WO2018157815A1 - Selective hydrogenation catalyst, method for preparing same, and catalytic evaluation method in generation of isobutyraldehyde - Google Patents

Selective hydrogenation catalyst, method for preparing same, and catalytic evaluation method in generation of isobutyraldehyde 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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French (fr)
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/en

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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:

Abstract

A selective hydrogenation catalyst, a method for preparing same, and a catalytic evaluation method in generation of isobutyraldehyde. The selective hydrogenation catalyst consists of two parts, i.e., a carrier and an active component. The active component comprises a precious metal material and a non-precious metal material. The carrier is one of fumed silica, precipitated silica, aluminum oxide, carbon nitride, and titanium dioxide. The precious metal material is precious 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 non-precious metal material to the precious metal material is 0.8-5. The catalyst can be used for selectively hydrogenating methacrolein to generate isobutyraldehyde under a mild reaction condition and in water.

Description

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Selective hydrogenation catalyst and preparation method thereof and catalytic evaluation method for producing isobutyraldehyde 技术领域Technical field
本发明涉及催化加氢技术领域，具体涉及一种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。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.
背景技术Background technique
工业生产中异丁醛主要由丙烯羰基化反应得到，一般是大型乙烯联合装置中由丙烯羰基化合成丁醇和辛醇的副产物，通常一套30万吨/年乙烯装置每年副产异丁醛约1万吨。但随丙烯羰基合成向低压法(铑催化剂法)的发展，粗羰基合成液中的正异构比升至10:1以上，导致异丁醛的来源日益下降，无法满足下游产品的强劲需求。因此，开发异丁醛新的合成途径已经迫在眉睫。此外，石油炼制催化裂化装置和蒸气裂解装置副产混合C4用途相对较小，价格较为低廉，因此以混合C4中的异丁烯为起始原料制备异丁醛具有重要意义。由于混合C4中分离出的异丁烯氧化合成MAL已工业化，若将MAL加氢制备异丁醛与该工艺对接将具有重要的经济意义和研究意义。In industrial production, 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. However, with the development of 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. Therefore, the development of new synthetic pathways for isobutyraldehyde is imminent. In addition, the petroleum refining catalytic cracking unit and the steam cracking unit by-product C4 are relatively small in use and relatively inexpensive, so it is important to prepare isobutyraldehyde by mixing isobutylene in C4 as a starting material. Since the oxidative synthesis of MAL separated from mixed C4 has been industrialized, it would be of great economic significance and research significance to hydrolyze MAL to prepare isobutyraldehyde to interface with the process.
异丁醛是一种重要的有机化工原料，可以用来生产异丁醇、新戊二醇、异丁酸、甲乙酮等化工产品，其中新戊二醇和异丁醇是最主要的两种下游产品。异丁醇是良好的溶剂，也可用于石油添加剂、抗氧化剂、防冻剂、合成橡胶、人造麝香、果子精油和合成药物等领域。从异丁醇出发，可以合成2，6-二叔丁基对甲酚以及邻苯二甲酸二异丁酯、醋酸异丁酯、丁酸异丁酯、乳酸异丁酯、柠檬酸三异丁酯、癸二酸异丁酯、硬酯酸异丁酯等酯类衍生物，广泛用于涂料、增塑剂、合成润滑剂、液压油等的生产中。新戊二醇是典型的新戊基结构二元醇，具有良好的化学反应性能，可快速参与酯化、缩合和氧化等多种化学反应，广泛用于生产聚酯类树脂、聚氨酯、粉末涂料及合成润滑油等。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. Starting from isobutanol, 2,6-di-tert-butyl-p-cresol and diisobutyl phthalate, isobutyl acetate, isobutyl butyrate, isobutyl lactate, triisobutyl citrate can be synthesized. 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.
由不饱和醛部分加氢制备饱和醛的反应也有专利报道。以往的报道中常用Ni系催化剂，但Ni活性过高，易于使不饱和醛完全加氢得到饱和醇，饱和醛最高收率仅有87％左右，不饱和醛与饱和醇的总选择性也只有90％左右，副 产物中有大量的不饱和醛裂解生成的CO及C3。众所周知，CO易于吸附在金属Ni表面，并与Ni形成羰基化合物，使Ni催化剂失活，降低催化剂的寿命。The reaction for the partial hydrogenation of unsaturated aldehydes to prepare saturated aldehydes has also been reported. Ni-based catalysts have been used in previous reports, but the activity of Ni is too high, and it is easy to completely hydrogenate unsaturated aldehydes to obtain saturated alcohols. The maximum yield of saturated aldehydes is only about 87%, and the total selectivity of unsaturated aldehydes and saturated alcohols is only About 90%, a by-product contains a large amount of CO and C3 formed by the cracking of unsaturated aldehydes. It is well known that CO is easily adsorbed on the surface of metal Ni and forms a carbonyl compound with Ni to deactivate the Ni catalyst and reduce the life of the catalyst.
专利GB1102796中向Ni催化剂中加入Ni质量的5～30％的硫化物或硫单质助剂，使部分Ni活性中心中毒，降低催化剂加氢活性。将该催化剂用于不饱和醛如巴豆醛、丙烯醛、2-乙基己烯醛的气相加氢制饱和醛，饱和醛的选择性可提高至94～97％，产物中饱和醇收率低于1％，但仍有少量的CO生成。虽然该方法可以提高不饱和醛选择性，但特意加入硫化物使金属Ni中毒造成了金属Ni的浪费，且活性收到抑制。In patent GB1102796, 5 to 30% of 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. Although 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.
专利CN102351667公开了一种甲基丙烯醛选择加氢制备异丁醛的方法。采用负载型Pd催化剂进行甲基丙烯醛选择加氢制备异丁醛，其中催化剂中Pd的含量为0.1wt％～5wt％，催化剂载体选自分子筛、金属氧化物、介孔二氧化硅、无定形硅酸铝、活性碳或碳纳米管中的一种或多种。反应条件温和，催化剂活性高、选择性好，其中甲基丙烯醛的转化率≥99％，最高可达100％，异丁醛的选择性≥95.4％。但是催化剂的寿命没有提供。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.
发明内容Summary of the invention
本发明的目的在于提供一种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，该催化剂在较温和的反应条件及一种环境友好的绿色溶剂水中能将甲基丙烯醛选择性加氢生成异丁醛。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.
为解决上述技术问题，本发明公开的一种选择性加氢催化剂，由载体和活性组分两部分组成，其特征在于：所述活性组分包括贵金属材料和非贵金属材料，所述载体为气相二氧化硅、沉淀二氧化硅、氧化铝、氮化碳、二氧化钛中的一种；其中，所述贵金属材料为贵金属Ir，所述非贵金属材料为非贵金属Mo、W、Ni、Co、Sm、Ce和Re中的任意一种，所述非贵金属材料与贵金属材料的原子比为0.8～5。In order to solve the above technical problem, 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. One of silicon dioxide, precipitated silica, alumina, carbon nitride, and titanium dioxide; wherein the noble metal material is a noble metal Ir, and the non-precious metal material is a non-precious metal Mo, W, Ni, Co, Sm, In any one of Ce and Re, the atomic ratio of the non-precious metal material to the noble metal material is 0.8 to 5.
一种上述选择性加氢催化剂的制备方法，它包括如下步骤：A method for preparing the above selective hydrogenation catalyst, comprising the steps of:
步骤1：称取一部分载体于烧杯中，称取另一部分载体作为浸渍用载体备用，搅拌条件下，在所述烧杯中滴入去离子水直至烧杯中的载体刚好吸附饱和 为止，记录消耗去离子水的体积，得到单位质量载体的吸水量，即载体的饱和吸水率W；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 of the unit mass carrier, that is, the saturated water absorption rate of the carrier W;
步骤2：将贵金属前驱体溶于水中，45～55℃加热0.5～2.0小时至贵金属前驱体完全溶解，标记为溶液A；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;
步骤3：将非贵金属前驱体溶于水中，标记为溶液B；Step 3: dissolving the non-precious metal precursor in water, labeled as solution B;
步骤4：将溶液A与溶液B混合均匀，稀释，备用，标记为浸渍液C，浸渍液C的体积等于浸渍用载体的重量乘以载体的饱和吸水率W；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;
步骤5：使用等体积浸渍法浸渍载体，搅拌条件下，将浸渍液C滴到浸渍用载体上，依次经干燥和焙烧，将焙烧后的样品进行还原处理，该还原处理过程是将氧化态贵金属氧化物还原为金属态贵金属，并将非贵金属高价态氧化物还原为低价态氧化物，从而得到选择性加氢催化剂m％D(n)；其中，m％为贵金属Ir的负载量，n表示非贵金属与贵金属的原子比。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.
一种上述选择性加氢催化剂的生成异丁醛的催化评价方法，其特征在于，它包括如下步骤：A catalytic evaluation method for producing isobutyraldehyde of the above selective hydrogenation catalyst, characterized in that it comprises the following steps:
步骤100：取0.02～0.2g的选择性加氢催化剂、0.3～2.0g的2-甲基丙烯醛、1.5～30g的溶剂水和0.015～0.1g的内标化合物置于反应釜的聚四氟衬里中，然后将反应釜封闭；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;
步骤200：反应釜中充入0.1～1.0MPa的氮气，进行换气操作，排除反应釜内的空气，再切换为氢气对反应釜进行换气操作，置换氮气；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;
步骤300：然后向反应釜中充入压力范围为1.0～4.0MPa的氢气；Step 300: Then charging the reaction vessel with hydrogen having a pressure in the range of 1.0 to 4.0 MPa;
步骤400：再将反应釜加热到50～80℃，在1～6MPa反应压力下，搅拌反应4～10小时，进行选择性加氢反应；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;
步骤500：上述选择性加氢反应结束后，将反应釜冷却，待温度降至室温以下后，释放未反应掉的氢气；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;
步骤600：打开反应釜，使用有机溶剂萃取水相，静置分层后，将上层有机溶剂取出，进行色谱分析，选择性加氢催化剂和水留在反应釜的聚四氟衬里中；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;
步骤700：不再取出步骤600中反应后的选择性加氢催化剂，直接重新加 入2-甲基丙烯醛和内标化合物，封闭反应釜，重复步骤200～600所述操作，对选择性加氢催化剂进行第一次循环套用；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;
步骤800：重复步骤200～700所述操作，直至步骤600的色谱分析结果显示选择性加氢催化剂失去反应活性和产物异丁醛的选择性为止，考察选择性加氢催化剂的循环套用次数，即寿命实验。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.
本发明的有益效果：The beneficial effects of the invention:
1、本发明使用贵金属与非贵金属组合的活性组分，加入非贵金属降低催化剂成本，载体亦便宜易得，且催化剂制备方法简单。1. 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.
2、相比传统的氯化水解法产生含盐含氯等难处理的废水，本发明使用的反应介质为绿色溶剂水，不使用有毒有害原料，是环境友好的工艺。2. Compared with the traditional chlorination hydrolysis method, it produces refractory wastewater containing salt and chlorine. 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.
3、本发明的催化反应条件的温度和压力较低，反应条件比较温和，原子利用率高，可以很好地抑制底物聚合，并提高C＝C双键选择性加氢的效果。3. The temperature and pressure of the catalytic reaction conditions of the invention are relatively low, the reaction conditions are relatively mild, and the atomic utilization rate is high, which can suppress the polymerization of the substrate well and improve the selective hydrogenation of the C=C double bond.
具体实施方式detailed description
以下结合具体实施例对本发明作进一步的详细说明：The present invention will be further described in detail below in conjunction with specific embodiments:
本发明所设计的一种选择性加氢催化剂，所述选择性加氢催化剂由载体和活性组分两部分组成，其中，活性组分包括贵金属材料和非贵金属材料，载体为气相二氧化硅、沉淀二氧化硅、氧化铝、氮化碳、二氧化钛中的一种(该材料特殊的结构更有利于底物2-甲基丙烯醛的吸附及活性组分的分散和活化，从而使得制备的催化剂具有较好的反应活性和较高的异丁醛的选择性)，贵金属材料为贵金属Ir，非贵金属材料为非贵金属Mo、W、Ni、Co、Sm、Ce和Re中的任意一种(使用这两类材料组合制备的催化剂，其表面更容易使氢气发生均裂，有利于C＝C双键的选择性加氢，从而提高反应的活性和异丁醛的选择性)，所述非贵金属材料与贵金属材料的原子比为0.8～5，该原子比范围内，催化反应具有较好的活性和较高的异丁醛的选择性。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. 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, and the non-precious metal material is any one of non-precious metals Mo, W, Ni, Co, Sm, Ce and Re. The catalyst prepared by the combination of these two materials has a surface which is more likely to homogenize hydrogen, and is advantageous for selective hydrogenation of C=C double bonds, thereby increasing the activity of the reaction and the selectivity of isobutyraldehyde, the non-precious metal 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.
上述技术方案中，所述贵金属材料的负载量为整个催化剂重量的0.5～5％，该负载量范围内催化反应具有较好的活性和较高的异丁醛的选择性。In the above technical solution, 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.
一种上述选择性加氢催化剂的制备方法，它包括如下步骤：A method for preparing the above selective hydrogenation catalyst, comprising the steps of:
步骤1：称取一部分载体于烧杯中，称取另一部分载体作为浸渍用载体备用，搅拌条件下，在所述烧杯中滴入去离子水直至烧杯中的载体刚好吸附饱和为止，记录消耗去离子水的体积，得到单位质量载体的吸水量，即载体的饱和吸水率W单位为mL/g；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;
步骤2：将贵金属前驱体溶于水中，加热条件下溶解，标记为溶液A；Step 2: the precious metal precursor is dissolved in water, dissolved under heating conditions, labeled as solution A;
步骤3：将非贵金属前驱体溶于水中，标记为溶液B；Step 3: dissolving the non-precious metal precursor in water, labeled as solution B;
步骤4：将溶液A与溶液B混合均匀，稀释，备用，标记为浸渍液C，浸渍液C的体积等于浸渍用载体的重量乘以载体的饱和吸水率W；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;
步骤5：使用等体积浸渍法浸渍载体，搅拌条件下将浸渍液C滴到浸渍用载体上，依次经干燥和焙烧，将焙烧后的样品进行还原处理，该还原处理过程是将氧化态贵金属氧化物还原为金属态贵金属，并将非贵金属高价态氧化物还原为低价态氧化物，从而得到选择性加氢催化剂m％D(n)；其中，m％为贵金属Ir的负载量，n表示非贵金属与贵金属的原子比，D表示选择性加氢催化剂的分子式。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.
上述技术方案中，所述贵金属前驱体为水合三氯化铱或水合四氯化铱。In the above technical solution, the noble metal precursor is hydrated antimony trichloride or hydrated antimony tetrachloride.
上述技术方案中，所述非贵金属前驱体为仲钼酸铵、钼酸铵、偏钨酸铵、硝酸镍、碱式碳酸镍、硝酸钴、硝酸钐、硝酸铈、硝酸铼中的一种。In the above technical solution, 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.
上述技术方案的步骤4中，所述浸渍液C中，贵金属原子的摩尔浓度范围为0.004～0.04mol/L，非贵金属原子的摩尔浓度范围为0.003～0.2mol/L，所述贵金属材料的负载量为整个催化剂重量的0.5～5％。In the step 4 of the above technical solution, 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.
上述技术方案的步骤5中，干燥温度范围为40～110℃，优选的为60～90℃，干燥时间为10～30小时，优选的为16～24小时，焙烧温度为400～600℃，优选的为500～550℃，还原处理温度为300～600℃，优选的为400～550℃，还原处理气氛为5％H 2与95％N 2体积百分比的混合气，还原处理时间为2～4小时。使用上述处理条件所得的催化剂活性组分分布均匀、贵金属材料和非贵金属材料的相互作用适中，使得催化反应活性较好，且异丁醛的选择性较高。 In the fifth step of the above technical solution, 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, and the reduction treatment atmosphere is a mixture of 5% H 2 and 95% N 2 volume percent, and 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.
一种上述选择性加氢催化剂的生成异丁醛的催化评价方法，其特征在于，它包括如下步骤：A catalytic evaluation method for producing isobutyraldehyde of the above selective hydrogenation catalyst, characterized in that it comprises the following steps:
步骤100：取0.02～0.2g的选择性加氢催化剂、0.3～2.0g的2-甲基丙烯醛、1.5～30g的溶剂水和0.015～0.1g的内标化合物置于50mL的不锈钢高压反应釜的聚四氟衬里中，然后将反应釜封闭；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;
步骤200：反应釜中充入0.1～1.0MPa的氮气，(99.99％体积分数比的高纯氮)(氮气为惰性气体，不与氢气和空气等发生反应，且便宜易得)，进行换气操作，排除反应釜内的空气，再切换为氢气对反应釜进行换气操作，置换氮气，使得反应釜内充分充满反应时所需要的氢源氢气；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;
步骤300：然后向反应釜中充入压力范围为1.0～4.0MPa的氢气用做选择性加氢反应的氢源；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;
步骤400：再将反应釜置于加热套中加热到50～80℃，在1～6MPa反应压力下，搅拌反应4～10小时，进行选择性加氢反应；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;
步骤500：上述选择性加氢反应结束后，将反应釜置于冰水浴中冷却，待温度降至室温(25℃)以下后，释放未反应掉的氢气；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;
步骤600：打开反应釜，使用有机溶剂萃取水相，静置分层后，将上层有机溶剂取出，进行色谱分析，选择性加氢催化剂和水留在反应釜的聚四氟衬里中；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;
步骤700：不再取出步骤600中反应后的选择性加氢催化剂，直接重新加入2-甲基丙烯醛和内标化合物，封闭反应釜，重复步骤200～600所述操作，对选择性加氢催化剂进行第一次循环套用；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;
步骤800：重复步骤200～700所述操作，直至步骤600的色谱分析结果显示选择性加氢催化剂失去反应活性和产物异丁醛的选择性为止，考察选择性加氢催化剂的循环套用次数，即寿命实验。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.
上述技术方案的步骤600中萃取用以色谱分析的有机溶剂为甲苯或乙酸乙酯，反应溶剂水不能作为色谱进样，而该溶剂可作为色谱进样。重要的是，该溶剂与水不互溶但可溶解底物2-甲基丙烯醛和异丁醛等产物，因此用作萃取溶剂，将底物和产物从水相中萃取出来进行色谱分析。In the step 600 of the above technical solution, 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. Importantly, 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.
上述技术方案中，所述内标化合物为正己烷。In the above technical solution, the internal standard compound is n-hexane.
上述技术方案中，所述内标化合物的加入质量为2-甲基丙烯醛质量的5％， 控制体系中内标化合物的加入量，防止对底物2-甲基丙烯醛造成稀释效应，影响催化反应的进行；溶剂水的加入质量为2-甲基丙烯醛体积的5～15倍，优选的为8～12倍，保证2-甲基丙烯醛合适的初始反应浓度，利于反应的高效进行。In the above technical solution, 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. .
实施例1：Example 1:
选择性加氢催化剂4％Ir-MoO 3/SiO 2(0.9)的制备为： The preparation of the selective hydrogenation catalyst 4% Ir-MoO 3 /SiO 2 (0.9) is:
步骤1：将0.286g购买的沉淀二氧化硅置于烧杯中，滴入去离子水直至载体吸附饱和为止，记录消耗水的体积为2.6mL，即载体的饱和吸水率W为9.1mL/g；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;
步骤2：取0.022g水合三氯化铱，溶于1.0mL水中，50℃加热0.5小时形成透明红色溶液，标记为溶液A；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;
步骤3：取0.01g仲钼酸铵，溶于0.5mL水中，标记为溶液B；Step 3: Take 0.01g of ammonium paramolybdate, dissolved in 0.5mL of water, labeled as solution B;
步骤4：将溶液A与溶液B混合均匀形成浸渍液，加水稀释至2.6mL，标记为浸渍液C，浸渍液C中贵金属原子的摩尔浓度为0.024mol/L，非贵金属原子的摩尔浓度为0.022mol/L；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;
步骤5：另取0.286g沉淀二氧化硅置于烧杯中，搅拌条件下，将浸渍液C滴到载体上，经80℃干燥24h，干燥后样品转移至马弗炉中550℃焙烧，焙烧后的样品在5％H 2与95％N 2体积百分比的混合气中，400℃条件下还原2小时，得到催化剂4％Ir-MoO 3/SiO 2(0.9)。 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).
上述技术方案中(0.9)表示非贵金属与贵金属的原子比为0.9，4％表示贵金属Ir的负载量。In the above technical solution (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.
实施例2：Example 2:
选择性加氢催化剂4％Ir-MoO 3/SiO 2(2)的制备为： The preparation of the selective hydrogenation catalyst 4% Ir-MoO 3 /SiO 2 (2) is:
步骤1：将0.286g购买的沉淀二氧化硅置于烧杯中，滴入去离子水直至载体刚刚吸附饱和为止，记录消耗水的体积为2.6mL，即载体的饱和吸水率W为9.1mL/g；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. ;
步骤2：取0.022g水合三氯化铱，溶于1.0mL水中，50℃加热0.5小时形 成透明红色溶液，标记为溶液A；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;
步骤3：取0.022g仲钼酸铵，溶于0.5mL水中，标记为溶液B；Step 3: take 0.022g of ammonium paramolybdate, dissolved in 0.5mL of water, labeled as solution B;
步骤4：将溶液A与溶液B混合均匀，加水稀释至2.6mL，形成浸渍液，标记为浸渍液C，浸渍液C中贵金属原子的摩尔浓度为0.024mol/L，非贵金属原子的摩尔浓度为0.048mol/L；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;
步骤5：另取0.286g沉淀二氧化硅置于烧杯中，搅拌条件下，将浸渍液C滴到载体上，经80℃干燥24小时，干燥后样品转移至马弗炉中550℃焙烧，焙烧后的样品在5％H 2与95％N 2体积百分比的混合气中，400℃条件下还原2小时，得到催化剂4％Ir-MoO 3/SiO 2(2)。 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).
上述技术方案中(2)表示非贵金属与贵金属的原子比为2，4％表示贵金属Ir的负载量。In the above aspect (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.
实施例3：Example 3:
选择性加氢催化剂4％Ir-MoO 3/SiO 2(0.9)的加氢性能评价为： The hydrogenation performance of the selective hydrogenation catalyst 4% Ir-MoO 3 /SiO 2 (0.9) was evaluated as:
步骤100：将0.1g的4％Ir-MoO 3/SiO 2(0.9)催化剂、0.45g的2-甲基丙烯醛、6g实验用水，0.0225g正己烷置于50mL不锈钢高压反应釜的聚四氟衬里中，然后将反应釜封闭； 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;
步骤200：在反应釜中充入氮气(99.99％体积分数比的高纯氮)对反应釜进行换气操作，排除反应釜内的空气，重复操作三次，再切换为氢气对反应釜进行换气操作，置换氮气，重复操作三次；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;
步骤300：然后向反应釜中充入2.0MPa氢气；Step 300: Then charging the reaction vessel with 2.0 MPa of hydrogen;
步骤400：然后将反应釜置于加热套中加热到60℃，搅拌反应8小时；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;
步骤500：上述选择性加氢反应结束后，将反应釜置于冰水浴中冷却，待温度降至室温以下后，释放未反应掉的氢气；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;
步骤600：氢气释放完成后，打开反应釜，使用有机溶剂甲苯萃取水相，静置分层后，将上层有机溶剂取出进行色谱分析，完成新鲜催化剂的加氢性能评价，具体数据见附表1。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 .
上述4％表示贵金属Ir的负载量。The above 4% represents the loading amount of the precious metal Ir.
实施例4：Example 4:
选择性加氢催化剂4％Ir-MoO 3/SiO 2(2)的加氢性能评价为： The hydrogenation performance of the selective hydrogenation catalyst 4% Ir-MoO 3 /SiO 2 (2) was evaluated as:
步骤100：将0.1g的4％Ir-MoO 3/SiO 2(2)、0.45g的2-甲基丙烯醛、6g实验用水，0.0225g正己烷置于50mL不锈钢高压反应釜的聚四氟衬里中，然后将反应釜封闭； 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;
步骤200：在反应釜中充入氮气(99.99％体积分数比的高纯氮)对反应釜进行换气操作，排除反应釜内的空气，重复操作三次，再切换为氢气对反应釜进行换气操作，置换氮气，重复操作三次；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;
步骤300：然后向反应釜中充入2.0MPa氢气；Step 300: Then charging the reaction vessel with 2.0 MPa of hydrogen;
步骤400：将反应釜置于加热套中加热到60℃，搅拌反应8小时，进行选择性加氢反应；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;
步骤500：上述选择性加氢反应结束后，将反应釜置于冰水浴中冷却，待温度降至室温以下后，释放未反应掉的氢气；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;
步骤600：氢气释放完成后，打开反应釜，使用有机溶剂甲苯萃取水相，静置分层后，将上层有机溶剂取出进行色谱分析，完成新鲜催化剂的C＝C双键选择性加氢生成异丁醛的性能评价，具体数据见附表2。Step 600: After the hydrogen release is completed, the reaction kettle is opened, 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 selective hydrogenation of the C=C double bond of the fresh catalyst. The performance evaluation of butyraldehyde is shown in Appendix 2.
上述4％表示贵金属Ir的负载量。The above 4% represents the loading amount of the precious metal Ir.
实施例5：Example 5:
选择性加氢催化剂4％Ir-MoO 3/SiO 2(0.9)的寿命评价为： The life of the selective hydrogenation catalyst 4% Ir-MoO 3 /SiO 2 (0.9) was evaluated as:
催化剂的寿命试验是在50mL的间歇反应釜中进行的。一次反应后的4％Ir-MoO 3/SiO 2(0.1)催化剂与溶剂水不从聚四氟衬里取出，直接重新加入新鲜的底物和内标，封闭反应釜。使用高纯氮对反应釜进行换气操作，排除反应釜内的空气，重复操作三次。再切换为氢气对反应釜进行换气操作，置换氮气，重复操作三次。然后向反应釜中充入2.0MPa氢气。将反应釜置于加热套中加热到60℃，搅拌反应8小时。反应结束后，将反应釜置于冰水浴中冷却，待温度降至室温以下后，释放未反应掉的氢气。氢气释放完成后，打开反应釜，使 用有机溶剂甲苯萃取水相，静置分层后，将上层有机溶剂取出进行色谱分析，完成一次循环试验，共计循环6次，催化活性没有明显下降，具体数据见附表1。 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. After the reaction was completed, the 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.
上述4％表示贵金属Ir的负载量。The above 4% represents the loading amount of the precious metal Ir.
实施例6：Example 6
选择性加氢催化剂4％Ir-MoO 3/SiO 2(2)的寿命评价： Selective hydrogenation catalyst 4% Ir-MoO 3 / SiO 2 (2) Evaluation of lifetime:
催化剂的寿命试验是在50mL的间歇反应釜中进行的。一次反应后的4％Ir-MoO 3/SiO 2(0.9)催化剂与溶剂水不从聚四氟衬里取出，直接重新加入新鲜的底物和内标，封闭反应釜。使用高纯氮对反应釜进行换气操作，排除反应釜内的空气，重复操作三次。再切换为氢气对反应釜进行换气操作，置换氮气，重复操作三次。然后向反应釜中充入2.0MPa的氢气。将反应釜置于加热套中加热到60℃，搅拌反应8小时。反应结束后，将反应釜置于冰水浴中冷却，待温度降至室温以下后，释放未反应掉的氢气。氢气释放完成后，打开反应釜，使用有机溶剂甲苯萃取水相，静置分层后，将上层有机溶剂取出进行色谱分析，完成一次循环试验，共计循环6次，催化活性没有明显下降，具体数据见附表2。 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. After the reaction was completed, the 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.
上述4％表示贵金属Ir的负载量。The above 4% represents the loading amount of the precious metal Ir.
本发明进行的选择性加氢反应为：The selective hydrogenation reaction carried out by the present invention is:
Figure PCTCN2018077548-appb-000001
Figure PCTCN2018077548-appb-000001
附表1、4％Ir-MoO 3/SiO 2(0.9)催化剂的性能评价及寿命试验结果 Performance evaluation and life test results of Table 1,4% Ir-MoO 3 / SiO 2 (0.9) Catalyst
Figure PCTCN2018077548-appb-000002
Figure PCTCN2018077548-appb-000002
附表2、4％Ir-MoO 3/SiO 2(2)催化剂的性能评价及寿命试验结果 Performance evaluation and life test results of Table 2,4% Ir-MoO 3 / SiO 2 (2) Catalyst
Figure PCTCN2018077548-appb-000003
Figure PCTCN2018077548-appb-000003
本发明所涉及的本说明书未作详细描述的内容属于本领域专业技术人员 公知的现有技术。The contents of the present invention which are not described in detail in the present specification belong to the prior art known to those skilled in the art.

Claims (11)

  1. 一种选择性加氢催化剂，由载体和活性组分两部分组成，其特征在于：所述活性组分包括贵金属材料和非贵金属材料，所述载体为气相二氧化硅、沉淀二氧化硅、氧化铝、氮化碳、二氧化钛中的一种；其中，所述贵金属材料为贵金属Ir，所述非贵金属材料为非贵金属Mo、W、Ni、Co、Sm、Ce和Re中的任意一种，所述非贵金属材料与贵金属材料的原子比为0.8～5。A selective hydrogenation catalyst consisting of a carrier and an active component, characterized in that the active component comprises a noble metal material and a non-precious metal material, the carrier is fumed silica, precipitated silica, and oxidized One of aluminum, carbon nitride, and titanium dioxide; wherein the noble metal material is a noble metal Ir, and 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 non-precious metal material to the noble metal material is 0.8 to 5.
  2. 根据权利要求1所述的选择性加氢催化剂，其特征在于：所述贵金属材料的负载量为整个催化剂重量的0.5～5％。The selective hydrogenation catalyst according to claim 1, wherein the noble metal material is supported in an amount of from 0.5 to 5% by weight based on the total of the catalyst.
  3. 一种权利要求1所述选择性加氢催化剂的制备方法，其特征在于，它包括如下步骤：A method of preparing a selective hydrogenation catalyst according to claim 1, characterized in that it comprises the following steps:
    步骤1：称取一部分载体于烧杯中，称取另一部分载体作为浸渍用载体备用，搅拌条件下，在所述烧杯中滴入去离子水直至烧杯中的载体刚好吸附饱和为止，记录消耗去离子水的体积，得到单位质量载体的吸水量，即载体的饱和吸水率W；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 of the unit mass carrier, that is, the saturated water absorption rate of the carrier W;
    步骤2：将贵金属前驱体溶于水中，45～55℃加热0.5～2.0小时至贵金属前驱体完全溶解，标记为溶液A；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;
    步骤3：将非贵金属前驱体溶于水中，标记为溶液B；Step 3: dissolving the non-precious metal precursor in water, labeled as solution B;
    步骤4：将溶液A与溶液B混合均匀，稀释，备用，标记为浸渍液C，浸渍液C的体积等于浸渍用载体的重量乘以载体的饱和吸水率W；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;
    步骤5：使用等体积浸渍法浸渍载体，搅拌条件下，将浸渍液C滴到浸渍用载体上，依次经干燥和焙烧，将焙烧后的样品进行还原处理，该还原处理过程是将氧化态贵金属氧化物还原为金属态贵金属，并将非贵金属高价态氧化物还原为低价态氧化物，从而得到选择性加氢催化剂m％D(n)；其中，m％为贵金属Ir的负载量，n表示非贵金属与贵金属的原子比。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.
  4. 根据权利要求3所述选择性加氢催化剂的制备方法，其特征在于：所述贵金属前驱体为水合三氯化铱或水合四氯化铱。The method for preparing a selective hydrogenation catalyst according to claim 3, wherein the noble metal precursor is hydrated antimony trichloride or hydrated antimony tetrachloride.
  5. 根据权利要求3所述选择性加氢催化剂的制备方法，其特征在于：所 述非贵金属前驱体为仲钼酸铵、钼酸铵、偏钨酸铵、硝酸镍、碱式碳酸镍、硝酸钴、硝酸钐、硝酸铈、硝酸铼中的一种。The method for preparing a selective hydrogenation catalyst according to claim 3, wherein the non-precious metal precursor is ammonium paramolybdate, ammonium molybdate, ammonium metatungstate, nickel nitrate, basic nickel carbonate, cobalt nitrate One of cerium nitrate, cerium nitrate, and cerium nitrate.
  6. 根据权利要求3所述选择性加氢催化剂的制备方法，其特征在于：所述浸渍液C中，贵金属原子的摩尔浓度范围为0.004～0.04mol/L，非贵金属原子的摩尔浓度范围为0.003～0.2mol/L，所述贵金属材料的负载量为整个催化剂重量的0.5～5％。The method for preparing a selective hydrogenation catalyst according to claim 3, wherein in the immersion liquid C, the molar concentration of the noble metal atoms 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, the loading amount of the noble metal material is 0.5 to 5% by weight of the entire catalyst.
  7. 根据权利要求3所述选择性加氢催化剂的制备方法，其特征在于：所述步骤5中，干燥温度范围为40～110℃，干燥时间为10～30小时，焙烧温度为400～600℃，焙烧时间为3～6小时，还原处理温度为300～600℃，还原处理气氛为5％H 2与95％N 2体积百分比的混合气，还原处理时间为2～4小时。 The method for preparing a selective hydrogenation catalyst according to claim 3, wherein in the step 5, the drying temperature ranges from 40 to 110 ° C, the drying time is 10 to 30 hours, and the baking temperature is 400 to 600 ° C. The calcination time is 3 to 6 hours, the reduction treatment temperature is 300 to 600 ° C, and the reduction treatment atmosphere is a mixture gas of 5% H 2 and 95% N 2 volume percent, and the reduction treatment time is 2 to 4 hours.
  8. 一种权利要求1所述选择性加氢催化剂生成异丁醛的催化评价方法，其特征在于，它包括如下步骤：A catalytic evaluation method for producing isobutyraldehyde by the selective hydrogenation catalyst according to claim 1, characterized in that it comprises the following steps:
    步骤100：取0.02～0.2g的选择性加氢催化剂、0.3～2.0g的2-甲基丙烯醛、1.5～30g的溶剂水和0.015～0.1g的内标化合物置于反应釜的聚四氟衬里中，然后将反应釜封闭；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;
    步骤200：反应釜中充入0.1～1.0MPa的氮气，进行换气操作，排除反应釜内的空气，再切换为氢气对反应釜进行换气操作，置换氮气；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;
    步骤300：然后向反应釜中充入压力范围为1.0～4.0MPa的氢气；Step 300: Then charging the reaction vessel with hydrogen having a pressure in the range of 1.0 to 4.0 MPa;
    步骤400：再将反应釜加热到50～80℃，在1～6MPa反应压力下，搅拌反应4～10小时，进行选择性加氢反应；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;
    步骤500：上述选择性加氢反应结束后，将反应釜冷却，待温度降至室温以下后，释放未反应掉的氢气；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;
    步骤600：打开反应釜，使用有机溶剂萃取水相，静置分层后，将上层有机溶剂取出，进行色谱分析，选择性加氢催化剂和水留在反应釜的聚四氟衬里中；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;
    步骤700：不再取出步骤600中反应后的选择性加氢催化剂，直接重新加入2-甲基丙烯醛和内标化合物，封闭反应釜，重复步骤200～600所述操作，对选择性加氢催化剂进行第一次循环套用；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;
    步骤800：重复步骤200～700所述操作，直至步骤600的色谱分析结果显示选择性加氢催化剂失去反应活性和产物异丁醛的选择性为止，考察选择性加氢催化剂的循环套用次数，即寿命实验。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.
  9. 根据权利要求8所述的选择性加氢催化剂生成异丁醛的催化评价方法，其特征在于：所述步骤600中萃取用以色谱分析的有机溶剂为甲苯或乙酸乙酯。The catalytic evaluation method for producing isobutyraldehyde by the selective hydrogenation catalyst according to claim 8, wherein the organic solvent extracted by chromatography in the step 600 is toluene or ethyl acetate.
  10. 根据权利要求8所述的选择性加氢催化剂生成异丁醛的催化评价方法，其特征在于：所述内标化合物为正己烷。The method for catalytically evaluating isobutyraldehyde produced by the selective hydrogenation catalyst according to claim 8, wherein the internal standard compound is n-hexane.
  11. 根据权利要求8所述的选择性加氢催化剂生成异丁醛的催化评价方法，其特征在于：所述内标化合物的加入质量为2-甲基丙烯醛质量的5％；溶剂水的加入质量为2-甲基丙烯醛质量的5～15倍。The method for catalytically evaluating the production of isobutyraldehyde by the selective hydrogenation catalyst according to claim 8, wherein the quality of the internal standard compound is 5% of the mass of 2-methylacrolein; the quality of the addition of the solvent water It is 5 to 15 times the mass of 2-methylacrolein.
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