WO2021109611A1 - Catalyst for hydrogenolysis and preparation method therefor - Google Patents

Catalyst for hydrogenolysis and preparation method therefor Download PDF

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WO2021109611A1
WO2021109611A1 PCT/CN2020/108910 CN2020108910W WO2021109611A1 WO 2021109611 A1 WO2021109611 A1 WO 2021109611A1 CN 2020108910 W CN2020108910 W CN 2020108910W WO 2021109611 A1 WO2021109611 A1 WO 2021109611A1
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salt
solution
oxide
catalyst
component
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PCT/CN2020/108910
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French (fr)
Chinese (zh)
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范春元
黄东平
魏斌
赵德喜
邢益辉
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红宝丽集团股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
    • C07C1/2076—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by a transformation in which at least one -C(=O)- moiety is eliminated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to a catalyst for hydrogenolysis and a preparation method thereof.
  • Propylene oxide is an important petrochemical organic raw material.
  • the main production methods of this substance are the chlorohydrin method and the ethylbenzene peroxide method.
  • the chlorohydrin method has serious environmental pollution, and the ethyl benzene peroxide method has a large amount of co-production by-product-styrene, so that the production cost of propylene oxide is affected by the price fluctuation of the co-product.
  • CHP cumene peroxide
  • the co-product ⁇ , ⁇ -dimethylbenzyl alcohol can be catalyzed
  • the hydrogenolysis reaction produces cumene, which can be returned to the peroxide unit for recycling.
  • this process Compared with the process of producing propylene oxide by the oxidation of ethyl peroxide benzene method, this process has the advantages of short process route, less equipment investment, and relatively stable production price.
  • ⁇ -methylstyrene is easy to form polymer due to the double bond in the structure, which leads to catalyst deactivation and pipeline blockage. Since the boiling point of acetophenone reaches 202°C, which is close to the boiling point of ⁇ , ⁇ -dimethylbenzyl alcohol and higher than that of cumene, the general method of distillation and separation is not economical.
  • the use of chemical methods to hydrogenolyze the above-mentioned by-products into materials that can be used as raw materials or easily removed with low boiling points is a common method currently adopted in the industry.
  • the current hydrogenolysis catalysts include palladium series, nickel series, copper series, etc., which are mainly simple substances, oxides, and supported types of the above-mentioned metal substances.
  • Common supports include alumina and carbon. The process mostly uses high pressure reactor or fixed bed reactor.
  • the hydrogenolysis reaction catalyst usually only uses one of palladium, nickel, copper, etc., and a single metal catalyst has certain defects in the actual application process: the palladium-based hydrogenolysis conversion rate is high, but it will cause the phenomenon of phenyl hydrogenation. ; Nickel-based catalysts require higher reaction conditions, requiring higher reaction temperature and pressure; copper-based catalysts generally have low reaction conversion rates.
  • researchers mostly only conduct hydrogenolysis studies on one of ⁇ , ⁇ -dimethylbenzyl alcohol, ⁇ -methylstyrene, and acetophenone mentioned in the present invention.
  • the ⁇ , ⁇ -dimethylbenzyl alcohol, ⁇ -methylstyrene, and acetophenone in the intermediate product of propylene oxide prepared by the CHP method need to be in the least process unit.
  • the hydrogenolysis catalyst is required to have high reaction activity and stability under complex raw material conditions.
  • the present invention provides a catalyst for hydrogenolysis, which is calculated by mass percentage, and includes:
  • component A is at least one of copper or copper oxide
  • component B which is at least one of nickel or nickel oxide
  • component D is an oxide, and the oxide is at least one of zinc oxide, magnesium oxide, calcium oxide, barium oxide, bismuth oxide, lead oxide, or chromium oxide;
  • component E 10-50% of component E, which is at least one of alumina, silica, and molecular sieve.
  • the catalyst is mainly composed of copper, nickel, and palladium, and a small amount of the second metal component containing zinc, magnesium, calcium, barium and other elements is added, which can effectively improve the dispersion effect of the main components of copper, nickel, and palladium in the catalyst. , While improving the reaction activity and reaction stability of the catalyst.
  • the hydrogenolysis reaction of ⁇ , ⁇ -dimethylbenzyl alcohol, ⁇ -methylstyrene and acetophenone can be completed in the same reaction unit.
  • ⁇ , ⁇ -dimethylbenzyl alcohol and ⁇ -methylstyrene are hydrogenated to form cumene
  • acetophenone is hydrogenated to form ethylbenzene.
  • Cumene is used as a raw material for the CHP method, and the boiling point of ethylbenzene is relatively low. , Easy to distill off from the system. And the catalyst has higher conversion rate and target product selectivity.
  • this application also provides a preparation method of the catalyst, which includes the following steps:
  • the sodium carbonate solution and the first metal salt solution dropwise to deionized water at a set temperature;
  • the first metal salt solution is a mixed solution of copper salt, nickel salt and palladium salt;
  • the reaction After the set time, adjust the pH of the solution, and add the second metal salt solution and component E to the solution; the second metal salt solution contains zinc salt, magnesium salt, A salt solution of at least one of calcium salt, barium salt, bismuth salt, lead salt or chromium salt;
  • adding the second metal salt solution and component E under a certain pH value can effectively improve the dispersibility of the main catalytic components of copper, nickel, and palladium in the final catalyst , The reaction activity of the prepared catalyst is effectively improved.
  • the copper salt, the nickel salt and the palladium salt are all hydrochloride, sulfate or nitrate.
  • one or more acid ions of hydrochloride, sulfate or nitrate can be selected, and the same acid ions are preferably selected in the preparation scheme.
  • the use of the same acid radical ion not only facilitates the preparation in the production process, but also avoids the mutual interference between different acid radical ions, which is beneficial to the precise control of the pH value.
  • the zinc salt, magnesium salt, calcium salt, barium salt, bismuth salt, lead salt or chromium salt are all hydrochloride, sulfuric acid Salt or nitrate.
  • the mixed salt solution one or more acid ions of hydrochloride, sulfate or nitrate can be selected, and the same acid ions are preferably selected in the preparation scheme.
  • the reaction temperature is set to 50-110°C.
  • the materials can be fully dissolved, and the reaction can be ensured to proceed under controllable conditions, so that the formed copper carbonate, nickel carbonate, and palladium carbonate can form an interpenetrating and uniform structure, and avoid partial homology.
  • the excessive concentration of various metal salts to form single metal salt particles affects the uniformity of the distribution of various metal elements. At the same time, it provides a good foundation for improving the uniform distribution of metal ions in the subsequent second metal salt solution.
  • the mass ratio of the sodium carbonate solution to the first metal salt solution is 3:1 to 0.5:1.
  • the sodium carbonate solution and the first metal salt solution are both prepared with deionized water, the concentration of the sodium carbonate solution is 0.1 to 1.0 mol/L; the total concentration of the first metal salt solution is 0.1 to 1.0 mol /L.
  • the total concentration of the first metal salt solution refers to the sum of the concentrations of all the salts in the first metal salt solution.
  • the concentration of the sodium carbonate solution is the same as the total concentration of the first metal salt solution, or the concentration difference between the two is controlled within 50%.
  • the formation of large-particle crystals can be effectively avoided, the formed crystals are more delicate, and the carbonate crystals formed by the subsequent second metal salt solution can penetrate into the second metal salt solution.
  • the metal ions are evenly distributed.
  • step (2) after the dropwise addition is completed, the time for continuing the reaction is 0.5 to 2.0 h. In the process of continuing the reaction, part of the crystals will dissolve and crystallize again, thereby making the distribution of the metal ions more uniform.
  • the pH is 6.5-12.
  • the pH is not lower than 7.0, in order to be more conducive to the formation of crystals in an alkaline state, although crystallization can also be carried out in a weakly acidic state.
  • step (3) the calcination temperature is 400-600°C, and the time is 4-12h. Under this condition, it can be ensured that the carbonates are decomposed to eliminate the carbonates and the metal elements can be in an effective state.
  • the beneficial effect of the present invention is that in the main components of the hydrogenolysis catalyst prepared by the method of the present invention, the amount of noble metals of nickel and palladium is significantly lower than that of the commercially available hydrogenolysis catalyst, and the preparation cost has certain advantages.
  • a copper-nickel-palladium multi-element catalyst is used.
  • copper is the main catalyst component. Due to the good catalytic effect of copper on the CO bond, it can effectively convert acetophenone into ethylbenzene with a high conversion rate; at the same time, it can catalyze most hydrogenation reactions and effectively curb the excess of phenyl groups. Hydrogenation avoids the formation of by-products of cyclohexyl compounds and improves reaction selectivity.
  • the addition of a small amount of palladium can ensure that ⁇ , ⁇ -dimethylbenzyl alcohol is fully dehydrated to form the required intermediate product ⁇ -methylstyrene, and on the other hand, it can provide hydrogenation.
  • Nickel can fully hydrogenate the unsaturated bonds on ⁇ -methylstyrene to form cumene, ensuring the conversion rate of the hydrogenolysis reaction.
  • the introduction of zinc oxide, magnesium oxide, calcium oxide, barium oxide, bismuth oxide, lead oxide, chromium oxide and other metal oxides can significantly improve the effective dispersibility of copper, nickel, and palladium in the catalyst preparation process, and increase the main components of the final catalyst.
  • Parameters such as specific surface area and pore volume, especially the specific surface area of copper and its degree of dispersion, can effectively inhibit the hydrogenation of phenyl groups and improve the reaction activity and stability of the catalyst.
  • the catalyst prepared by the invention has high reaction activity, high conversion rate and selectivity to ⁇ , ⁇ -dimethylbenzyl alcohol, ⁇ -methylstyrene, acetophenone, etc., and can be used in the same process unit or The hydrogenolysis reaction of multiple substances is completed in the same reaction equipment.
  • the conversion rate of ⁇ , ⁇ -dimethylbenzyl alcohol is more than 99.91%, and the selectivity of cumene is more than 99.92%.
  • the ⁇ -methylstyrene conversion rate is over 99.93%, and the cumene selectivity is 100%.
  • the conversion rate of acetophenone is over 99.91%, and the selectivity of ethylbenzene is 100%.
  • the target hydrogenolysis product of ⁇ , ⁇ -dimethylbenzyl alcohol is cumene
  • the target hydrogenolysis product of ⁇ -methylstyrene is cumene
  • the target hydrogenolysis product of acetophenone is ethylbenzene.
  • the catalyst in this application has high technical adaptability to the hydrogenolysis process of relatively complicated raw materials in the industrial application of the CHP method for preparing propylene oxide.
  • the first metal salt solution is a mixed solution of copper nitrate, nickel nitrate and palladium nitrate, and the total concentration of the first metal salt solution is each of the three salts of copper nitrate, nickel nitrate and palladium nitrate. The sum of the concentrations.
  • the total concentration of the second metal salt solution is the sum of the concentrations of various salts in the second metal salt solution.
  • the 1# catalyst contains 80.0% copper, 2.0% nickel, 0.01% palladium, 0.5% chromium oxide, 1.5% zinc oxide, and 15.99% alumina in terms of mass percentage.
  • a first metal salt solution with a total concentration of 0.5 mol/L and a second metal salt solution with a total concentration of 0.5 mol/L are prepared.
  • the second metal salt solution is a mixed salt solution of chromium nitrate and zinc nitrate.
  • 2# catalyst in terms of mass percentage, contains 40.0% copper, 8.0% nickel, 0.05% palladium, 1.0% magnesium oxide, 0.5% barium oxide, 0.5% lead oxide, 1.5% chromium oxide, and 48.45% silicon oxide.
  • the second metal salt solution is a mixture of magnesium hydrochloride, barium hydrochloride, lead hydrochloride, and chromium hydrochloride Salt solution.
  • 3# catalyst in terms of mass percentage, it contains 60.0% copper, 3.0% nickel, 0.01% palladium, 1.5% zinc oxide, 1.0% lead oxide, 1.5% chromium oxide, and 32.99% molecular sieve.
  • a first metal salt solution with a total concentration of 0.2 mol/L and a second metal salt solution with a total concentration of 0.2 mol/L are prepared.
  • the second metal salt solution is a mixed salt solution of zinc sulfate, lead sulfate and chromium sulfate.
  • 4# catalyst in terms of mass percentage, it contains 80.0% copper, 5.0% nickel, 0.05% palladium, 2.0% zinc oxide, 1.0% magnesium oxide, and 11.95% silicon oxide.
  • a first metal salt solution with a total concentration of 0.35 mol/L and a second metal salt solution with a total concentration of 0.35 mol/L are prepared.
  • the second metal salt solution is a mixed salt solution of magnesium nitrate and zinc nitrate.
  • Catalyst 5# in terms of mass percentage, contains 60.0% copper, 0.5% nickel, 1.0% palladium, 0.5% calcium oxide, 0.5% barium oxide, 1.0% chromium oxide, and 36.5% alumina.
  • a first metal salt solution with a total concentration of 0.25 mol/L and a second metal salt solution with a total concentration of 0.25 mol/L are prepared.
  • the second metal salt solution is a mixed salt solution of calcium hydrochloride, barium hydrochloride, and chromium hydrochloride.
  • the 6# catalyst contains 45.0% copper, 5.0% nickel, 0.1% palladium, 1.0% magnesium oxide, 1.0% bismuth oxide, 1.5% chromium oxide, and 46.4% molecular sieve in terms of mass percentage.
  • a first metal salt solution with a total concentration of 0.7 mol/L and a second metal salt solution with a total concentration of 0.7 mol/L are prepared.
  • the second metal salt solution is a mixed salt solution of magnesium sulfate, bismuth sulfate, and chromium sulfate.
  • reaction vessel with a stirring blade, add 1.0L of deionized water, and after the temperature is raised to 80°C, while stirring, add 0.7mol/L of sodium carbonate solution and the first metal salt solution dropwise at the same time, and the sodium carbonate solution and the first The mass ratio of the metal salt solution is 0.7:1.
  • the reaction is continued at 80°C for 2.0 hours, the pH is adjusted to 7.0-8.0, and the required amount of the second metal salt solution and molecular sieve are added. After full reaction, it is filtered and washed with water, dried and formed and calcined at 500°C for 10 hours to prepare.
  • Comparative Example 1 Selected from commercially available Pd/C (0.5% Pd content) catalysts
  • Comparative Example 2 Selected from commercially available Raney nickel catalysts
  • Comparative Example 3 Using the preparation method described in Example 1, the difference is that the second metal salt solution is not added in the reaction process, and 2% alumina is used instead.
  • the final composition of the prepared catalyst is: 80.0% copper, 2.0% nickel, 0.01 % Palladium, 17.99% alumina.
  • the catalyst prepared in the example place it in a fixed bed reactor, and gradually increase the temperature to 180°C for full activation under the condition of continuous hydrogen flow.
  • the mixed solution containing ⁇ , ⁇ -dimethylbenzyl alcohol, ⁇ -methylstyrene and acetophenone is continuously pumped at 200°C and 0.5MPa at a liquid space velocity of 2.0h -1 for hydrogen Decompose the reaction, and the product after the reaction is sampled and tested after gas-liquid separation.
  • the raw materials used in the evaluation of catalyst hydrogenation come from the epoxidation process in the preparation of propylene oxide by the CHP method.
  • the composition by mass contains about 45% of cumene, 43% of ⁇ , ⁇ -dimethylbenzyl alcohol, and 2.3% of benzene.

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  • Engineering & Computer Science (AREA)
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Abstract

A catalyst for hydrogenolysis which, when calculating on the basis of mass percent, comprises: (a) 40-80% of a component A; (b) 0.5-10% of a component B; (c) 0.01-1% of a component C; (d) 0.1-5% of a component D; (e) 10-50% of a component E. The preparation method for the catalyst comprises the following steps: (1) adding drops of a sodium carbonate solution and a first metal salt solution into deionized water; (2) adding a second metal salt solution and component E; (3) filtering, shaping, and calcinating the solution, and forming a catalyst product. By adding a small amount of a second metal component containing elements such as zinc, magnesium, calcium, and barium to the main components of the catalyst, which are copper, nickel, and palladium, it is possible to effectively increase the dispersion effects of the copper, nickel, and palladium main components in the catalyst while increasing the reactivity and reaction stability of the catalyst.

Description

一种氢解用催化剂及其制备方法Catalyst for hydrogenolysis and preparation method thereof 技术领域Technical field
本发明涉及一种氢解用催化剂及其制备方法。The invention relates to a catalyst for hydrogenolysis and a preparation method thereof.
背景技术Background technique
环氧丙烷是一种重要的石油化工有机原料，该物质主要的生产方法是氯醇法与过氧化乙苯法。氯醇法对环境的污染严重，过氧化乙苯法有大量联产副产物—苯乙烯生成，从而使环氧丙烷的生产成本受到联产物的价格波动的影响。近年来，以过氧化异丙苯(CHP)为氧源，氧化丙烯生产环氧丙烷的方法逐渐发展起来，该过程环保、安全性高，联产物α,α-二甲基苄醇可以通过催化氢解反应生成异丙苯，异丙苯可以返回过氧化单元实现循环利用。与过氧化乙苯法氧化生产环氧丙烷的工艺比，该过程具有工艺路线短，设备投资少，生产价格比较稳定等优点。Propylene oxide is an important petrochemical organic raw material. The main production methods of this substance are the chlorohydrin method and the ethylbenzene peroxide method. The chlorohydrin method has serious environmental pollution, and the ethyl benzene peroxide method has a large amount of co-production by-product-styrene, so that the production cost of propylene oxide is affected by the price fluctuation of the co-product. In recent years, using cumene peroxide (CHP) as the oxygen source, the method of producing propylene oxide from propylene oxide has gradually developed. The process is environmentally friendly and safe. The co-product α,α-dimethylbenzyl alcohol can be catalyzed The hydrogenolysis reaction produces cumene, which can be returned to the peroxide unit for recycling. Compared with the process of producing propylene oxide by the oxidation of ethyl peroxide benzene method, this process has the advantages of short process route, less equipment investment, and relatively stable production price.
CHP法在生产过程中，产生大量中间产物α,α-二甲基苄醇以及少量的α-甲基苯乙烯、苯乙酮等副产物。其中α,α-二甲基苄醇根据生产工艺需要，氢解形成异丙苯后循环利用；而α-甲基苯乙烯、苯乙酮等副产物需要从反应体系中去除，否则多次循环积累达到一定浓度后，将对CHP法制备环氧丙烷生产工艺带来不利影响。其中α-甲基苯乙烯由于结构中含有双键，易形成聚合物，而导致催化剂失活及管路堵塞。苯乙酮由于沸点达到202℃，与α,α-二甲基苄醇沸点接近且高于异丙苯的沸点，一般蒸馏分离的方法不具有经济性。采用化学方法使上述副产物氢解成原料套用或低沸点易于脱除的物质，是目前工业上普遍采取的方式。In the production process of CHP method, a large amount of intermediate product α,α-dimethylbenzyl alcohol and a small amount of by-products such as α-methylstyrene and acetophenone are produced. Among them, α,α-dimethylbenzyl alcohol is recycled after hydrogenolysis to form cumene according to the requirements of the production process; while the by-products such as α-methylstyrene and acetophenone need to be removed from the reaction system, otherwise multiple cycles After the accumulation reaches a certain concentration, it will have an adverse effect on the production process of propylene oxide prepared by the CHP method. Among them, α-methylstyrene is easy to form polymer due to the double bond in the structure, which leads to catalyst deactivation and pipeline blockage. Since the boiling point of acetophenone reaches 202°C, which is close to the boiling point of α,α-dimethylbenzyl alcohol and higher than that of cumene, the general method of distillation and separation is not economical. The use of chemical methods to hydrogenolyze the above-mentioned by-products into materials that can be used as raw materials or easily removed with low boiling points is a common method currently adopted in the industry.
目前氢解用催化剂包括钯系、镍系、铜系等，主要为上述金属物质的单质、氧化物、负载型态，常见的负载物有氧化铝、碳等。工艺多采用高压反应釜或固定床反应器。The current hydrogenolysis catalysts include palladium series, nickel series, copper series, etc., which are mainly simple substances, oxides, and supported types of the above-mentioned metal substances. Common supports include alumina and carbon. The process mostly uses high pressure reactor or fixed bed reactor.
氢解反应催化剂通常仅采用钯、镍、铜等中的1种，而单一的金属催化剂在实际应用过程中各有一定缺陷：钯系氢解转化率较高，但会引起苯基加氢现象；镍系催化剂所需反应条件要求较高，需要较高的反应温度及压力；铜系催化剂反应转化率普遍较低。另一方面，研究者多仅对本发明中提及的α,α-二甲基苄醇、α-甲基苯乙烯、苯乙酮中的一种进行氢解研究。而现实中，由于生成成本及设备的要求，需要将CHP法制备环氧丙烷中间产物中的α,α-二甲基苄醇、α-甲基苯乙烯、苯乙酮在最少的工艺单元内完成氢解反应，以达到更大的设备利用率及生产效率，同时需要氢解催化剂具有在复杂原料条件下具有较高的反应活性及稳定性。The hydrogenolysis reaction catalyst usually only uses one of palladium, nickel, copper, etc., and a single metal catalyst has certain defects in the actual application process: the palladium-based hydrogenolysis conversion rate is high, but it will cause the phenomenon of phenyl hydrogenation. ; Nickel-based catalysts require higher reaction conditions, requiring higher reaction temperature and pressure; copper-based catalysts generally have low reaction conversion rates. On the other hand, researchers mostly only conduct hydrogenolysis studies on one of α,α-dimethylbenzyl alcohol, α-methylstyrene, and acetophenone mentioned in the present invention. In reality, due to the production cost and equipment requirements, the α,α-dimethylbenzyl alcohol, α-methylstyrene, and acetophenone in the intermediate product of propylene oxide prepared by the CHP method need to be in the least process unit. Complete the hydrogenolysis reaction to achieve greater equipment utilization and production efficiency. At the same time, the hydrogenolysis catalyst is required to have high reaction activity and stability under complex raw material conditions.
发明内容Summary of the invention
本发明针对上述现有工艺的缺陷及经济生产的要求，提供一种氢解用催化剂，以质量百分数计，包括：In view of the defects of the above-mentioned existing technology and the requirements of economic production, the present invention provides a catalyst for hydrogenolysis, which is calculated by mass percentage, and includes:
(a)40～80％的组分A，该组分A为铜或氧化铜中的至少一种；(a) 40-80% of component A, the component A is at least one of copper or copper oxide;
(b)0.5～10％的组分B,该组分B为镍或氧化镍中的至少一种；(b) 0.5-10% of component B, which is at least one of nickel or nickel oxide;
(c)0.01～1％的组分C，该组分C为钯；(c) 0.01-1% of component C, which is palladium;
(d)0.1～5％的组分D，该组分D为氧化物，该氧化物为氧化锌、氧化镁、氧化钙、氧化钡、氧化铋、氧化铅或氧化铬中的至少一种；(d) 0.1-5% of component D, the component D is an oxide, and the oxide is at least one of zinc oxide, magnesium oxide, calcium oxide, barium oxide, bismuth oxide, lead oxide, or chromium oxide;
(e)10～50％的组分E，该组分E为氧化铝、氧化硅、分子筛中的至少一种。(e) 10-50% of component E, which is at least one of alumina, silica, and molecular sieve.
该催化剂在以铜、镍、钯为主成分中，加入少量含有锌、镁、钙、钡等元素的第二金属组分，能够有效的提高铜、镍、钯主要成分在催化剂中的分散效果，同时提高催化剂的反应活性及反应稳定性。The catalyst is mainly composed of copper, nickel, and palladium, and a small amount of the second metal component containing zinc, magnesium, calcium, barium and other elements is added, which can effectively improve the dispersion effect of the main components of copper, nickel, and palladium in the catalyst. , While improving the reaction activity and reaction stability of the catalyst.
在实际应用过程中能够在同一个反应单元完成α,α-二甲基苄醇、α-甲基苯乙烯、苯乙酮的氢解反应。其中α,α-二甲基苄醇、α-甲基苯乙烯氢解形成异丙苯，苯乙酮氢解形成乙苯，异丙苯作为CHP法原料进行套用，而乙苯沸点相对较低，易于从体系中蒸馏脱去。且该催化剂具有较高的转化率及目标产物选择性。In the actual application process, the hydrogenolysis reaction of α,α-dimethylbenzyl alcohol, α-methylstyrene and acetophenone can be completed in the same reaction unit. Among them, α,α-dimethylbenzyl alcohol and α-methylstyrene are hydrogenated to form cumene, and acetophenone is hydrogenated to form ethylbenzene. Cumene is used as a raw material for the CHP method, and the boiling point of ethylbenzene is relatively low. , Easy to distill off from the system. And the catalyst has higher conversion rate and target product selectivity.
为实现上述催化剂，本申请还提供了该催化剂的制备方法，其包括如下步骤：In order to realize the above-mentioned catalyst, this application also provides a preparation method of the catalyst, which includes the following steps:
(1)在搅拌条件下，将碳酸钠溶液、第一金属盐溶液滴加到设定温度的去离子水中；该第一金属盐溶液为铜盐、镍盐以及钯盐的混合溶液；(1) Under stirring conditions, add the sodium carbonate solution and the first metal salt solution dropwise to deionized water at a set temperature; the first metal salt solution is a mixed solution of copper salt, nickel salt and palladium salt;
(2)滴加完成后，继续进行反应，在设定时间后，调节溶液pH，在溶液中加入第二金属盐溶液和组分E；该第二金属盐溶液为含有锌盐、镁盐、钙盐、钡盐、铋盐、铅盐或铬盐中至少一种的盐溶液；(2) After the dripping is completed, continue the reaction. After the set time, adjust the pH of the solution, and add the second metal salt solution and component E to the solution; the second metal salt solution contains zinc salt, magnesium salt, A salt solution of at least one of calcium salt, barium salt, bismuth salt, lead salt or chromium salt;
(3)溶液经过滤、水洗、预烘干后，成型并干燥，再经过煅烧，形成催化剂成品。(3) After the solution is filtered, washed with water, pre-dried, it is shaped and dried, and then calcined to form a finished catalyst.
该方法中，第一金属盐溶液与碳酸钠充分反应后，在一定pH值条件下加入第二金属盐溶液及组分E能有效提高铜、镍、钯主要催化成分在最终催化剂中的分散性，所制得的催化剂反应活性有效提高。In this method, after the first metal salt solution and sodium carbonate are fully reacted, adding the second metal salt solution and component E under a certain pH value can effectively improve the dispersibility of the main catalytic components of copper, nickel, and palladium in the final catalyst , The reaction activity of the prepared catalyst is effectively improved.
优选地，为保证第一金属盐溶液中各金属盐的充分溶解，在该制备方法中，铜盐、镍盐以及钯盐均为盐酸盐、硫酸盐或硝酸盐。在混合盐溶液中可选择盐酸盐、硫酸盐或硝酸盐中的一种或多种酸根离子，优选在制备方案中选用同一酸根离子。采用同一酸根离子，不但可以方便生产过程中的配制，还可以避免不同酸根离子之间的相互干扰，以有利于对pH值的精确控制。Preferably, in order to ensure the full dissolution of each metal salt in the first metal salt solution, in the preparation method, the copper salt, the nickel salt and the palladium salt are all hydrochloride, sulfate or nitrate. In the mixed salt solution, one or more acid ions of hydrochloride, sulfate or nitrate can be selected, and the same acid ions are preferably selected in the preparation scheme. The use of the same acid radical ion not only facilitates the preparation in the production process, but also avoids the mutual interference between different acid radical ions, which is beneficial to the precise control of the pH value.
优选地，为保证第二金属盐溶液中各金属盐的充分溶解，该制备方法中，锌盐、镁盐、钙盐、钡盐、铋盐、铅盐或铬盐均为盐酸盐、硫酸盐或硝酸盐。在混合盐溶液中可选择盐酸盐、硫酸盐或硝酸盐中的一种或多种酸根离子，优选在制备方案中选用同一酸根离子。Preferably, in order to ensure the full dissolution of each metal salt in the second metal salt solution, in the preparation method, the zinc salt, magnesium salt, calcium salt, barium salt, bismuth salt, lead salt or chromium salt are all hydrochloride, sulfuric acid Salt or nitrate. In the mixed salt solution, one or more acid ions of hydrochloride, sulfate or nitrate can be selected, and the same acid ions are preferably selected in the preparation scheme.
进一步，步骤(1)中，设定反应温度为50～110℃。在该温度范围内，能够使各物料充分地溶解，且保证反应能够在可控的条件下进行，使所形成的碳酸铜、碳酸镍和碳酸钯能够形成相互渗透且均匀的结构，避免部分同种金属盐过分集中形成单一金属盐颗粒，影响各金属元素的分布均匀性。同时为后续的第二金属盐溶液中的金属离子的均匀分布提高良好的基础。Furthermore, in step (1), the reaction temperature is set to 50-110°C. In this temperature range, the materials can be fully dissolved, and the reaction can be ensured to proceed under controllable conditions, so that the formed copper carbonate, nickel carbonate, and palladium carbonate can form an interpenetrating and uniform structure, and avoid partial homology. The excessive concentration of various metal salts to form single metal salt particles affects the uniformity of the distribution of various metal elements. At the same time, it provides a good foundation for improving the uniform distribution of metal ions in the subsequent second metal salt solution.
为避免反应体系中，溶液量过大，影响可操作性，同时保证反应速度，碳酸钠溶液与第一金属盐溶液的质量比为3:1～0.5:1。In order to avoid excessively large amount of the solution in the reaction system, which affects operability, and at the same time to ensure the reaction speed, the mass ratio of the sodium carbonate solution to the first metal salt solution is 3:1 to 0.5:1.
进一步，步骤(1)中，碳酸钠溶液与第一金属盐溶液均采用去离子水配制，碳酸钠溶液的浓度为0.1～1.0mol/L；第一金属盐溶液的总浓度为0.1～1.0mol/L。该第一金属盐溶液的总浓度是指在第一金属盐溶液中所有盐的各浓度的总和。优选碳酸钠溶液的浓度与第一金属盐溶液的总浓度相同，或两者的浓度差控制在50％以内。上述浓度范围内，在保证反应速度的情况下，可以有效地避免大颗粒晶体的形成，使所形成的晶体较为细腻，使后续的第二金属盐溶液所形成的碳酸盐晶体能够渗入到第一金属盐溶液所形成的碳酸盐晶体中，使各金属离子均匀分布。Further, in step (1), the sodium carbonate solution and the first metal salt solution are both prepared with deionized water, the concentration of the sodium carbonate solution is 0.1 to 1.0 mol/L; the total concentration of the first metal salt solution is 0.1 to 1.0 mol /L. The total concentration of the first metal salt solution refers to the sum of the concentrations of all the salts in the first metal salt solution. Preferably, the concentration of the sodium carbonate solution is the same as the total concentration of the first metal salt solution, or the concentration difference between the two is controlled within 50%. In the above concentration range, under the condition of ensuring the reaction speed, the formation of large-particle crystals can be effectively avoided, the formed crystals are more delicate, and the carbonate crystals formed by the subsequent second metal salt solution can penetrate into the second metal salt solution. In the carbonate crystals formed by a metal salt solution, the metal ions are evenly distributed.
进一步，为使各金属离子能够分布的更加均匀，步骤(2)中，滴加完成后，继续进行反应的时间为0.5～2.0h。在继续反应的过程中，部分晶体会进入溶解，并再次进行结晶，从而使各金属离子的分布更加均匀。Further, in order to make the distribution of the metal ions more uniform, in step (2), after the dropwise addition is completed, the time for continuing the reaction is 0.5 to 2.0 h. In the process of continuing the reaction, part of the crystals will dissolve and crystallize again, thereby making the distribution of the metal ions more uniform.
为顺利地形成晶体，pH为6.5～12。在反应过程中，优选pH不低于7.0，以在碱性状态下，更有利于晶体的形成，虽然在弱酸性状态下也可以进行结晶。In order to form crystals smoothly, the pH is 6.5-12. During the reaction, it is preferable that the pH is not lower than 7.0, in order to be more conducive to the formation of crystals in an alkaline state, although crystallization can also be carried out in a weakly acidic state.
步骤(3)中，所述煅烧的温度为400～600℃，时间为4～12h。在该条件下，能够保证各碳酸盐进行分解，以消除其中的碳酸根，使各金属元素能够处于有效状态。In step (3), the calcination temperature is 400-600°C, and the time is 4-12h. Under this condition, it can be ensured that the carbonates are decomposed to eliminate the carbonates and the metal elements can be in an effective state.
有益效果Beneficial effect
本发明的有益效果在于采用发明所述方法制得的氢解催化剂主要成分中，镍、钯贵金属用量明显低于市售氢解催化剂，制备成本上具有一定优势。The beneficial effect of the present invention is that in the main components of the hydrogenolysis catalyst prepared by the method of the present invention, the amount of noble metals of nickel and palladium is significantly lower than that of the commercially available hydrogenolysis catalyst, and the preparation cost has certain advantages.
针对氢解原料特性，采用铜-镍-钯多元催化剂。其中铜为主要催化剂成分，由于铜对C-O键的良好催化效果，能够有效地将苯乙酮转化为乙苯，且转化率较高；同时能够催化大多数氢化反应，并有效遏制苯基的过度加氢，避免形成环己基化合物的副产物，提高反应选择性。少量钯的加入，能保证α,α-二甲基苄醇充分脱水，形成所需的中间产物α-甲基苯 乙烯，另一方面提供氢化。镍能够对α-甲基苯乙烯上不饱和键进行充分的加氢反应，形成异丙苯，保证氢解反应的转化率。In view of the characteristics of hydrogenolysis raw materials, a copper-nickel-palladium multi-element catalyst is used. Among them, copper is the main catalyst component. Due to the good catalytic effect of copper on the CO bond, it can effectively convert acetophenone into ethylbenzene with a high conversion rate; at the same time, it can catalyze most hydrogenation reactions and effectively curb the excess of phenyl groups. Hydrogenation avoids the formation of by-products of cyclohexyl compounds and improves reaction selectivity. The addition of a small amount of palladium can ensure that α,α-dimethylbenzyl alcohol is fully dehydrated to form the required intermediate product α-methylstyrene, and on the other hand, it can provide hydrogenation. Nickel can fully hydrogenate the unsaturated bonds on α-methylstyrene to form cumene, ensuring the conversion rate of the hydrogenolysis reaction.
氧化锌、氧化镁、氧化钙、氧化钡、氧化铋、氧化铅、氧化铬等金属氧化物的引入，能够明显提高催化剂制备过程中铜、镍、钯的有效分散性，增加最终催化剂主要成分的比表面积、孔容积等参数，尤其是铜的比表面积及其分散程度，可有效抑制苯基的氢化，并提高催化剂的反应活性及稳定性。The introduction of zinc oxide, magnesium oxide, calcium oxide, barium oxide, bismuth oxide, lead oxide, chromium oxide and other metal oxides can significantly improve the effective dispersibility of copper, nickel, and palladium in the catalyst preparation process, and increase the main components of the final catalyst. Parameters such as specific surface area and pore volume, especially the specific surface area of copper and its degree of dispersion, can effectively inhibit the hydrogenation of phenyl groups and improve the reaction activity and stability of the catalyst.
采用本发明制备的催化剂反应活性高，对α,α-二甲基苄醇、α-甲基苯乙烯、苯乙酮等均具有较高的转化率和选择性，并且可在同一工艺单元或同一反应设备中完成多种物质的氢解反应。其中α,α-二甲基苄醇转化率达99.91％以上，异丙苯选择性99.92％以上。α-甲基苯乙烯转化率99.93％以上，异丙苯选择性100％。苯乙酮转化率99.91％以上，乙苯选择性100％。有效避免由于α-甲基苯乙烯聚合而导致催化剂失活及设备管路堵塞。其中α,α-二甲基苄醇的目标氢解产物为异丙苯，α-甲基苯乙烯的目标氢解产物为异丙苯，苯乙酮的目标氢解产物是乙苯。The catalyst prepared by the invention has high reaction activity, high conversion rate and selectivity to α,α-dimethylbenzyl alcohol, α-methylstyrene, acetophenone, etc., and can be used in the same process unit or The hydrogenolysis reaction of multiple substances is completed in the same reaction equipment. The conversion rate of α,α-dimethylbenzyl alcohol is more than 99.91%, and the selectivity of cumene is more than 99.92%. The α-methylstyrene conversion rate is over 99.93%, and the cumene selectivity is 100%. The conversion rate of acetophenone is over 99.91%, and the selectivity of ethylbenzene is 100%. Effectively avoid catalyst deactivation and blockage of equipment pipeline due to polymerization of α-methylstyrene. Among them, the target hydrogenolysis product of α,α-dimethylbenzyl alcohol is cumene, the target hydrogenolysis product of α-methylstyrene is cumene, and the target hydrogenolysis product of acetophenone is ethylbenzene.
本申请中的催化剂，在CHP法制备环氧丙烷产业应用中，对原料相对较为复杂的氢解工艺过程具有较高的技术适应性。The catalyst in this application has high technical adaptability to the hydrogenolysis process of relatively complicated raw materials in the industrial application of the CHP method for preparing propylene oxide.
具体实施方式Detailed ways
在以下各实施例中，第一金属盐溶液均为硝酸铜、硝酸镍和硝酸钯的混合溶液，该第一金属盐溶液的总浓度均为硝酸铜、硝酸镍和硝酸钯三种盐的各浓度的总和。第二金属盐溶液的总浓度为该第二金属盐溶液中各种盐的浓度的总和。In the following embodiments, the first metal salt solution is a mixed solution of copper nitrate, nickel nitrate and palladium nitrate, and the total concentration of the first metal salt solution is each of the three salts of copper nitrate, nickel nitrate and palladium nitrate. The sum of the concentrations. The total concentration of the second metal salt solution is the sum of the concentrations of various salts in the second metal salt solution.
实施例1Example 1
1#催化剂，以质量百分数计，其含80.0％铜、2.0％镍、0.01％钯、0.5％氧化铬、1.5％氧化锌、15.99％氧化铝。The 1# catalyst contains 80.0% copper, 2.0% nickel, 0.01% palladium, 0.5% chromium oxide, 1.5% zinc oxide, and 15.99% alumina in terms of mass percentage.
配制总浓度为0.5mol/L的第一金属盐溶液，以及总浓度为0.5mol/L的第二金属盐溶液，该第二金属盐溶液为硝酸铬和硝酸锌的混合盐溶液。A first metal salt solution with a total concentration of 0.5 mol/L and a second metal salt solution with a total concentration of 0.5 mol/L are prepared. The second metal salt solution is a mixed salt solution of chromium nitrate and zinc nitrate.
在具有搅拌桨的反应容器中，投入1.5L去离子水，升温至80℃后，在搅拌状态下同时滴加0.5mol/L碳酸钠溶液和第一金属盐溶液，碳酸钠溶液与第一金属盐溶液的质量比为2:1。滴加完毕后在80℃下继续反应2h，调节pH至7.5～8.0，加入所需量的第二金属盐溶液及氧化铝。充分反应后过滤并水洗，干燥成型后在500℃下煅烧8h，制得。Put 1.5L deionized water into a reaction vessel with a stirring blade, and after the temperature is raised to 80°C, add 0.5mol/L sodium carbonate solution and the first metal salt solution dropwise while stirring, and the sodium carbonate solution and the first metal The mass ratio of the salt solution is 2:1. After the dripping is completed, the reaction is continued at 80°C for 2 hours, the pH is adjusted to 7.5-8.0, and the required amount of the second metal salt solution and alumina are added. After fully reacting, it is filtered and washed with water, dried and formed and calcined at 500°C for 8 hours to prepare.
实施例2Example 2
2#催化剂，以质量百分数计，其含40.0％铜、8.0％镍、0.05％钯、1.0％氧化镁、0.5％氧化 钡、0.5％氧化铅、1.5％氧化铬，48.45％氧化硅。2# catalyst, in terms of mass percentage, contains 40.0% copper, 8.0% nickel, 0.05% palladium, 1.0% magnesium oxide, 0.5% barium oxide, 0.5% lead oxide, 1.5% chromium oxide, and 48.45% silicon oxide.
配制总浓度为0.6mol/L的第一金属盐溶液，以及总浓度为0.6mol/L的第二金属盐溶液，该第二金属盐溶液为盐酸镁、盐酸钡、盐酸铅和盐酸铬的混合盐溶液。Prepare a first metal salt solution with a total concentration of 0.6 mol/L and a second metal salt solution with a total concentration of 0.6 mol/L. The second metal salt solution is a mixture of magnesium hydrochloride, barium hydrochloride, lead hydrochloride, and chromium hydrochloride Salt solution.
在具有搅拌桨的反应容器中，投入1.0L去离子水，升温至85℃后，在搅拌状态下同时滴加0.5mol/L碳酸钠溶液和第一金属盐溶液，碳酸钠溶液与第一金属盐溶液的质量比为3:1。滴加完毕后在85℃下继续反应1.5h，调节pH至8.5～9.0，加入所需量的第二金属盐溶液及氧化硅。充分反应后过滤并水洗，干燥成型后在400℃下煅烧12h，制得。In a reaction vessel with a stirring blade, put in 1.0L deionized water, and after the temperature is raised to 85°C, add 0.5mol/L sodium carbonate solution and the first metal salt solution dropwise while stirring, and the sodium carbonate solution and the first metal The mass ratio of the salt solution is 3:1. After the dripping is completed, the reaction is continued at 85°C for 1.5 hours, the pH is adjusted to 8.5-9.0, and the required amount of the second metal salt solution and silicon oxide are added. After fully reacting, it is filtered and washed with water, dried and formed and calcined at 400°C for 12 hours to prepare.
实施例3Example 3
3#催化剂，以质量百分数计，其含60.0％铜、3.0％镍、0.01％钯、1.5％氧化锌、1.0％氧化铅、1.5％氧化铬、32.99％分子筛。3# catalyst, in terms of mass percentage, it contains 60.0% copper, 3.0% nickel, 0.01% palladium, 1.5% zinc oxide, 1.0% lead oxide, 1.5% chromium oxide, and 32.99% molecular sieve.
配制总浓度为0.2mol/L的第一金属盐溶液，以及总浓度为0.2mol/L的第二金属盐溶液，该第二金属盐溶液为硫酸锌、硫酸铅和硫酸铬的混合盐溶液。A first metal salt solution with a total concentration of 0.2 mol/L and a second metal salt solution with a total concentration of 0.2 mol/L are prepared. The second metal salt solution is a mixed salt solution of zinc sulfate, lead sulfate and chromium sulfate.
在具有搅拌桨的反应容器中，投入1.5L去离子水，升温至90℃后，在搅拌状态下同时滴加0.3mol/L碳酸钠溶液和第一金属盐溶液，碳酸钠溶液与第一金属盐溶液的质量比为2:1。滴加完毕后在90℃下继续反应0.5h，调节pH至7.5～8.0，加入所需量的第二金属盐溶液及分子筛。充分反应后过滤并水洗，干燥成型后在400℃下煅烧12h，制得。Put 1.5L of deionized water into a reaction vessel with a stirring blade, and after the temperature is raised to 90°C, add 0.3mol/L sodium carbonate solution and the first metal salt solution dropwise while stirring, and the sodium carbonate solution and the first metal The mass ratio of the salt solution is 2:1. After the dripping is completed, the reaction is continued at 90°C for 0.5h, the pH is adjusted to 7.5-8.0, and the required amount of the second metal salt solution and molecular sieve are added. After fully reacting, it is filtered and washed with water, dried and formed and calcined at 400°C for 12 hours to prepare.
实施例4Example 4
4#催化剂，以质量百分数计，其含80.0％铜、5.0％镍、0.05％钯、2.0％氧化锌、1.0％氧化镁、11.95％氧化硅。4# catalyst, in terms of mass percentage, it contains 80.0% copper, 5.0% nickel, 0.05% palladium, 2.0% zinc oxide, 1.0% magnesium oxide, and 11.95% silicon oxide.
配制总浓度为0.35mol/L的第一金属盐溶液，以及总浓度为0.35mol/L的第二金属盐溶液，该第二金属盐溶液为硝酸镁和硝酸锌的混合盐溶液。A first metal salt solution with a total concentration of 0.35 mol/L and a second metal salt solution with a total concentration of 0.35 mol/L are prepared. The second metal salt solution is a mixed salt solution of magnesium nitrate and zinc nitrate.
在具有搅拌桨的反应容器中，投入1.0L去离子水，升温至85℃后，在搅拌状态下同时滴加0.45mol/L的碳酸钠溶液和第一金属盐溶液，碳酸钠溶液与第一金属盐溶液的质量比为1.5:1。滴加完毕后在85℃下继续反应1.5h，调节pH至8.0～8.5，加入所需量的第二金属盐溶液及分子筛。充分反应后过滤并水洗，干燥成型后在600℃下煅烧6h，制得。Put 1.0L of deionized water into a reaction vessel with a stirring blade, and after the temperature is raised to 85°C, add 0.45mol/L sodium carbonate solution and the first metal salt solution dropwise at the same time while stirring, and the sodium carbonate solution and the first metal salt solution The mass ratio of the metal salt solution is 1.5:1. After the dripping is completed, the reaction is continued at 85°C for 1.5 hours, the pH is adjusted to 8.0-8.5, and the required amount of the second metal salt solution and molecular sieve are added. After fully reacting, it is filtered and washed with water, dried and formed and calcined at 600°C for 6 hours to prepare.
实施例5Example 5
5#催化剂，以质量百分数计，其含60.0％铜、0.5％镍、1.0％钯、0.5％氧化钙、0.5％氧化钡、1.0％氧化铬，36.5％氧化铝。Catalyst 5#, in terms of mass percentage, contains 60.0% copper, 0.5% nickel, 1.0% palladium, 0.5% calcium oxide, 0.5% barium oxide, 1.0% chromium oxide, and 36.5% alumina.
配制总浓度为0.25mol/L的第一金属盐溶液，以及总浓度为0.25mol/L的第二金属盐溶液，该第二金属盐溶液为盐酸钙、盐酸钡、盐酸铬的混合盐溶液。A first metal salt solution with a total concentration of 0.25 mol/L and a second metal salt solution with a total concentration of 0.25 mol/L are prepared. The second metal salt solution is a mixed salt solution of calcium hydrochloride, barium hydrochloride, and chromium hydrochloride.
在具有搅拌桨的反应容器中，投入1.5L去离子水，升温至90℃后，在搅拌状态下同时滴加0.35mol/L的碳酸钠溶液和第一金属盐溶液，碳酸钠溶液与第一金属盐溶液的质量比为2.5:1。滴加完毕后在90℃下继续反应1.0h，调节pH至7.5～8.0，加入所需量的第二金属盐溶液及氧化铝。充分反应后过滤并水洗，干燥成型后在600℃下煅烧5h，制得。Put 1.5L of deionized water into a reaction vessel with a stirring blade. After the temperature is raised to 90°C, add 0.35mol/L of sodium carbonate solution and the first metal salt solution dropwise at the same time while stirring. The mass ratio of the metal salt solution is 2.5:1. After the dripping is completed, the reaction is continued at 90°C for 1.0 h, the pH is adjusted to 7.5-8.0, and the required amount of the second metal salt solution and alumina are added. After full reaction, it is filtered and washed with water, dried and formed and calcined at 600°C for 5 hours to prepare.
实施例6Example 6
6#催化剂，以质量百分数计，其含45.0％铜、5.0％镍、0.1％钯、1.0％氧化镁、1.0％氧化铋、1.5％氧化铬、46.4％分子筛。The 6# catalyst contains 45.0% copper, 5.0% nickel, 0.1% palladium, 1.0% magnesium oxide, 1.0% bismuth oxide, 1.5% chromium oxide, and 46.4% molecular sieve in terms of mass percentage.
配制总浓度为0.7mol/L的第一金属盐溶液，以及总浓度为0.7mol/L的第二金属盐溶液，该第二金属盐溶液为硫酸镁、硫酸铋、硫酸铬的混合盐溶液。A first metal salt solution with a total concentration of 0.7 mol/L and a second metal salt solution with a total concentration of 0.7 mol/L are prepared. The second metal salt solution is a mixed salt solution of magnesium sulfate, bismuth sulfate, and chromium sulfate.
在具有搅拌桨的反应容器中，投入1.0L去离子水，升温至80℃后，在搅拌状态下同时滴加0.7mol/L的碳酸钠溶液和第一金属盐溶液，碳酸钠溶液与第一金属盐溶液的质量比为0.7:1。滴加完毕后在80℃下继续反应2.0h，调节pH至7.0～8.0，加入所需量的第二金属盐溶液及分子筛。充分反应后过滤并水洗，干燥成型后在500℃下煅烧10h，制得。In a reaction vessel with a stirring blade, add 1.0L of deionized water, and after the temperature is raised to 80°C, while stirring, add 0.7mol/L of sodium carbonate solution and the first metal salt solution dropwise at the same time, and the sodium carbonate solution and the first The mass ratio of the metal salt solution is 0.7:1. After the dripping is completed, the reaction is continued at 80°C for 2.0 hours, the pH is adjusted to 7.0-8.0, and the required amount of the second metal salt solution and molecular sieve are added. After full reaction, it is filtered and washed with water, dried and formed and calcined at 500°C for 10 hours to prepare.
对比例1:选自市售Pd/C(0.5％Pd含量)催化剂；Comparative Example 1: Selected from commercially available Pd/C (0.5% Pd content) catalysts;
对比例2：选自市售雷尼镍催化剂；Comparative Example 2: Selected from commercially available Raney nickel catalysts;
对比例3：采用实施例1所述制备方法，区别在于反应过程不加入第二金属盐溶液，以2％氧化铝替代，即制成的催化剂最终组成为：80.0％铜、2.0％镍、0.01％钯、17.99％氧化铝。Comparative Example 3: Using the preparation method described in Example 1, the difference is that the second metal salt solution is not added in the reaction process, and 2% alumina is used instead. The final composition of the prepared catalyst is: 80.0% copper, 2.0% nickel, 0.01 % Palladium, 17.99% alumina.
催化剂评价Catalyst evaluation
采用在固定床反应器进行氢解反应，对上述实施例进行催化剂评价。The hydrogenolysis reaction in a fixed bed reactor was used to evaluate the catalysts in the above examples.
取实施例制备的催化剂25ml，置于固定床反应器中，持续通入氢气的条件下，逐步升温至180℃充分活化。完成活化程序后，在200℃、0.5MPa下按2.0h -1的液体空速连续泵入含有α,α-二甲基苄醇、α-甲基苯乙烯、苯乙酮的混合溶液进行氢解反应，完成反应的产物经过气液分离后取样检测。 Take 25ml of the catalyst prepared in the example, place it in a fixed bed reactor, and gradually increase the temperature to 180°C for full activation under the condition of continuous hydrogen flow. After the activation procedure is completed, the mixed solution containing α,α-dimethylbenzyl alcohol, α-methylstyrene and acetophenone is continuously pumped at 200℃ and 0.5MPa at a liquid space velocity of 2.0h -1 for hydrogen Decompose the reaction, and the product after the reaction is sampled and tested after gas-liquid separation.
实施例催化剂氢化评价的原料来自CHP法制备环氧丙烷中的环氧化工艺，按质量组成含约45％的异丙苯，43％的α,α-二甲基苄醇，2.3％的苯乙酮，1.5％的α-甲基苯乙烯。Examples The raw materials used in the evaluation of catalyst hydrogenation come from the epoxidation process in the preparation of propylene oxide by the CHP method. The composition by mass contains about 45% of cumene, 43% of α,α-dimethylbenzyl alcohol, and 2.3% of benzene. Ethyl ketone, 1.5% α-methylstyrene.
将各实施例所制备的催化剂以及对比例中的催化剂按照催化剂评价中的步骤进行检测， 检测数据列入表1。The catalyst prepared in each example and the catalyst in the comparative example were tested according to the steps in the catalyst evaluation, and the test data are listed in Table 1.
表1Table 1
Figure PCTCN2020108910-appb-000001
Figure PCTCN2020108910-appb-000001
通过表1可以看出，采用本申请中的催化剂能够同时提高α,α-二甲基苄醇、α-甲基苯乙烯及苯乙酮的转化率及相应氢解产物的选择性。It can be seen from Table 1 that the use of the catalyst in this application can simultaneously increase the conversion rate of α,α-dimethylbenzyl alcohol, α-methylstyrene and acetophenone and the selectivity of the corresponding hydrogenolysis products.

Claims (10)

  1. 一种氢解用催化剂，以质量百分数计，包括：A catalyst for hydrogenolysis, in terms of mass percentage, includes:
    (a)40～80％的组分A，该组分A为铜或氧化铜中的至少一种；(a) 40-80% of component A, the component A is at least one of copper or copper oxide;
    (b)0.5～10％的组分B,该组分B为镍或氧化镍中的至少一种；(b) 0.5-10% of component B, which is at least one of nickel or nickel oxide;
    (c)0.01～1％的组分C，该组分C为钯；(c) 0.01-1% of component C, which is palladium;
    (d)0.1～5％的组分D，该组分D为氧化物，该氧化物为氧化锌、氧化镁、氧化钙、氧化钡、氧化铋、氧化铅或氧化铬中的至少一种；(d) 0.1-5% of component D, the component D is an oxide, and the oxide is at least one of zinc oxide, magnesium oxide, calcium oxide, barium oxide, bismuth oxide, lead oxide, or chromium oxide;
    (e)10～50％的组分E，该组分E为氧化铝、氧化硅、分子筛中的至少一种。(e) 10-50% of component E, which is at least one of alumina, silica, and molecular sieve.
  2. 一种催化剂的制备方法，其用于制备权利要求1所述的氢解用催化剂，其特征在于，包括如下步骤：A method for preparing a catalyst, which is used to prepare the catalyst for hydrogenolysis according to claim 1, characterized in that it comprises the following steps:
    (1)在搅拌条件下，将碳酸钠溶液、第一金属盐溶液滴加到设定温度的去离子水中；该第一金属盐溶液为铜盐、镍盐以及钯盐的混合溶液；(1) Under stirring conditions, drop the sodium carbonate solution and the first metal salt solution into deionized water at a set temperature; the first metal salt solution is a mixed solution of copper salt, nickel salt and palladium salt;
    (2)滴加完成后，继续进行反应，在设定时间后，调节溶液pH，在溶液中加入第二金属盐溶液和组分E；该第二金属盐溶液为含有锌盐、镁盐、钙盐、钡盐、铋盐、铅盐或铬盐中至少一种的盐溶液；(2) After the dripping is completed, continue the reaction. After the set time, adjust the pH of the solution, and add the second metal salt solution and component E to the solution; the second metal salt solution contains zinc salt, magnesium salt, A salt solution of at least one of calcium salt, barium salt, bismuth salt, lead salt or chromium salt;
    (3)溶液经过滤、水洗、预烘干后，成型并干燥，再经过煅烧，形成催化剂成品。(3) After the solution is filtered, washed with water, pre-dried, it is shaped and dried, and then calcined to form a finished catalyst.
  3. 根据权利要求2所述的制备方法，其特征在于，步骤(1)中，铜盐、镍盐以及钯盐均为盐酸盐、硫酸盐或硝酸盐。The preparation method according to claim 2, wherein in step (1), the copper salt, nickel salt and palladium salt are all hydrochloride, sulfate or nitrate.
  4. 根据权利要求2所述的制备方法，其特征在于，锌盐、镁盐、钙盐、钡盐、铋盐、铅盐或铬盐均为盐酸盐、硫酸盐或硝酸盐。The preparation method according to claim 2, wherein the zinc salt, magnesium salt, calcium salt, barium salt, bismuth salt, lead salt or chromium salt are all hydrochloride, sulfate or nitrate.
  5. 根据权利要求2所述的制备方法，其特征在于，步骤(1)中，所述设定温度为50～110℃。The preparation method according to claim 2, wherein in step (1), the set temperature is 50-110°C.
  6. 根据权利要求2所述的制备方法，其特征在于，步骤(1)中，所述碳酸钠溶液与第一金属盐溶液的质量比为3:1～0.5:1。The preparation method according to claim 2, wherein in step (1), the mass ratio of the sodium carbonate solution to the first metal salt solution is 3:1 to 0.5:1.
  7. 根据权利要求2所述的制备方法，其特征在于，步骤(1)中，所述碳酸钠溶液与第一金属盐溶液均采用去离子水配制，碳酸钠溶液的浓度为0.1～1.0mol/L；第一金属盐溶液的总浓度为0.1～1.0mol/L。The preparation method according to claim 2, wherein in step (1), the sodium carbonate solution and the first metal salt solution are both prepared with deionized water, and the concentration of the sodium carbonate solution is 0.1-1.0 mol/L ; The total concentration of the first metal salt solution is 0.1 to 1.0 mol/L.
  8. 根据权利要求2所述的制备方法，其特征在于，步骤(2)中，滴加完成后，继续进行反应的时间为0.5～2.0h。The preparation method according to claim 2, characterized in that, in step (2), after the dropwise addition is completed, the time for continuing the reaction is 0.5-2.0h.
  9. 根据权利要求2所述的制备方法，其特征在于，步骤(2)中，pH为6.5～12。The preparation method according to claim 2, wherein in step (2), the pH is 6.5-12.
  10. 根据权利要求2所述的制备方法，其特征在于，步骤(3)中，所述煅烧的温度为400～600℃，时间为4～12h。The preparation method according to claim 2, characterized in that, in step (3), the calcination temperature is 400-600°C, and the time is 4-12h.
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