CN109569619B - Catalyst composition, method of manufacture and use - Google Patents
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/8892—Manganese
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- 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
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- 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
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Abstract
The invention relates to a catalyst composition, a preparation method and application thereof, and mainly solves the technical problems of low activity and selectivity and poor stability in the prior art. The catalyst composition has a chemical formula of M-Cu-X/SiO2‑TiO2(ii) a Wherein M is at least one selected from the group consisting of oxides of Mg, Ca, Sr, and Ba; x is at least one selected from the group consisting of oxides of V, Cr, Zn, Fe, Ni, Co and Mn; the weight portion of M is 2-12 portions, Cu element is 10-40 portions, X is 2-20 portions, SiO2‑TiO2The content of (A) is 28-86 parts; SiO 22‑TiO2Medium, TiO2Is SiO2‑TiO2The weight ratio of (A) is 1-20%. The catalyst can be used in the industrial production of ethylene glycol by hydrogenation of oxalate.
Description
Technical Field
The invention relates to a catalyst composition, a preparation method and application.
Background
Ethylene glycol (EG for short) is an important petrochemical basic organic raw material, and more than 100 chemicals can be derived from the ethylene glycol. Wherein, the polyester (including polyester fiber, polyester bottle, polyester film, etc.) is the main consumption field of ethylene glycol in China, and the consumption amount of the polyester (including polyester fiber, polyester bottle, polyester film, etc.) accounts for about 90 percent of the total domestic consumption amount; and the other 10% is used for antifreeze, adhesive, paint solvent, cold-resistant lubricating oil, surfactant and the like. The current route for the industrial production of ethylene glycol is the cracking of naphtha to produce ethylene, the oxidation of ethylene to produce ethylene oxide (EO for short), and finally the hydration of ethylene oxide to obtain ethylene glycol. Under the economic environment that the price of petroleum is high, people increasingly recognize the limitation of petroleum resources, and various countries begin to research the production of ethylene glycol by using coal and natural gas as primary raw materials. The route for preparing the ethylene glycol from the synthesis gas has the advantages of wide raw materials, good economical efficiency and more reasonable process, and gradually becomes a research hotspot for synthesizing the ethylene glycol by a non-petroleum route. The route of preparing glycol from synthetic gas is to synthesize oxalate through CO gas phase catalytic coupling from the synthetic gas, and then prepare glycol through hydrogenation. The method gets rid of the dependence on petroleum resources from raw materials, actively conforms to the development trend of ethylene glycol production technology, and particularly has an extremely important significance for developing a coal process route in China with more coal and less oil.
One of the key technologies for preparing ethylene glycol from coal-based synthesis gas is the development of a catalyst for synthesizing ethylene glycol by hydrogenating oxalate. The American ARCO company in patent US54112245 suggests that the Cu-Cr series catalyst has better hydrogenation activity and selectivity, and adopts Al loaded2O3、SiO2Or the Cu-Cr catalyst on the glass beads, the reaction temperature is 200 ℃ and 230 ℃, but the yield of the ethylene glycol is only 11.7-18.9 percent. In order to improve the selectivity and yield of the reaction, researchers have developed oxalate gas phase hydrogenation catalysts, and EP46983 proposed a route for the gas phase hydrogenation of oxalate over a copper-chromium based catalyst to ethylene glycol.
In the 80 s of the last century, the Japanese ministry of Japan disclosed a lot of patents (Sho 57-122939, Sho 57-122946, Sho 57-123127, etc.), which examined a carrier (Al) for a catalyst mainly composed of copper2O3、SiO2、La2O3Etc.), auxiliaries (K, Zn, Ag, Mo, Ba, etc.), production methods, etc., on the activity and selectivity of the catalyst. The selectivity of reaction is changed by adding an auxiliary agent into a catalyst taking copper as a main body, the selectivity of ethylene glycol can be improved by adding Zn, the selectivity of methyl glycolate can be improved by adding Ag, the distribution of products can be adjusted by changing reaction conditions (temperature, pressure, space velocity, hydrogen-ester ratio and the like) under the same catalyst, and thus, methyl glycolate and ethylene glycol are taken as main bodiesThe main product.
The related research institutions in China begin to research oxalate hydrogenation catalysts from the last 80 th century. A Cu-Cr catalyst adopted in the literature (Industrial catalysis 1996, 4: 24-29) is subjected to a model study of diethyl oxalate hydrogenation under the conditions of 230 ℃ at 208 ℃ and 2.5-3.0MPa, the reaction result is that the conversion rate of diethyl oxalate is 99.8%, the average selectivity of ethylene glycol is 95.3%, and the catalyst can run for 1134 hours. In recent years, the research on oxalate hydrogenation catalysts is vigorous in China. Document CN101524646A proposes using Al2O3A copper-based catalyst which is used as a carrier and takes one or more of Zn, Mn, Mg and Cr as an auxiliary agent, the reaction pressure is 0.1 to 1.0MPa, the reaction temperature is 145-220 ℃, and the hourly space velocity of oxalate solution is 0.1 to 0.6h-1The conversion rate of oxalate is more than 99%, and the selectivity of glycol is more than 90%. Document CN101342489A discloses a copper-silicon hydrogenation catalyst containing an auxiliary agent, wherein the auxiliary agent is selected from one or more of alkaline earth metal, transition metal elements or rare earth metal elements, and under the process conditions of 3.0MPa reaction pressure and 0.7h-1 of polyacid ester liquid hourly space velocity, the conversion rate of the raw material is more than 99%, and the selectivity of ethylene glycol is more than 95%. Document CN101138725A discloses a catalyst for synthesizing ethylene glycol from oxalate and a preparation method thereof, wherein the catalyst is prepared by using copper as an active component and zinc as an auxiliary agent by an impregnation method, the conversion rate of oxalate of the catalyst is about 95%, and the selectivity of ethylene glycol is about 90%. In the latter, there are many patents reporting that a catalyst composed of Mo, Ni, Ba, Fe, Ag, La and other additives is added to the catalyst components, and is applied to a process for synthesizing ethylene glycol from oxalate.
The current state of the prior art still needs an oxalate hydrogenation catalyst with higher activity and selectivity and better stability. Meanwhile, the catalyst also meets the requirements of simple preparation process and cheap and easily-obtained raw materials.
Disclosure of Invention
Based on the prior art, the inventors of the present invention have assiduously studied and found that by using SiO2-TiO2The composite is used as a catalyst carrier, and at least one of alkaline earth metals and metals selected from the group consisting of V, Cr, Zn, Fe, Ni, Co and Mn is usedA copper catalyst which is an assistant, can solve at least one of the aforementioned problems, and thus the present invention has been completed.
Specifically, the present invention relates to the following aspects.
The present invention relates to a catalyst composition. The catalyst composition has a chemical formula of M-Cu-X/SiO2-TiO2(ii) a Wherein M is at least one selected from the group consisting of oxides of Mg, Ca, Sr, and Ba;
x is at least one selected from the group consisting of oxides of V, Cr, Zn, Fe, Ni, Co and Mn;
the weight portion of M is 2-12 portions, Cu element is 10-40 portions, X is 2-20 portions, SiO2-TiO2The content of (A) is 28-86 parts; SiO 22-TiO2Medium, TiO2Is SiO2-TiO2The weight ratio of (A) is 1-20%.
According to one aspect of the present invention, the content of M is 2 to 10 parts, the content of Cu element is 15 to 35 parts, the content of X is 5 to 15 parts, SiO is2-TiO2The content of (A) is 40-78 parts; SiO 22-TiO2Medium, TiO2Is SiO2-TiO2The weight ratio of (A) is 5-20%.
According to one aspect of the present invention, the content of M is 3 to 8 parts, the content of Cu element is 20 to 33 parts, the content of X is 7 to 13 parts, SiO is2-TiO2The content of (A) is 46-70 parts; SiO 22-TiO2Medium, TiO2Is SiO2-TiO2The weight ratio of (A) is 5-15%.
According to one aspect of the invention, SiO2-TiO2Medium, TiO2Is at least one of the group consisting of anatase, rutile and brookite.
According to an aspect of the present invention, M is at least one selected from the group consisting of oxides of Mg, Ca and Ba.
According to an aspect of the present invention, M is at least one selected from the group consisting of oxides of Mg and Ba.
According to an aspect of the present invention, X is at least one selected from the group consisting of oxides of Zn, Fe, Ni, Co, and Mn.
According to an aspect of the present invention, X is at least one selected from the group consisting of oxides of Zn, Co, and Mn.
According to an aspect of the present invention, X is at least one selected from the group consisting of oxides of Zn and Mn.
According to one aspect of the invention, the catalyst composition does not contain rare earth oxides.
According to an aspect of the present invention, the rare earth element is at least one selected from the group consisting of La, Eu, Gd, and Tb.
The invention also relates to a method for producing said catalyst composition. The method comprises the following steps:
a) hydrolyzing the mixture containing the silicon source solution, titanate and titanium oxide to obtain SiO carrier2-TiO2(ii) a Wherein the pH value of the silicon source solution is 6-7, and the pH value of the mixture is 8-9;
b) making copper salt, X salt and carrier SiO2-TiO2Coprecipitating with a precipitator to obtain CuO-X/SiO2-TiO2；
c) M is supported on CuO-X/SiO2-TiO2Thereby obtaining M-CuO-X/SiO2-TiO2；
d) Making M-CuO-X/SiO2-TiO2Contacting with reducing gas to obtain the catalyst composition M-Cu-X/SiO2-TiO2。
The invention also relates to application of the catalyst composition in catalyzing oxalate hydrogenation reaction.
According to one aspect of the invention, the hydrogenation reaction conditions include: the reaction temperature is 160 ℃ and 260 ℃, and the weight space velocity of the oxalic ester is 0.1-1.0 h－1The molar ratio of hydrogen to oxalate (60-150) is 1, and the reaction pressure is 2.0-5.0 MPa.
According to one aspect of the invention, the hydrogenation reaction conditions include: the reaction temperature is 180 ℃ and 240 ℃, and the weight space velocity of the oxalic ester is 0.3-0.7 h－1The molar ratio of hydrogen to oxalate is (80-120):1, and the reaction is carried outThe pressure is 2.5-3.5 MPa.
The invention has the beneficial effects that: the catalyst has higher activity, selectivity and stability in the reaction of synthesizing the ethylene glycol by hydrogenating the dimethyl oxalate. For example, by adopting the method, the conversion rate of the oxalate can reach 99.9 percent, the corresponding selectivity of the glycol can reach 97.3 percent, the stability of the catalyst is good, and the performance of the catalyst does not decline after 6000 hours of operation.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, to derive materials, substances, methods, procedures, devices, or components, etc., it is intended that the subject matter derived from the heading encompass those conventionally used in the art at the time of filing this application, but also include those that are not currently in use, but would become known in the art to be suitable for a similar purpose.
In the context of the present specification, anything or things which are not mentioned, except where explicitly stated, are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or concepts resulting therefrom are considered part of the original disclosure or original disclosure of the invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such a combination to be clearly unreasonable.
Unless otherwise expressly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise not in accordance with the conventional knowledge of those skilled in the art.
Where not explicitly stated, all pressures mentioned in this specification are gauge pressures.
The present invention relates to a catalyst composition. The catalyst composition has the chemical formula M-Cu-X/SiO2-TiO2. Wherein Cu is an active component, M and X are auxiliary agents, SiO2-TiO2Is a carrier.
According to the present invention, M is at least one selected from the group consisting of oxides of Mg, Ca, Sr and Ba; preferably at least one of the group consisting of oxides of Mg, Ca and Ba; more preferably at least one of the group consisting of oxides of Mg and Ba.
According to the present invention, X is at least one selected from the group consisting of oxides of Ti, V, Cr, Zn, Fe, Ni, Co and Mn; preferably at least one of the group consisting of oxides of Zn, Fe, Ni, Co and Mn; more preferably at least one of the group consisting of oxides of Zn, Co and Mn; most preferably at least one of the group consisting of oxides of Zn and Mn.
According to the invention, the content of M is 2-12 parts, the content of Cu element is 10-40 parts, the content of X is 2-20 parts, and SiO is calculated by weight parts2-TiO2The content of (A) is 28-86 parts; preferably, the content of M is 2-10 parts, the content of Cu element is 15-35 parts, the content of X is 5-15 parts, SiO2-TiO2The content of (A) is 40-78 parts; more preferably, the content of M is 3 to 8 parts, the content of Cu element is 20 to 33 parts, the content of X is 7 to 13 parts, SiO2-TiO2The content of (A) is 46-70 parts.
According to the invention, the support is SiO2-TiO2Composites, not SiO2And TiO2The mechanical mixture of (1). SiO carrier2-TiO2Medium, TiO2Is SiO2-TiO2Is 1 to 20% by weight, preferably 5 to 20% by weight, more preferably 5 to 15% by weight.
According to the invention, SiO2-TiO2In (1),TiO2is AT least one of the group consisting of Anatase (AT), Rutile (RT), and Brookite (BT).
According to the invention, the catalyst composition does not contain oxides of rare earth elements. In particular, oxides of La, Eu, Gd and Tb are not contained.
The invention also relates to a method for producing the catalyst composition. The manufacturing method comprises the following steps:
a) hydrolyzing the mixture containing the silicon source solution, titanate and titanium oxide to obtain SiO carrier2-TiO2(ii) a Wherein the pH value of the silicon source solution is 6-7, and the pH value of the mixture is 8-9;
b) making copper salt, X salt and carrier SiO2-TiO2Coprecipitating with a precipitator to obtain CuO-X/SiO2-TiO2；
c) M is supported on CuO-X/SiO2-TiO2Thereby obtaining M-CuO-X/SiO2-TiO2；
d) Making M-CuO-X/SiO2-TiO2Contacting with reducing gas to obtain the catalyst composition M-Cu-X/SiO2-TiO2。
According to the present invention, the silicon source solution may be an aqueous sodium silicate solution in step a). The titanate may be tetraethyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, and tetra-isobutyl titanate, or mixtures thereof. The titanium oxide may be Anatase (AT), Rutile (RT), Brookite (BT), or a mixture thereof. The pH of the silicon source solution is controlled to 6-7 by methods well known to those skilled in the art, such as adjustment with an acid, which may be hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, or an aqueous solution thereof. Comprising a mixture of a silicon source solution, titanate and titanium oxide, controlled to a pH of 8-9, again in a manner well known to those skilled in the art, for example with a base such as ammonia, sodium hydroxide, potassium hydroxide, rubidium hydroxide, or an aqueous solution thereof. The hydrolysis time of the mixture is 4-24 hours.
According to the invention, after the hydrolysis step in step a), it is possible to proceed by means of the methods known in the artAny separation method separates the prepared SiO carrier from the product mixture obtained2-TiO2. The separation method includes, for example, a method of filtering, washing, drying and calcining the obtained product mixture. Here, the filtering, washing, drying and calcining may be performed in any manner conventionally known in the art. As a specific example, as the filtration, for example, the obtained product mixture may be simply filtered with suction. Examples of the washing include washing with deionized water. The drying temperature is, for example, 80 to 160 ℃ and the drying time is, for example, 4 to 24 hours. The drying may be carried out under normal pressure or under reduced pressure. The calcination temperature may be, for example, 350-650 ℃ and the calcination time may be, for example, 2-8 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen.
According to the invention, step b) is the preparation of CuO-X/SiO by coprecipitation2-TiO2. Coprecipitation methods are also well known in the art, i.e. copper salts, X salts, SiO as a carrier2-TiO2And precipitating agent coprecipitation. Specifically, adding copper salt and X salt into water to obtain a mixed solution A; adding a precipitant into water to obtain a solution B; SiO the carrier obtained in the step a)2-TiO2Dispersing in water, heating the suspension to 40-80 deg.C, adding solution A and solution B into the suspension, maintaining pH at 6-7, and aging to obtain precipitate CuO-X/SiO2-TiO2. Wherein, the copper salt and the X salt can be nitrate, organic acid salt or the mixture thereof. The precipitant may be aqueous ammonia, ammonium carbonate, ammonium bicarbonate, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, or a mixture thereof. The aging temperature is 40-90 deg.C, and the aging time is 2-24 hr.
According to the invention, in step b), after the end of the coprecipitation step, the intermediate CuO-X/SiO prepared can be separated from the product mixture obtained by any separation method known in the art2-TiO2. As the separation means, for exampleThe method of filtering, washing, drying and calcining the obtained product mixture is exemplified. Here, the filtering, washing, drying and calcining may be performed in any manner conventionally known in the art. As a specific example, as the filtration, for example, the obtained product mixture may be simply filtered with suction. Examples of the washing include washing with deionized water. The drying temperature is, for example, 80 to 160 ℃ and the drying time is, for example, 4 to 24 hours. The drying may be carried out under normal pressure or under reduced pressure. The calcination temperature may be, for example, 350-650 ℃ and the calcination time may be, for example, 2-8 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen.
According to the invention, step c) consists in loading the alkaline earth metal M on the intermediate CuO-X/SiO2-TiO2The above. The method for supporting M may employ impregnation methods well known in the art. Specifically, the intermediate CuO-X/SiO2-TiO2Dispersing in M salt solution to obtain precursor M-CuO-X/SiO2-TiO2。
According to the invention, in step c), after the end of the impregnation step, the precursor M-CuO-X/SiO prepared can be separated from the product mixture obtained by any separation method known in the art2-TiO2. The separation method includes, for example, a method of filtering, washing, drying and calcining the obtained product mixture. Here, the filtering, washing, drying and calcining may be performed in any manner conventionally known in the art. As a specific example, as the filtration, for example, the obtained product mixture may be simply filtered with suction. Examples of the washing include washing with deionized water. The drying temperature is, for example, 80 to 160 ℃ and the drying time is, for example, 4 to 24 hours. The drying may be carried out under normal pressure or under reduced pressure. The baking temperature may be, for example, 350-650 ℃ and the baking time may be, for example, 28 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen.
According to the invention, step d) consists in making the precursor M-CuO-X/SiO2-TiO2Contacting with reducing gas to obtain the catalyst composition M-Cu-X/SiO2-TiO2. The reducing gas being H2A mixture of inert gases, which may be N2Or at least one of Ar, the volume content of hydrogen in the mixed gas is 5-30%, and the flow rate of the mixed gas is 10-150 ml/min/g of catalyst; the reduction temperature is preferably 200 ℃ to 400 ℃, and the reduction time is preferably 8 to 20 hours.
The invention also relates to application of the catalyst composition in catalyzing oxalate hydrogenation reaction. The raw material oxalate and hydrogen contact with a catalyst under the condition of hydrogenation reaction to obtain an effluent containing ethylene glycol.
According to the invention, the hydrogenation reaction conditions include: the reaction temperature is 160 ℃ and 260 ℃, and the weight space velocity of the oxalic ester is 0.1-1.0 h－1The molar ratio of hydrogen to oxalate (60-150) is 1, and the reaction pressure is 2.0-5.0 MPa; preferably, the reaction temperature is 180 ℃ and 240 ℃, and the weight space velocity of the oxalic ester is 0.3-0.7 h－1The molar ratio of hydrogen to oxalate is (80-120):1, and the reaction pressure is 2.5-3.5 MPa.
The invention is further illustrated by the following examples.
[ example 1 ]
234.5 g of sodium silicate nonahydrate are dissolved in 800 ml of water, 5 wt% of dilute sulfuric acid is added with stirring to adjust the pH to 6-7, and then 23.4 g of tetra-n-butyl titanate and 5 g of AT-TiO are added2Uniformly stirring the powder, adjusting the pH value to 8-9 by using a 5 wt% sodium hydroxide solution, hydrolyzing for 12h, filtering, washing with deionized water, drying at 120 ℃ for 16h, and roasting at 500 ℃ for 4h to obtain SiO2-TiO2Catalyst support ST-1.
Dissolving 113.4 g of copper nitrate trihydrate and 36.7 g of zinc nitrate hexahydrate in 500 ml of water to obtain a solution A1; 65.9 g of anhydrous sodium carbonate are dissolved in 500 ml of water to obtain a solution B1; dispersing 54.0g of carrier ST-1 in 300 ml of water, heating to 60 ℃, simultaneously dropwise adding the solution A1 and the solution B1 into the dispersion under vigorous stirring, keeping the temperature at 60 ℃ and the pH value at 6-7 in the dropwise adding process, aging at 60 ℃ for 10h after finishing, filtering, washing precipitates with deionized water, drying at 120 ℃ for 16h, and roasting at 450 ℃ for 4h to obtain an intermediate PST-1.
Dispersing 94 g of intermediate PST-1 in 500 ml of water, adding 10.2 g of barium nitrate, heating to 80 ℃, evaporating the solvent, drying at 120 ℃ for 16h, and roasting at 450 ℃ for 4h to obtain a catalyst precursor MPST-1.
With H having a hydrogen content of 25% by volume2-N2Reducing the solid with mixed gas at 320 deg.c for 10 hr to obtain M-Cu-X/SiO in the flow rate of 140 ml/min/g catalyst2-TiO2Catalyst C1.
In the catalyst C1, the weight portion of M (Ba) is 6.1, the weight portion of Cu is 29.9, the weight portion of X (Zn) is 10.0, and the carrier SiO2-TiO254 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
[ example 2 ]
The catalyst carrier ST-2 was prepared in the same manner as in example 1 except that sodium nonahydrate and tetra-n-butyl titanate were used in amounts of 255.1 g and 4.7 g, respectively, and BT-TiO was added22.5 g of powder AT-TiO22.5 g of powder, intermediate PST-2, precursor MPST-2 and the reduction method were the same as in example 1, yielding catalyst C2.
In the catalyst C2, the weight portion of M is 6.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-TiO254 parts by weight of TiO in the carrier2The content of (B) was 1.8% by weight.
[ example 3 ]
The catalyst carrier ST-3 was prepared in the same manner as in example 1 except that sodium nonahydrate and tetra-n-butyl titanate were used in amounts of 247.3 g and 11.7 g, respectively, and RT-TiO was added25 g of powder, intermediate PST-3, precursor MPST-3 and the reduction method were the same as in example 1, yielding catalyst C3.
In the presence of the catalyst C3, the catalyst C,6.1 parts of M, 29.9 parts of Cu, 10.0 parts of X and SiO serving as a carrier2-TiO254 parts by weight of TiO in the carrier2The content of (B) was 5.1% by weight.
[ example 4 ]
The catalyst carrier ST-4 was prepared in the same manner as in example 1 except that sodium nonahydrate and tetra-n-butyl titanate were used in amounts of 221.3 g and 35.1 g, respectively, and BT-TiO was added25 g of powder, intermediate PST-4, precursor MPST-4 and the reduction method were the same as in example 1, yielding catalyst C4.
In the catalyst C4, the weight portion of M is 6.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-TiO254 parts by weight of TiO in the carrier2The content of (b) was 15.1% by weight.
[ example 5 ]
The catalyst carrier ST-5 was prepared in the same manner as in [ example 1 ] except that sodium nonahydrate and tetra-n-butyl titanate were used in amounts of 210.9 g and 44.4 g, respectively, and the intermediate PST-5, the precursor MPST-5 and the reduction method were the same as in [ example 1 ], to obtain catalyst C5.
In the catalyst C5, the weight portion of M is 6.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-TiO254 parts by weight of TiO in the carrier2The content of (B) was 19.1% by weight.
Comparative example 1
The catalyst carrier CST-1 was prepared in the same manner as in example 1 except that sodium silicate nonahydrate was used in an amount of 255.6 g and that tetra-n-butyl titanate and titanium oxide powder were not added. Intermediate CPST-1, precursor CMPST-1 and the reduction method were the same as in [ example 1 ], yielding catalyst CC 1.
In the catalyst CC1, the weight portion of M is 6.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier is SiO2Free of TiO2And 54 parts by weight.
[ example 6 ]
234.5 g of sodium nonahydrate dissolved in800 ml of water, 5 wt.% of dilute hydrochloric acid is added with stirring to adjust the pH to 6-7, and then 19.5 g of tetraisopropyl titanate and 5 g of AT-TiO are added2Uniformly stirring the powder, adjusting the pH value to 8-9 by using 5 wt% ammonia water, hydrolyzing for 24h, filtering, washing by using deionized water, drying at 150 ℃ for 20h, and roasting at 600 ℃ for 7h to obtain SiO2-TiO2Catalyst support ST-6.
93.8 g of copper acetate monohydrate and 27.0 g of zinc acetate dihydrate were dissolved in 500 ml of water to give a solution A6; 75.5 g of 28 wt% concentrated ammonia water was added to 500 ml of water to obtain a solution B6; dispersing 55.0g of carrier ST-6 in 300 ml of water, heating to 80 ℃, simultaneously dropwise adding the solution A6 and the solution B6 into the dispersion under vigorous stirring, keeping the temperature at 80 ℃ and the pH value at 6-7 in the dropwise adding process, aging at 90 ℃ for 23h after finishing, filtering, washing precipitates with deionized water, drying at 90 ℃ for 24h, and roasting at 600 ℃ for 8h to obtain an intermediate PST-6.
Dispersing 94 g of intermediate PST-1 in 500 ml of water, adding 10.4 g of barium acetate, heating to 95 ℃, evaporating the solvent, drying at 150 ℃ for 22h, and roasting at 600 ℃ for 4h to obtain a catalyst precursor MPST-6.
With H having a hydrogen content of 10% by volume2Reducing the solid for 18 hours at 250 ℃ by using-Ar mixed gas, wherein the flow rate of the mixed gas is 30 ml/min-g of the catalyst, and then obtaining the M-Cu-X/SiO2Catalyst C6-TiO 2.
In the catalyst C6, the weight portion of M is 6.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-TiO254 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
[ example 7 ]
Catalyst carrier SiO2-TiO2The procedure of (1) was the same as in example 1 to obtain ST-1, and the procedure of preparing intermediate PST was the same as in example 1 except that 61.1 g of ST-1, 11.0 g of zinc nitrate hexahydrate and 56.3 g of anhydrous sodium carbonate as a precipitant were used to obtain intermediate PST-7.
The alkaline earth metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C7.
In the catalyst C7, the weight portion of M is 6.1, the weight portion of Cu is 29.9, the weight portion of X is 3.1, and the carrier SiO is2-TiO260.9 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
[ example 8 ]
Catalyst carrier SiO2-TiO2The procedure of (1) was the same as in example 1 to obtain ST-1, and the procedure of preparing intermediate PST was the same as in example 1 except that 57.0 g of ST-1, 25.7 g of zinc nitrate hexahydrate, and 61.8 g of anhydrous sodium carbonate as a precipitant were used to obtain intermediate PST-8.
The alkaline earth metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C8.
In the catalyst C8, the weight portion of M is 6.1, the weight portion of Cu is 29.9, the weight portion of X is 7.0, and the carrier SiO2-TiO257.0 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
[ example 9 ]
Catalyst carrier SiO2-TiO2Was prepared in the same manner as in example 1 to obtain ST-1, and intermediate PST was prepared in the same manner as in example 1 except that 51.0 g of ST-1, 47.7 g of zinc nitrate hexahydrate and 70.0 g of anhydrous sodium carbonate as a precipitant were used to obtain intermediate PST-9.
The alkaline earth metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C9.
In the catalyst C9, the weight portion of M is 6.1, the weight portion of Cu is 29.9, the weight portion of X is 13.0, and the carrier SiO is2-TiO2Is 51.0 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
[ example 10 ]
Catalyst carrier SiO2-TiO2Was prepared in the same manner as in example 1 to obtain ST-1, and the intermediate PST was prepared in the same manner as in example 1 except thatThe amount of ST-1 used was 45.0 g, the amount of zinc nitrate hexahydrate was 69.7 g and the amount of precipitant anhydrous sodium carbonate was 78.3 g, giving intermediate PST-10.
The alkaline earth metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C10.
In the catalyst C10, the weight portion of M is 6.1, the weight portion of Cu is 29.9, the weight portion of X is 19.0, and the carrier SiO is2-TiO245.0 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
Comparative example 2
Catalyst carrier SiO2-TiO2Was prepared in the same manner as in example 1 to obtain ST-1, and intermediate CPST was prepared in the same manner as in example 1 except that 64.0 g of ST-1 was used, zinc nitrate hexahydrate was not added, and 52.2 g of anhydrous sodium carbonate as a precipitant was used to obtain intermediate CPST-2.
The alkaline earth metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst CC 2.
In the catalyst CC2, the weight portion of M is 6.1, the weight portion of Cu is 29.9, X is not contained, and SiO is a carrier2-TiO2In 64.0 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
[ example 11 ]
Catalyst carrier SiO2-TiO2Was prepared in the same manner as in example 1 to obtain ST-1, and intermediate PST was prepared in the same manner as in example 1 except that 73.0 g of ST-1, 41.6 g of copper nitrate trihydrate and 32.9 g of anhydrous sodium carbonate as a precipitant were used to obtain intermediate PST-11.
The alkaline earth metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C11.
In the catalyst C11, the weight portion of M is 6.1, the weight portion of Cu is 10.9, the weight portion of X is 10.0, and the carrier SiO is2-TiO273.0 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
[ example 12 ]
Catalyst carrier SiO2-TiO2The procedure of (1) was the same as in example 1 to obtain ST-1, and the procedure of preparing intermediate PST was the same as in example 1 except that 65.0 g of ST-1, 71.8 g of copper nitrate trihydrate and 46.8 g of anhydrous sodium carbonate as a precipitant were used to obtain intermediate PST-12.
The alkaline earth metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C12.
In the catalyst C12, the weight portion of M is 6.1, the weight portion of Cu is 18.9, the weight portion of X is 10.0, and the carrier SiO is2-TiO2In 65.0 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
[ example 13 ]
Catalyst carrier SiO2-TiO2The procedure of (1) was the same as in example 1 to obtain ST-1, and the procedure of preparing intermediate PST was the same as in example 1 except that 59.0 g of ST-1, 94.5 g of copper nitrate trihydrate and 57.2 g of anhydrous sodium carbonate as a precipitant were used to obtain intermediate PST-13.
The alkaline earth metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C13.
In the catalyst C13, the weight portion of M is 6.1, the weight portion of Cu is 24.9, the weight portion of X is 10.0, and the carrier SiO is2-TiO2Is 59.0 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
[ example 14 ]
Catalyst carrier SiO2-TiO2The procedure of (1) was the same as in example 1 to obtain ST-1, and the procedure of preparing intermediate PST was the same as in example 1 except that 45.0 g of ST-1, 147.5 g of copper nitrate trihydrate and 81.6 g of anhydrous sodium carbonate as a precipitant were used to obtain intermediate PST-14.
The alkaline earth metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C14.
CatalysisIn the agent C14, the weight portion of M is 6.1, the weight portion of Cu is 38.9, the weight portion of X is 10.0, and the carrier SiO is2-TiO245.0 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
[ example 15 ]
Catalyst carrier SiO2-TiO2Was prepared in the same manner as in [ example 1 ] to obtain ST-1, and intermediate PST was prepared in the same manner as in [ example 1 ] except that the amount of ST-1 used was 58.0 g to obtain intermediate PST-15.
Alkaline earth metal modification and catalyst reduction method was the same as [ example 1 ], except Ba (NO) was used3)2In an amount of 4.3 g and PST-15 in an amount of 97.9 g, affording catalyst C15.
In the catalyst C15, the weight portion of M is 2.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-TiO2Is 58.0 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
[ example 16 ]
Catalyst carrier SiO2-TiO2Was prepared in the same manner as in [ example 1 ] to obtain ST-1, and intermediate PST was prepared in the same manner as in [ example 1 ] except that the amount of ST-1 used was 56.0 g to obtain intermediate PST-16.
Alkaline earth metal modification and catalyst reduction method was the same as [ example 1 ], except Ba (NO) was used3)2In an amount of 6.8 g and PST-16 in an amount of 95.9 g, affording catalyst C16.
In the catalyst C16, the weight portion of M is 4.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-TiO256.0 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
[ example 17 ]
Catalyst carrier SiO2-TiO2Was prepared in the same manner as in [ example 1 ] to obtain ST-1, and the intermediate PST was prepared in the same manner as in [ example 1 ] except that the amount of ST-1 used was 53.0 g to obtain intermediate PST-17。
Alkaline earth metal modification and catalyst reduction method was the same as [ example 1 ], except Ba (NO) was used3)2In an amount of 11.9 g and PST-17 in an amount of 92.9 g, affording catalyst C17.
In the catalyst C17, the weight portion of M is 7.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-TiO2Is 53.0 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
[ example 18 ]
Catalyst carrier SiO2-TiO2Was prepared in the same manner as in [ example 1 ] to obtain ST-1, and intermediate PST was prepared in the same manner as in [ example 1 ] except that the amount of ST-1 used was 49.0 g to obtain intermediate PST-18.
Alkaline earth metal modification and catalyst reduction method was the same as [ example 1 ], except Ba (NO) was used3)2In an amount of 18.8 g and PST-18 in an amount of 88.9 g, affording catalyst C18.
In the catalyst C18, the weight portion of M is 11.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO2-TiO249.0 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
Comparative example 3
Catalyst carrier SiO2-TiO2Was prepared in the same manner as in example 1 to obtain ST-1, and intermediate CPST was prepared in the same manner as in example 1 except that the amount of ST-1 used was 60.0 g to obtain intermediate CPST-3.
In this example, the catalyst was reduced in the same manner as in [ example 1 ] without modification with an alkaline earth metal to obtain a catalyst CC 3.
In the catalyst CC3, the weight portion of M is 0, the weight portion of Cu is 30.0, the weight portion of X is 10.0, and the carrier SiO is2-TiO260.0 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
[ example 19 ]
Catalyst carrier SiO2-TiO2The procedure of (1) was the same as in example 1 to obtain ST-1, and intermediate PST was the same as in example 1 except that 36.7 g of zinc nitrate hexahydrate was replaced with 41.4 g of a 50% by weight aqueous solution of manganese nitrate and the amount of precipitant anhydrous sodium carbonate was 65.0 g to obtain intermediate PST-19.
The alkaline earth metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C19.
In the catalyst C19, the weight portion of M is 6.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-TiO2Is 54.0 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
[ example 20 ]
Catalyst carrier SiO2-TiO2The procedure of (1) was the same as in example 1 to obtain ST-1, and the procedure of intermediate PST was the same as in example 1 except that 36.7 g of zinc nitrate hexahydrate was replaced with 50.5 g of iron nitrate nonahydrate, and the amount of precipitant anhydrous sodium carbonate was 73.1 g to obtain intermediate PST-20.
The alkaline earth metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C20.
In the catalyst C20, the weight portion of M is 6.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-TiO2Is 54.0 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
[ example 21 ]
Catalyst carrier SiO2-TiO2The procedure of (1) was the same as in example 1 to obtain ST-1, and the procedure of preparation of intermediate PST was the same as in example 1 except that 36.7 g of zinc nitrate hexahydrate was replaced with 35.1 g of cobalt nitrate hexahydrate, and the amount of precipitant anhydrous sodium carbonate was 65.6 g to obtain intermediate PST-21.
The alkaline earth metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C21.
In catalyst C21, the weight portion of M was 6.1, the weight portion of Cu was 29.9, and the weight of X was10.0 parts by weight of carrier SiO2-TiO2Is 54.0 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
[ example 22 ]
Catalyst carrier SiO2-TiO2The procedure of (1) was the same as in example 1 to obtain ST-1, and the procedure of preparation of intermediate PST was the same as in example 1 except that 36.7 g of zinc nitrate hexahydrate was replaced with 35.1 g of nickel nitrate hexahydrate, and the amount of precipitant anhydrous sodium carbonate was 65.6 g to obtain intermediate PST-22.
The alkaline earth metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C22.
In the catalyst C22, the weight portion of M is 6.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-TiO2Is 54.0 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
[ example 23 ]
Catalyst carrier SiO2-TiO2The intermediate PST was prepared in the same manner as in example 1 to give ST-1 and PST-1.
The alkaline earth metal modification and catalyst reduction procedure was the same as in example 1 except that the alkaline earth metal salt used was 38.4 grams of magnesium nitrate hexahydrate, yielding catalyst C23.
In the catalyst C23, the weight portion of M is 6.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-TiO2Is 54.0 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
[ example 24 ]
Catalyst carrier SiO2-TiO2The intermediate PST was prepared in the same manner as in example 1 to give ST-1 and PST-1.
The alkaline earth metal modification and catalyst reduction procedure was the same as in example 1 except that the alkaline earth metal salt used was 25.3 g of calcium nitrate tetrahydrate to give catalyst C24.
In catalyst C24, the weight portion of M was 6.1, the weight portion of Cu was 29.9, and the weight of X wasPart is 10.0, carrier SiO2-TiO2Is 54.0 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
[ example 25 ]
Catalyst carrier SiO2-TiO2The intermediate PST was prepared in the same manner as in example 1 to give ST-1 and PST-1.
The alkaline earth modification and catalyst reduction procedure was the same as in example 1 except that 12.1 g of strontium nitrate was used as the alkaline earth salt to give catalyst C25.
In the catalyst C25, the weight portion of M is 6.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-TiO2In 55.0 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
Comparative example 4
The catalyst support CST-4 was prepared by the same method as in example 1 except that sodium silicate nonahydrate was not added. Intermediate CPST-4, precursor CMPST-4 and the reduction method were the same as in [ example 1 ], yielding catalyst CC 4.
In the catalyst CC4, the weight portion of M is 6.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier is AT-TiO2Is free of SiO2And 54 parts by weight.
Comparative example 5
The catalyst support CST-5 was prepared in the same manner as in example 1 except that sodium silicate nonahydrate was not added and AT-TiO was added2The powder was replaced with RT-titania powder. Intermediate CPST-5, precursor CMPST-5 and the reduction method were the same as in [ example 1 ], yielding catalyst CC 5.
In the catalyst CC5, the weight portion of M is 6.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier is RT-TiO2Is free of SiO2And 54 parts by weight.
Comparative example 6
The catalyst support CST-6 was prepared in the same manner as in example 1 except that sodium silicate nonahydrate was not added and AT-TiO was added2The powder is replaced by BT-titanium oxide powderAnd (3) grinding. Intermediate CPST-6, precursor CMPST-6 and the reduction method were the same as in [ example 1 ], yielding catalyst CC 6.
In the catalyst CC6, the weight portion of M is 6.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier is BT-TiO2Is free of SiO2And 54 parts by weight.
Comparative example 7
The catalyst support CST-7 was prepared by the same method as in example 1 except that the zinc nitrate used was replaced with lanthanum nitrate. Intermediate CPST-7, precursor CMPST-7 and the reduction method were the same as in [ example 1 ], yielding catalyst CC 7.
In the catalyst CC7, the weight portion of M is 6.1, the weight portion of Cu is 29.9, the weight portion of La is 10.0, Zn is not contained, and a carrier SiO is2-TiO254 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
Comparative example 8
The catalyst carrier CST-8 was prepared in the same manner as in example 1 except that the zinc nitrate used was replaced with europium nitrate. Intermediate CPST-8, precursor CMPST-8 and the reduction method were the same as in [ example 1 ], yielding catalyst CC 8.
In the catalyst CC8, the weight portion of M is 6.1, the weight portion of Cu is 29.9, the weight portion of Eu is 10.0, Zn is not contained, and a carrier SiO is2-TiO254 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
Comparative example 9
The preparation of the catalyst support CST-9 was the same as in [ example 1 ], except that the pH of the silicon source solution was adjusted to 8; the pH was adjusted to 9 during the preparation with 5 wt% sodium hydroxide solution. Intermediate CPST-9, precursor CMPST-9 and the reduction method were the same as in [ example 1 ], yielding catalyst CC 9.
In the catalyst CC9, the weight portion of M is 6.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and a carrier SiO is2-TiO254 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
Comparative example 10
The preparation of the catalyst support CST-10 was the same as in [ example 1 ], except that the pH of the silicon source solution was adjusted to 5; the pH was adjusted to 6 during the preparation with 5 wt% sodium hydroxide solution. Intermediate CPST-10, precursor CMPST-10 and the reduction method were the same as in [ example 1 ], yielding catalyst CC 10.
In the catalyst CC10, the weight portion of M is 6.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and a carrier SiO is2-TiO254 parts by weight of TiO in the carrier2The content of (B) was 9.8% by weight.
The compositions of catalysts C1-25, examples 1-25, and CC1-3, comparative examples 1-3 are shown in table 1.
[ examples 26 to 50 ]
This example illustrates the use of the catalysts obtained in [ examples 1-25 ] in the hydrogenation of oxalic esters to Ethylene Glycol (EG).
The catalysts C1 to C26 obtained in the present invention [ examples 1 to 25 ] were each charged in an amount of 10 g into a stainless steel reaction tube having an inner diameter of 20 mm, and dimethyl oxalate (DMO) and hydrogen were introduced to conduct a reaction and evaluation. The catalyst is at the pressure of 3.0MPa, the temperature of 210 ℃ and the space velocity of 0.5h-1The reaction is carried out under the condition that the molar ratio of hydrogen to ester is 100, and the hydrogenation products comprise Methyl Glycolate (MG), Ethanol (ET), 1, 2-Butanediol (BDO) and the like. The reaction results are shown in Table 2. TABLE 1
| Catalyst and process for preparing same | Cu fraction | M number of copies | X number of parts | Proportion of titanium oxide in the support |
| C1 | 29.9 | Ba 6.1 | Zn 10 | 9.8 |
| C2 | 29.9 | Ba 6.1 | Zn 10 | 1.8 |
| C3 | 29.9 | Ba 6.1 | Zn 10 | 5.1 |
| C4 | 29.9 | Ba 6.1 | Zn 10 | 15.1 |
| C5 | 29.9 | Ba 6.1 | Zn 10 | 19.1 |
| CC1 | 29.9 | Ba 6.1 | Zn 10 | 0 |
| C6 | 29.9 | Ba 6.1 | Zn 10 | 9.8 |
| C7 | 29.9 | Ba 6.1 | Zn 3.1 | 9.8 |
| C8 | 29.9 | Ba 6.1 | Zn 7 | 9.8 |
| C9 | 29.9 | Ba 6.1 | Zn 13 | 9.8 |
| C10 | 29.9 | Ba 6.1 | Zn 19 | 9.8 |
| CC2 | 29.9 | Ba 6.1 | 0 | 9.8 |
| C11 | 10.9 | Ba 6.1 | Zn 10 | 9.8 |
| C12 | 18.9 | Ba 6.1 | Zn 10 | 9.8 |
| C13 | 24.9 | Ba 6.1 | Zn 10 | 9.8 |
| C14 | 38.9 | Ba 6.1 | Zn 10 | 9.8 |
| C15 | 29.9 | Ba 6.1 | Zn 10 | 9.8 |
| C16 | 29.9 | Ba 4.1 | Zn 10 | 9.8 |
| C17 | 29.9 | Ba 7.1 | Zn 10 | 9.8 |
| C18 | 29.9 | Ba 11.1 | Zn 10 | 9.8 |
| CC3 | 30 | 0 | Zn 10 | 9.8 |
| C19 | 29.9 | Ba 6.1 | Mn 10 | 9.8 |
| C20 | 29.9 | Ba 6.1 | Fe 10 | 9.8 |
| C21 | 29.9 | Ba 6.1 | Co 10 | 9.8 |
| C22 | 29.9 | Ba 6.1 | Ni 10 | 9.8 |
| C23 | 29.9 | Mg 6.1 | Zn 10 | 9.8 |
| C24 | 29.9 | Ca 6.1 | Zn 10 | 9.8 |
| C25 | 29.9 | Sr 6.1 | Zn 10 | 9.8 |
| CC4 | 29.9 | Ba 6.1 | Zn 10 | 100 |
| CC5 | 29.9 | Ba 6.1 | Zn 10 | 100 |
| CC6 | 29.9 | Ba 6.1 | Zn 10 | 100 |
| CC7 | 29.9 | Ba 6.1 | La 10 | 9.8 |
| CC8 | 29.9 | Ba 6.1 | Eu 10 | 9.8 |
| CC9 | 29.9 | Ba 6.1 | Zn 10 | 9.8 |
| CC10 | 29.9 | Ba 6.1 | Zn 10 | 9.8 |
TABLE 2
Comparative examples 11 to 20
Evaluation conditions of the catalyst were the same as in example 26, and the results obtained are shown in Table 3.
TABLE 3
[ examples 51 to 55 ]
The conditions used for evaluation of the catalyst were varied, and the other conditions were the same as [ example 26 ], and the results obtained are shown in Table 4.
TABLE 4
[ example 56 ]
The life of the catalyst C1 was evaluated under the same conditions as in example 26, and the results obtained are shown in table 5.
TABLE 5
| Reaction time (h) | XDMO(％) | SEG(％) |
| 1000 | 100 | 96.3 |
| 2000 | 100 | 96.2 |
| 3000 | 100 | 96.1 |
| 4000 | 100 | 96 |
| 5000 | 99.9 | 96.2 |
| 6000 | 99.8 | 96.1 |
Comparative example 21
The lifetime of the catalyst CC1 was evaluated under the same conditions as in example 26, and the results obtained are shown in table 6.
TABLE 6
| Reaction time (h) | XDMO(％) | SEG(％) |
| 100 | 90.1 | 84.4 |
| 200 | 88.5 | 83.5 |
| 300 | 86.3 | 82.4 |
Claims (9)
1. A catalyst composition for preparing ethanediol by hydrogenating oxalate has the chemical formula of M-Cu-X/SiO2-TiO2(ii) a Wherein M is at least one selected from the group consisting of oxides of Mg or Ba;
x is at least one selected from the group consisting of oxides of Zn or Mn;
the weight portion of M is 2-12 portions, Cu element is 10-40 portions, X is 2-20 portions, SiO2-TiO2The content of (A) is 28-86 parts; SiO 22-TiO2Medium, TiO2Is SiO2-TiO2The weight ratio of (A) is 1-20%;
the preparation method of the catalyst composition comprises the following steps:
a) hydrolyzing the mixture containing the silicon source solution, titanate and titanium oxide to obtain SiO carrier2-TiO2(ii) a Wherein the silicon source solution is sodium silicate aqueous solution, the pH value is 6-7, and the pH value of the mixture is 8-9;
b) making copper salt, X salt and carrier SiO2-TiO2Coprecipitating with a precipitator to obtain CuO-X/SiO2-TiO2；
c) M is supported on CuO-X/SiO2-TiO2Thereby obtaining M-CuO-X/SiO2-TiO2；
d) Making M-CuO-X/SiO2-TiO2Contacting with reducing gas to obtain the catalyst composition M-Cu-X/SiO2-TiO2。
2. The catalyst composition of claim 1, wherein the amount of M is 2-10 parts, the amount of Cu is 15-35 parts, the amount of X is 5-15 parts, and SiO is calculated by weight parts2-TiO2The content of (A) is 40-78 parts; SiO 22-TiO2Medium, TiO2Is SiO2-TiO2The weight ratio of (A) is 5-20%.
3. The catalyst composition of claim 1, wherein the amount of M is 3 to 8 parts, the amount of Cu is 20 to 33 parts, the amount of X is 7 to 13 parts, and SiO is calculated by weight parts2-TiO2The content of (A) is 46-70 parts; SiO 22-TiO2Medium, TiO2Is SiO2-TiO2The weight ratio of (A) is 5-15%.
4. The catalyst composition of claim 1, wherein the SiO is2-TiO2Medium, TiO2Is at least one of the group consisting of anatase, rutile and brookite.
5. The catalyst composition of claim 1, wherein the catalyst composition is free of rare earth oxides.
6. A process for preparing the catalyst composition of any of claims 1-5, comprising the steps of:
a) hydrolyzing the mixture containing the silicon source solution, titanate and titanium oxide to obtain SiO carrier2-TiO2(ii) a Wherein the silicon source solution is sodium silicate aqueous solution, the pH value is 6-7, and the pH value of the mixture is 8-9;
b) making copper salt, X salt and carrier SiO2-TiO2Coprecipitating with a precipitator to obtain CuO-X/SiO2-TiO2；
c) M is supported on CuO-X/SiO2-TiO2Thereby obtaining M-CuO-X/SiO2-TiO2；
d) Making M-CuO-X/SiO2-TiO2Contacting with reducing gas to obtain the catalyst composition M-Cu-X/SiO2-TiO2。
7. Use of the catalyst composition according to any one of claims 1 to 5 for catalyzing the reaction of hydrogenation of oxalate to ethylene glycol.
8. The use of the catalyst composition according to claim 7 for catalyzing the reaction of hydrogenating oxalate to ethylene glycol, wherein the hydrogenation reaction conditions comprise: the reaction temperature is 160 ℃ and 260 ℃, and the weight space velocity of the oxalic ester is 0.1-1.0 h－1Hydrogen/oxalate molar ratio (60-150):1, reaction pressure 2.0-5.0MPa。
9. The use of the catalyst composition according to claim 8 for catalyzing the reaction of hydrogenating oxalate to ethylene glycol, wherein the hydrogenation reaction conditions comprise: the reaction temperature is 180 ℃ and 240 ℃, and the weight space velocity of the oxalic ester is 0.3-0.7 h－1The molar ratio of hydrogen to oxalate is (80-120):1, and the reaction pressure is 2.5-3.5 MPa.
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