WO2022041218A1 - 铜基催化剂及制备方法 - Google Patents

铜基催化剂及制备方法 Download PDF

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WO2022041218A1
WO2022041218A1 PCT/CN2020/112582 CN2020112582W WO2022041218A1 WO 2022041218 A1 WO2022041218 A1 WO 2022041218A1 CN 2020112582 W CN2020112582 W CN 2020112582W WO 2022041218 A1 WO2022041218 A1 WO 2022041218A1
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copper
catalyst
oxalate
based catalyst
reaction
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PCT/CN2020/112582
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English (en)
French (fr)
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袁兴东
吉本亮介
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高化学株式会社
袁兴东
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Priority to PCT/CN2020/112582 priority Critical patent/WO2022041218A1/zh
Priority to CN202080001735.XA priority patent/CN114450086A/zh
Publication of WO2022041218A1 publication Critical patent/WO2022041218A1/zh

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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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • 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
    • B01J23/72—Copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/20—Dihydroxylic alcohols
    • 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 copper-based catalyst and a preparation method thereof.
  • Ethylene glycol is an important basic organic raw material for petrochemicals, mainly used in the manufacture of polyester fibers, antifreeze, nonionic surfactants, ethanolamine and explosives, etc. It can also be used directly as a solvent. In addition, it also has a wide range of uses in the tobacco industry, textile industry and cosmetics industry.
  • CN 106563449A discloses a method for preparing Cu/SiO catalyst by precipitation method.
  • copper nitrate or copper acetate is used as copper source
  • alkaline silica sol is used as silicon source
  • urea and ammonia water are used as precipitants
  • Polyhydroxy organics were added to tune the size and dispersion of copper species. It utilizes the carbon deposition produced in the roasting process of organic matter to inhibit the agglomeration of copper species, and better solves the problem of easy sintering of copper species at high temperature.
  • the carbon deposition will affect the pore size of the catalyst, resulting in an increase in the diffusion resistance; in addition, the carbon deposition will cover a part of the active center and affect the activity of the catalyst.
  • CN 107376980A discloses a preparation method of CuO/KIT-6 with mesoporous silicon as carrier. During the synthesis, copper nanoparticles were directly introduced into the pores of KIT-6 using a one-step method. This facilitates the dispersion of the active components, avoids the loss and agglomeration of the active components, thereby improving the catalytic efficiency and prolonging the service life of the catalyst.
  • the catalyst has problems such as complicated preparation process and serious diffusion effect.
  • CN 107694572A discloses a method for preparing catalyst by sol-gel method, wherein a second metal salt is added to a solution of silicon source, copper salt and ethanol, and then the solution is subjected to gelation, aging, drying and roasting , to obtain a catalyst for oxalate hydrogenation to ethylene glycol.
  • the gel temperature is 70°C-100°C, and the room temperature aging time is 12-24 hours.
  • the catalyst did not solve the problem of desiliconization during use.
  • the Cu/SiO catalyst for the hydrogenation of DMO to ethylene glycol can also be prepared by the ammonia distillation method, in which NH 4 OH is first formed into a complex with Cu 2+ and then reacted with the Si-OH groups on the surface of SiO, Thus, a Cu-( NH4 ) n -O-Si-O structure is formed, and then ammonia is removed by firing, thereby forming a Si-O-Cu structure.
  • the active components of the catalyst in the prior art are unevenly distributed, the copper species are not matched, silicon loss is likely to occur during the reaction process, and copper as the active component is easy to sinter. Therefore, it is necessary to find a Cu/SiO 2 catalyst with good catalyst performance, less loss of support and long life.
  • the purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art, and to provide a Cu/SiO 2 catalyst with good catalyst performance, a carrier that is not easily lost, and a long service life.
  • the above object can be achieved by a copper-based catalyst and a preparation method thereof, the catalyst comprises a SiO 2 carrier and a copper catalytically active species, wherein the copper catalytically active species are Cu + , Cu 0 and -Si-O-Cu- The form of O-Si-.
  • the copper-based catalyst of the present invention with copper catalytically active species in the form of Cu + , Cu 0 and -Si-O-Cu-O-Si- is used in the hydrogenation of oxalate to ethylene glycol It not only has high activity and high ethylene glycol selectivity, but also because of the more stable -Si-O-Cu-O-Si- species, the catalyst support is not easy to be lost, and the copper active species is not easy to aggregate, so it has a very high efficiency. High stability.
  • a copper-based catalyst comprising a SiO 2 support and a copper catalytically active species, wherein the copper catalytically active species are Cu + , Cu 0 and -Si-O -Cu-O-Si- form.
  • the copper catalytically active species Cu + and Cu0 are distributed on the surface of the SiO2 support, while the highly stable species -Si-O-Cu-O-Si- is located in the SiO2 support framework .
  • the copper in the copper-based catalyst of the present invention accounts for 5-80% of the total weight of the catalyst, preferably 10-75%, more preferably 20-65%.
  • the amount of Cu + in the copper-based catalyst of the present invention is 40-95%, preferably 50-90%, more preferably 60-80% ; the amount of Cu0 is 1-40% , preferably 5-35%, more preferably 10-30%; the amount of -Si-O-Cu-O-Si- is 1-50%, preferably 2-40%, more preferably 5-35%; Based in each case on the total weight of Cu + , Cu 0 and Cu 2+ in -Si-O-Cu-O-Si- in the copper-based catalyst, and the sum of the individual components is 100% by weight.
  • the copper-based catalyst of the present invention may have a specific surface area of 300-600 m 2 /g, preferably 300-500 m 2 /g.
  • the copper-based catalyst of the present invention may have a pore volume of 0.40-0.80 m 3 /g, preferably 0.50-0.70 m 3 /g.
  • the pore size of the copper-based catalyst of the present invention may be 6.0-12.0 nm.
  • a method for preparing a copper-based catalyst comprising the steps of:
  • the copper source used in the present invention can be selected from soluble copper salts and copper complexes.
  • the soluble copper salt can be various soluble copper salts, such as copper nitrate, copper sulfate, copper acetate, copper oxalate or copper halide, wherein the copper halide can be selected from copper chloride or copper bromide.
  • the water-soluble copper salt is copper nitrate, copper sulfate or copper chloride.
  • the copper complex may be a copper ammine complex.
  • the silicon source used in the present invention can be various silicon sources used in the catalyst field, such as silica sol or silica powder.
  • the present invention has no special requirements for the selection of the types of silica sol and silica powder, and various silica sols and silica powders in the prior art can be used in the present invention.
  • the silicon source can also be prepared in the form of a precursor by a method known in the prior art, for example, the silicon source precursor can be prepared by dispersing silica powder in water, and then adding an alkaline substance for reaction.
  • step (1) of the method of the present invention there is no particular restriction on the amount of copper source and silicon source used in step (1) of the method of the present invention, as long as it is ensured that the copper catalytically active species in the finally obtained copper-based catalyst accounts for 5-80% of the total weight of the catalyst, preferably 10- 75%, more preferably 20-65%.
  • a sustained release agent can be added.
  • Suitable sustained release agents are, for example, but not limited to, urea, ammonium acetate, ammonium oxalate or ammonium carbonate.
  • the slow release agent can be used in an amount of 0-2.0 wt%, preferably 0.01-1.5 wt%, more preferably 0.1-1.0 wt%, based on the total weight of the reaction mixture.
  • the aggregation rate of the silicon source is slowed down when a slow release agent is used, which results in a uniform distribution of the copper catalytically active species, thereby improving the performance of the resulting catalyst (including oxalate conversion and ethylene glycol selectivity) be improved.
  • a surfactant can also be added.
  • Suitable surfactants are, for example, but not limited to, tetramethylammonium hydroxide, tetraethylammonium hydroxide, cetylammonium chloride or tetramethylammonium chloride.
  • the surfactant can be used in an amount of 0-2.0% by weight, preferably 0.01-1.5% by weight, more preferably 0.1-1.0% by weight, based on the total weight of the reaction mixture.
  • the use of surfactants can modulate the size and dispersion of copper catalytically active species, resulting in improved catalyst performance, including oxalate conversion and ethylene glycol selectivity.
  • the reaction in step (1) can be carried out in a closed vessel (eg, an autoclave) under the autogenous pressure of the reaction system.
  • the reaction temperature may be 60-400°C, preferably 80-350°C, more preferably 120-250°C.
  • the reaction time may be 1-24 hours, preferably 1-12 hours, more preferably 2-8 hours.
  • the reaction is carried out in the presence of a solvent, such as an alcohol such as methanol, ethanol, propanol or butanol, or water, preferably water.
  • the copper source solution and the silicon source solution may be prepared separately, then the two are mixed and stirred, and then the resulting mixture is added to an autoclave for reaction. If used, slow release agents and surfactants can be added to the copper source solution and then mixed with the silicon source solution.
  • the reaction mixture can be filtered and washed with distilled water several times (eg, 1-10 times, preferably 1-3 times) until the washings are neutral. Then, the filtrate was dried. Drying can be carried out by various drying methods known in the art, such as conventional heating drying, microwave drying and/or spray drying. In the case of heating and drying, the drying temperature may be 50-200°C, preferably 80-150°C, and the drying time may be 1-24 hours, more preferably 4-20 hours, and more preferably 8-15 hours.
  • the resulting product can be shaped, which can be carried out in a manner known in the art, such as tableting, rolling or extrusion. Shaping can be carried out with the addition of lubricants.
  • the lubricant is, for example, graphite or the like.
  • the amount of lubricant may be 1-10%, preferably 1-5%, based on the total weight of lubricant and dried product.
  • the resulting shaped body can be crushed and sieved through a 40-60 mesh sieve.
  • the resulting product is calcined. Calcination can be carried out in various ways known in the art, for example in a muffle furnace.
  • the roasting temperature can be 300-800°C, preferably 350-600°C, more preferably 350-500°C; the roasting time can be 1-24 hours, preferably 1-12 hours, more preferably 1-5 hours.
  • step (3) of the method of the present invention the calcined product is reduced.
  • the reduction can be carried out using a hydrogen-containing gas, such as pure H2 or a mixture of H2 and N2 ( H2 / N2 ).
  • the volume content of H 2 may be 1-20%, more preferably 2-10%.
  • the hydrogen-containing gas flow rate may be 10-500ml/min, preferably 20-400ml/min, more preferably 50-300ml/min, most preferably 80-200ml/min.
  • the reduction temperature may be 100-400°C, preferably 150-300°C, more preferably 200-300°C.
  • the reduction time may be 0.5-50 hours, preferably 1-20 hours, more preferably 2-10 hours.
  • a preparation method of a copper-based catalyst comprising:
  • step (3) the mixture that step (2) obtains is added in the autoclave, and reacts;
  • the method of the invention can uniformly disperse the copper catalytic active species on the surface of the carrier and in the framework, easily form highly dispersed copper catalytic active species with a high ratio of Cu + /Cu 0 , and at the same time form new inhibitory species in the framework of the carrier
  • the desiliconized -Si-O-Cu-O-Si- species improves the stability of the catalyst and can achieve good catalytic effect.
  • a method for preparing ethylene glycol from oxalate by hydrogenation which comprises, in the presence of the copper-based catalyst of the present invention, under hydrogenation reaction conditions, making oxalate and ethylene glycol Hydrogen contact is carried out for hydrogenation to obtain ethylene glycol.
  • the oxalic acid ester used in the present invention is preferably an oxalic acid diester having the following structure:
  • R 1 and R 2 are the same or different, and are each independently a C 1 -C 10 alkyl group, preferably a C 1 -C 6 alkyl group, especially preferably a C 1 -C 4 alkyl group.
  • the oxalate diester can be methyl ethyl oxalate, dimethyl oxalate, diethyl oxalate, dipropyl oxalate, dibutyl oxalate, dipentyl oxalate, dihexyl oxalate, ethyl propyl oxalate, ethyl butyl oxalate ester, propyl butyl oxalate, amyl hexyl oxalate and methyl propyl oxalate one or more.
  • the oxalate of the present invention is dimethyl oxalate and/or diethyl oxalate.
  • the conditions of the hydrogenation reaction include: the liquid mass space velocity of the oxalate can be 0.01-10h -1 , preferably 0.1-5h -1 , preferably 0.3-2h -1 ; the molar ratio of hydrogen to oxalate (hydrogen ester ratio) can be 20-200, preferably 30-150, more preferably 50-120; the reaction temperature can be 100-300 °C, More preferably, it is 120-250°C; the reaction pressure can be 0.1-15MPa, preferably 0.5-10MPa, more preferably 1.0-5.0MPa.
  • the oxalate is preferably fed in a liquid phase, eg a methanolic solution of the oxalate (at a concentration of eg 1-60% by weight, preferably 5-40% by weight, more preferably 10-30% by weight).
  • a liquid phase eg a methanolic solution of the oxalate (at a concentration of eg 1-60% by weight, preferably 5-40% by weight, more preferably 10-30% by weight).
  • the method for preparing ethylene glycol from oxalate hydrogenation of the present invention can be carried out in any reactor capable of realizing the above reaction conditions, such as in a fixed bed reactor, a fluidized bed reactor or a slurry bed reactor, It is preferably carried out in a fixed bed reactor.
  • the Cu + , Cu 0 and -Si-O-Cu-O-Si- contents in the catalyst were determined by XRF (X-ray fluorescence spectrometry) using an EA1400 from Hitachi.
  • the specific surface area, pore distribution and pore size were determined by the BET method with N 2 adsorption-desorption using a BELMORP MR 6 from BEL Japan.
  • the steps of the preparation method of the catalyst for hydrogenating oxalate to ethylene glycol of the present embodiment are as follows: weigh 4.35g of copper nitrate hexahydrate, 1.0g of urea and 0.2g of tetramethylammonium chloride, place them in 100ml of water, It was dissolved by stirring for 30 minutes at a stirring speed of 200 rpm.
  • silica sol with a mass concentration of 20% (ST-C from Shidai Chemical Industry Co., Ltd.) was added to the solution, stirred at a stirring speed of 200 rpm for 2 hours, then put into an autoclave, and heated to 150° C. to react for 4 hours ,
  • the temperature was lowered to room temperature (ie, 25° C., the same below), filtered, washed with distilled water three times, and dried at 120° C. for 12 hours.
  • the dried solids were mixed with 3 wt% graphite, tableted, crushed, sieved through a 40-mesh sieve, and then calcined in a muffle furnace at 450° C. for 3 hours.
  • Catalyst evaluation pure hydrogen was introduced into the reactor, the temperature was adjusted to the reaction temperature of 185°C, the control pressure was 3.0MPa, the hydrogen-ester ratio was 80, the liquid mass space velocity of dimethyl oxalate was 0.6h -1 , and the raw material was 20 weight % Dimethyl oxalate in methanol was fed with a liquid phase high pressure pump. Samples were taken every 12 hours to analyze product composition by gas chromatography and to calculate DMO conversion and ethylene glycol (EG) selectivity. After long-term reaction evaluation, the life of the catalyst is determined. The results are shown in Table 2.
  • the DMO conversion rate and EG selectivity at the initial stage and termination of the reaction are given in Table 2, where the initial stage of the reaction refers to the time when the activity and selectivity become stable after the reaction passes through the induction period; the termination of the reaction refers to the time when the intermediate product The selectivity of methyl glycolate was higher than 0.3%, and the catalyst was considered to have been deactivated, thereby terminating the reaction.
  • Example 2 It is basically the same as Example 1, except that: the synthesis temperature is adjusted to 160° C., and finally Cu/SiO 2 -A-2 catalyst is obtained.
  • Example 2 It is basically the same as Example 1, except that: the synthesis temperature is adjusted to 170° C., and finally Cu/SiO 2 -A-3 catalyst is obtained.
  • Example 2 It is basically the same as Example 1, the difference is: the synthesis temperature is adjusted to 180°C, and finally Cu/SiO 2 -A-4 catalyst is obtained.
  • Example 2 It is basically the same as Example 1, except that: the synthesis temperature is adjusted to 190° C., and finally Cu/SiO 2 -A-5 catalyst is obtained.
  • silica powder (EVONIC's 380) 50g, dissolved in 600mL deionized water, adjusted pH value to 7.0 with 25% by weight ammonia water, stirred for 120 minutes at room temperature and at a stirring speed of 150rpm to obtain a carrier precursor;
  • step (3) mixing the carrier precursor obtained in step (1) and the cuprammonium solution obtained in step (2) at room temperature and stirring, and stirring for 15 minutes at a stirring speed of 600 rpm; then stirring at a temperature of 60° C. and 600 rpm Agitation was carried out under stirring for 48 hours at a high speed, and then ammonia was distilled at 85°C under stirring at 300 rpm to form a viscous material;
  • step (3) drying the viscous material obtained in step (3) at a temperature of 80° C. for the first time for 20 hours to obtain a dry matter;
  • step (4) Wash the dried product obtained in step (4) with deionized water until the washing solution is neutral, then carry out the second drying at 120° C. for 24 hours, and mix the dried solid with 3% by weight of graphite , after tableting, crushing, sieving through a 40-mesh sieve, and then roasting in a muffle furnace at 450°C for 3h, and
  • Comparative Example 2 It is basically the same as Comparative Example 1, except that the silica powder is changed to 250 g of silica sol with a mass concentration of 20% (ST-C of Shidai Chemical Industry Co., Ltd.) to obtain a Comparative-2 catalyst.
  • solution A 25g of ethyl orthosilicate and 25g of absolute ethanol were mixed and stirred at room temperature for 20min to obtain solution A.
  • Solution B was 11.29 g Cu(NO 3 ) 2 ⁇ 3H 2 O and 20 g H 2 O. Then, the solution B was dropped into the solution A, and the temperature was raised to 70° C. after the dropping, and the stirring was stopped, kept for 4 hours, cooled to room temperature, and allowed to stand for 24 hours. The left-standing mixture was filtered and washed with distilled water until the washings were neutral.
  • Example 2 Basically the same as Example 1, the difference is: the silica sol is changed to 4 g of silica powder (EVONIC's 380), and finally Cu/SiO 2 -A-6 catalyst was obtained.
  • Example 2 It is basically the same as Example 1, except that 1.0 g of urea is changed to 1.0 g of ammonium oxalate, and finally a Cu/SiO 2 -A-7 catalyst is obtained.
  • Example 2 It is basically the same as Example 1, except that 1.0 g of urea is changed to 1.0 g of ammonium acetate to finally obtain a Cu/SiO 2 -A-8 catalyst.
  • Example 2 It is basically the same as Example 1, except that 1.0 g of urea is changed to 1.0 g of ammonium carbonate to finally obtain a Cu/SiO 2 -A-9 catalyst.
  • Example 2 It is basically the same as Example 1, except that 0.2 g of tetramethylammonium chloride is changed to 1.0 g of an aqueous solution of 20% tetramethylammonium hydroxide to finally obtain a Cu/SiO 2 -A-10 catalyst.
  • Example 2 It is basically the same as Example 1, except that 0.2 g of tetramethylammonium chloride is changed to 1.0 g of an aqueous solution of 20% tetraethylammonium hydroxide to finally obtain a Cu/SiO 2 -A-11 catalyst.
  • Example 2 It is basically the same as Example 1, except that 0.2 g of tetramethyl ammonium chloride is changed to 0.1 g of hexadecyl ammonium chloride, and finally Cu/SiO 2 -A-12 catalyst is obtained.
  • silica powder (EVONIC's 380) 50g, dispersed in 600mL deionized water, adjusted pH value to 7.0 with 25% by weight ammonia water, stirred for 120 minutes at room temperature and a stirring speed of 150rpm to obtain a carrier precursor;
  • step (3) mixing the carrier precursor obtained in step (1) and the cupro ammonia solution obtained in step (2) at room temperature and stirring, and stirring for 15 minutes at a stirring speed of 600 rpm; then in an autoclave at a temperature of 150° C. It was stirred for 4 hours, then cooled and filtered. Washed with deionized water until the washings were neutral, then dried at 120°C for 24 hours, then calcined in a muffle furnace at 450°C for 4 hours, and then reduced as described in Example 1 to obtain the catalyst Cu/SiO 2 -A-13 powder, 64 g in total.
  • a new species -Si-O-Cu-O-Si- is generally generated.
  • the appearance of this species improves the stability of the carrier and prolongs the use of the catalyst. life.
  • the catalyst of the present invention also has high activity.

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Abstract

本发明涉及一种铜基催化剂及其制备方法。本发明铜基催化剂的载体不容易流失，催化剂寿命长，具有提高的催化剂稳定性，能够取得良好的催化效果。此外，本发明铜基催化剂的制备工艺简单。特别地，本发明的铜基催化剂在草酸酯加氢制取乙二醇反应中具有很高的DMO转化率和乙二醇选择性，反应平稳，寿命长的特点。

Description

铜基催化剂及制备方法 技术领域
本发明涉及一种铜基催化剂及其制备方法。
背景技术
乙二醇是重要的石油化工基础有机原料，主要用于制造聚酯纤维、防冻剂、非离子表面活性剂、乙醇胺以及炸药等，也可直接用作溶剂。另外，其在烟草工业、纺织工业和化妆品业中也有着广泛的用途。
现有的乙二醇生产工艺大部分采用石油路线，即先用直接氧化法生产环氧乙烷，再经液相催化或非催化水合制得乙二醇。该路线存在生产工艺长、所需设备多、能耗高等缺点，从而造成乙二醇的生产成本高。
上世纪70年代末，L.R.Jehner等在日本专利JP5323011、JP5542971中首先提出草酸酯气相加氢制备乙二醇的技术路线。煤基合成气制乙二醇的工艺路线目前已经实现工业化。但煤制乙二醇这一工业化的工艺仍存在诸多技术缺陷和难题亟需解决与研究。在目前已经建成的合成气制乙二醇的工业装置上，一般采用铜基硅(Cu/SiO 2)催化剂对草酸二甲酯(DMO)进行气相加氢。该催化剂具有活性高，乙二醇选择性好的特点，但是使用过程中存在催化剂脱硅，影响稳定性等问题。需要进一步提高该催化剂的使用寿命。
CN 106563449A公开了一种采用沉淀法制备Cu/SiO 2催化剂的方法，在制备过程中以硝酸铜或醋酸铜为铜源，以碱性硅溶胶为硅源，以尿素和氨水为沉淀剂，再添加多羟基有机物来调控铜物种的尺寸及分散度。其利用有机物焙烧过程中产生的积碳来抑制铜物种的团聚，较好地解决了铜物种高温易烧结的问题。但是积碳会影响催化剂的孔径，造成扩散阻力增加；另外积碳会覆盖一部分活性中心，影响催化剂的活性。
CN 107376980A公开了一种以介孔硅为载体的CuO/KIT-6制备方法。在合成过程中，利用一步法将铜纳米颗粒直接引入到KIT-6孔道中。这有利于活性组分的分散，避免了活性组分的流失以及团聚，从而提高了催化 效率，延长了催化剂的使用寿命。但该催化剂存在制备过程复杂，扩散影响严重等问题。
CN 107694572A公开了一种通过溶胶凝胶法制备催化剂的方法，其中在硅源、铜盐以及乙醇的溶液中添加一种第二金属盐，然后将该溶液经凝胶、老化、烘干、焙烧，得到草酸酯加氢制乙二醇催化剂。所述的凝胶温度为70℃-100℃，室温老化时间为12-24小时。但该催化剂没有解决使用过程中的脱硅问题。
此外，DMO加氢制备乙二醇的Cu/SiO 2催化剂还可通过蒸氨法制备，其中首先使NH 4OH与Cu 2+形成络合物，然后与SiO 2表面的Si-OH基反应，从而形成Cu-(NH 4) n-O-Si-O结构，然后通过焙烧除去氨，从而形成Si-O-Cu结构。在蒸氨法中，需要使用大量的氨水，这造成工作环境不友好；另外Si-O-Cu中的铜由于与Si的结合力比较弱，不稳定，铜容易聚集，硅容易流失，影响Cu的分散度。
现有技术中的催化剂活性组分分布不均，铜物种不匹配，反应过程中容易发生硅流失，作为活性组分的铜易烧结。因此，需要寻找一种催化剂性能好、载体不容易流失、寿命长的Cu/SiO 2催化剂。
发明内容
本发明的目的是克服上文所述的现有技术缺点，提供一种催化剂性能好、载体不容易流失、寿命长的Cu/SiO 2催化剂。
上述的目的可通过一种铜基催化剂及其制备方法实现，所述催化剂包含SiO 2载体和铜催化活性物种，其中所述铜催化活性物种呈Cu +、Cu 0和-Si-O-Cu-O-Si-的形式。
令人惊讶地发现，本发明的具有呈Cu +、Cu 0和-Si-O-Cu-O-Si-形式的铜催化活性物种的铜基催化剂在草酸酯加氢制取乙二醇反应中不仅具有高活性和很高的乙二醇选择性，而且由于有更稳定的-Si-O-Cu-O-Si-物种，催化剂载体不容易流失，铜活性物种不容易聚集，因此具有很高的稳定性。
因此，在本发明的第一方面中，提供了一种铜基催化剂，所述催化剂包含SiO 2载体和铜催化活性物种，其中所述铜催化活性物种呈Cu +、Cu 0和 -Si-O-Cu-O-Si-的形式。
在本发明的铜基催化剂中，铜催化活性物种Cu +和Cu 0分布在SiO 2载体的表面上，而高稳定性的物种-Si-O-Cu-O-Si-位于SiO 2载体骨架中。
在本发明的一个实施方案中，本发明铜基催化剂中的铜占催化剂总重量的5-80％，优选占10-75％，更优选占20-65％。
在本发明的另一个实施方案中，本发明铜基催化剂中Cu +的量为40-95％，优选为50-90％，更优选为60-80％；Cu 0的量为1-40％，优选为5-35％，更优选为10-30％；-Si-O-Cu-O-Si-的量为1-50％，优选为2-40％，更优选为5-35％；在每种情况下基于所述铜基催化剂中的Cu +、Cu 0和-Si-O-Cu-O-Si-中的Cu 2+的总重量，且各组分之和为100重量％。
在本发明的又一个实施方案中，本发明铜基催化剂的比表面积可为300-600m 2/g，优选为300-500m 2/g。
在本发明的再一个实施方案中，本发明的铜基催化剂的孔体积可为0.40-0.80m 3/g，优选为0.50-0.70m 3/g。
本发明铜基催化剂的孔径可为6.0-12.0nm。
在本发明的第二方面中，提供了一种铜基催化剂的制备方法，其包括如下步骤：
(1)使铜源和硅源发生反应；
(2)对步骤(1)的反应产物进行焙烧；和
(3)将焙烧的产物还原。
本发明所用的铜源可选自可溶性铜盐和铜络合物。所述可溶性铜盐可为各种可溶性铜盐，例如硝酸铜、硫酸铜、醋酸铜、草酸铜或卤化铜，其中卤化铜可选自氯化铜或溴化铜。优选地，所述水溶性铜盐为硝酸铜、硫酸铜或氯化铜。所述铜络合物可为铜氨络合物。
本发明所用的硅源可为催化剂领域使用的各种硅源，例如硅溶胶或二氧化硅粉末。本发明对于硅溶胶和二氧化硅粉末的型号选择没有特别的要求，现有技术中各种硅溶胶和二氧化硅粉末均可以用于本发明。硅源也可以通过现有技术已知的方法以前驱体的形式制备，例如可通过将二氧化硅粉末分散在水中，然后加入碱性物质进行反应，从而制得硅源前驱体。
对本发明方法步骤(1)中所用的铜源和硅源的用量没有特别的限制，只要确保最终得到的铜基催化剂中的铜催化活性物种占催化剂总重量的5-80％，优选占10-75％，更优选占20-65％即可。
在本发明方法的步骤(1)中，可加入缓释剂。合适的缓释剂例如为但不限于尿素、醋酸铵、草酸铵或碳酸铵。缓释剂的用量可为0-2.0重量％，优选为0.01-1.5重量％，更优选为0.1-1.0重量％，基于反应混合物的总重量。令人惊讶地发现，当使用缓释剂时，硅源的聚集速率减缓，这导致铜催化活性物种的均匀分布，从而使得所得催化剂的性能(包括草酸酯转化率和乙二醇选择性)得以提高。
在本发明方法的步骤(1)中，还可加入表面活性剂。合适的表面活性剂例如为但不限于四甲基氢氧化铵、四乙基氢氧化铵、十六烷基氯化铵或四甲基氯化铵。表面活性剂的用量可为0-2.0重量％，优选为0.01-1.5重量％，更优选为0.1-1.0重量％，基于反应混合物的总重量。使用表面活性剂能调控铜催化活性物种的尺寸及分散度，从而使得所得催化剂的性能(包括草酸酯转化率和乙二醇选择性)得以提高。
步骤(1)中的反应可在密闭容器(例如高压釜)中在反应体系的自生压力下进行。反应温度可为60-400℃，优选为80-350℃，更优选为120-250℃。反应时间可为1-24小时，优选为1-12小时，更优选为2-8小时。所述反应在溶剂存在下进行，所述溶剂例如为醇如甲醇、乙醇、丙醇或丁醇，或水，优选为水。
在本发明的一个实施方案中，可分别配制铜源溶液和硅源溶液，然后将二者混合并搅拌，然后将所得混合物加入高压釜中进行反应。如果使用的话，可将缓释剂和表面活性剂加入到铜源溶液中，然后与硅源溶液混合。
在反应后，可将反应混合物过滤，并用蒸馏水洗涤数次(例如1-10次，优选1-3次)，直到洗液呈中性。然后，将滤出物干燥。干燥可采用现有技术中已知的各种干燥方式进行，例如普通加热干燥、微波干燥和/或喷雾干燥。在加热干燥的情况下，干燥温度可为50-200℃，优选为80-150℃，干燥时间可为1-24小时，更优选为4-20小时，更优选为8-15小时。
在干燥后，可将所得产物成型，成型可采用现有技术中已知的方式进 行，例如压片成型、滚球成型或挤出成型。成型可在加入润滑剂下进行。所述润滑剂例如为石墨等。润滑剂的用量可为1-10％，优选为1-5％，基于润滑剂和干燥后产物的总重量。在成型后，可将所得成型体破碎并经40-60目筛筛分。
在筛分后，将所得产物焙烧。焙烧可采用现有技术已知的各种方式进行，例如在马弗炉中进行。焙烧温度可为300-800℃，优选为350-600℃，更优选为350-500℃；焙烧时间可为1-24小时，优选为1-12小时，更优选为1-5小时。
在本发明方法的步骤(3)中，将焙烧产物还原。还原可使用含氢气体进行，例如纯H 2或H 2和N 2的混合物(H 2/N 2)。在使用H 2/N 2的情况下，H 2的体积含量可为1-20％，更优选为2-10％。含氢气体流速可为10-500ml/min，优选为20-400ml/min，更优选为50-300ml/min，最优选为80-200ml/min。还原温度可为100-400℃，优选为150-300℃，更优选为200-300℃。还原时间可为0.5-50小时，优选为1-20小时，更优选为2-10小时。
在本发明的优选实施方案中，提供了一种铜基催化剂的制备方法，其包括：
(1)将铜源溶液、任选的缓释剂和任选的表面活性剂混合均匀；
(2)将硅源加入到步骤(1)中获得的混合物中并混合均匀；
(3)将步骤(2)得到的混合物加入高压釜中，进行反应；
(4)对步骤(3)的反应产物进行焙烧；和
(5)将焙烧的产物还原。
本发明的方法能使铜催化活性物种均匀分散在载体表面上和骨架中，易于形成高分散的铜催化活性物种，并具有高的Cu +/Cu 0比例，同时在载体骨架内形成新的抑制脱硅的-Si-O-Cu-O-Si-物种，提高催化剂的稳定性，能够取得良好的催化效果。
在本发明的第三方面中，提供了一种由草酸酯加氢制备乙二醇的方法，其包括在本发明的铜基催化剂存在下，在加氢反应条件下，使草酸酯与氢气接触进行氢化反应以得到乙二醇。
根据本发明，本发明使用的草酸酯优选为具有如下结构的草酸二酯：
Figure PCTCN2020112582-appb-000001
其中R 1和R 2相同或不同，且各自独立地为C 1-C 10烷基，优选为C 1-C 6烷基，尤其优选为C 1-C 4烷基。例如，草酸二酯可为草酸甲乙酯、草酸二甲酯、草酸二乙酯、草酸二丙酯、草酸二丁酯、草酸二戊酯、草酸二己酯、草酸乙丙酯、草酸乙丁酯、草酸丙丁酯、草酸戊己酯和草酸甲丙酯中的一种或多种。优选地，本发明的草酸酯为草酸二甲酯和/或草酸二乙酯。
根据本发明的由草酸酯加氢制备乙二醇的制备方法，所述加氢反应的条件包括：草酸酯的液体质量空速可为0.01-10h -1，优选为0.1-5h -1，优选为0.3-2h -1；氢气与草酸酯的摩尔比(氢酯比)可为20-200，优选为30-150，更优选为50-120；反应温度可为100-300℃，更优选为120-250℃；反应压力可为0.1-15MPa，优选为0.5-10MPa，更优选为1.0-5.0MPa。草酸酯优选以液相供入，例如草酸酯的甲醇溶液(以例如1-60重量％，优选5-40重量％，更优选10-30重量％的浓度)。
本发明的由草酸酯加氢制备乙二醇的方法可在任何能够实现上述反应条件的反应器中进行，例如在固定床反应器、流化床反应器或浆态床反应器中进行，优选在固定床反应器中进行。
具体实施方式
以下通过具体实施例对本发明的发明内容做进一步的阐释，但不应理解为本发明的范围仅限于以下实施例。
测试方法
Cu +、Cu 0和-Si-O-Cu-O-Si-含量的测定
催化剂中的Cu +、Cu 0和-Si-O-Cu-O-Si-含量通过XRF(X射线荧光光谱分析)使用日立公司的EA1400测定。
比表面积、孔体积和孔径的测定
比表面积、孔分布和孔径通过BET法以N 2吸附-脱附使用BEL日本公司的BELMORP MR 6测定。
实施例1
本实施例的草酸酯加氢制乙二醇催化剂的制备方法的步骤如下：称取4.35g六水硝酸铜、1.0g尿素和0.2g四甲基氯化铵，将其置于100ml水中，在200rpm的搅拌速度下搅拌30分钟使之溶解。
在该溶液中加入20g质量浓度为20％的硅溶胶(日常化学工业株式会社的ST-C)，在200rpm的搅拌速度下搅拌2小时，然后装入高压釜中，升温至150℃反应4小时，
反应结束后降温到室温(即25℃，下同)，过滤，用蒸馏水洗3次，120℃干燥12小时。
将干燥后的固体和3重量％的石墨混合，经过压片，破碎，经40目筛筛分，然后在马弗炉中焙烧，450℃焙烧3小时。
将焙烧产物称重1g放入固定床反应器中，使用5体积％H 2的H 2/N 2还原，总流速控制在100ml/min，还原温度240℃，还原时间4小时。在还原结束后，得到Cu/SiO 2-A-1催化剂。通过XRF测定催化剂中的Cu +、Cu 0和-Si-O-Cu-O-Si-含量。
该催化剂的物性参数见表1。
催化剂评价：将纯氢气通入反应器中，调整温度到185℃的反应温度，控制压力为3.0MPa，氢酯比为80，草酸二甲酯液体质量空速为0.6h -1，原料20重量％草酸二甲酯的甲醇溶液用液相高压泵进料。每隔12小时取样以气相色谱分析产物组成，并计算得到DMO转化率和乙二醇(EG)选择性。经过长时间反应评价，确定催化剂的寿命。结果见表2。表2中给出了反应初始阶段和终止时的DMO转化率和EG选择性，其中反应初始阶段是指在反应经过诱导期之后，活性与选择性达到稳定的时候；反应终止是指当中间产物乙醇酸甲酯的选择性高于0.3％，认为催化剂已经发生失活，从而终止反应。
实施例2
与实施例1基本相同，不同的是：将合成温度调整为160℃，最终得到Cu/SiO 2-A-2催化剂。
该催化剂的物性参数见表1，性能评价结果见表2。
实施例3
与实施例1基本相同，不同的是：将合成温度调整为170℃，最终得到Cu/SiO 2-A-3催化剂。
该催化剂的物性参数见表1，性能评价结果见表2。
实施例4
与实施例1基本相同，不同的是：将合成温度调整为180℃，最终得到Cu/SiO 2-A-4催化剂。
该催化剂的物性参数见表1，性能评价结果见表2。
实施例5
与实施例1基本相同，不同的是：将合成温度调整为190℃，最终得到Cu/SiO 2-A-5催化剂。
该催化剂的物性参数见表1，性能评价结果见表2。
对比实施例1
(1)称取二氧化硅粉末(EVONIC的
Figure PCTCN2020112582-appb-000002
380)50g，溶解在600mL去离子水中，用25重量％氨水调节pH值到7.0，在室温和150rpm的搅拌速度下搅拌120分钟，得到载体前驱体；
(2)在室温下，将硝酸铜44g溶解到25重量％氨水中配制铜氨溶液1125mL，溶液中铜与氨的摩尔比为90，pH值为14，在150rpm的搅拌速度下搅拌5分钟，得到铜氨溶液；
(3)在室温和搅拌下将步骤(1)得到的载体前驱体和步骤(2)得到的铜氨溶液混合，在600rpm的搅拌速度下搅拌15分钟；然后在60℃的温度和 600rpm的搅拌速度下搅拌48小时进行陈化，然后在85℃下和300rpm搅拌下蒸氨，形成粘稠物料；
(4)将步骤(3)得到的粘稠物料在温度80℃下进行第一次干燥20小时，得到干燥物；
(5)将步骤(4)得到的干燥物用去离子水洗涤，直到洗液呈中性，然后在120℃下进行第二次干燥24小时，将干燥后的固体和3重量％的石墨混合，经过压片，破碎，经40目筛筛分，然后在马弗炉中焙烧，450℃焙烧3h，以及
(6)如实施例1所述进行还原，从而得到对比-1催化剂。
该催化剂的物性参数见表1，性能评价结果见表2。
对比实施例2
与对比实施例1基本相同，不同的是：将二氧化硅粉末改为250g质量浓度为20％的硅溶胶(日常化学工业株式会社的ST-C)，得到对比-2催化剂。
该催化剂的物性参数见表1，性能评价结果见表2。
对比实施例3
将25g正硅酸乙酯与25g无水乙醇在常温下混合搅拌20min，得到溶液A。溶液B为11.29g Cu(NO 3) 2·3H 2O和20g H 2O。然后将溶液B滴入溶液A中，滴完后开始升温到70℃，停止搅拌，保持4小时，降温至室温，并静置24小时。对静置后的混合物过滤，并用蒸馏水洗净，直到洗液呈中性。然后在120℃下干燥24小时，将干燥后的固体和3重量％的石墨混合，经过压片，破碎，经40目筛筛分，然后在马弗炉中焙烧，450℃焙烧3h，然后如实施例1所述进行还原，从而得到对比-3催化剂。
实施例6
与实施例1基本相同，不同的是：将硅溶胶改为4g二氧化硅粉末(EVONIC的
Figure PCTCN2020112582-appb-000003
380)，最终得到Cu/SiO 2-A-6催化剂。
该催化剂的物性参数见表1，性能评价结果见表2。
实施例7
与实施例1基本相同，不同的是：将1.0g尿素改为1.0g草酸铵，最终得到Cu/SiO 2-A-7催化剂。
该催化剂的物性参数见表1，性能评价结果见表2。
实施例8
与实施例1基本相同，不同的是：将1.0g尿素改为1.0g醋酸铵，最终得到Cu/SiO 2-A-8催化剂。
该催化剂的物性参数见表1，性能评价结果见表2。
实施例9
与实施例1基本相同，不同的是：将1.0g尿素改为1.0g碳酸铵，最终得到Cu/SiO 2-A-9催化剂。
该催化剂的物性参数见表1，性能评价结果见表2。
实施例10
与实施例1基本相同，不同的是：将0.2g四甲基氯化铵改为1.0g浓度为20％的四甲基氢氧化铵水溶液，最终得到Cu/SiO 2-A-10催化剂。
该催化剂的物性参数见表1，性能评价结果见表2。
实施例11
与实施例1基本相同，不同的是：将0.2g四甲基氯化铵改为1.0g浓度为20％的四乙基氢氧化铵水溶液，最终得到Cu/SiO 2-A-11催化剂。
该催化剂的物性参数见表1，性能评价结果见表2。
实施例12
与实施例1基本相同，不同的是：将0.2g四甲基氯化铵改为0.1g十六烷基氯化铵，最终得到Cu/SiO 2-A-12催化剂。
该催化剂的物性参数见表1，性能评价结果见表2。
实施例13
(1)称取二氧化硅粉末(EVONIC的
Figure PCTCN2020112582-appb-000004
380)50g，分散在600mL去离子水中，用25重量％氨水调节pH值到7.0，在室温和150rpm的搅拌速度下搅拌120分钟，得到载体前驱体；
(2)在室温下，将硝酸铜44g溶解到25重量％氨水中配制铜氨溶液1125mL，所述溶液的铜与氨的摩尔比为90，pH值为14，在150rpm的搅拌速度下搅拌5分钟，得到铜氨溶液；
(3)在室温和搅拌下将步骤(1)得到的载体前驱体和步骤(2)得到的铜氨溶液混合，在600rpm的搅拌速度下搅拌15分钟；然后在高压釜中在150℃的温度下搅拌4小时，然后冷却过滤。用去离子水洗涤，直到洗液呈中性，然后在120℃下进行干燥24小时，然后在马弗炉中于450℃下焙烧4小时，然后如实施例1所述进行还原，从而得到催化剂Cu/SiO 2-A-13粉末，共64g。
该催化剂的物性参数见表1，性能评价结果见表2。
表1.催化剂的物性参数
Figure PCTCN2020112582-appb-000005
Figure PCTCN2020112582-appb-000006
表2.催化剂的性能评价结果
Figure PCTCN2020112582-appb-000007
从催化剂的物性参数看，在本发明的实施例中，普遍生成了新的物种-Si-O-Cu-O-Si-，该物种的出现，提高了载体的稳定性，延长了催化剂的使用寿命。此外，由于Cu +和Cu 0的存在，本发明的催化剂还具有很高的活性。

Claims (13)

  1. 一种铜基催化剂，所述催化剂包含SiO 2载体和铜催化活性物种，其中所述铜催化活性物种呈Cu +、Cu 0和-Si-O-Cu-O-Si-的形式。
  2. 如权利要求1所述的铜基催化剂，其中Cu +的量为40-95％，优选为50-90％，更优选为60-80％；Cu 0的量为1-40％，优选为5-35％，更优选为10-30％；-Si-O-Cu-O-Si-的量为1-50％，优选为2-40％，更优选为5-35％；在每种情况下基于所述铜基催化剂中的Cu +、Cu 0和-Si-O-Cu-O-Si-中的Cu 2+的总重量。
  3. 如权利要求1或2所述的铜基催化剂，其中所述催化剂的比表面积为300-600m 2/g，优选为300-500m 2/g；和/或，孔体积为0.40-0.80m 3/g，优选为0.50-0.70m 3/g；和/或，孔径为6.0-12.0nm。
  4. 如权利要求1-3中任一项所述的铜基催化剂，其中铜催化活性物种占催化剂总重量的5-80％，优选占10-75％，更优选占20-65％。
  5. 一种制备如权利要求1-4中任一项所述的铜基催化剂的制备方法，其包括如下步骤：
    (1)使铜源和硅源发生反应；
    (2)对步骤(1)的反应产物进行焙烧；和
    (3)将焙烧的产物还原。
  6. 如权利要求5所述的方法，其中所述铜源选自可溶性铜盐和铜络合物。
  7. 如权利要求5或6所述的方法，其中在步骤(1)中加入缓释剂和/或表面活性剂。
  8. 如权利要求7所述的方法，其中所述缓释剂选自尿素、醋酸铵、草酸铵或碳酸铵。
  9. 如权利要求5-8中任一项所述的方法，其中步骤(1)的反应在60-400℃，优选80-350℃，更优选120-250℃的温度下在溶剂的存在下进行。
  10. 如权利要求9所述的方法，其中所述溶剂为醇如甲醇、乙醇、丙醇或丁醇，或水，优选为水。
  11. 如权利要求5-10中任一项所述的方法，其中焙烧在300-800℃，优选为350-600℃，更优选为350-500℃的温度下进行。
  12. 一种由草酸酯加氢制备乙二醇的方法，其包括在如权利要求1-4中任一项所述的铜基催化剂存在下，在加氢反应条件下，使草酸酯与氢气接触进行氢化反应以得到乙二醇。
  13. 如权利要求12所述的方法，其中草酸酯的液体质量空速为0.01-10h -1，优选为0.1-5h -1，优选为0.3-2h -1；氢气与草酸酯的摩尔比为20-200，优选为30-150，更优选为50-120；反应温度为100-300℃，更优选为120-250℃；反应压力为0.1-15MPa，优选为0.5-10MPa，更优选为1.0-5.0MPa。
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