WO2018157815A1 - Catalyseur d'hydrogénation sélective, procédé de préparation de celui-ci et procédé d'évaluation catalytique dans la production d'isobutyraldéhyde - Google Patents

Catalyseur d'hydrogénation sélective, procédé de préparation de celui-ci et procédé d'évaluation catalytique dans la production d'isobutyraldéhyde Download PDF

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WO2018157815A1
WO2018157815A1 PCT/CN2018/077548 CN2018077548W WO2018157815A1 WO 2018157815 A1 WO2018157815 A1 WO 2018157815A1 CN 2018077548 W CN2018077548 W CN 2018077548W WO 2018157815 A1 WO2018157815 A1 WO 2018157815A1
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selective hydrogenation
hydrogenation catalyst
carrier
precious metal
reaction
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PCT/CN2018/077548
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Chinese (zh)
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张然
许莉
明卫星
王杰华
杨伟光
朱吟昊
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武汉凯迪工程技术研究总院有限公司
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Publication of WO2018157815A1 publication Critical patent/WO2018157815A1/fr

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6525—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention relates to the field of catalytic hydrogenation technology, in particular to a selective hydrogenation catalyst and a preparation method thereof and a catalytic evaluation method for forming isobutyraldehyde.
  • isobutyraldehyde is mainly obtained by carbonylation of propylene. It is usually a by-product of the carbonylation of propylene to butanol and octanol in a large ethylene unit. Usually a set of 300,000 tons/year ethylene plant produces by-product isobutyraldehyde per year. About 10,000 tons.
  • propylene carbonylation to the low pressure method ruthenium catalyst method
  • the positive isomer ratio in the crude carbonyl synthesis liquid rises to more than 10:1, resulting in an increasing source of isobutyraldehyde, which cannot meet the strong demand of downstream products.
  • Isobutyraldehyde is an important organic chemical raw material, which can be used to produce chemical products such as isobutanol, neopentyl glycol, isobutyric acid and methyl ethyl ketone. Among them, neopentyl glycol and isobutanol are the two most important downstream products. . Isobutanol is a good solvent and can also be used in petroleum additives, antioxidants, antifreeze, synthetic rubber, artificial musk, fruit essential oils and synthetic drugs.
  • isobutanol 2,6-di-tert-butyl-p-cresol and diisobutyl phthalate
  • isobutyl acetate isobutyl butyrate
  • isobutyl lactate triisobutyl citrate
  • Ester derivatives such as esters, isobutyl phthalate and isobutyl citrate are widely used in the production of coatings, plasticizers, synthetic lubricants, hydraulic oils, and the like.
  • Neopentyl glycol is a typical neopentyl structural diol with good chemical reaction properties and can be quickly involved in various chemical reactions such as esterification, condensation and oxidation. It is widely used in the production of polyester resins, polyurethanes and powder coatings. And synthetic lubricants, etc.
  • a sulfide or sulfur elemental additive of Ni mass is added to the Ni catalyst to poison a part of the Ni active center and reduce the hydrogenation activity of the catalyst.
  • the catalyst is used for the vapor phase hydrogenation of unsaturated aldehydes such as crotonaldehyde, acrolein and 2-ethylhexenal to a saturated aldehyde, and the selectivity of the saturated aldehyde can be increased to 94 to 97%, and the yield of the saturated alcohol in the product is low. At 1%, there is still a small amount of CO production.
  • this method can improve the selectivity of unsaturated aldehydes, the intentional addition of sulfides causes metal Ni poisoning to cause waste of metal Ni, and the activity is inhibited.
  • Patent CN102351667 discloses a process for the selective hydrogenation of methacrolein to prepare isobutyraldehyde.
  • the isobutylaldehyde is prepared by selective hydrogenation of methacrolein using a supported Pd catalyst, wherein the content of Pd in the catalyst is 0.1 wt% to 5 wt%, and the catalyst support is selected from the group consisting of molecular sieves, metal oxides, mesoporous silica, amorphous One or more of aluminum silicate, activated carbon or carbon nanotubes.
  • the reaction conditions are mild, the catalyst activity is high, and the selectivity is good.
  • the conversion rate of methacrolein is ⁇ 99%, the highest is 100%, and the selectivity of isobutyraldehyde is ⁇ 95.4%. However, the life of the catalyst is not provided.
  • the object of the present invention is to provide a selective hydrogenation catalyst and a preparation method thereof, and a catalytic evaluation method for producing isobutyraldehyde, which can be used to treat methacrolein under mild reaction conditions and an environmentally friendly green solvent water. Selective hydrogenation produces isobutyraldehyde.
  • a selective hydrogenation catalyst disclosed in the present invention is composed of a carrier and an active component, wherein the active component comprises a noble metal material and a non-precious metal material, and the carrier is a gas phase.
  • the active component comprises a noble metal material and a non-precious metal material
  • the carrier is a gas phase.
  • the noble metal material is a noble metal Ir
  • the non-precious metal material is a non-precious metal Mo, W, Ni, Co, Sm
  • the atomic ratio of the non-precious metal material to the noble metal material is 0.8 to 5.
  • a method for preparing the above selective hydrogenation catalyst comprising the steps of:
  • Step 1 Weigh a part of the carrier in a beaker, and weigh another part of the carrier as a carrier for impregnation. Under stirring, deionized water is added to the beaker until the carrier in the beaker is just saturated, and the deionization is recorded.
  • Step 2 the precious metal precursor is dissolved in water, heated at 45 ⁇ 55 ° C for 0.5 ⁇ 2.0 hours until the precious metal precursor is completely dissolved, labeled as solution A;
  • Step 3 dissolving the non-precious metal precursor in water, labeled as solution B;
  • Step 4 Mixing solution A and solution B uniformly, diluted, and reserved, labeled as impregnation liquid C, the volume of impregnation liquid C is equal to the weight of the impregnation carrier multiplied by the saturated water absorption rate W of the carrier;
  • Step 5 impregnating the carrier by an equal volume impregnation method, and dropping the impregnation liquid C onto the impregnation carrier under stirring, sequentially drying and calcining, and subjecting the calcined sample to reduction treatment, the reduction treatment is to treat the oxidation state precious metal
  • the oxide is reduced to a metallic noble metal, and the non-precious metal high-valent oxide is reduced to a low-valent oxide, thereby obtaining a selective hydrogenation catalyst m%D(n); wherein m% is the loading amount of the noble metal Ir, n Indicates the atomic ratio of non-noble metals to precious metals.
  • a catalytic evaluation method for producing isobutyraldehyde of the above selective hydrogenation catalyst characterized in that it comprises the following steps:
  • Step 100 taking 0.02 to 0.2 g of a selective hydrogenation catalyst, 0.3 to 2.0 g of 2-methylacrolein, 1.5 to 30 g of solvent water, and 0.015 to 0.1 g of an internal standard compound to be placed in the reaction vessel. In the lining, then the reactor is closed;
  • Step 200 charging the reactor with nitrogen gas of 0.1-1.0 MPa, performing a gas exchange operation, excluding air in the reaction vessel, and then switching to hydrogen gas to perform a gas exchange operation on the reaction vessel, and replacing the nitrogen gas;
  • Step 300 Then charging the reaction vessel with hydrogen having a pressure in the range of 1.0 to 4.0 MPa;
  • Step 400 heating the reaction vessel to 50-80 ° C, stirring the reaction at a reaction pressure of 1 to 6 MPa for 4 to 10 hours to carry out a selective hydrogenation reaction;
  • Step 500 After the above selective hydrogenation reaction is finished, the reaction vessel is cooled, and after the temperature is lowered to below room temperature, the unreacted hydrogen gas is released;
  • Step 600 The reaction vessel is opened, the aqueous phase is extracted with an organic solvent, and after standing and layering, the upper organic solvent is taken out for chromatographic analysis, and the selective hydrogenation catalyst and water are left in the polytetrafluoro liner of the reaction vessel;
  • Step 700 The selective hydrogenation catalyst after the reaction in the step 600 is no longer taken out, the 2-methyl acrolein and the internal standard compound are directly added again, the reaction kettle is closed, and the operations described in steps 200 to 600 are repeated to selectively hydrogenate.
  • the catalyst is applied for the first cycle;
  • Step 800 repeating the operations of steps 200-700 until the chromatographic analysis result of step 600 shows that the selective hydrogenation catalyst loses the reactivity and the selectivity of the product isobutyraldehyde, and the number of cycles of the selective hydrogenation catalyst is investigated. Life test.
  • the present invention uses an active component in which a precious metal is combined with a non-noble metal, and a non-precious metal is added to reduce the catalyst cost, the carrier is also inexpensive and easily available, and the catalyst preparation method is simple.
  • the reaction medium used in the present invention is green solvent water, and does not use toxic and harmful raw materials, and is an environmentally friendly process.
  • the invention provides a selective hydrogenation catalyst, wherein the selective hydrogenation catalyst is composed of a carrier and an active component, wherein the active component comprises a precious metal material and a non-precious metal material, and the carrier is fumed silica.
  • the active component comprises a precious metal material and a non-precious metal material
  • the carrier is fumed silica.
  • One of precipitated silica, alumina, carbon nitride, and titanium dioxide the special structure of the material is more favorable for the adsorption of the substrate 2-methylacrolein and the dispersion and activation of the active component, thereby preparing the catalyst It has good reactivity and high selectivity to isobutyraldehyde.
  • the precious metal material is noble metal Ir
  • the non-precious metal material is any one of non-precious metals Mo, W, Ni, Co, Sm, Ce and Re.
  • the atomic ratio of the material to the precious metal material is 0.8 to 5. In the atomic ratio range, the catalytic reaction has better activity and higher selectivity to isobutyraldehyde.
  • the precious metal material is loaded in an amount of 0.5 to 5% by weight of the entire catalyst, and the catalytic reaction has better activity and higher isobutyraldehyde selectivity in the loading range.
  • a method for preparing the above selective hydrogenation catalyst comprising the steps of:
  • Step 1 Weigh a part of the carrier in a beaker, and weigh another part of the carrier as a carrier for impregnation. Under stirring, deionized water is added to the beaker until the carrier in the beaker is just saturated, and the deionization is recorded.
  • the volume of water, the water absorption per unit mass of the carrier, that is, the saturated water absorption of the carrier W unit is mL / g;
  • Step 2 the precious metal precursor is dissolved in water, dissolved under heating conditions, labeled as solution A;
  • Step 3 dissolving the non-precious metal precursor in water, labeled as solution B;
  • Step 4 Mixing solution A and solution B uniformly, diluted, and reserved, labeled as impregnation liquid C, the volume of impregnation liquid C is equal to the weight of the impregnation carrier multiplied by the saturated water absorption rate W of the carrier;
  • Step 5 impregnating the carrier by an equal volume impregnation method, dropping the impregnation liquid C onto the impregnation carrier under stirring, sequentially drying and calcining, and subjecting the calcined sample to a reduction treatment, the reduction treatment is to oxidize the oxidation state noble metal
  • the material is reduced to a metallic noble metal, and the non-precious metal high-valent oxide is reduced to a low-valent oxide, thereby obtaining a selective hydrogenation catalyst m%D(n); wherein m% is the loading amount of the noble metal Ir, and n represents The atomic ratio of the non-noble metal to the noble metal, and D represents the molecular formula of the selective hydrogenation catalyst.
  • the noble metal precursor is hydrated antimony trichloride or hydrated antimony tetrachloride.
  • the non-precious metal precursor is one of ammonium paramolybdate, ammonium molybdate, ammonium metatungstate, nickel nitrate, basic nickel carbonate, cobalt nitrate, cerium nitrate, cerium nitrate, and cerium nitrate.
  • the molar concentration of the noble metal atoms in the immersion liquid C is in the range of 0.004 to 0.04 mol/L, and the molar concentration of the non-precious metal atoms is in the range of 0.003 to 0.2 mol/L, and the noble metal material is loaded.
  • the amount is 0.5 to 5% by weight of the entire catalyst.
  • the drying temperature is in the range of 40 to 110 ° C, preferably 60 to 90 ° C, the drying time is 10 to 30 hours, preferably 16 to 24 hours, and the baking temperature is 400 to 600 ° C, preferably
  • the reduction treatment temperature is 300 to 550 ° C
  • the reduction treatment temperature is 300 to 600 ° C, preferably 400 to 550 ° C
  • the reduction treatment atmosphere is a mixture of 5% H 2 and 95% N 2 volume percent
  • the reduction treatment time is 2 to 4 hour.
  • the catalyst active component obtained by using the above treatment conditions has a uniform distribution, and the interaction between the noble metal material and the non-precious metal material is moderate, so that the catalytic reaction activity is good, and the selectivity of isobutyraldehyde is high.
  • a catalytic evaluation method for producing isobutyraldehyde of the above selective hydrogenation catalyst characterized in that it comprises the following steps:
  • Step 100 taking 0.02 to 0.2 g of a selective hydrogenation catalyst, 0.3 to 2.0 g of 2-methylacrolein, 1.5 to 30 g of solvent water, and 0.015 to 0.1 g of an internal standard compound in a 50 mL stainless steel autoclave In the PTFE lining, then the reactor is closed;
  • Step 200 The reactor is filled with nitrogen gas of 0.1-1.0 MPa, (99.99% by volume of high-purity nitrogen) (nitrogen is an inert gas, does not react with hydrogen and air, and is cheap and easy to obtain), and is ventilated. Operation, excluding the air in the reaction vessel, switching to hydrogen to ventilate the reaction vessel, replacing the nitrogen gas, so that the reactor is sufficiently filled with hydrogen source hydrogen required for the reaction;
  • Step 300 then charging the reaction vessel with hydrogen having a pressure in the range of 1.0 to 4.0 MPa as a hydrogen source for selective hydrogenation;
  • Step 400 further heating the reaction vessel to 50-80 ° C in a heating jacket, stirring the reaction for 4 to 10 hours under a reaction pressure of 1 to 6 MPa, and performing a selective hydrogenation reaction;
  • Step 500 After the selective hydrogenation reaction is completed, the reaction kettle is cooled in an ice water bath, and after the temperature is lowered to below room temperature (25 ° C), the unreacted hydrogen gas is released;
  • Step 600 The reaction vessel is opened, the aqueous phase is extracted with an organic solvent, and after standing and layering, the upper organic solvent is taken out for chromatographic analysis, and the selective hydrogenation catalyst and water are left in the polytetrafluoro liner of the reaction vessel;
  • Step 700 The selective hydrogenation catalyst after the reaction in the step 600 is no longer taken out, the 2-methyl acrolein and the internal standard compound are directly added again, the reaction kettle is closed, and the operations described in steps 200 to 600 are repeated to selectively hydrogenate.
  • the catalyst is applied for the first cycle;
  • Step 800 repeating the operations of steps 200-700 until the chromatographic analysis result of step 600 shows that the selective hydrogenation catalyst loses the reactivity and the selectivity of the product isobutyraldehyde, and the number of cycles of the selective hydrogenation catalyst is investigated. Life test.
  • the organic solvent extracted by chromatography is toluene or ethyl acetate, and the reaction solvent water cannot be used as a chromatographic injection, and the solvent can be used as a chromatographic injection.
  • the solvent is immiscible with water but dissolves the products such as the substrate 2-methylacrolein and isobutyraldehyde, and thus is used as an extraction solvent to extract the substrate and product from the aqueous phase for chromatographic analysis.
  • the internal standard compound is n-hexane.
  • the quality of the internal standard compound is 5% of the mass of 2-methylacrolein, and the amount of the internal standard compound in the control system is prevented from causing a dilution effect on the substrate 2-methylacrolein.
  • the catalytic reaction proceeds; the solvent water is added in a mass ratio of 5 to 15 times, preferably 8 to 12 times, to ensure a suitable initial reaction concentration of 2-methylacrolein, which is advantageous for efficient reaction. .
  • Step 1 0.286 g of the purchased precipitated silica was placed in a beaker, and deionized water was added until the carrier was saturated, and the volume of the consumed water was recorded as 2.6 mL, that is, the saturated water absorption W of the carrier was 9.1 mL/g;
  • Step 2 take 0.022g of hydrated antimony trichloride, dissolved in 1.0mL of water, heated at 50 ° C for 0.5 hours to form a transparent red solution, labeled as solution A;
  • Step 3 Take 0.01g of ammonium paramolybdate, dissolved in 0.5mL of water, labeled as solution B;
  • Step 4 Mix solution A and solution B to form an immersion liquid, dilute to 2.6 mL with water, and mark it as immersion liquid C.
  • the molar concentration of noble metal atoms in immersion liquid C is 0.024 mol/L, and the molar concentration of non-precious metal atoms is 0.022. Mol/L;
  • Step 5 Another 0.286 g of precipitated silica is placed in a beaker. Under stirring, the impregnating solution C is dropped onto the carrier and dried at 80 ° C for 24 hours. After drying, the sample is transferred to a muffle furnace at 550 ° C for calcination. The sample was reduced in a mixture of 5% H 2 and 95% N 2 by volume at 400 ° C for 2 hours to obtain a catalyst 4% Ir-MoO 3 /SiO 2 (0.9).
  • the atomic ratio of the non-noble metal to the noble metal is 0.9, and 4% represents the loading amount of the noble metal Ir.
  • Step 1 0.286 g of the purchased precipitated silica was placed in a beaker, and deionized water was added until the carrier was just saturated, and the volume of the consumed water was recorded as 2.6 mL, that is, the saturated water absorption W of the carrier was 9.1 mL/g. ;
  • Step 2 take 0.022g of hydrated antimony trichloride, dissolved in 1.0mL of water, heated at 50 ° C for 0.5 hours to form a transparent red solution, labeled as solution A;
  • Step 3 take 0.022g of ammonium paramolybdate, dissolved in 0.5mL of water, labeled as solution B;
  • Step 4 Mix solution A and solution B uniformly, dilute with water to 2.6 mL, form an immersion liquid, and mark it as immersion liquid C.
  • the molar concentration of noble metal atoms in immersion liquid C is 0.024 mol/L, and the molar concentration of non-precious metal atoms is 0.048 mol/L;
  • Step 5 Another 0.286 g of precipitated silica is placed in a beaker, and the impregnating solution C is dropped onto the carrier under stirring, and dried at 80 ° C for 24 hours. After drying, the sample is transferred to a muffle furnace and calcined at 550 ° C to be calcined. The latter sample was reduced in a mixture of 5% H 2 and 95% N 2 by volume at 400 ° C for 2 hours to obtain a catalyst 4% Ir-MoO 3 /SiO 2 (2).
  • the atomic ratio of the non-noble metal to the noble metal is 2, and 4% represents the loading amount of the noble metal Ir.
  • Step 100 0.1 g of 4% Ir-MoO 3 /SiO 2 (0.9) catalyst, 0.45 g of 2-methylacrolein, 6 g of experimental water, and 0.0225 g of n-hexane were placed in a 50 mL stainless steel autoclave of polytetrafluoroethylene. In the lining, then the reactor is closed;
  • Step 200 The reactor is filled with nitrogen (99.99% by volume of high-purity nitrogen) to ventilate the reactor, the air in the reactor is removed, and the operation is repeated three times, and then switched to hydrogen to ventilate the reactor. Operate, replace the nitrogen, and repeat the operation three times;
  • Step 300 Then charging the reaction vessel with 2.0 MPa of hydrogen;
  • Step 400 The reaction vessel is then placed in a heating mantle to be heated to 60 ° C, and the reaction is stirred for 8 hours;
  • Step 500 After the above selective hydrogenation reaction is finished, the reaction kettle is cooled in an ice water bath, and after the temperature is lowered to below room temperature, the unreacted hydrogen gas is released;
  • Step 600 After the hydrogen release is completed, the reaction kettle is opened, and the aqueous phase is extracted with an organic solvent toluene, and after standing and layering, the upper organic solvent is taken out for chromatographic analysis to complete the hydrogenation performance evaluation of the fresh catalyst, and the specific data is shown in Table 1 .
  • the above 4% represents the loading amount of the precious metal Ir.
  • Step 100 0.1 g of 4% Ir-MoO 3 /SiO 2 (2), 0.45 g of 2-methylacrolein, 6 g of experimental water, and 0.0225 g of n-hexane were placed in a polytetrafluoroethylene lining of a 50 mL stainless steel autoclave. Medium, then the reactor is closed;
  • Step 200 The reactor is filled with nitrogen (99.99% by volume of high-purity nitrogen) to ventilate the reactor, the air in the reactor is removed, and the operation is repeated three times, and then switched to hydrogen to ventilate the reactor. Operate, replace the nitrogen, and repeat the operation three times;
  • Step 300 Then charging the reaction vessel with 2.0 MPa of hydrogen;
  • Step 400 The reaction kettle is placed in a heating mantle to be heated to 60 ° C, and the reaction is stirred for 8 hours to carry out a selective hydrogenation reaction;
  • Step 500 After the above selective hydrogenation reaction is finished, the reaction kettle is cooled in an ice water bath, and after the temperature is lowered to below room temperature, the unreacted hydrogen gas is released;
  • the performance evaluation of butyraldehyde is shown in Appendix 2.
  • the above 4% represents the loading amount of the precious metal Ir.
  • the life test of the catalyst was carried out in a 50 mL batch reactor.
  • the 4% Ir-MoO 3 /SiO 2 (0.1) catalyst and solvent water after one reaction were not taken out from the polytetrafluoro liner, and the fresh substrate and internal standard were directly added again to close the reaction vessel.
  • the reactor was ventilated using high purity nitrogen, and the air in the reactor was removed, and the operation was repeated three times. Then switch to hydrogen to ventilate the reactor, replace the nitrogen, and repeat the operation three times.
  • the reactor was then charged with 2.0 MPa of hydrogen.
  • the reaction kettle was placed in a heating mantle to be heated to 60 ° C, and the reaction was stirred for 8 hours.
  • reaction vessel was cooled in an ice water bath, and after the temperature was lowered to below room temperature, unreacted hydrogen gas was released. After the hydrogen release is completed, the reaction kettle is opened, and the aqueous phase is extracted with an organic solvent toluene. After standing to separate the layers, the upper organic solvent is taken out for chromatographic analysis, and a cycle test is completed. The total cycle is 6 times, and the catalytic activity is not significantly decreased. See attached table 1.
  • the above 4% represents the loading amount of the precious metal Ir.
  • the life test of the catalyst was carried out in a 50 mL batch reactor.
  • the 4% Ir-MoO 3 /SiO 2 (0.9) catalyst and solvent water after one reaction were not taken out from the polytetrafluoro liner, and the fresh substrate and internal standard were directly added again to close the reaction vessel.
  • the reactor was ventilated using high purity nitrogen, and the air in the reactor was removed, and the operation was repeated three times. Then switch to hydrogen to ventilate the reactor, replace the nitrogen, and repeat the operation three times.
  • the reactor was then charged with 2.0 MPa of hydrogen.
  • the reaction kettle was placed in a heating mantle to be heated to 60 ° C, and the reaction was stirred for 8 hours.
  • reaction vessel was cooled in an ice water bath, and after the temperature was lowered to below room temperature, unreacted hydrogen gas was released. After the hydrogen release is completed, the reaction kettle is opened, and the aqueous phase is extracted with an organic solvent toluene. After standing to separate the layers, the upper organic solvent is taken out for chromatographic analysis, and a cycle test is completed. The total cycle is 6 times, and the catalytic activity is not significantly decreased. See attached table 2.
  • the above 4% represents the loading amount of the precious metal Ir.
  • the selective hydrogenation reaction carried out by the present invention is:

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Abstract

L'invention concerne un catalyseur d'hydrogénation sélective, un procédé de préparation de celui-ci, et un procédé d'évaluation catalytique dans la production d'isobutyraldéhyde. Le catalyseur d'hydrogénation sélective est constitué de deux parties, à savoir un support et un composant actif. Le composant actif comprend un matériau métallique précieux et un matériau métallique non précieux. Le support est de la silice fumée, de la silice précipitée, de l'oxyde d'aluminium, du nitrure de carbone ou du dioxyde de titane. Le matériau métallique précieux est un métal précieux Ir. Le matériau métallique non précieux est l'un quelconque parmi les métaux non précieux Mo, W, Ni, Co, Sm, Ce et Re. Le rapport atomique du matériau métallique non précieux sur le matériau métallique précieux est de 0,8 à 5. Le catalyseur peut être utilisé pour hydrogéner sélectivement de la méthacroléine en vue de produire de l'isobutyraldéhyde dans une condition de réaction modérée et dans de l'eau.
PCT/CN2018/077548 2017-03-01 2018-02-28 Catalyseur d'hydrogénation sélective, procédé de préparation de celui-ci et procédé d'évaluation catalytique dans la production d'isobutyraldéhyde WO2018157815A1 (fr)

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CN106925267A (zh) * 2017-03-01 2017-07-07 武汉凯迪工程技术研究总院有限公司 选择性加氢催化剂和制备方法及其生成异丁醛的催化评价方法
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CN112206803B (zh) * 2020-09-30 2023-05-23 润泰化学（泰兴）有限公司 一种用于甲基丙烯醛选择性加氢生成异丁醛的催化剂及其制备方法
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CN116139879B (zh) * 2023-02-14 2024-01-26 安徽大学 二氧化硅负载铱镍催化剂IrNi/SiO2及其高选择性催化苯甲腈、巴豆醛和苄叉丙酮中的加氢方法和应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1275441A (zh) * 1999-05-26 2000-12-06 中国科学院大连化学物理研究所 一种α、β－不饱和醛选择加氢反应催化剂
CN101570469A (zh) * 2009-06-15 2009-11-04 上海华谊丙烯酸有限公司 一种由甲基丙烯醛加氢连续生产异丁醇的方法
CN102351667A (zh) * 2011-09-21 2012-02-15 上海华谊（集团）公司 一种甲基丙烯醛选择加氢制备异丁醛的方法
WO2016022601A1 (fr) * 2014-08-04 2016-02-11 ClearWaterBay Technology, Inc. Système et procédé de production de néopentylglycol
CN106631691A (zh) * 2016-12-08 2017-05-10 上海华谊（集团）公司 甲基丙烯醛选择加氢制甲基烯丙醇的方法
CN106902862A (zh) * 2017-03-01 2017-06-30 武汉凯迪工程技术研究总院有限公司 选择性加氢催化剂和制备方法及其生成2‑甲基烯丙醇的催化评价方法
CN106925267A (zh) * 2017-03-01 2017-07-07 武汉凯迪工程技术研究总院有限公司 选择性加氢催化剂和制备方法及其生成异丁醛的催化评价方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101260028B (zh) * 2008-04-16 2011-03-23 上海华谊丙烯酸有限公司 一种以异丁烯或叔丁醇为原料制备异丁醛的方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1275441A (zh) * 1999-05-26 2000-12-06 中国科学院大连化学物理研究所 一种α、β－不饱和醛选择加氢反应催化剂
CN101570469A (zh) * 2009-06-15 2009-11-04 上海华谊丙烯酸有限公司 一种由甲基丙烯醛加氢连续生产异丁醇的方法
CN102351667A (zh) * 2011-09-21 2012-02-15 上海华谊（集团）公司 一种甲基丙烯醛选择加氢制备异丁醛的方法
WO2016022601A1 (fr) * 2014-08-04 2016-02-11 ClearWaterBay Technology, Inc. Système et procédé de production de néopentylglycol
CN106631691A (zh) * 2016-12-08 2017-05-10 上海华谊（集团）公司 甲基丙烯醛选择加氢制甲基烯丙醇的方法
CN106902862A (zh) * 2017-03-01 2017-06-30 武汉凯迪工程技术研究总院有限公司 选择性加氢催化剂和制备方法及其生成2‑甲基烯丙醇的催化评价方法
CN106925267A (zh) * 2017-03-01 2017-07-07 武汉凯迪工程技术研究总院有限公司 选择性加氢催化剂和制备方法及其生成异丁醛的催化评价方法

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