CN114433100B - Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic anhydride by maleic anhydride hydrogenation - Google Patents

Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic anhydride by maleic anhydride hydrogenation Download PDF

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CN114433100B
CN114433100B CN202011118431.XA CN202011118431A CN114433100B CN 114433100 B CN114433100 B CN 114433100B CN 202011118431 A CN202011118431 A CN 202011118431A CN 114433100 B CN114433100 B CN 114433100B
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catalyst
nickel
precursor compound
complex
copper
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CN114433100A (en
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冯海强
赵开径
朱跃辉
高继东
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/60—Two oxygen atoms, e.g. succinic anhydride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention relates to the technical field of catalysts, in particular to a hydrogenation catalyst, a preparation method and application thereof, and a method for preparing succinic anhydride by hydrogenating maleic anhydride, wherein the catalyst comprises a carrier and an active component loaded on the carrier, the active component contains Ni element, cu element and Ce element, and the carrier contains SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the In the catalyst, the total weight of the catalyst is taken as a reference, the content of the Ni element is 10-40 wt%, the content of the Cu element is 1-5 wt%, the content of the Ce element is 1-8 wt%, and the content of the carrier is 47-88 wt%, based on oxides. The catalyst has excellent catalytic activity and succinic anhydride selectivity, is low in cost and simple in process, and can be applied to continuous mass production.

Description

Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic anhydride by maleic anhydride hydrogenation
Technical Field
The invention relates to the technical field of catalysts, in particular to a hydrogenation catalyst, a preparation method and application thereof, and a method for preparing succinic anhydride by maleic anhydride hydrogenation.
Background
Succinic anhydride, also known as succinic anhydride, is an important organic synthesis intermediate and fine chemical raw material, and is widely applied to the fields of foods, surfactants, coatings, medicines, agriculture, plastics and the like. Due to the unique molecular structure, succinic anhydride can undergo hydrolysis, alcoholysis, esterification, halogenation and other reactions, and the demand for succinic anhydride is increased year by year along with the development of industries such as pesticide, medicine, petrochemical industry and the like in China, and particularly, the high-purity succinic anhydride has higher external dependency.
At present, the production method of succinic anhydride adopted in industry comprises the following steps: biological fermentation, succinic acid dehydration and maleic anhydride catalytic hydrogenation. The biological fermentation method is environment-friendly, but has high production cost and low product yield, and is difficult to meet the requirements of industrial production; the succinic acid dehydration method has lower technical threshold, but has small production scale and lower product quality, and is difficult to meet the market supply of high-purity succinic anhydride raw materials; the maleic anhydride catalytic hydrogenation method has the advantages of simple process flow, convenient operation, high equipment utilization rate, low running cost and high product purity, and is the most efficient process for producing succinic anhydride at present.
Maleic anhydride molecules have a C=C bond and two C=O bonds, and succinic anhydride can be synthesized by selectively hydrogenating the C=C bond under certain catalytic conditions; continuously hydrogenating one of the C=O bonds to synthesize gamma-butyrolactone; then hydrogenates the other c=o bond, tetrahydrofuran can be synthesized. Thus, the deep hydrogenation can reduce the selectivity of the succinic anhydride, and how to control the hydrogenation reaction in the hydrogenation stage of the c=c bond is the most important problem in the preparation of the succinic anhydride by hydrogenating the maleic anhydride, so that a proper catalyst needs to be searched for to improve the selectivity of the succinic anhydride.
US5616730A discloses a catalyst for preparing succinic anhydride by catalyzing maleic anhydride to hydrogenate and a method for continuously producing succinic anhydride, wherein the catalyst uses SiO 2 The supported nickel is added with Pd or Pt as an auxiliary agent, in the process conditions, the reaction conditions are more severe, the reaction pressure is up to 15MPa, special requirements on the arrangement and the materials of the reactor are needed, and the large-scale application of the catalyst is limited.
In the methods disclosed in US1541210A and EP0691335A, noble metal Pd is selected as a main active component to prepare the catalyst, and the dosage of the noble metal accounts for 3.0-10.0 wt% of the total weight of the catalyst although the hydrogenation selectivity is higher, so that the production cost is greatly increased, and industrialization is difficult to realize.
CN109529850a discloses a kind of SiO 2 The catalyst is used in liquid phase hydrogenation reaction at high pressure (5.0 MPa), and can only be used in batch synthesis reaction, but not continuous mass production.
In summary, the activity, succinic anhydride selectivity and other performances of the existing hydrogenation catalyst need to be further improved, and the catalyst has high cost and complex process flow and cannot be applied to continuous large-scale production.
Disclosure of Invention
The invention aims to overcome the defects that the activity and the succinic anhydride selectivity of a hydrogenation catalyst in the prior art are to be further improved, the catalyst is high in cost and complex in process flow, and cannot be applied to continuous mass production, and provides a hydrogenation catalyst, a preparation method and application thereof, and a method for preparing succinic anhydride by hydrogenating maleic anhydride.
In order to achieve the above object, a first aspect of the present invention provides a hydrogenation catalyst comprising a carrier and an active component supported on the carrier, the active component containing Ni element, cu element and Ce element, the carrier containing SiO 2 ；
In the catalyst, the total weight of the catalyst is taken as a reference, the content of the Ni element is 10-40 wt%, the content of the Cu element is 1-5 wt%, the content of the Ce element is 1-8 wt%, and the content of the carrier is 47-88 wt%, based on oxides.
In a second aspect, the present invention provides a process for preparing a hydrogenation catalyst, the process comprising:
(1) First mixing a precursor compound containing Ni, a precursor compound containing Cu and a carrier to obtain a first mixed solution; the precursor compound of the carrier contains SiO 2 ；
(2) Sequentially aging and optionally first drying the first mixed solution to obtain a catalyst precursor;
(3) Contacting the catalyst precursor with a Ce-containing precursor compound to obtain a matrix catalyst;
(4) Optionally second drying the base catalyst, and then roasting and optionally forming;
the Ni-containing precursor compound, the Cu-containing precursor compound, the precursor compound of the carrier and the Ce-containing precursor compound are used in amounts such that the catalyst is prepared, based on the total weight of the catalyst, the content of Ni element is 10-40 wt%, the content of Cu element is 1-5 wt%, the content of Ce element is 1-8 wt%, and the content of the carrier is 47-88 wt%, based on the total weight of the catalyst.
In a third aspect, the present invention provides a hydrogenation catalyst prepared by the method of the second aspect.
In a fourth aspect, the present invention provides the use of a hydrogenation catalyst according to the first or third aspect in the hydrogenation of maleic anhydride to succinic anhydride.
The fifth aspect of the invention provides a method for preparing succinic anhydride by hydrogenating maleic anhydride, comprising the following steps: under the hydrogenation condition, in the presence of an activated catalyst, carrying out contact reaction on hydrogen and maleic anhydride; the activated catalyst is obtained by reducing and activating the hydrogenation catalyst in the first aspect or the third aspect.
The inventor of the present invention has found that the hydrogenation catalyst having the aforementioned specific composition has high activity and succinic anhydride selectivity. The catalyst with the specific composition can be prepared by the method provided by the invention, has higher catalytic activity and succinic anhydride selectivity, can be used for preparing succinic anhydride by hydrogenating maleic anhydride under the conditions of lower catalytic reaction temperature (less than or equal to 140 ℃) and lower catalytic reaction pressure (less than or equal to 2 MPa), and saves energy consumption.
The method for preparing the succinic anhydride by hydrogenating the maleic anhydride can prepare the succinic anhydride by continuously hydrogenating at a low catalytic reaction temperature (less than or equal to 140 ℃) and a low catalytic reaction pressure (less than or equal to 2 MPa), saves energy consumption, simplifies production operation flow, reduces production operation cost and can be applied to continuous large-scale production.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a hydrogenation catalyst comprising a carrier and an active component supported on the carrier, the active component containing Ni element, cu element and Ce element, the carrier containing SiO 2 ；
In the catalyst, the total weight of the catalyst is taken as a reference, the content of the Ni element is 10-40 wt%, the content of the Cu element is 1-5 wt%, the content of the Ce element is 1-8 wt%, and the content of the carrier is 47-88 wt%, based on oxides.
In the invention, the active component can be loaded in the carrier, can be loaded on the surface of the carrier, can also be partially loaded in the carrier, and can be partially loaded on the surface of the carrier; the third is preferred.
In the present invention, the existence forms of the Ni element, the Cu element and the Ce element in the catalyst are not limited, and the Ni element, the Cu element and the Ce element may exist in the catalyst in an oxidized form, may exist in the catalyst in a reduced form, may exist in the catalyst in a partially oxidized form and a partially reduced form, and may be selected by those skilled in the art according to actual needs; the existence forms of the Ni element, the Cu element and the Ce element can be the same or at least partially different.
According to the present invention, in the catalyst, the content of the Ni element is preferably 15 to 25 wt%, the content of the Cu element is preferably 1 to 3 wt%, the content of the Ce element is preferably 3 to 6 wt%, and the content of the carrier is preferably 66 to 81 wt%, based on the total weight of the catalyst, on an oxide basis. Under the preferred scheme, the catalytic activity and the succinic anhydride selectivity of the hydrogenation catalyst are improved more favorably.
In the present invention, siO contained in the carrier 2 Without limitation, existing SiO's in the art 2 Can be used in the present invention as long as it is advantageous to improve the catalytic activity of the catalyst and the succinic anhydride selectivity.
The hydrogenation catalyst provided by the invention has excellent catalytic activity and succinic anhydride selectivity, and is low in cost and simple in process.
As previously described, the second aspect of the present invention provides a process for preparing a hydrogenation catalyst, the process comprising:
(1) First mixing a precursor compound containing Ni, a precursor compound containing Cu and a carrier to obtain a first mixed solution; the precursor compound of the carrier contains SiO 2 ；
(2) Sequentially aging and optionally first drying the first mixed solution to obtain a catalyst precursor;
(3) Contacting the catalyst precursor with a Ce-containing precursor compound to obtain a matrix catalyst;
(4) Optionally second drying the base catalyst, and then roasting and optionally forming;
the Ni-containing precursor compound, the Cu-containing precursor compound, the precursor compound of the carrier and the Ce-containing precursor compound are used in amounts such that the catalyst is prepared, based on the total weight of the catalyst, the content of Ni element is 10-40 wt%, the content of Cu element is 1-5 wt%, the content of Ce element is 1-8 wt%, and the content of the carrier is 47-88 wt%, based on the total weight of the catalyst.
Preferably, the Ni-containing precursor compound, the Cu-containing precursor compound, and the precursor compound of the carrier, and the Ce-containing precursor compound are used in amounts such that the catalyst is produced, based on the total weight of the catalyst, the Ni element is 15 to 25 wt%, the Cu element is 1 to 3 wt%, the Ce element is 3 to 6 wt%, and the carrier is 66 to 81 wt%, based on the total weight of the catalyst.
In the method of the present invention, ni element, cu element and Ce element and Si element in the respective raw materials (i.e., ni-containing precursor compound, cu-containing precursor compound and precursor compound of carrier, and Ce-containing precursor compound) can be completely converted into the hydrogenation catalyst with little loss.
In the present invention, the optional range of the carrier is the same as that of the carrier in the first aspect, and will not be described herein. In the present invention, preferably, the precursor compound of the carrier is selected from silica sol, more preferably acidic silica sol and/or alkaline silica sol, further preferably alkaline silica sol. The source of the acidic silica sol and the basic silica sol is not limited in any way, as long as the acidic or basic silica sol can be used in the present invention. The invention aims at SiO in the silica sol 2 The content of (2) is not limited, preferably SiO in the silica sol 2 The content of (C) is 10-40 wt%.
The invention has wider selection range for the types of the Ni-containing precursor compound, the Cu-containing precursor compound and the Ce-containing precursor compound, and is only beneficial to improving the catalytic activity of the catalyst and the selectivity of succinic anhydride; for example, the salts may be Ni-containing salts, cu-containing salts, ce-containing salts, and the salts may be at least one of nitrate, chloride, acetate, basic carbonate, and sulfate, or may be complexes of the corresponding salts and ammonia, respectively.
According to the present invention, preferably, the Cu-containing precursor compound is a copper ammine complex.
According to the present invention, preferably, the Ni-containing precursor compound is a nickel ammine complex.
According to the present invention, preferably, the Ce-containing precursor compound is selected from at least one of cerium nitrate, cerium sulfate, cerium chloride, and cerium acetate. In the present invention, the Ce-containing precursor compound is preferably introduced in the form of a solution, and the concentration of the Ce-containing precursor compound solution is not limited as long as the desired amount of the Ce-containing precursor compound can be supported, and can be freely selected by those skilled in the art according to the need, for example, the concentration of the Ce-containing precursor compound in the solution is preferably 0.1 to 30% by weight. Preferably, the Ce-containing precursor compound is introduced as a hydrate, e.g. Ce (NO 3 ) 3 ·6H 2 O。
The inventor finds that the nickel ammonia complex, the copper ammonia complex and the cerium nitrate are respectively used as the Ni-containing precursor compound, the Cu-containing precursor compound and the Ce-containing precursor compound, and the prepared catalyst has more excellent catalytic activity and succinic anhydride selectivity by matching other characteristics of the invention.
The synthesis method of the copper ammonia complex and the nickel ammonia complex has wider optional range, and can be used for preparing the copper ammonia complex and the nickel ammonia complex, thereby being beneficial to improving the performance of the catalyst. In the present invention, when a nickel ammine complex and a copper ammine complex are used as the Ni-containing precursor compound and the Cu-containing precursor compound, the copper ammine complex and the nickel ammine complex may be prepared separately or synthesized simultaneously by a one-step method.
In a preferred embodiment of the invention, the method further comprises synthesizing said cuprammonium complex by: the copper salt and the first complexing agent are subjected to a second mixing in the presence of a first solvent and ammonia.
According to the invention, preferably, the copper salt and the first complexing agent are used in a molar ratio of 1:0.5-2.
Preferably, the copper salt is selected from at least one of copper nitrate, copper sulfate, copper chloride, basic copper carbonate and copper acetate, more preferably copper nitrate.
Preferably, the first complexing agent is selected from at least one of ethylenediamine tetraacetic acid, monoethanolamine, diethanolamine and triethanolamine, more preferably ethylenediamine tetraacetic acid and/or monoethanolamine.
According to the invention, preferably, the ammonia is used in such an amount that the pH of the system is between 9 and 12 during the synthesis of the cuprammonium complex.
In the present invention, the ammonia is used to dissolve the complex, and may be liquid ammonia or ammonia gas, preferably the former. The liquid ammonia is preferably introduced in the form of aqueous ammonia, the concentration of which is preferably 15 to 25% by weight. In the present invention, if the ammonia is used in such an amount that the complex in the system (i.e., the cuprammonium complex and/or the nickel rammonium complex described below) is not completely dissolved, then the pH of the system may be preferably adjusted to a value in the range of 9 to 12 by passing ammonia gas therethrough so that the corresponding complex is completely dissolved.
According to the present invention, preferably, the first solvent is used in an amount such that the concentration of the copper ammine complex in the prepared copper ammine complex solution is 0.01 to 1.1mol/L. When the ammonia is introduced in the form of aqueous ammonia, the amount of water in the aqueous ammonia and the amount of the first solvent are used together so that the concentration of the copper ammine complex in the prepared copper ammine complex solution is 0.01 to 1.1mol/L.
The present invention is not limited in the kind of the first solvent as long as the copper salt, the first complexing agent and ammonia can be dissolved; preferably, the first solvent is water, more preferably deionized and/or distilled water.
According to the present invention, preferably, the conditions of the second mixing include: the temperature is 40-90 ℃. The time of the second mixing is not limited in any way, as long as all solids can be dissolved; preferably, the time is 1-10 hours. In the present invention, the second mixing is preferably performed under stirring for a time such that all solids are dissolved.
According to the present invention, preferably, the conditions of the second mixing further include: the pH value of the system is adjusted to 9-12. The regulator for regulating the pH value of the regulating system is not limited, so long as the regulator can regulate the pH value within the range; preferably, the pH of the system is adjusted by passing ammonia gas.
In a preferred embodiment of the invention, the method further comprises synthesizing the nickel ammine complex by: and thirdly mixing the nickel salt and the second complexing agent in the presence of a second solvent and ammonia.
According to the present invention, preferably, the nickel salt and the second complexing agent are used in a molar ratio of 1:0.5-2.
Preferably, the nickel salt is selected from at least one of nickel nitrate, nickel sulfate, nickel chloride, basic nickel carbonate and nickel acetate.
Preferably, the second complexing agent is selected from at least one of ethylenediamine tetraacetic acid, monoethanolamine, diethanolamine, and triethanolamine.
According to the invention, preferably, the ammonia is used in such an amount that the pH of the system is between 9 and 12 during the synthesis of the nickel ammonia complex. The ammonia is the same as the optional ranges and forms of ammonia described above in the synthesis of the cuprammonium complex, and will not be described in detail herein.
According to the present invention, preferably, the second solvent is used in an amount such that the concentration of the nickel ammine complex in the prepared nickel ammine complex solution is 0.01-2mol/L. When the ammonia is introduced in the form of aqueous ammonia, the amount of water in the aqueous ammonia and the amount of the second solvent are used together so that the concentration of the nickel ammine complex in the prepared nickel ammine complex solution is 0.01 to 2mol/L.
The invention is not limited in the kind of the second solvent as long as the nickel salt, the second complexing agent and ammonia can be dissolved; preferably, the second solvent is water, more preferably deionized and/or distilled water.
According to the present invention, preferably, the conditions of the third mixing include: the temperature is 40-90 ℃. The time of the third mixing is not limited in any way, as long as all solids can be dissolved; preferably, the time is 1-10 hours. In the present invention, the third mixing is preferably performed under stirring for a time such that all solids are dissolved.
According to the present invention, preferably, the conditions of the third mixing further include: the pH value of the system is adjusted to 9-12. The regulator for regulating the pH value of the regulating system is not limited, so long as the regulator can regulate the pH value within the range; preferably, the pH of the system is adjusted by passing ammonia gas.
In another preferred embodiment of the present invention, the method comprises synthesizing said cuprammonium complex and nickel rammonium complex by the following one-step process: the nickel salt, copper salt and third complexing agent are co-mixed in the presence of a third solvent and ammonia. In the present invention, the nickel salt and copper salt are the same as the optional ranges of the nickel salt and copper salt, and are not described herein.
According to the present invention, it is further preferred that the molar ratio of the total molar amount of the nickel salt and copper salt to the molar amount of the third complexing agent is 1:0.5-2.
Preferably, the third complexing agent is selected from at least one of ethylenediamine tetraacetic acid, monoethanolamine, diethanolamine, and triethanolamine.
The present invention is not limited in the kind of the third solvent as long as the nickel salt, copper salt, third complexing agent and ammonia can be dissolved; preferably, the third solvent is water, more preferably deionized and/or distilled water.
Preferably, the third solvent is used in an amount such that the total concentration of the copper ammonia complex and nickel ammonia complex in the prepared solution is 0.01 to 1mol/L. When the ammonia is introduced in the form of aqueous ammonia, the amounts of water and the third solvent in the aqueous ammonia are used together so that the total concentration of the copper ammonia complex and nickel ammonia complex in the prepared solution is within the aforementioned range.
Preferably, during the one-step synthesis of the cuprammonium complex and nickel ammine complex, the ammonia is used in an amount such that the pH of the system is between 9 and 12. The ammonia herein is the same as the optional ranges and forms of ammonia in the synthesis of the cuprammonium complex or nickel amminium complex described above, and will not be described in detail herein.
Preferably, the conditions of the blending further include: the temperature is 40-90 ℃. The present invention does not have any limitation on the time of the co-mixing, as long as all solids can be dissolved; preferably, the time is 1-10 hours. In the present invention, the blending is preferably performed with stirring for a time period such that all solids are dissolved.
According to a preferred embodiment of the present invention, the method comprises synthesizing said cuprammonium complex and nickel rammonium complex by the following one-step method: in the presence of a third solvent and ammonia, nickel salt, copper salt and a third complexing agent are mixed together, the pH value of the system is regulated by introducing ammonia gas, and the mixture is stirred at 40-90 ℃ until all solids are dissolved; the molar ratio of the total molar amount of the nickel salt and the copper salt to the molar amount of the third complexing agent is 1:0.5-2.
According to the present invention, the condition of the first mixing in the step (1) is not limited at all as long as it is uniformly mixed, and for example, it may be mixed at room temperature (20.+ -. 5 ℃ C.).
The aging condition is not limited, so long as the catalyst activity and succinic anhydride selectivity are improved; preferably, in step (2), the aging conditions include: the temperature is 40-90 ℃ and the time is 12-36h.
According to the present invention, preferably, in step (3), the contacting conditions include: and carrying out saturated impregnation and/or saturated spray impregnation on the Ce-containing precursor compound and the catalyst precursor.
According to the present invention, preferably, in step (4), the conditions of the firing include: the temperature is 350-500 ℃ and the time is 2-6h.
The conditions of the first drying and the second drying are not limited, so long as the catalyst activity and the succinic anhydride selectivity are improved; preferably, the conditions of the first drying and the second drying each independently include: the temperature is 100-120 ℃ and the time is 10-20h. In the present invention, the conditions of the first drying and the second drying may be the same or different.
In the present invention, the molding method and the shape in the step (4) are not particularly limited, and may be freely selected by those skilled in the art, and may be, for example, compression molding or extrusion molding.
According to a preferred embodiment of the present invention, the preparation method of the hydrogenation catalyst comprises:
(1) First mixing a precursor compound containing Ni, a precursor compound containing Cu and a carrier to obtain a first mixed solution;
the Cu-containing precursor compound is a cuprammonium complex, the Ni-containing precursor compound is a nickel rammonium complex, and the precursor compound of the carrier contains SiO 2 The precursor compound of the carrier is selected from silica sol;
(2) Sequentially aging and optionally first drying the first mixed solution to obtain a catalyst precursor;
(3) Contacting the catalyst precursor with a Ce-containing precursor compound to obtain a matrix catalyst;
the Ce-containing precursor compound is at least one selected from cerium nitrate, cerium sulfate, cerium chloride and cerium acetate;
(4) Optionally second drying the base catalyst, and then roasting and optionally forming;
the Ni-containing precursor compound, the Cu-containing precursor compound, the precursor compound of the carrier and the Ce-containing precursor compound are used in amounts such that the catalyst is prepared, based on the total weight of the catalyst, the content of Ni element is 10-40 wt%, the content of Cu element is 1-5 wt%, the content of Ce element is 1-8 wt%, and the content of the carrier is 47-88 wt%, based on the total weight of the catalyst.
According to a particularly preferred embodiment of the present invention, the hydrogenation catalyst is prepared by a process comprising:
(1) First mixing a precursor compound containing Ni, a precursor compound containing Cu and a carrier to obtain a first mixed solution;
the Cu-containing precursor compound is a cuprammonium complex, the Ni-containing precursor compound is a nickel rammonium complex, and the precursor compound of the carrier contains SiO 2 The precursor compound of the carrier is selected from silica sol;
(2) Sequentially aging and optionally first drying the first mixed solution to obtain a catalyst precursor;
(3) Contacting the catalyst precursor with a Ce-containing precursor compound to obtain a matrix catalyst;
the Ce-containing precursor compound is at least one selected from cerium nitrate, cerium sulfate, cerium chloride and cerium acetate;
(4) Optionally second drying the base catalyst, and then roasting and optionally forming;
the Ni-containing precursor compound, the Cu-containing precursor compound, the precursor compound of the carrier and the Ce-containing precursor compound are used in amounts such that the catalyst is prepared, based on the total weight of the catalyst, the Ni element is 18-22 wt%, the Cu element is 1-2 wt%, the Ce element is 3-4 wt% and the carrier is 72-78 wt%, based on the total weight of the catalyst. The preferential scheme is more beneficial to improving the activity of the catalyst and the selectivity of succinic anhydride.
The preparation method provided by the invention can be used for preparing the catalyst with better catalytic activity and higher succinic anhydride selectivity, has the advantages of simple process, energy consumption saving, simplified production operation flow, reduced production operation cost and capability of being used for continuous industrial production.
In a third aspect, the present invention provides a hydrogenation catalyst prepared by the method of the second aspect. The composition and performance of the catalyst are the same as those of the catalyst of the first aspect, and are not described in detail herein.
In a fourth aspect, the present invention provides the use of a hydrogenation catalyst according to the first or third aspect in the hydrogenation of maleic anhydride to succinic anhydride.
The hydrogenation catalyst can be used for preparing succinic anhydride by hydrogenating maleic anhydride under the conditions of lower catalytic reaction temperature (less than or equal to 140 ℃) and lower catalytic reaction pressure (less than or equal to 2 MPa), thereby saving energy consumption.
The fifth aspect of the invention provides a method for preparing succinic anhydride by hydrogenating maleic anhydride, comprising the following steps: under the hydrogenation condition, in the presence of an activated catalyst, carrying out contact reaction on hydrogen and maleic anhydride; the activated catalyst is obtained by reducing and activating the hydrogenation catalyst in the first aspect or the third aspect.
According to the present invention, preferably, the hydrogenation conditions include: the temperature is 80-140 ℃, and the pressure is 0.5-2MPa, preferably 1-2MPa. Unless otherwise indicated, the pressures used in the present invention are absolute pressures.
According to the present invention, preferably, the hydrogen gas and the maleic anhydride are used in a molar ratio of 10 to 30:1.
According to the present invention, preferably, the liquid hourly space velocity of the maleic anhydride is 0.1 to 0.5h -1 。
According to the invention, the maleic anhydride is preferably introduced in the form of a maleic anhydride solution, preferably at a concentration of 10-30% by weight.
Further preferably, the solvent of the maleic anhydride solution is selected from at least one of tetrahydrofuran, γ -butyrolactone, cyclohexane and 1, 4-dioxane.
In the present invention, the process of subjecting the hydrogenation catalyst to the reduction activation treatment may be performed during the process of preparing succinic anhydride by hydrogenation, or may be performed before the process of preparing succinic anhydride by hydrogenation (i.e., the process of directly using the activated catalyst obtained after the reduction activation treatment for preparing succinic anhydride by hydrogenation), so long as the contact reaction is performed in the presence of the activated catalyst.
According to the present invention, preferably, the process of the reductive activation treatment includes: and under the condition of reduction and activation, adopting hydrogen-containing gas to contact with the hydrogenation catalyst.
According to the present invention, preferably, the conditions for the reductive activation include: the temperature is 350-450 ℃ and the time is 1-8h; the space velocity of hydrogen is 20-100h -1 . In the present invention, the space velocity of hydrogen refers to the volume space velocity.
Preferably, the hydrogen content in the hydrogen-containing gas is 5 to 100% by volume.
Preferably, the hydrogen-containing gas consists of hydrogen and an inert gas. The inert gas is not limited in the present invention as long as it does not participate in the reduction reaction, and may be, for example, at least one of nitrogen, argon and helium. More preferably, the hydrogen-containing gas consists of hydrogen and nitrogen.
In the present invention, the equipment used in the method for producing succinic anhydride by hydrogenating maleic anhydride is not limited as long as the reaction can be effected, and for example, the reaction can be performed in a fixed bed reactor.
The present invention will be described in detail by examples. In the following preparation examples, all the materials involved are commercially available unless otherwise specified.
The following preparation examples are illustrative of the hydrogenation catalyst of the present invention and a process for preparing the same.
Preparation example 1
(1) 50.00g of basic nickel carbonate (wherein the content of nickel in terms of element was 45% by weight) and 9.16g of Cu (NO) were weighed out 3 ) 2 ·3H 2 Mixing O,49.91g of ethylenediamine tetraacetic acid, 500g of deionized water and 100g of 25 wt% ammonia water, introducing ammonia gas, regulating the pH value of the solution to 10.5, and stirring at 45 ℃ until all solids are dissolved to obtain a solution of nickel-copper ammonia complex (namely a solution of copper ammonia complex and nickel ammonia complex);
(2) 458.31g of silica sol (SiO therein 2 25 wt%) and the nickel-copper ammonia complex solution obtained in the step (1) are mixed to obtain a mixed solution;
(3) Aging the mixed solution for 14 hours at the temperature of 60 ℃ under stirring, and drying for 12 hours at the temperature of 120 ℃ to obtain a catalyst precursor;
(4) Will contain 11.41g of Ce (NO) 3 ) 3 ·6H 2 Cerium nitrate solution of O (wherein Ce (NO 3 ) 3 ·6H 2 The O concentration is 15 wt%) saturated impregnating the catalyst precursor to obtain a matrix catalyst;
(5) Drying the matrix catalyst at 115 ℃ for 12 hours, then roasting at 400 ℃ for 4 hours, and forming to obtain the catalyst S1.
The catalyst S1 was tested to contain, based on the total weight of the catalyst S1: 19 wt% NiO, 2 wt% CuO, 3 wt% CeO 2 And 76% by weight of SiO 2 。
Preparation example 2
(1) Basic nickel carbonate (nickel content same as preparation example 1), cu (NO 3 ) 2 ·3H 2 Mixing O,49.91g of ethylenediamine tetraacetic acid, 500g of deionized water and 100g of 25 wt% ammonia water, introducing ammonia gas, regulating the pH value of the solution to 12, and stirring at 70 ℃ until all solids are dissolved to obtain a solution of nickel-copper ammonia complex (namely a solution of copper ammonia complex and nickel ammonia complex);
(2) Mixing silica sol (same as preparation example 1) with the nickel-copper ammonia complex solution obtained in the step (1) to obtain a mixed solution;
(3) Aging the mixed solution for 12 hours at 90 ℃ under stirring, and drying for 15 hours at 110 ℃ to obtain a catalyst precursor;
(4) Will contain 11.41g of Ce (NO) 3 ) 3 ·6H 2 Saturated impregnation of the catalyst precursor with a cerium nitrate solution of O (same as in preparation example 1) gives a base catalyst;
(5) And drying the matrix catalyst at 120 ℃ for 11 hours, then roasting at 500 ℃ for 3 hours, and forming to obtain the catalyst S2.
The raw material (i.e. basic nickel carbonate, cu (NO) 3 ) 2 ·3H 2 The amounts of O and cerium nitrate solution (concentration as in example 1)) are such that the catalyst S2 is produced, the catalyst S2 comprising, based on the total weight of the catalyst S2: 23 wt% NiO, 3 wt% CuO, 5 wt% CeO 2 And 69% by weight of SiO 2 。
Preparation example 3
(1) Synthesizing a cuprammonia complex: 10 g of Cu (NO) 3 ) 2 ·3H 2 Mixing O, 2.5g of monoethanolamine, 500g of deionized water and 100g of 25 wt% ammonia water, introducing ammonia gas, regulating the pH value of the solution to 10, and stirring at 80 ℃ until all solids are dissolved to obtain a copper ammonia complex solution;
synthesis of nickel ammine complex: mixing basic nickel carbonate (nickel content is the same as that of preparation example 1), 22g of monoethanolamine, 500g of deionized water and 100g of 25 wt% ammonia water, introducing ammonia gas, adjusting the pH value of the solution to 10, and stirring at 80 ℃ until all solids are dissolved to obtain a nickel ammonia complex solution;
(2) Mixing silica sol (same as preparation example 1) with the copper ammonia complex solution and the nickel ammonia complex solution obtained in the step (1) to obtain a mixed solution;
(3) Aging the mixed solution for 20 hours at 50 ℃ under stirring, and drying for 15 hours at 110 ℃ to obtain a catalyst precursor;
(4) Saturated impregnating the catalyst precursor with a cerium acetate solution (the concentration of which is the same as that of preparation example 1) to obtain a matrix catalyst;
(5) And drying the matrix catalyst at 120 ℃ for 11 hours, then roasting at 400 ℃ for 3 hours, and forming to obtain the catalyst S3.
The raw materials (i.e. basic nickel carbonate and cerium acetate solution) are used in such an amount that the catalyst S3 is prepared, based on the total weight of the catalyst S3The agent S3 contains: 17 wt% NiO, 2 wt% CuO, 5 wt% CeO 2 And 76% by weight of SiO 2 。
PREPARATION EXAMPLES 4 to 5
A catalyst was prepared in a similar manner to preparation 1, except that the starting materials used (i.e., basic nickel carbonate, cu (NO) 3 ) 2 ·3H 2 Catalysts S4 and S5 were prepared, respectively, in the same manner as in preparation example 1, except that the amounts of O and cerium nitrate solutions (concentrations were different from those of example 1).
The raw materials are used in an amount such that the catalyst S4 is prepared, wherein the catalyst S4 comprises, based on the total weight of the catalyst S4: 12 wt% NiO, 1 wt% CuO, 2 wt% CeO 2 And 85% by weight of SiO 2 。
The raw materials are used in an amount such that the catalyst S5 is prepared, wherein the catalyst S5 comprises, based on the total weight of the catalyst S5: 36 wt% NiO, 1 wt% CuO, 3 wt% CeO 2 And 60% by weight of SiO 2 。
Preparation example 6
(1) 50.00g of Ni (NO) 3 ) 2 ·6H 2 O, 6.54g Cu (NO) 3 ) 2 ·3H 2 Mixing O with 500g of deionized water to obtain a nickel nitrate-copper nitrate mixed solution;
(2) Weighing 327.13g of silica sol (the source is the same as that of preparation example 1) and uniformly mixing the silica sol with the nickel nitrate-copper nitrate mixed solution obtained in the step (1) to obtain a mixed solution;
(3) Aging the mixed solution for 14 hours at the temperature of 60 ℃ under stirring, and drying for 12 hours at the temperature of 120 ℃ to obtain a catalyst precursor;
(4) Will contain 8.14g of Ce (NO 3 ) 3 ·6H 2 Saturated impregnation of the catalyst precursor with a cerium nitrate solution of O (concentration the same as in preparation example 1) to obtain a base catalyst;
(5) And drying the matrix catalyst at 115 ℃ for 12 hours, then roasting at 400 ℃ for 4 hours, and forming to obtain the catalyst S6.
Tested, based on the total weight of the catalyst S6,the catalyst S6 contains: 19 wt% NiO, 2 wt% CuO, 3 wt% CeO 2 And 76% by weight of SiO 2 。
Comparative preparation example 1
A catalyst was prepared by a similar method to preparation example 1, except that the cerium nitrate impregnation process of step (4) was not performed in this comparative preparation example, but the catalyst precursor obtained in step (3) was directly subjected to step (5) to prepare the catalyst CS1.
The catalyst CS1 was tested to contain, based on the total weight of the catalyst CS 1: 19 wt% NiO, 2 wt% CuO and 79 wt% SiO 2 。
Comparative preparation example 2
A catalyst was prepared in a similar manner to preparation 1, except that the starting materials used (i.e., basic nickel carbonate, cu (NO) 3 ) 2 ·3H 2 The catalyst CS2 was prepared with different amounts of O and cerium nitrate solutions (concentrations as in example 1).
The raw materials are used in an amount such that the catalyst CS2 is prepared, wherein the catalyst CS2 comprises, based on the total weight of the catalyst CS 2: 8 wt% NiO, 1 wt% CuO, 1 wt% CeO 2 And 90% by weight of SiO 2 。
Comparative preparation example 3
Weighing nickel nitrate, cu (NO) 3 ) 2 ·3H 2 O and cerium nitrate are dissolved in 500g of deionized water to obtain a mixed solution; then, silica sol (same as in preparation example 1) was immersed in the obtained mixed solution; then, the obtained mixed solution is aged for 14 hours at the temperature of 60 ℃ under stirring, then dried for 12 hours at the temperature of 120 ℃, finally baked for 4 hours at the temperature of 400 ℃ and molded to obtain the finished catalyst CS3.
The raw materials (nickel nitrate, cu (NO) 3 ) 2 ·3H 2 O and cerium nitrate) in such an amount that the catalyst CS3 is prepared, the catalyst CS3 comprises, based on the total weight of the catalyst CS 3: 19 wt% NiO, 2 wt% CuO, 3 wt% CeO 2 And 76% by weight of SiO 2 。
The following examples are presented to illustrate the use of the hydrogenation catalyst of the present invention and the process for the hydrogenation of maleic anhydride to succinic anhydride.
Example 1
The catalyst prepared in example 1 was evaluated for activity by the following method:
(1) The catalyst prepared in preparation example 1 above was treated with a mixture of nitrogen and hydrogen at 400℃in a stainless steel fixed bed reactor (hydrogen content in the mixture: 50% by volume, hydrogen space velocity: 50 h) -1 ) Reducing for 6h to activate to obtain an activated catalyst;
(2) In the presence of the activated catalyst, carrying out contact reaction on hydrogen and maleic anhydride solution (tetrahydrofuran is used as a solvent), wherein the concentration of the maleic anhydride solution is 20% by weight, and the contact reaction conditions comprise: the reaction temperature is 120 ℃, the pressure is 2MPa, and the liquid hourly space velocity of maleic anhydride is 0.4h -1 The molar ratio of hydrogen to maleic anhydride is 25:1, a step of;
(3) Condensing the product obtained after the reaction in the step (2) to obtain a liquid product, analyzing the content of each component in the liquid product by gas chromatography, and calculating the conversion rate of maleic anhydride and the selectivity of succinic anhydride by the following formula, wherein the specific results are shown in table 1.
Wherein the maleic anhydride conversion and the succinic anhydride selectivity are calculated by the following formula:
(1) Maleic anhydride conversion = (Mo-Ma)/mo×100%
(2) Selectivity of succinic anhydride = Mi/(Mo-Ma) ×100%
Wherein Mo is the amount and mol of the maleic anhydride material;
ma-the amount of maleic anhydride remaining after the reaction, mol;
mi-amount of substance of succinic anhydride formed after the reaction, mol.
Examples 2 to 6
The procedure was carried out in a similar manner to example 1, except that the catalysts prepared in preparation examples 2 to 6 were used in place of the catalyst prepared in preparation example 1 described above, respectively, and the procedure was otherwise identical to that of example 1.
The maleic anhydride conversion and succinic anhydride selectivity were tested, and the specific results are shown in Table 1.
Example 7
The procedure was carried out in a similar manner to example 1, except that the conditions for the contact reaction used were different from those of example 1, and the conditions for the contact reaction specifically included: the reaction temperature is 80 ℃, the pressure is 1MPa, and the liquid hourly space velocity of maleic anhydride is 0.2h -1 The molar ratio of hydrogen to maleic anhydride is 15:1, a step of; otherwise, the same as in example 1 was used.
The maleic anhydride conversion and succinic anhydride selectivity were tested, and the specific results are shown in Table 1.
Comparative examples 1 to 3
The procedure was carried out in a similar manner to example 1, except that the catalysts prepared in comparative preparation examples 1 to 3 were used in place of the catalyst prepared in preparation example 1 described above, respectively, and the other was the same as in example 1.
The maleic anhydride conversion and succinic anhydride selectivity were tested, and the specific results are shown in Table 1.
TABLE 1
As can be seen from the results in Table 1, the hydrogenation catalyst provided by the invention has higher catalytic activity and succinic anhydride selectivity.
The catalyst prepared by the method provided by the invention has more excellent catalytic activity and succinic anhydride selectivity.
The catalyst prepared by the method provided by the invention can be used for preparing succinic anhydride by continuous hydrogenation of maleic anhydride, the catalytic reaction temperature is low, the reaction pressure is low, and the energy consumption is further saved.
The above comparative examples are not all prior art, but are provided for the purpose of contrast with the present invention, and are not to be construed as limiting the present invention.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (48)

1. A method of preparing a hydrogenation catalyst, the method comprising:
(1) First mixing a precursor compound containing Ni, a precursor compound containing Cu and a carrier to obtain a first mixed solution; the precursor compound of the carrier contains SiO 2 ；
(2) Sequentially aging and optionally first drying the first mixed solution to obtain a catalyst precursor;
(3) Contacting the catalyst precursor with a Ce-containing precursor compound to obtain a matrix catalyst;
(4) Optionally second drying the base catalyst, and then roasting and optionally forming;
the Ni-containing precursor compound, the Cu-containing precursor compound, the precursor compound of the carrier and the Ce-containing precursor compound are used in amounts such that the catalyst is prepared, based on the total weight of the catalyst, the content of Ni element is 15-25 wt%, the content of Cu element is 1-3 wt%, the content of Ce element is 3-6 wt%, and the content of the carrier is 66-81 wt%, based on the total weight of the catalyst;
wherein the Cu-containing precursor compound is a cuprammonium complex;
wherein the Ni-containing precursor compound is a nickel ammine complex.
2. The method of claim 1, wherein the Ce-containing precursor compound is selected from at least one of cerium nitrate, cerium sulfate, cerium chloride, and cerium acetate.
3. The method of claim 1, wherein the precursor compound of the carrier is selected from the group consisting of silica sols.
4. A method according to claim 3, wherein the precursor compound of the carrier is an acidic silica sol and/or an alkaline silica sol.
5. The method of claim 1, further comprising synthesizing the cuprammonium complex by: the copper salt and the first complexing agent are subjected to a second mixing in the presence of a first solvent and ammonia.
6. The method of claim 5, wherein the copper salt and the first complexing agent are present in a molar ratio of 1:0.5-2.
7. The method of claim 5, wherein the ammonia is used in an amount such that the pH of the system is 9-12 during the synthesis of the cuprammonium complex.
8. The method according to claim 5, wherein the first solvent is used in an amount such that the concentration of the copper ammine complex in the prepared copper ammine complex solution is 0.01 to 1.1mol/L.
9. The method of claim 5, wherein the copper salt is selected from at least one of copper nitrate, copper sulfate, copper chloride, basic copper carbonate, and copper acetate.
10. The method of claim 5, wherein the first complexing agent is selected from at least one of ethylenediamine tetraacetic acid, monoethanolamine, diethanolamine, and triethanolamine.
11. The method of claim 5, wherein the first solvent is water.
12. The method of claim 5, wherein the second mixing conditions comprise: the temperature is 40-90 ℃.
13. The method of claim 5, wherein the second mixing conditions further comprise: the pH value of the system is adjusted to 9-12.
14. A process according to claim 13, wherein the pH of the system is adjusted by passing ammonia gas.
15. The method of claim 1, wherein the method further comprises synthesizing the nickel ammine complex by: and thirdly mixing the nickel salt and the second complexing agent in the presence of a second solvent and ammonia.
16. The method of claim 15, wherein the nickel salt and the second complexing agent are present in a molar ratio of 1:0.5-2.
17. The method of claim 15, wherein the ammonia is used in an amount such that the pH of the system is 9-12 during the synthesis of the nickel ammine complex.
18. The method according to claim 15, wherein the second solvent is used in an amount such that the concentration of the nickel ammine complex in the prepared nickel ammine complex solution is 0.01-2mol/L.
19. The method of claim 15, wherein the nickel salt is selected from at least one of nickel nitrate, nickel sulfate, nickel chloride, basic nickel carbonate, and nickel acetate.
20. The method of claim 15, wherein the second complexing agent is selected from at least one of ethylenediamine tetraacetic acid, monoethanolamine, diethanolamine, and triethanolamine.
21. The method of claim 15, wherein the second solvent is water.
22. The method of claim 15, wherein the third mixing conditions comprise: the temperature is 40-90 ℃.
23. The method of claim 15, wherein the third mixing conditions further comprise: the pH value of the nickel ammine complex system is adjusted to 9-12.
24. The method of claim 15, wherein the pH of the nickel ammine system is adjusted by passing ammonia gas through.
25. A method according to claim 1, wherein the method comprises synthesizing the cuprammonium complex and the nickel rammonium complex by: the nickel salt, copper salt and third complexing agent are co-mixed in the presence of a third solvent and ammonia.
26. The method of claim 25, wherein the molar ratio of the total number of moles of nickel salt, copper salt, and the amount of the third complexing agent is 1:0.5-2.
27. The method of claim 25, wherein the third complexing agent is selected from at least one of ethylenediamine tetraacetic acid, monoethanolamine, diethanolamine, and triethanolamine.
28. The method of claim 25, wherein the third solvent is water.
29. The method of claim 25, wherein the third solvent is used in an amount such that the total concentration of the copper ammine complex and nickel ammine complex in the prepared solution is 0.01-1mol/L.
30. The method of claim 25, wherein the ammonia is used in an amount such that the pH of the system is 9-12 during the one-step synthesis of the cuprammonium complex and nickel ammine complex.
31. The method of claim 25, wherein the conditions of blending further comprise: the temperature is 40-90 ℃.
32. The method of claim 1, wherein in step (2), the aging conditions comprise: the temperature is 40-90 ℃ and the time is 12-36h.
33. The method of claim 1, wherein in step (3), the contacting conditions comprise: and carrying out saturated impregnation and/or saturated spray impregnation on the Ce-containing precursor compound and the catalyst precursor.
34. The method of claim 1, wherein in step (4), the firing conditions include: the temperature is 350-500 ℃ and the time is 2-6h.
35. The method of claim 1, wherein the conditions of the first drying and the second drying each independently comprise: the temperature is 100-120 ℃ and the time is 10-20h.
36. A hydrogenation catalyst prepared by the process of any one of claims 1-35.
37. The use of the hydrogenation catalyst of claim 36 in the hydrogenation of maleic anhydride to succinic anhydride.
38. A method for preparing succinic anhydride by hydrogenating maleic anhydride, which comprises the following steps: under the hydrogenation condition, in the presence of an activated catalyst, carrying out contact reaction on hydrogen and maleic anhydride; the activated catalyst is obtained by reducing and activating the hydrogenation catalyst in claim 36.
39. The method of claim 38, wherein the hydrogenation conditions comprise: the temperature is 80-140 ℃ and the pressure is 0.5-2MPa.
40. The method of claim 38 or 39, wherein the molar ratio of hydrogen to maleic anhydride is from 10 to 30:1.
41. The method of claim 38 or 39, wherein the liquid hourly space velocity of the maleic anhydride is from 0.1 to 0.5h -1 。
42. The method of claim 38 or 39, wherein the maleic anhydride is introduced in the form of a maleic anhydride solution, preferably at a concentration of 10-30 wt%.
43. A process according to claim 42, wherein the solvent of the maleic anhydride solution is selected from at least one of tetrahydrofuran, gamma-butyrolactone, cyclohexane and 1, 4-dioxane.
44. The method of claim 38 or 39, wherein the reductive activation treatment comprises: and under the condition of reduction and activation, adopting hydrogen-containing gas to contact with the hydrogenation catalyst.
45. The method of claim 38 or 39, wherein the conditions of reductive activation comprise: the temperature is 350-450 ℃ and the time is 1-8h; the space velocity of hydrogen is 20-100h -1 。
46. A process as set forth in claim 44 wherein the hydrogen-containing gas comprises from 5 to 100% by volume hydrogen.
47. A method according to claim 44, wherein the hydrogen-containing gas consists of hydrogen and an inert gas.
48. The method of claim 47, wherein the hydrogen-containing gas consists of hydrogen and nitrogen.
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CN101502802A (en) * 2009-03-18 2009-08-12 山西大学 Catalyst for continuous production of succinic anhydride from hydrogenation of maleic anhydride and preparation method thereof
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CN104607204A (en) * 2015-01-29 2015-05-13 武汉科林精细化工有限公司 Catalyst for continuously producing succinic anhydride by hydrogenating maleic anhydride and preparation method of catalyst
CN111097443A (en) * 2018-10-25 2020-05-05 中国石油化工股份有限公司 Catalyst for preparing gamma-butyrolactone through maleic anhydride gas-phase hydrogenation, preparation method and application of catalyst and method for preparing gamma-butyrolactone

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* Cited by examiner, † Cited by third party
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CN101502802A (en) * 2009-03-18 2009-08-12 山西大学 Catalyst for continuous production of succinic anhydride from hydrogenation of maleic anhydride and preparation method thereof
CN103769105A (en) * 2012-10-24 2014-05-07 中国石油化工股份有限公司 Catalyst for hydrogenating cis-butenedioic anhydride to prepare butanedioic anhydride and its preparation method and application
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