC(=O)CC(C)(C#N)C1 JJDFVIDVSCYKDS-UHFFFAOYSA-N 0.000 abstract description 15
- 229910000838 Al alloy Inorganic materials 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007868 Raney catalyst Substances 0.000 abstract description 4
- 238000003723 Smelting Methods 0.000 abstract description 4
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract 2
- 229910052726 zirconium Inorganic materials 0.000 abstract 2
- 229910000531 Co alloy Inorganic materials 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 208000014117 bile duct papillary neoplasm Diseases 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 150000001414 amino alcohols Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 241000234314 Zingiber Species 0.000 description 1
- 235000006886 Zingiber officinale Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 238000009530 blood pressure measurement Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000008397 ginger Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 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
- B01J25/00—Catalysts of the Raney type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of a zirconium-based framework cobalt catalyst with a double-function catalytic effect. The preparation method comprises the following steps: preparing zirconia synthetic sol; smelting cobalt and aluminum alloy, and crushing into alloy powder; adding cobalt-aluminum alloy powder into gel, drying, tabletting and activating to obtain the zirconium-based framework cobalt catalyst. Compared with the common Raney catalyst, the catalyst has certain acidity, and can simultaneously play roles of imidization and hydrogenation, inhibit hydrolysis of intermediate isophorone nitrile imine and improve the conversion rate of IPN when being applied to the amination hydrogenation of isophorone nitrile (IPN) to prepare isophorone diamine (IPDA). Experiments show that the IPN conversion rate can reach 100%, the IPDA selectivity is more than 99%, and the byproducts are greatly reduced.
Description
Technical Field
The patent relates to preparation and application of a bifunctional framework Co catalyst, and the catalyst can be applied to preparation of 3-aminomethyl-3, 5-trimethylcyclohexanone (IPDA) by amination and hydrogenation of 3-cyano-3, 5-trimethylcyclohexanone (IPN).
Background
The 3-aminomethyl-3, 5-trimethyl cyclohexylamine (isophorone diamine, IPDA) is mainly applied to preparing isophorone diisocyanate, polyamide and other high polymer materials, and is also applied to curing agents and the like, and the materials have the advantages of good chemical resistance, thermosetting property and the like. IPDA is a mixture of cis/trans isomers, and different cis/trans isomer ratios of IPDA are suitable for different fields. According to German laid-open patent DEA421154, IPDA having a cis-isomer of less than 60% is advantageous for lowering the maximum curing temperature of the epoxy resin, while IPDA having a cis-isomer content of more than 70% is advantageous for increasing the reaction rate of the polymeric resin.
U.S. patent publication Nos. 3352913 and 570569 disclose a two-step process for producing IPDA, which is the main process of industrial production at present, namely, 3-cyano-3, 5-trimethylcyclohexanone (isophorone nitrile, IPN) is reacted with excessive ammonia, imidized under the action of an acidic or basic catalyst to prepare isophorone nitrile imine, and then reacted with hydrogen to prepare isophorone diamine under the action of a Raney-based catalyst. The reaction of isophorone nitrile and ammonia to form isophorone nitrile imine is a reversible reaction, the reverse reaction is a hydrolysis reaction of Schiff base, and the generated IPN can be directly hydrogenated to obtain amino alcohol, which is also the most main byproduct of the reaction.
In addition, the catalyst applicable to the hydrogenation reaction in the second step of the process is a framework cobalt catalyst, and U.S. publication patent No. 6087296 discloses a preparation method of the framework cobalt catalyst, specifically, co-Al alloy powder is directly subjected to alkali treatment and activation, however, the method has low yield, low catalyst strength and easy pulverization, and indirectly increases the cost. Patent CN1557918A, US6489521 discloses a method for preparing a shaped skeletal cobalt catalyst, which uses a series of methods after mixing an inorganic or organic binder with a metal powder, but is not applied to the IPDA reaction.
Disclosure of Invention
In view of the above-mentioned drawbacks, the present invention provides a class of skeletal cobalt catalysts with dual imidization-hydrogenation functions, which have a higher strength and a longer lifetime than conventional skeletal cobalt catalysts.
The invention also aims at the application of the catalyst, which is used as the catalyst for preparing the IPDA by the IPN, can inhibit the hydrolysis reaction of the intermediate product isophorone nitrile imine, has hydrogenation performance, and greatly improves the yield of the IPDA.
In order to achieve the above purpose, the invention provides a preparation method of a dual-function molded framework cobalt catalyst, which comprises the following steps:
(1) Preparing Co-Al alloy, crushing the Co-Al alloy into alloy powder, and doping a certain amount of metal auxiliary agent and binder;
(2) Preparing zirconium oxide synthetic gel;
(3) Mixing the products obtained in the step (1) and the step (2), drying, tabletting and activating in-situ alkali liquor to obtain the catalyst.
By "manner of adding a Raney precursor during the preparation of the gel and then activating it in situ", this solution has the advantage that the Raney is coupled with the acidic catalyst during the preparation instead of the conventional loading, enhancing the interaction between the catalysts and ensuring the catalytic performance. Meanwhile, in-situ activation is adopted, so that the strength problem of the coupling catalyst is fundamentally solved, pulverization, agglomeration and the like are avoided, and the catalytic activity is maintained to the maximum extent.
In the method, in the step (1), the mass ratio of cobalt to aluminum in the cobalt-aluminum alloy is 0.5-1.5, the smelting temperature is 1600-1800 ℃, stirring is applied during smelting, the stirring time is 2-5min, and the stirring speed is 20-50r/min. And naturally cooling to room temperature after stirring to obtain an alloy block. The diameter of the obtained particles after crushing the alloy blocks is between 100 and 400 meshes, preferably between 200 and 300 meshes.
In the method of the invention, in the step (1), the binder is one or more of graphite, sesbania powder and cellulose. The addition amount is 5-20wt% based on the mass of the alloy powder. In the traditional IPDA hydrogenation catalyst, alloy blocks are directly activated and applied to a fixed bed, if the hydrogenation performance of the catalyst is improved, the activation degree must be increased, and if the activation degree is deepened, the strength of the catalyst is directly reduced, the strength is reduced, the catalyst is easy to pulverize during reaction, and materials are polluted.
In the method, in the step (1), the added metal auxiliary agent is one or more of Ca, mg, P, ni, pt, cr, co, ti, mg, B, zn and Mo, and the addition amount is 0.1-5wt% based on the mass of the alloy powder.
In the method of the present invention, step (2) is used for preparing a zirconia synthetic gel. Uniformly mixing a certain amount of tetrabutyl zirconate, deionized water and ruthenium acetate, wherein the mass ratio of the tetrabutyl zirconate to the deionized water to the ruthenium acetate is 1: x: y, wherein x is 1 to 20, preferably 2 to 10, y is 1 to 10, preferably 2 to 8. Sulfuric acid is then added to adjust the pH to 1-5. Stirring for 5-72h to obtain the zirconium oxide synthetic gel.
In the method of the invention, in the step (3), the alloy powder and zirconia gel are mixed according to the proportion of 1: mixing at a mass ratio of 5-15, preferably 1:6-12, stirring uniformly, and drying at 80-100deg.C for 6-12 hr. And then tabletting. The tablet grinding tool is a cylinder with the diameter of 1-5mm and the height of 2-6 mm. Preferably a cylinder with a diameter of 2-4mm and a height of 3-5 mm.
In the method of the invention, in the step (3), the activation mode is in-situ alkali liquor washing activation. The alkali is one of sodium hydroxide, potassium hydroxide, sodium carbonate and ammonia water. The alkali lye concentration required is 5-30 wt.%, preferably 10-25 wt.%. The activation temperature is 60-90 ℃, preferably 70-90 ℃. The activation time is 1-3h, and the space velocity of the alkali liquor in the activation is controlled to be 5-20h -1 。
The obtained high-strength bifunctional catalyst with both acid and hydrogenation performances is applied to a fixed bed IPN one-step method for preparing IPDA. During evaluation, a single-tube reactor is adopted, 50mL of catalyst is filled, ammonia gas, hydrogen gas and IPN are mixed and then enter the reactor, wherein the ammonia gas ratio IPN is 1.2-2.5:1 (molar ratio), and the hydrogen gas ratio IPN is 3-10:1 (molar ratio). The reaction pressure is 0.3-0.8Mpa, and the temperature is 100-300 ℃. Controlling the total airspeed to be 50-200h -1 。
At present, IPN is used for preparing IPDA, and the first step is that IPN is reacted with ammonia through an acid catalyst (silicon, titanium oxide) to generate IPDI, and then the IPDI is reacted with hydrogen and liquid ammonia through a Raney catalyst to generate IPDA. Since the first step is a reversible reaction, high conversion of the IPN cannot be ensured, and the IPN regenerated by the reverse reaction is directly hydrogenated to amino alcohol in the second step, which is detrimental to the quality of the product. According to the preparation method, the Raney catalyst is coupled to the acid catalyst through a certain scheme, and the dual-function catalyst for imidization and hydrogenation of amination is prepared, so that the previous two-step reaction is directly upgraded into one-step reaction, and the conversion rate and the selectivity are greatly improved.
The pressures described in the present invention are gauge pressures.
The invention has the positive effects that:
(1) The traditional skeleton Co catalyst for preparing IPDA by IPN hydrogenation is easy to pulverize pollutant materials in the reaction process and has low strength. The catalyst obtains a high-strength molded framework cobalt catalyst through a reasonable molding means, and improves the mechanical strength of the catalyst while not affecting the hydrogenation effect of the catalyst. Thereby indirectly improving the stability and safety in the reaction evaluation process.
(2) The zirconium oxide is introduced in the forming process of the catalyst, and the existence of the zirconium oxide provides a certain acid site, so that forward progress of the imidization reaction of isophorone nitrile is promoted. Isophorone nitrile imine is used as a Schiff base, has the characteristic of instability, is easy to hydrolyze to generate isophorone nitrile, and can influence the reaction yield when isophorone nitrile is directly hydrogenated. The acidic site is used as an active site for protecting isophorone nitrile imine, and can obviously reduce the amount of byproducts in the product, thereby improving the activity and stability of the catalyst.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to illustrate the present invention further, but are not to be construed as limiting the present invention.
N used in the examples of the present invention 2 The specific surface area and the pore structure of the catalyst microsphere are measured by an adsorption method (BET), and the model of the instrument is as follows: ASP2020, manufactured by american microphone instruments.
The inductively coupled plasma emission spectrometer (ICP-OES) used in the examples of the present invention was manufactured by Agilent Technologies and was model 720ICP-OES.
The particle intensity analyzer used in the embodiment of the invention is a digital display particle intensity analyzer of a ginger weir city analytical instrument factory, and the model is KC-3.
The gas chromatographic conditions used in the examples of the present invention were: agilent DB-5 chromatographic column, sample inlet temperature: 280 ℃; detector temperature: 280 ℃; h 2 Flow rate: 35ml/minThe method comprises the steps of carrying out a first treatment on the surface of the Air flow rate: 360ml/min. The column box temperature-raising program is as follows: the initial temperature is-100 ℃, the heating rate is 20 ℃/min, and the temperature is kept for 1min; the temperature is raised at 100-280 deg.c and 15 deg.c/min for 8min.
Example 1
350g of metallic cobalt and 650g of metallic aluminum were mixed and placed in a melting crucible. Then the crucible is placed in a smelting furnace, the temperature is raised to 1700 ℃, the temperature is kept for 5min, and meanwhile, stirring is started, and the stirring speed is 40r/min. Pouring the molten slurry on a graphite plate after completion, and naturally cooling to room temperature to obtain an alloy block. Crushing the alloy blocks into powder by a crusher, and sieving out 200-300 mesh samples by using a screen to obtain alloy powder. 50g of alloy powder, 6.55g of sesbania powder, 0.3g of copper powder and 0.2g of magnesium powder are taken and uniformly mixed for standby.
20g of tetrabutyl zirconate, 40g of deionized water and 160g of ruthenium acetate were mixed and the pH was adjusted to 3 by the addition of sulfuric acid. After stirring for 24 hours, 40g of alloy powder doped with binder and metal was added. Pressing into cylinder with diameter of 2mm and height of 3.5 mm. And drying at 100 ℃ for 12 hours for standby.
Placing in a reaction tube for in-situ activation, adopting 25wt% sodium hydroxide solution, circulating for 2h at 70 ℃ and having a space velocity of 8h -1 . And washing with deionized water to neutrality after finishing to obtain the catalyst.
The catalyst obtained was characterized and its BET specific surface area was measured to be 62m 2 And/g, the measured intensity is 340N/grain.
The catalyst was evaluated for IPN IPDA reaction, 50mL of the catalyst was charged into a single tube reactor, and the space velocity was 50h -1 The molar ratio of ammonia gas to IPN is 1.2:1, the molar ratio of hydrogen gas to IPN is 3.2:1, the reaction pressure is 0.3Mpa, and the temperature is 100 ℃. The operation was continued for 100 hours, and samples were taken every 10 hours for chromatographic analysis. The results were as follows: the average conversion of IPN was 99.3%, the average selectivity of IPDA was 99.9% and the other products (predominantly amino alcohols) were 0.8%. ICP-OES analysis is carried out on the product, and the existence of metals such as Co, al and the like is not found, which indicates that the catalyst is not pulverized and the catalyst shape is kept intact.
Example 2
The Co-Al alloy powder was prepared in the manner described in example 1.
50g of alloy powder, 3g of graphite, 0.5g of boron powder and 0.2g of magnesium powder are taken and uniformly mixed for standby.
20g of tetrabutylzirconate, 60g of deionized water and 80g of ruthenium acetate were mixed and the pH was adjusted to 1.5 by the addition of sulfuric acid. After stirring for 48 hours, 25g of alloy powder doped with binder and metal was added. Pressing into cylinder with diameter of 2.5mm and height of 3.5 mm. And drying at 80 ℃ for 9 hours for standby.
The mixture is placed in a reaction tube for in-situ activation, 20wt% sodium hydroxide solution is taken, and the mixture is circulated for 3 hours at 60 ℃. Airspeed is set to 11h -1 . And washing with deionized water to neutrality after finishing to obtain the catalyst.
The catalyst obtained was characterized and its BET specific surface area was found to be 65m 2 And/g, the measured intensity is 335N/grain.
The catalyst was evaluated for IPN IPDA reaction, 50mL of the catalyst was charged in a single tube reactor, and the space velocity was 120h -1 The ammonia gas ratio of IPN is 1.85:1, the hydrogen gas ratio of IPN is 6.5:1, the reaction pressure is 0.52Mpa, and the temperature is 150 ℃. The operation was continued for 100 hours, and samples were taken every 10 hours for chromatographic analysis. The results were as follows: the average conversion of IPN was 100%, the average selectivity of IPDA was 99.3% and the other products (predominantly amino alcohols) was 0.5%. ICP-OES analysis is carried out on the product, and the existence of metals such as Co, al and the like is not found, which indicates that the catalyst is not pulverized and the catalyst shape is kept intact.
Example 3
The Co-Al alloy powder was prepared in the manner described in example 1, with a cobalt-aluminum alloy mass ratio of 1.3.
50g of alloy powder, 9g of cellulose, 0.8g of molybdenum powder and 0.2g of phosphorus powder are taken and uniformly mixed for standby.
20g of tetrabutylzirconate, 80g of deionized water and 100g of ruthenium acetate were mixed and the pH was adjusted to 2.5 by the addition of sulfuric acid. After stirring for 24 hours, 25g of alloy powder doped with binder and metal was added. Pressing into cylinder with diameter of 2mm and height of 4.5 mm. And drying at 90 ℃ for 6 hours for standby.
The metal sheet was placed in a reaction tube and 25wt% sodium hydroxide solution was taken and circulated at 80℃for 1.5 hours. Airspeed is set to 18h -1 . And washing with deionized water to neutrality after finishing to obtain the catalyst.
The catalyst obtained was characterized and its BET specific surface area was found to be 65m 2 And/g, the measured intensity was 320N/grain.
The catalyst was evaluated for IPN IPDA reaction, 50mL of the catalyst was charged into a single tube reactor, and the space velocity was 200h -1 The molar ratio of ammonia gas to IPN is 2.4:1, the molar ratio of hydrogen gas to IPN is 9.5:1, the reaction pressure is 0.75Mpa, and the temperature is 260 ℃. The operation was continued for 100 hours, and samples were taken every 10 hours for chromatographic analysis. The results were as follows: the average conversion of IPN was 100%, the average selectivity of IPDA was 99.9%, and no aminoalcohol was detected. ICP-OES analysis is carried out on the product, and the existence of metals such as Co, al and the like is not found, which indicates that the catalyst is not pulverized and the catalyst shape is kept intact.
Comparative example 1
The commercially available catalyst for the hydrogenation of commercial IPNs to IPDA (from Graves chemical Co., U.S.A.) was used for characterization and evaluation with reference to the evaluation method in example 1. The industrial catalyst of the company is prepared by directly activating the alloy block without the step of extrusion molding. The specific surface area was found to be 61m 2 And/g, the pressure measurement intensity is 290N/grain, the average conversion rate of IPN is 99.5 percent, the average selectivity of IPDA is 99.1 percent, and meanwhile, the existence of a small amount of Co in the reaction liquid is detected, which indicates that the catalyst has the chalking phenomenon. The catalyst has slightly poorer catalytic performance than the catalyst of the patent.
Comparative example 2
Reference is made to the preparation of Raney catalyst according to example two of patent CN1557918A, in which the Ni-Al alloy is replaced by Co-Al alloy. Characterizing the catalyst, the specific surface area of the catalyst being 25m 2 And/g, the measured intensity is 200N/grain. The reaction evaluation was also carried out in the same manner as in example 1, with an average conversion of IPN of 96.3% and an average selectivity of IPDA of 98.2%. The catalyst has poorer catalytic performance than the catalyst in the patent.
Claims (10)
1. A method for preparing a dual function shaped skeletal cobalt catalyst, the method comprising:
(1) Preparing Co-Al alloy, crushing the Co-Al alloy into alloy powder, and doping a certain amount of metal auxiliary agent and binder;
(2) Preparing zirconium oxide synthetic gel;
(3) Mixing the products obtained in the step (1) and the step (2), drying, tabletting and activating in-situ alkali liquor to obtain the catalyst.
2. The method according to claim 1, characterized in that: the mass ratio of cobalt to aluminum in the Co-Al alloy powder prepared in the step (1) is 0.5-1.5, and the particle size of the crushed alloy powder is 100-400 meshes.
3. The method according to claim 1 or 2, characterized in that: the binder selected in the step (1) is one or more of graphite, sesbania powder and cellulose, and the addition amount is 5-20wt% based on the mass of the alloy powder.
4. A method according to any one of claims 1-3, characterized in that: the metal auxiliary agent used in the step (1) is one or more of Ca, mg, P, ni, pt, cr, co, ti, mg, B, zn and Mo, and the addition amount is 0.1-5wt% based on the mass of the alloy powder.
5. The method according to any one of claims 1-4, wherein: in the step (2), a certain amount of tetrabutyl zirconate, water and ruthenium acetate are uniformly mixed, and the mass ratio of the tetrabutyl zirconate to the water to the ruthenium acetate is 1: x: y, wherein x is 1-20 and y is 1-10. Then adding sulfuric acid to adjust the pH value to 1-5, and stirring for 5-72h to obtain the zirconia synthetic gel.
6. The method according to any one of claims 1-5, wherein: mixing the alloy powder and zirconia gel according to a ratio of 1: mixing the materials according to the mass ratio of 5-15, and uniformly stirring the materials.
7. The method according to any one of claims 1-6, wherein: the drying temperature in the step (3) is 80-100 ℃ and the drying time is 6-12h.
8. The method according to any one of claims 1-7, wherein: the tablet grinding tool is a cylinder with the diameter of 1-5mm and the height of 2-6 mm.
9. The method according to any one of claims 1-8, wherein: the concentration of alkali liquor required by in-situ activation is 5-30wt%; the temperature required in the activation process is 60-90 ℃, and the activation time is 1-3 hours; the space velocity of the alkali liquor in the activation process is controlled to be 5-20h -1 。
10. Catalyst prepared according to the process of any one of claims 1-9 for the amination and hydrogenation of 3-cyano-3, 5-trimethylcyclohexanone (IPN) to 3-aminomethyl-3, 5-trimethylcyclohexylamine (IPDA).
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