WO2019011005A1 - 一种对草酸酯进行催化加氢的方法 - Google Patents

一种对草酸酯进行催化加氢的方法 Download PDF

Info

Publication number
WO2019011005A1
WO2019011005A1 PCT/CN2018/080544 CN2018080544W WO2019011005A1 WO 2019011005 A1 WO2019011005 A1 WO 2019011005A1 CN 2018080544 W CN2018080544 W CN 2018080544W WO 2019011005 A1 WO2019011005 A1 WO 2019011005A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
ethylene glycol
oxalate
copper
diameter
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2018/080544
Other languages
English (en)
French (fr)
Inventor
马新宾
王悦
药大卫
吕静
赵玉军
王胜平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin University
Original Assignee
Tianjin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN201710571590.7A external-priority patent/CN109248682B/zh
Priority claimed from CN201710572107.7A external-priority patent/CN109248683B/zh
Application filed by Tianjin University filed Critical Tianjin University
Priority to US16/628,986 priority Critical patent/US10894756B2/en
Publication of WO2019011005A1 publication Critical patent/WO2019011005A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/035—Precipitation on carriers
    • 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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J21/18—Carbon
    • B01J21/185—Carbon nanotubes
    • 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
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • B01J35/52—Hollow spheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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 belongs to the technical field of catalytic hydrogenation, and in particular relates to a method for catalytic hydrogenation of oxalate.
  • ethylene glycol is widely used in the production of polyester and its downstream products, antifreeze, lubricating oil, etc., and has a broad market prospect.
  • the process of synthesizing dimethyl oxalate (abbreviated as DMO) and dimethyl oxalate to ethylene glycol by syngas with synthesis gas has high atomic economy, mild reaction conditions, high product selectivity, green environmental protection, etc. It is characterized by one of the important routes for the synthesis of ethylene glycol from non-oil routes. Among them, hydrogenation of dimethyl oxalate is the core of the process.
  • Other types of oxalates such as diethyl oxalate or dibutyl oxalate can also form ethylene glycol after hydrogenation, and by-product corresponding ethyl ethoxide or butyl glycolate.
  • Copper-based catalysts have achieved good activity and selectivity in the reaction system, but the hydrogen-ester ratio required for the reaction feed (ie, the molar ratio of hydrogen to dimethyl oxalate H 2 /DMO) is higher and the product distribution is regulated. Difficult problems are still difficult to get an effective solution.
  • a large excess of hydrogen is required in the hydrogenation reaction of dimethyl oxalate (H 2 /DMO molar feed ratio is generally between 80 and 200) to achieve an ethylene glycol yield of greater than 90%.
  • H 2 /DMO molar feed ratio is generally between 80 and 200
  • such a high hydrogen ester ratio will lead to an increase in the amount of hydrogen circulation, which increases the requirements for equipment parameters such as compressors, and greatly increases the equipment cost and power cost required for the process. Therefore, the design of a new high-activity copper-based catalyst, hydrogenation of dimethyl oxalate can also achieve high selectivity and yield of ethylene glycol under low hydrogen-ester ratio conditions. The key to technology.
  • the present invention is directed to solving the above problems.
  • the invention provides a method for catalytic hydrogenation of oxalate, which brings oxalate and hydrogen into contact with a bulb composite catalyst to produce a product comprising glycolate or ethylene glycol, the main chemical composition of the catalyst It is copper and silicon oxide, wherein copper accounts for 5 to 60 wt.% of the weight of the catalyst, and silica accounts for 40 to 95 wt.% of the weight of the catalyst.
  • the catalyst has a specific surface area of 450 to 500 m 2 /g and an average pore volume of 0.5- 1cm 3 /g, an average pore diameter of 5-6nm;
  • the catalyst structure is a hollow sphere assembled with nanotubes, the hollow sphere has a diameter of 50-450nm, a wall thickness of 10-20nm; the nanotube is vertically disposed at The surface of the hollow sphere has a diameter of 3-5 nm and a tube length of 40-300 nm.
  • silicon ball as used herein is merely a shorthand for the skilled person, and its true meaning means “silica ball”, so “silicon ball” and “silicon dioxide ball” are synonymous in this patent.
  • the copper accounts for 10-40 wt.% of the catalyst and the silica accounts for 60-90 wt.% of the weight of the catalyst.
  • the catalyst has a specific surface area of 460 to 470 m 2 /g, an average pore volume of 0.7 to 0.8 cm 3 /g, and an average pore diameter of 5.1 to 5.5 nm.
  • the hollow sphere has a diameter of 200-350 nm and a wall thickness of 10-15 nm.
  • the nanotubes have a diameter of 3.5-4 nm and a tube length of preferably 180-230 nm.
  • the bulb composite catalyst having a nanotube length of from 40 to 65 nm, more preferably from 40 to 60 nm, is used to achieve a selectivity of glycolate in the product of from 84% to 100%.
  • a bulb composite catalyst having a nanotube length of 110-300 nm is used to achieve a selectivity of ethylene glycol in the product of 85% to 98%.
  • the molar ratio of hydrogen to oxalate can be as low as 20, that is, H 2 /DMO ⁇ 20, the reaction temperature is 160-220 ° C, and the reaction pressure is 1.5-3 MPa.
  • the mass hour velocity of the liquid is 0.5-5 h -1 , and the yield of ethylene glycol can still be higher than 95% under this condition.
  • the liquid hour mass space velocity refers to the mass space velocity of the oxalate.
  • the tube composite catalyst itself and its preparation method are known in the art, for example, see Wang Y, et al., Chem. Commun., 6555-6557 (2008) and Sheng Y, et al., Chem. Mat., 27, 658-667 (2015).
  • a common preparation method includes the following steps:
  • Step 1 Using a silicon source as a raw material, mixing with a different volume ratio of an alkaline agent and water, and a volume ratio of the alkaline agent to water of 0.13-1.9, preparing an ultrapure having a regular geometry and having a particle diameter of 50-450 nm.
  • Silicon ball material temperature 30-80 ° C, pH 8.5-13.5.
  • the silicon source is sodium silicate, silica sol or tetraethyl orthosilicate; the alkaline agent is ammonia water, ammonium chloride or sodium hydroxide.
  • Step 2 uniformly mixing the obtained ultrapure silicon ball material with a copper precursor salt solution, adding copper content of 5 to 60 wt.% based on the metal oxide, and continuously dissolving the silicon ball in an alkaline environment, the copper precursor
  • the salt solution reacts with it and gradually deposits to form a tubular structure, and is hydrothermally treated under alkaline conditions for 5-30 hours, and the hydrothermal treatment temperature is 120-180 ° C. After drying and roasting, the hollow sphere nanomaterials assembled with the nanotubes are obtained.
  • the catalyst precursor is copper acetate or copper nitrate.
  • Step 3 the obtained hollow sphere nanomaterials assembled with nanotubes are dried at 50-120 ° C for 4-12 h; then calcined at 300-700 ° C for 3-12 h, the calcination atmosphere is air, and calcination per gram of catalyst is required.
  • the air flow rate is 6-150 mL/min; finally, the catalyst is reduced by in-situ reduction in situ, the reduction temperature is 150-400 ° C, and the reducing atmosphere is hydrogen or 10% hydrogen/argon mixed gas, which is required for each gram of catalyst reduction.
  • the hydrogen flow rate is 40-200 mL/min.
  • the drying method described therein is a general drying method or a vacuum drying method.
  • the silicon source is tetraethyl orthosilicate.
  • the alkaline agent is ammonia water.
  • the copper precursor salt solution is copper nitrate.
  • the drying method is a vacuum drying method.
  • the size of the ultrapure silicon sphere can be controlled by adjusting the volume ratio of the alkaline agent to water.
  • the alkaline agent is ammonia water
  • an ultrapure silica microsphere having a particle diameter of 84 nm can be obtained when the volume ratio of ammonia water to water is 0.15; when the volume ratio of ammonia water to water is 0.77, a particle diameter of 369 nm can be obtained.
  • Other alkaline agents have similar laws. The higher the ratio of alkaline agent to water, the larger the diameter of the obtained ultrapure silica microspheres.
  • the length of the nanotubes is controlled by adjusting the hydrothermal treatment time in the step 2 described.
  • the hydrothermal time when the hydrothermal time is extended from 5 h to 30 h, the nanotube length can be extended from 63 nm to 232 nm.
  • the longer the hydrothermal time the longer the length of the nanotubes, but when the copper ions or silicate ions in the solution are exhausted, the length of the nanotubes is basically no longer increased with the prolongation of the hydrothermal time.
  • the invention can also flexibly modulate the product distribution of glycolate and ethylene glycol by changing the length of the nanotubes on the hollow sphere, thereby giving greater flexibility in production regulation;
  • the process of the present invention has production process stability due to the excellent stability exhibited by the catalyst during the hydrogenation process.
  • Figure 1 is a transmission electron micrograph of a bulb composite catalyst used in the present invention, wherein A and B are transmission electron micrographs of the catalyst before being reduced by H 2 , and C and D are transmission electron micrographs of the catalyst itself.
  • Figure 2 is a transmission electron microscope effect of the catalyst precursor synthesized under different hydrothermal treatment times, wherein the hydrothermal treatment time is A: 5h, B: 10h, C: 15h, D: 20h, E: 25h, F: 30h; 100nm;
  • FIG. 3 is a transmission electron micrograph of each catalyst precursor shown in FIG. 2 after hydrogen reduction, wherein the hydrothermal treatment time is A: 5h, B: 10h, C: 15h, D: 20h, E: 25h, F: 30h; scale: 20nm;
  • Fig. 4 is a chart showing the nanotube diameter of the bulb composite catalyst used in the present invention.
  • Figure 5 is a graph showing the catalyst life data of hydrogenation of dimethyl oxalate to ethylene glycol.
  • Figure 6 is a graph showing the catalytic performance evaluation of the catalyst of the present invention and the existing catalyst at different hydrogen/dimethyl oxalate molar ratios.
  • the existing catalyst is a Cu/SiO 2 catalyst prepared by a steaming method which has good activity in the hydrogenation of oxalate to ethylene glycol, see Gong J, et al. J. Am. Chem. Soc., 134. , 13922-13925 (2012) and Chen L, et al. J. Catal., 257, 172-180 (2008).
  • Figure 7 is a graph showing the evaluation of the catalytic performance of the catalyst of the present invention and the prior catalyst at different hydrogen/diethyl oxalate molar ratios.
  • the existing catalyst is the same as the existing catalyst used in Fig. 6.
  • Figure 8 is a graph showing the evaluation of the catalytic performance of the catalyst of the present invention and the prior catalyst at different hydrogen/dibutyl oxalate molar ratios.
  • the existing catalyst is the same as the existing catalyst used in Fig. 6.
  • Fig. 9 is an X-ray diffraction (XRD) pattern of the bulb composite catalyst used in the present invention.
  • the vapor phase dimethyl oxalate hydrogenation reaction is carried out in a fixed bed reactor.
  • the calcined catalyst was tableted and sieved into 40-60 mesh granules, and 0.58 g was weighed into an isothermal reactor, and subjected to reduction in a 10% H 2 /N 2 atmosphere at 300 ° C for reduction. After 4 hours, the catalyst used in the present invention was obtained after on-line reduction. After reduction, the temperature was lowered to a reaction temperature of 190 ° C, and dimethyl oxalate was vaporized and mixed with hydrogen into a reaction tube. The hydrogen ester ratio was 20, and the mass space velocity of dimethyl oxalate was 3 h -1 , and the reaction was carried out at 3 MPa.
  • the product was analyzed by gas chromatography to obtain the components of dimethyl oxalate (DMO), ethylene glycol (EG), methyl glycolate (MG) and ethanol (EtOH), and the conversion rate of dimethyl oxalate was analyzed. The selectivity of each product.
  • the catalyst evaluation results are shown in Table 1.
  • the preparation method of the ultrapure silicon sphere is the same as in the first embodiment.
  • the catalyst evaluation method was the same as in Example 1, and the results are shown in Table 1.
  • the preparation method of the ultrapure silicon sphere is the same as in the first embodiment.
  • the catalyst evaluation method was the same as in Example 1, and the results are shown in Table 1.
  • the preparation method of the ultrapure silicon sphere is the same as in the first embodiment.
  • the catalyst evaluation method was the same as in Example 1, and the results are shown in Table 1.
  • the preparation method of the ultrapure silicon sphere is the same as in the first embodiment.
  • the catalyst evaluation method was the same as that in Example 1. The results are shown in Table 1. It can be seen that copper nitrate was used as the copper salt precursor, and the ultrapure silicon sphere solution was added dropwise (1 drop per second) of dimethyl oxalate (DMO). The conversion rate is as high as 100% and the selectivity of ethylene glycol (EG) is 98%.
  • DMO dimethyl oxalate
  • the stability evaluation of Example 1 is shown in Fig. 5, and it can be seen that the catalyst of the present invention exhibits excellent stability.
  • the catalyst preparation method and evaluation conditions were the same as those in Example 1.
  • the catalysts with different copper loadings (5 wt%, 10 wt.%, 30 wt.%, 40 wt.%) were respectively obtained by changing the amount of copper nitrate trihydrate added. Table 2, it can be seen that when the Cu loading is more than 20 wt.%, the selectivity of ethylene glycol is higher than 90%.
  • the preparation method and evaluation conditions of the catalyst were the same as those in Example 1.
  • the hollow sphere catalysts assembled with nanotubes of different lengths were respectively obtained by changing the time of the hydrothermal treatment, and the length of the nanotubes was determined by TEM, as shown in FIG. 2 and FIG. 3, the tubes of the nanotubes.
  • the path is shown in Figure 4.
  • the evaluation of the catalyst results is shown in Table 3. It can be seen that when the length of the nanotubes in the catalyst is less than 65 nm, the main product is methyl glycolate. When the length of the nanotubes in the catalyst is greater than 110 nm, the main product is ethylene glycol.
  • the catalysts evaluated were the same as those in the catalyst of Example 1, and the reaction temperature in the reaction conditions was changed, and the other reaction conditions were unchanged, and Examples 11 to 14 were obtained.
  • the evaluation of the catalyst results is shown in Table 4, and it can be seen that the reaction temperature was 190-200. At °C, the selectivity of the catalyst to ethylene glycol is as high as 95% or more.
  • Example 1 The catalyst used in the present invention in Example 1 and the conventional catalyst in Comparative Example 5 were subjected to hydrogenation of dimethyl oxalate, diethyl oxalate and dibutyl oxalate to ethylene glycol at different hydrogen ester ratios, and the others were evaluated.
  • the reaction conditions were the same as in Example 1.
  • the results are shown in Fig. 6 to Fig. 8 of the accompanying drawings. It can be seen that the catalyst for the hydrogenation of dimethyl oxalate is ensured by the use of the bulb composite catalyst of the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Nanotechnology (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

一种对草酸酯进行催化加氢的方法，该方法使草酸酯和氢气与球管复合型催化剂接触，产物为乙醇酸酯或乙二醇，该催化剂主要化学成分为铜和氧化硅，其中铜占催化剂重量的5-60wt.％，氧化硅占催化剂重量的40-95wt.％，催化剂的比表面积为450-500m 2/g，平均孔容为0.5-1cm 3/g，平均孔径为5-6nm；催化剂结构为空心球上组装着纳米管，空心球的直径为50-450nm，壁厚为10-20nm；纳米管垂直设置在空心球表面，管径为3-5nm，管长为40-300nm。该方法能够在较低的H 2/DMO进料比下仍表现出优异的草酸酯加氢活性及乙二醇选择性，降低了氢气循环量，节约了动力成本及设备成本，并可灵活调变乙二醇和乙醇酸酯的选择性，具有很高的工业前景和应用价值。

Description

一种对草酸酯进行催化加氢的方法 技术领域
本发明属于催化加氢工艺技术领域，特别是涉及一种对草酸酯进行催化加氢的方法。
背景技术
乙二醇作为一种重要的化工原料或溶剂，被广泛地应用于聚酯及其下游产品、防冻剂、润滑油等生产中，市场前景广阔。用合成气经一氧化碳偶联制草酸二甲酯(缩写为DMO)、草酸二甲酯再加氢制乙二醇的工艺，具有原子经济性高、反应条件温和、产品选择性高、绿色环保等特点，是以非石油路线合成乙二醇的重要路径之一。其中，草酸二甲酯加氢是该工艺的核心环节。其它类型的草酸酯例如草酸二乙酯或草酸二丁酯等，加氢后也能生成乙二醇，并副产相应的乙醇酸乙酯或乙醇酸丁酯。
铜基催化剂在该反应体系中取得了较好的活性和选择性，但反应进料所需的氢酯比(即氢气与草酸二甲酯的摩尔比H 2/DMO)较高和产物分布调控难的问题尚难以得到有效的解决。目前，草酸二甲酯加氢反应进料中需大大过量的氢气(H 2/DMO摩尔进料比一般在80到200之间)以获得高于90％的乙二醇收率。然而工业应用中，如此高的氢酯比将导致氢气循环量加大，提高了对压缩机等设备参数的要求，使得该工艺所需的设备成本和动力成本大大增加。因此，设计新型的高活性铜基催化剂，使草酸二甲酯加氢反应在低氢酯比的条件下也可以达到乙二醇的高选择性和收率，是优化合成气制乙二醇工艺技术的关键。
本发明旨在解决上述问题。
发明内容
本发明提出了一种对草酸酯进行催化加氢的方法，该方法使草酸酯和氢气与球管复合型催化剂接触，生成包含乙醇酸酯或乙二醇的产物，该催化剂主要化学成分为铜和氧化硅，其中铜占催化剂重量的5-60wt.％，氧化硅占催化剂重量的40-95wt.％，所述催化剂的比表面积为450-500m 2/g，平均孔容为0.5-1cm 3/g，平均孔径为5-6nm；所述催化剂结构为空心球上组装着纳米管，所述空心球的直径为50-450nm，壁厚为10-20nm；所述纳米管垂直设置在空心球表面，管径为3-5nm，管长为40-300nm。
本文中术语“硅球”仅仅是技术人员的一种简略称呼，其真实含义是指“二氧化硅球”，因此本专利中“硅球”与“二氧化硅球”是同义语。
优选地，所述的铜在催化剂中占的比重为10-40wt.％，氧化硅占催化剂重量的60-90wt.％。
优选地，所述催化剂的比表面积为460-470m 2/g，平均孔容为0.7-0.8cm 3/g，平均孔径为 5.1-5.5nm。
优选地，所述空心球的直径为200-350nm，壁厚为10-15nm。
优选地，所述纳米管的管径为3.5-4nm，管长优选为180-230nm。
优选地，使用纳米管长度为40-65nm、更优选为40-60nm的所述球管复合型催化剂，以使得产物中乙醇酸酯的选择性达到84％～100％。
优选地，使用纳米管长度为110-300nm的球管复合型催化剂，以使得产物中乙二醇的选择性达到85％～98％。
进一步优选地，使用本发明的球管复合型催化剂，氢气与草酸酯的摩尔比可以低至20，即H 2/DMO≥20，反应温度为160-220℃，反应压力为1.5-3MPa，液时质量空速为0.5-5h -1，此条件下乙二醇产率仍能高于95％。其中液时质量空速是指草酸酯的质量空速。
其中所述球管复合型催化剂本身及其制备方法是现有技术中已知的，例如参见Wang Y,et al.,Chem.Commun.,6555-6557(2008)以及Sheng Y,et al.,Chem.Mat.,27,658-667(2015).
一种常见的制备方法包括以下步骤：
步骤1：利用硅源作为原料，与不同体积比例的碱性剂和水混合，碱性剂和水的体积比例为0.13-1.9，制备具有规则的几何形状、粒径为50-450nm的超纯硅球材料，温度30-80℃，pH为8.5-13.5。其中所述的硅源为硅酸钠、硅溶胶或者正硅酸乙酯；所述的碱性剂为氨水、氯化铵或者氢氧化钠。
步骤2，将得到的超纯硅球材料与铜前驱体盐溶液均匀混合，以金属氧化物计的加入铜的含量为5-60wt.％，硅球在碱性环境下不断溶解，铜前驱体盐溶液与之反应并逐渐沉积蜷曲形成管状结构，在碱性条件下进行水热处理5-30h，水热处理温度为120-180℃，干燥焙烧后得到组装着纳米管的空心球纳米材料，将其称为催化剂前体。其中所述的铜前驱体盐溶液为醋酸铜或者硝酸铜。
步骤3，将得到的组装着纳米管的空心球纳米材料在50-120℃下干燥4-12h；然后在300-700℃下焙烧3-12h，焙烧的气氛为空气，每克催化剂焙烧所需空气流量为6-150mL/min；最后以在线原位还原方式还原得到所述的催化剂，还原温度为150-400℃，还原气氛为氢气或10％氢/氩混合气，每克催化剂还原所需氢气流量为40-200mL/min。其中所述的干燥方法为普通干燥方法或者真空干燥方法。
优选地，所述的硅源为正硅酸乙酯。
优选地，所述的碱性剂为氨水。
优选地，所述的铜前驱体盐溶液为硝酸铜。
优选地，所述的干燥方法为真空干燥方法。
在所述的步骤1中可通过调整碱性剂和水的体积比例来控制超纯硅球的大小。例如，当碱性剂为氨水时，氨水和水的体积比例为0.15时可以得到粒径为84nm的超纯二氧化硅微球；氨水和水的体积比例为0.77时可以得到粒径为369nm的超纯二氧化硅微球。其他碱性剂也有类似规律，碱性剂与水的比例越高，则得到的超纯二氧化硅微球直径越大。
在所述的步骤2中通过调整水热处理时间控制纳米管的长度。例如，当水热时间从5h延长到30h时，纳米管长度可以从63nm延长到232nm。基本上水热时间越长，纳米管长度也就越长，但当溶液中的铜离子或硅酸根离子消耗尽后，纳米管长度基本上就不再随水热时间的延长而增长了。
本发明的优点及有益效果：
1、本发明首次将现有技术中用于催化其它反应的球管复合型催化剂移植过来用于催化草酸二甲酯加氢反应，并意外发现，该催化剂解决了加氢反应中所需较高氢分压或高氢酯比的问题。实验中发现，在诸如反应温度、压力、反应时间等其他因素基本相同的条件下，本发明的方法在低氢酯比(H 2/DMO＝20)下仍能表现出卓越的催化活性和目标产物选择性(草酸二甲酯转化率>98％，乙二醇产量和选择性均>97％)，使所需氢气循环量下降75％，大大节约了气体压缩机动力消耗并提高了单位体积反应器的处理能力。
2、本发明还能通过改变空心球上纳米管的长度来灵活调变乙醇酸酯、乙二醇的产物分布，赋予了更大的生产调节灵活性；
3、本发明的方法因该催化剂在加氢过程中表现出的优异稳定性而具有生产工艺稳定性。
附图说明
图1为本发明中使用的球管复合型催化剂的透射电镜图，其中A和B为该催化剂在未被H 2还原前的透射电镜图，C和D为催化剂本身的透射电镜图。
图2为不同水热处理时间下合成的催化剂前体的透射电镜效果图，其中水热处理时间为A：5h，B：10h，C：15h，D：20h，E：25h，F：30h；标尺：100nm；
图3为图2所示各催化剂前体在氢气还原后得到的各催化剂还原后的透射电镜图，其中水热处理时间A：5h，B：10h，C：15h，D：20h，E：25h，F：30h；标尺：20nm；
图4为本发明中使用的球管复合型催化剂的纳米管管径统计图。
图5为草酸二甲酯加氢制乙二醇的催化剂寿命数据图。
图6为本发明催化剂和现有催化剂在不同氢气/草酸二甲酯摩尔比下的催化性能评价图。其中现有催化剂为当前在草酸酯加氢生成乙二醇反应中具有良好活性的蒸氨法制备的 Cu/SiO 2催化剂，参见Gong J,et al.J.Am.Chem.Soc.,134,13922-13925(2012)以及Chen L,et al.J.Catal.,257,172-180(2008)。
图7是本发明的催化剂和现有催化剂在不同氢气/草酸二乙酯摩尔比下的催化性能评价图。其中现有催化剂同图6中所使用的现有催化剂。
图8是本发明的催化剂和现有催化剂在不同氢气/草酸二丁酯摩尔比下的催化性能评价图。其中现有催化剂同图6中所使用的现有催化剂。
图9为本发明中使用的球管复合型催化剂的X射线衍射(XRD)图谱。
具体实施方式
下面结合附图与具体的实施方式对本发明作进一步详细描述。需要说明的是：下述实施例是说明性的，不是限定性的，不能以下述实施例来限定本发明的保护范围。以下实施例和对比例中所需要的原料均为市售，所述的碱性剂(氨水、氯化铵、氢氧化钠)均为水溶液。
实施例1
超纯硅球的制备：
称取正硅酸乙酯80g，与200mL乙醇中搅拌溶解，得到澄清溶液A；量取氨水132mL与98mL去离子水，86mL乙醇混合均匀，得到澄清溶液B；在40℃下将A、B两种溶液混合并搅拌5h，得到表面均匀、粒径均一的超纯硅球溶液。
催化剂前体制备：
称取三水合硝酸铜18g，与氨水80mL一起溶解于200mL去离子水中，搅拌均匀得到澄清溶液，然后将超纯硅球溶液逐滴加入(每秒1滴)，并在60℃下搅拌1h，得到均匀分散的溶液。将溶液置于密闭容器中，在150℃下水热处理30h，分离出固体物质并在80℃下真空干燥6h，500℃下焙烧6h，得到催化剂。
催化剂在线还原和催化效果评价：
本发明中气相草酸二甲酯加氢反应在固定床反应器中进行。将焙烧完毕的催化剂压片，并筛分成40-60目大小的颗粒，称取0.58g置于等温反应器中，并通入10％H 2/N 2气氛中在300℃下进行还原，还原时间4小时，在线还原后得到本发明所用的催化剂。还原后降温到反应温度190℃，将草酸二甲酯气化并与氢气混合进入反应管中，氢酯比为20，草酸二甲酯质量空速为3h -1，在3MPa下进行反应。利用气相色谱对产物进行分析得到草酸二甲酯(DMO)、乙二醇(EG)、乙醇酸甲酯(MG)和乙醇(EtOH)的成分，并分析得出草酸二甲酯的转化率及各个产物的选择性。催化剂评价结果见表1。
还用XRD对本发明的催化剂(即在线还原后的产物)进行表征，从图9本发明催化剂的X射线衍射(XRD)图谱中可以看出2θ＝22°处有一个较宽的衍射峰，该峰归属为无定型的 SiO 2的特征衍射峰，说明其中硅以氧化硅形式存在。2θ＝37.0°处的特征衍射峰为Cu 2O(111)的衍射峰(JCPDS 34-1354)，而2θ为43.3°、50.6°和74.1°处的特征衍射峰为金属铜(Cu)的衍射峰(JCPDS 65-9743)，这些峰均较弱且宽泛，说明Cu和Cu 2O在还原后催化剂中高度分散，催化剂活性好。
比较例1
超纯硅球的制备：
超纯硅球制备方法同实施例1。
催化剂前体的制备：
称取二水合氯化铜13g，与氨水80mL一起溶解于200mL去离子水中，搅拌均匀得到澄清溶液，然后将超纯硅球溶液逐滴加入(每秒1滴)，并在60℃下搅拌1h，得到均匀分散的溶液。将溶液置于密闭容器中，在150℃下水热处理30h，分离出固体物质并在80℃下真空干燥6h，500℃下焙烧6h，得到催化剂。
催化剂评价：
催化剂评价方法同实施例1，结果见表1。
比较例2
超纯硅球的制备：
超纯硅球制备方法同实施例1。
催化剂制备：
称取三水合醋酸铜22g，与氨水80mL一起溶解于200mL去离子水中，搅拌均匀得到澄清溶液，然后将超纯硅球溶液逐滴加入(每秒1滴)，并在60℃下搅拌1h，得到均匀分散的溶液。将溶液置于密闭容器中，在150℃下水热处理30h，分离出固体物质并在80℃下真空干燥6h，500℃下焙烧6h，得到催化剂。
催化剂评价：
催化剂评价方法同实施例1，结果见表1。
比较例3
超纯硅球的制备：
超纯硅球制备方法同实施例1。
催化剂制备：
称取五水合硫酸铜19g，与氨水80mL一起溶解于200mL去离子水中，搅拌均匀得到澄清溶液，然后将超纯硅球溶液逐滴加入(每秒1滴)，并在60℃下搅拌1h，得到均匀分散的溶液。将溶液置于密闭容器中，在150℃下水热处理30h，分离出固体物质并在80℃ 下真空干燥6h，500℃下焙烧6h，得到催化剂。
催化剂评价：
催化剂评价方法同实施例1，结果见表1。
比较例4
超纯硅球的制备：
超纯硅球制备方法同实施例1。
催化剂制备：
称取三水合硝酸铜18g，与氨水80mL一起溶解于与200mL去离子水中，搅拌均匀得到澄清溶液，然后将超纯硅球溶液快速加入(成连续水柱加入)，并在60℃下搅拌1h，得到均匀分散的溶液。将溶液置于密闭容器中，在150℃下水热处理30h，分离出固体物质并在80℃下真空干燥6h，500℃下焙烧6h，得到催化剂。
催化剂评价：
催化剂评价方法同实施例1，结果见表1，可以看出：把硝酸铜作为铜盐前驱体，并将超纯硅球溶液逐滴加入(每秒1滴)时草酸二甲酯(DMO)的转化率高达100％，乙二醇(EG)的选择性为98％。实施例1的稳定性评价见图5，可以看出本发明的催化剂表现出优异的稳定性。
表1使用不同方法和前驱体制备的催化剂评价
Figure PCTCN2018080544-appb-000001
实施例2-5
催化剂制备方法和评价条件与实施例1相同，通过改变三水合硝酸铜的加入量分别得到不同铜负载量的催化剂(5wt％、10wt.％、30wt.％、40wt.％)，催化剂结果评价见表2，可以看出当Cu负载量大于20wt.％时，乙二醇的选择性高于90％。
表2不同负载量的催化剂性能评价
Figure PCTCN2018080544-appb-000002
Figure PCTCN2018080544-appb-000003
实施例6-10
催化剂制备方法和评价条件与实施例1相同，通过改变水热处理的时间分别得到组装着不同长度纳米管的空心球催化剂，纳米管的长度由TEM确定，见图2和图3，纳米管的管径见图4。催化剂结果评价见表3，可以看出当催化剂中纳米管长度小于65nm时主要产物为乙醇酸甲酯，当催化剂中纳米管长度大于110nm时主要产物为乙二醇。
表3不同纳米管长度的催化剂性能评价
Figure PCTCN2018080544-appb-000004
实施例11-14
所评价的催化剂与实施例1中的催化剂相同，改变反应条件中的反应温度，其他反应条件不变，得到实施例11-14，催化剂结果评价见表4，可以看出反应温度为190-200℃时，催化剂对乙二醇的选择性高达95％以上。
表4不同反应温度下的催化剂性能评价
Figure PCTCN2018080544-appb-000005
比较例5
称取三水合硝酸铜18g并加入去离子水搅拌溶解，之后缓慢加入适宜量的28％氨水配成 铜氨溶液并补加一定量的去离子水。然后向铜氨溶液中加入30％的硅溶胶溶液77g，持续搅拌老化4小时。升温至80℃去除溶液中的氨至pH＝6-7。过滤分离出固体物质并在80℃下真空干燥6h，500℃下焙烧6h，得到现有技术文献(Gong J,et al.Synthesis of Ethanol via Syngas on Cu/SiO 2Catalysts with Balanced Cu 0-Cu +Sites.Journal Of the American Chemical Society 134,13922-13925(2012)；Chen L,et al.Cu/SiO 2Catalysts Prepared by the Ammonia-Evaporation Method:Texture,Structure,and Catalytic Performance in Hydrogenation of Dimethyl Oxalate to Ethylene Glycol.Journal of Catalysis 257,172-180(2008).)中报导过的现有催化剂，该催化剂为金属物种活性点位均匀分散在多孔载体内外表面上的常规负载型催化剂。
将实施例1中本发明中使用的催化剂和比较例5中现有催化剂在不同氢酯比下进行草酸二甲酯、草酸二乙酯和草酸二丁酯加氢制乙二醇反应评价，其他反应条件和实施例1中相同，结果如附图中图6-图8所示，可以看出采用本发明的球管复合型催化剂，对于草酸二甲酯加氢反应，在保证乙二醇产率高于95％的情况下，原料中氢酯比可以低至20，而对于草酸二乙酯和草酸二丁酯加氢反应，原料中氢酯比可以低至＝30。这说明本发明的方法取得了意外技术效果。
以上对本发明做了示例性的描述，应该说明的是，在不脱离本发明的核心的情况下，任何简单的变形、修改或者其他本领域技术人员能够不花费创造性劳动的等同替换均落入本发明的保护范围。

Claims (8)

  1. 一种对草酸酯进行催化加氢的方法，其特征在于：使草酸酯和氢气与球管复合型催化剂接触，生成包含乙醇酸酯或乙二醇的产物，该催化剂主要化学成分为铜和氧化硅，其中铜占催化剂重量的5-60wt.％，氧化硅占催化剂重量的40-95wt.％，所述催化剂的比表面积为450-500m 2/g，平均孔容为0.5-1cm 3/g，平均孔径为5-6nm；所述催化剂结构为空心球上组装着纳米管，所述空心球的直径为50-450nm，壁厚为10-20nm；所述纳米管垂直设置在空心球表面，管径为3-5nm，管长为40-300nm。
  2. 根据权利要求1所述的方法，其特征在于：使用纳米管长度为40-65nm、优选为40-60nm的所述球管复合型催化剂，以使得产物中乙醇酸酯的选择性达到84％～100％。
  3. 根据权利要求1所述的方法，其特征在于：使用纳米管长度为60-300nm、优选为110-300nm的球管复合型催化剂，以使得产物中乙二醇的选择性达到85％～98％。
  4. 根据权利要求3所述的方法，其特征在于，氢气与草酸酯的摩尔比≥20，反应温度为160-220℃，反应压力为1.5-3MPa，液时质量空速为0.5-5h -1，此条件下乙二醇产率高于95％。
  5. 根据权利要求1所述的方法，其特征在于：所述的铜在催化剂中占的比重为10-40wt.％，氧化硅占催化剂重量的60-90wt.％。
  6. 根据权利要求1所述的方法，其特征在于：所述催化剂的比表面积为460-470m 2/g，平均孔容为0.7-0.8cm 3/g，平均孔径为5.1-5.5nm。
  7. 根据权利要求1所述的方法，其特征在于：所述空心球的直径为200-350nm，壁厚为10-15nm。
  8. 根据权利要求1所述的方法，其特征在于：所述纳米管的管径为3.5-4nm，管长为180-230nm。
PCT/CN2018/080544 2017-07-13 2018-03-26 一种对草酸酯进行催化加氢的方法 Ceased WO2019011005A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US16/628,986 US10894756B2 (en) 2017-07-13 2018-03-26 Method for catalytically hydrogenating oxalates

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201710571590.7A CN109248682B (zh) 2017-07-13 2017-07-13 一种用于草酸酯加氢的催化剂及其制备方法
CN201710571590.7 2017-07-13
CN201710572107.7A CN109248683B (zh) 2017-07-13 2017-07-13 一种用于草酸酯加氢的球管复合型催化剂及其制备方法
CN201710572107.7 2017-07-13

Publications (1)

Publication Number Publication Date
WO2019011005A1 true WO2019011005A1 (zh) 2019-01-17

Family

ID=65002279

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/080544 Ceased WO2019011005A1 (zh) 2017-07-13 2018-03-26 一种对草酸酯进行催化加氢的方法

Country Status (2)

Country Link
US (1) US10894756B2 (zh)
WO (1) WO2019011005A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116764633A (zh) * 2023-03-24 2023-09-19 天津大学 一种用于酯加氢的核-壳型铜基催化剂及其制备方法与使用方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115007172B (zh) * 2022-07-25 2024-03-26 合肥飞木生物科技有限公司 一种草酸二甲酯选择性加氢催化剂的制备方法及应用
CN115414952B (zh) * 2022-08-22 2023-09-12 中国五环工程有限公司 一种合成乙醇酸甲酯的多组分加氢催化剂及制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003062372A2 (en) * 2001-10-02 2003-07-31 The Regents Of The University Of California Nanoparticle assembled hollow spheres
CN101757915A (zh) * 2010-01-08 2010-06-30 厦门大学 一种用于草酸酯加氢制乙二醇的催化剂及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9721008D0 (en) * 1997-10-03 1997-12-03 Hewlett Packard Co Power management method foruse in a wireless local area network (LAN)
US8178734B2 (en) * 2008-12-18 2012-05-15 China Petroleum & Chemical Corporation Processes for producing ethylene glycol from oxalate(s)
CN101879448B (zh) * 2010-06-24 2012-05-23 天津大学 用于草酸酯加氢制乙二醇的规整结构催化剂及其制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003062372A2 (en) * 2001-10-02 2003-07-31 The Regents Of The University Of California Nanoparticle assembled hollow spheres
CN101757915A (zh) * 2010-01-08 2010-06-30 厦门大学 一种用于草酸酯加氢制乙二醇的催化剂及其制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MA, XINBIN ET AL.: "Nano-structured Cu/Si02 Catalysts for Ester Hydrogenation Systems", ABSTRACT BOOK OF THE 30TH ANNUAL ACADEMIC MEETING OF THE CHINESE CHEMICAL SOCIETY-THIRTY -THIRD SESSION: GREEN CHEMISTRY, 1 July 2016 (2016-07-01), pages 1 *
WANG, YONGQIANG ET AL.: "One-pot Synthesis of Nanotube-based Hierarchical Copper Silicate Hollow Spheres", CHEM. COMMUN., 11 November 2008 (2008-11-11), pages 6555 - 6557, XP055569867 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116764633A (zh) * 2023-03-24 2023-09-19 天津大学 一种用于酯加氢的核-壳型铜基催化剂及其制备方法与使用方法

Also Published As

Publication number Publication date
US20200140359A1 (en) 2020-05-07
US10894756B2 (en) 2021-01-19

Similar Documents

Publication Publication Date Title
CN113145155B (zh) 一种应用于组装生物乙醇合成高碳醇的氮掺杂碳包覆镍催化剂及其制备方法
CN109305880B (zh) 一种醇类化合物的合成方法
JP7019813B2 (ja) アセトフェノンの水素化によってα－フェニルエタノールを製造するための触媒、その製造方法および応用
EP2586528B1 (en) Catalyst having monolithic structure for manufacturing ethylene glycol by oxalate hydrogenation, preparation method and application thereof
CN104998649B (zh) 核壳结构镍基甲烷干重整催化剂的制备方法
CN105597739B (zh) 一种Pt@CNTs催化剂及其制备和应用
CN103949254B (zh) 一种用于氨硼烷和肼硼烷水解制氢的 Cu@mSiO2核壳纳米催化剂及其制备方法
CN109876843B (zh) 铜合金修饰二氧化钛/氮化碳异质结光催化剂及制备方法
CN115646498B (zh) 一种乙醇脱氢用高稳定铜基催化剂及其制备方法
CN114558612A (zh) 多级孔ZSM-5分子筛封装Pt-Ni双金属催化剂及其制备方法和用途
CN111514889A (zh) 一种钌基二氧化碳加氢甲烷化催化剂及其制备方法
CN114917912B (zh) 用于碳酸乙烯酯加氢制甲醇联产乙二醇的催化剂及制备方法和使用方法
WO2019011005A1 (zh) 一种对草酸酯进行催化加氢的方法
CN105536802A (zh) 微纳结构铜基催化剂及其制备方法与应用
WO2022041218A1 (zh) 铜基催化剂及制备方法
CN115228477A (zh) 一种碳包覆铜锌铝催化剂及其制备方法和应用
CN105498780A (zh) 一种Cu/ZnO催化剂及其制备方法和在CO2化学转化中的应用
CN114618491A (zh) 铜基催化剂的制备方法及铜基催化剂催化加氢制备烷醇的方法
CN110368953A (zh) 一种复合氧化物负载铂催化剂及其制备和应用
CN107335465B (zh) Silicate-1分子筛催化剂的制备方法和催化剂以及制备己内酰胺的方法
CN116603523A (zh) 一种改性氧化铈载体负载的Pt基催化剂的制备及其应用
CN109248682B (zh) 一种用于草酸酯加氢的催化剂及其制备方法
CN118122334B (zh) 硝基苯加氢生产苯胺的结构化合金催化剂及其制备方法和应用
CN113751004B (zh) 碳包覆过渡金属氧化物的催化剂及其制备方法和应用
CN111686726B (zh) 碳基贵金属催化剂的制备方法及应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18831210

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 10/06/2020).

122 Ep: pct application non-entry in european phase

Ref document number: 18831210

Country of ref document: EP

Kind code of ref document: A1