CN116020474A - 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 PDFInfo
- Publication number
- CN116020474A CN116020474A CN202111248934.3A CN202111248934A CN116020474A CN 116020474 A CN116020474 A CN 116020474A CN 202111248934 A CN202111248934 A CN 202111248934A CN 116020474 A CN116020474 A CN 116020474A
- Authority
- CN
- China
- Prior art keywords
- hydrogenation catalyst
- content
- catalyst
- maleic anhydride
- hydrogenation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
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 hydrogenation catalyst comprises a carrier and an active component loaded on the carrier, and the active component comprises the following components: a Ni element, a Sn element, a Ca element and/or a Ba element; the carrier contains SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the In the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, the content of Ni element is 10-40wt%, the content of Sn element is 5-15wt%, the content of Ca element and/or Ba element is 0.5-5wt%, and the content of carrier is 20-80wt% based on oxide. The hydrogenation catalyst of the invention has high catalytic activity and succinic anhydride selectivity under low-temperature reaction, has simple preparation process and can be applied to continuous large-scale reactionAnd (3) production.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst for preparing succinic anhydride by maleic anhydride liquid phase hydrogenation and a preparation method thereof, application of the catalyst for preparing succinic anhydride by maleic anhydride liquid phase hydrogenation, and a method for preparing succinic anhydride by maleic anhydride liquid phase 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. And succinic acid, a hydrolysate of succinic anhydride, is a main raw material of the biodegradable material of the poly butylene succinate. With the importance and development of environmental protection policies in China, the demand of succinic acid is increasing. Therefore, the demand for succinic anhydride is also increasing year by year, and particularly, high-purity succinic anhydride has high external dependency.
At present, the production method of succinic anhydride adopted in industry comprises the following steps: biological fermentation, electrochemical and maleic anhydride catalytic hydrogenation. The biological fermentation method is environment-friendly, but has high production cost and lower product purity, and is difficult to meet the requirements of industrial production; the electrochemical method has small production scale, and is difficult to meet the increasing market demands; the maleic anhydride 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.
US5616730 discloses a catalyst for preparing succinic anhydride by catalyzing maleic anhydride hydrogenation 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 US1541210 and EP0691335, 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.
Disclosure of Invention
The invention aims to solve the problems that the activity of a catalyst and the selectivity of succinic anhydride are low, the catalyst cost is high, the process flow is complex, and the catalyst cannot be applied to continuous mass production in the prior art, and provides a hydrogenation catalyst, a preparation method and application thereof, and a method for preparing succinic anhydride by hydrogenating maleic anhydride. The hydrogenation catalyst has the characteristics of high catalyst activity and selectivity, simple preparation process and low catalyst price, and can be applied to continuous large-scale industrial production.
In order to achieve the above object, a first aspect of the present invention provides a hydrogenation catalyst, characterized in that the hydrogenation catalyst comprises a carrier and an active component supported on the carrier, the active component comprising: a Ni element, a Sn element, a Ca element and/or a Ba element; the carrier contains SiO 2 ；
In the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, the content of Ni element is 10-40wt%, the content of Sn element is 5-15wt%, the content of Ca element and/or Ba element is 0.5-5wt%, and the content of carrier is 20-80wt% based on oxide.
In a second aspect, the present invention provides a method for preparing a hydrogenation catalyst, characterized in that the method is a coprecipitation method comprising the steps of:
(1) First mixing a Ni-containing precursor compound, a precursor compound of a carrier containing SiO, and a first solvent to obtain a first mixed solution 2 The method comprises the steps of carrying out a first treatment on the surface of the Carrying out second mixing on the Sn-containing precursor compound solution and the first mixed solution to obtain a second mixed solution;
(2) Carrying out a first contact reaction on the second mixed solution and the alkali solution to obtain a precipitate;
(3) Filtering, washing, drying and crushing the precipitate to obtain a powder matrix catalyst;
(4) Mixing and molding the powder matrix catalyst with a Ca-containing precursor compound and/or a Ba-containing precursor compound, and roasting to obtain a hydrogenation catalyst;
wherein, in the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, the content of Ni element is 10-40wt%, the content of Sn element is 5-15wt%, the content of Ca element and/or Ba element is 0.5-5wt%, and the content of carrier is 20-80wt% based on oxide.
In a third aspect, the present invention provides a hydrogenation catalyst prepared by the above process.
The fourth aspect of the invention provides an application of the hydrogenation catalyst and/or the preparation method of the hydrogenation catalyst in preparing succinic anhydride by hydrogenating maleic anhydride.
The fifth aspect of the invention provides a method for preparing succinic anhydride by liquid-phase hydrogenation of maleic anhydride, which is characterized by comprising the following steps: in the presence of an activated catalyst, carrying out a second contact reaction on hydrogen and maleic anhydride to obtain the succinic anhydride;
the activated catalyst is obtained by reducing and activating the hydrogenation catalyst and/or the hydrogenation catalyst obtained by the preparation method by using gas containing hydrogen.
The conditions of the reductive activation include: the temperature is 300-600 ℃ and the time is 0.5-20h.
Through the technical scheme, the hydrogenation catalyst, the preparation method and the application thereof, and the method for preparing succinic anhydride by hydrogenating maleic anhydride have the following beneficial effects:
the hydrogenation catalyst provided by the invention has higher activity and selectivity, the maleic anhydride conversion rate is more than or equal to 95%, and the succinic anhydride selectivity is more than or equal to 90%;
furthermore, the hydrogenation catalyst has simple preparation process, low catalyst price and cost saving.
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.
The first aspect of the present invention provides a hydrogenation catalyst, which is characterized in that the hydrogenation catalyst comprises a carrier and an active component supported on the carrier, wherein the active component comprises: a Ni element, a Sn element, a Ca element and/or a Ba element; the carrier contains SiO 2 ；
In the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, the content of Ni element is 10-40wt%, the content of Sn element is 5-15wt%, the content of Ca element and/or Ba element is 0.5-5wt%, and the content of carrier is 20-80wt% based on oxide.
In the invention, the hydrogenation catalyst has higher catalytic activity and selectivity when meeting the above range.
According to the invention, in the hydrogenation catalyst, the total weight of the hydrogenation catalyst is taken as a reference, the content of Ni element is 17-28wt%, the content of Sn element is 7-12wt%, the content of Ca and/or Ba element is 1-3wt%, and the content of carrier is 40-75wt%, based on oxides.
In a second aspect, the present invention provides a method for preparing a hydrogenation catalyst, characterized in that the method is a coprecipitation method comprising the steps of:
(1) First mixing a Ni-containing precursor compound, a precursor compound of a carrier containing SiO, and a first solvent to obtain a first mixed solution 2 The method comprises the steps of carrying out a first treatment on the surface of the Carrying out second mixing on the Sn-containing precursor compound solution and the first mixed solution to obtain a second mixed solution;
(2) Carrying out a first contact reaction on the second mixed solution and the alkali solution to obtain a precipitate;
(3) Filtering, washing, drying and crushing the precipitate to obtain a powder matrix catalyst;
(4) Mixing the powder matrix catalyst with a Ca-containing precursor compound and/or a Ba-containing precursor compound for forming, and roasting to obtain a hydrogenation catalyst;
wherein, in the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, the content of Ni element is 10-40wt%, the content of Sn element is 5-15wt%, the content of Ca element and/or Ba element is 0.5-5wt%, and the content of carrier is 20-80wt% based on oxide.
According to the invention, the hydrogenation catalyst prepared by the coprecipitation method can make the catalytic activity and succinic anhydride selectivity higher, and the preparation process is simple.
In the present invention, in the step (1), the specific conditions of the first mixing are not particularly limited as long as the Ni-containing precursor compound and the precursor compound of the support can be sufficiently and uniformly mixed.
In the present invention, the first solvent is not limited at all, and is preferably at least one of water, deionized water, or distilled water.
In the invention, the Sn-containing precursor compound solution is preferably added later, so that the Sn-containing precursor compound solution can be fully dispersed in the first mixed solution, and the components in the prepared hydrogenation catalyst are more uniformly mixed.
According to the invention, in the hydrogenation catalyst, the total weight of the hydrogenation catalyst is taken as a reference, the content of Ni element is 17-28wt%, the content of Sn element is 7-12wt%, the content of Ca and/or Ba element is 1-3wt%, and the content of carrier is 40-75wt%, based on oxides.
According to the present invention, the Ni-containing precursor compound is a soluble nickel salt, preferably at least one of nickel nitrate, nickel sulfate, nickel chloride and nickel acetate.
Further, the Sn-containing precursor compound is a soluble tin salt, preferably potassium stannate and/or sodium stannate.
Further, the precursor compound of the carrier is selected from acidic silica sol and/or basic silica sol, preferably acidic silica sol.
In the invention, the hydrogenation catalyst contains Ca-containing precursor compound and/or Ba-containing precursor compound, so that the acid center of the catalyst can be effectively reduced, and side reaction in the reaction process is inhibited, so that the reaction has the characteristics of high maleic anhydride conversion rate and high succinic anhydride selectivity.
Further, the Ca-containing precursor compound is CaCO.
Further, the Ba-containing precursor compound is BaCO 3 。
According to the present invention, in step (1), the conditions of the second mixing include: the temperature is 40-90 ℃, and the stirring time is 0.5-10h.
According to the invention, in step (2), the pH value of the first contact reaction system is controlled to be 5-8.
According to the invention, the alkaline solution is at least one of ammonia water, ammonium carbonate solution and ammonium bicarbonate solution.
According to the present invention, in step (2), the conditions of the first contact reaction include: the temperature is 40-90 ℃, and the reaction time is 0.5-10h.
According to the present invention, in step (3), the drying conditions include: the temperature is 100-120 ℃ and the time is 10-20h.
According to the present invention, in step (4), the firing conditions include: the temperature is 300-600 ℃ and the time is 10-20h.
Further, in the step (4), the firing conditions include: the temperature is 450-550 ℃ and the time is 2-6h.
According to a preferred embodiment of the invention:
(1) In the presence of deionized water, nickel nitrate and silica sol are subjected to first mixing to obtain a first mixed solution; mixing potassium stannate aqueous solution with the first mixed solution for a second time at 40-90 ℃ and stirring for 1-4 hours to obtain a second mixed solution;
(2) Carrying out a first contact reaction on the second mixed solution and the alkali solution at 40-90 ℃ for 0.5-3h to obtain a precipitate;
(3) Filtering and washing the precipitate, drying at 100-120 ℃ for 10-20 hours, and crushing to obtain a powder matrix catalyst;
(4) Powder matrix catalyst and CaCO 3 And/or BaCO 3 And (3) after mixing and molding, roasting for 10-20 hours at 450-600 ℃ to obtain the hydrogenation catalyst.
In a third aspect, the present invention provides a hydrogenation catalyst prepared by the above process.
In the invention, the hydrogenation catalyst obtained by the preparation method has higher catalytic activity and selectivity, and is more beneficial to being applied to large-scale industrial production.
The fourth aspect of the invention provides an application of the hydrogenation catalyst and/or the preparation method of the hydrogenation catalyst in preparing succinic anhydride by hydrogenating maleic anhydride.
The fifth aspect of the invention provides a method for preparing succinic anhydride by liquid-phase hydrogenation of maleic anhydride, which is characterized by comprising the following steps: in the presence of an activated catalyst, carrying out a second contact reaction on hydrogen and maleic anhydride to obtain the succinic anhydride;
the activated catalyst is obtained by reducing and activating the hydrogenation catalyst and/or the hydrogenation catalyst obtained by the preparation method by using gas containing hydrogen.
In the present invention, the equipment used for the second contact reaction is not limited as long as the reaction can be effected, and for example, it may be carried out in a slurry bed or a suspension bed reactor.
According to the invention, the conditions for the reductive activation include: the temperature is 300-600 ℃ and the time is 0.5-20h.
In the present invention, the environment for the reductive activation of the hydrogenation catalyst is not limited as long as the activation can be performed.
According to the present invention, the conditions of the second contact reaction include: the molar ratio of the hydrogen to the maleic anhydride is 10-30:1, the temperature is 40-70 ℃, the time is 1-6h, and the pressure is 1-5MPa.
Further, the mass ratio of the activated catalyst to the maleic anhydride is 0.01-0.05:1.
according to the present invention, the maleic anhydride solution contains a second solvent, and the second solvent is at least one of tetrahydrofuran, 1, 4-dioxane and gamma-butyrolactone.
According to a preferred embodiment of the invention:
(a) The hydrogenation catalyst is mixed with nitrogen and hydrogen at 400-600 ℃ in a slurry bed reactor (the hydrogen content in the mixture is 50% by volume, the hydrogen space velocity is 100 h) -1 ) Reducing for 3-10h to activate to obtain an activated catalyst;
(b) In the presence of the activated catalyst, carrying out a second contact reaction of hydrogen and maleic anhydride solution (solvent is at least one selected from tetrahydrofuran, 1.4-dioxane and gamma-butyrolactone, the concentration of the maleic anhydride solution is 10-30 wt%) at 60-150 ℃ and the pressure is 1-5MPa, wherein the dosage mole ratio of the activated catalyst to maleic anhydride is 0.01-0.05:1, a step of;
(c) Condensing the product obtained after the reaction in the step (b) to obtain a liquid product, and analyzing the content of each component in the liquid product through gas chromatography. Wherein the maleic anhydride conversion and the succinic anhydride selectivity are calculated by the following formula:
maleic anhydride conversion = (Mo-Ma)/mo×100%
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.
The invention will be described in detail below by way of examples.
The pressures used in the present invention are absolute pressures.
SiO in the silica sol used below 2 The content of (2) was 25% by weight.
Unless otherwise specified, the raw materials used in the following examples and comparative examples are all commercially available.
In the following preparation examples and comparative preparation examples, the hydrogenation catalyst composition and its content were obtained by XRF testing.
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) 233.55g Ni (NO) 3 ) 2 ·6H 2 O, 828g of acidic silica sol are mixed and dissolved in 2000mL of deionized water to obtain a first mixed solution; 53.56g K 2 Sn(OH) 6 Dissolving in 250mL deionized water; the first mixed solution is put into a reaction kettle, and K is stirred at 70 DEG C 2 Sn(OH) 6 Adding the mixture into the first mixed solution, and stirring for 2 hours to obtain a second mixed solution;
(2) Adding 10wt% ammonium bicarbonate solution into the second mixed solution in the step (1), controlling the pH value to be 7.2, and stirring for 1 hour at 65 ℃ to obtain a precipitate;
(3) Filtering, washing and drying the precipitate in the step (2) at 120 ℃ for 12 hours, and then mixing with 10.71g of CaCO 3 And (3) mixing and molding, and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain the hydrogenation catalyst S1.
The hydrogenation catalyst S1 contains NiO20wt% and SnO based on the total weight of the hydrogenation catalyst S1 2 9 wt％、SiO 2 69wt％、CaO 2wt％。
Preparation example 2
(1) 315.3g Ni (NO) 3 ) 2 ·6H 2 O and 696g of acidic silica sol are mixed and dissolved in 2000mL of deionized water to obtain a first mixed solution; 71.41g K 2 Sn(OH) 6 Dissolving in 250mL deionized water; adding the first mixed solution into a reaction kettle, stirring at 70 ℃, adding the potassium stannate aqueous solution into the first mixed solution, and stirring for 2 hours to obtain a second mixtureA liquid;
(2) Adding 10wt% ammonium bicarbonate solution into the second mixed solution in the step (1), controlling the pH value to be 7.2, and stirring for 1 hour at 65 ℃ to obtain a precipitate;
(3) Filtering, washing, drying at 120 ℃ for 12 hours, and then mixing with 16.07g CaCO 3 And (3) mixing and molding, and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain the hydrogenation catalyst S2.
The hydrogenation catalyst S2 contains NiO 27wt% and SnO based on the total weight of the hydrogenation catalyst S2 2 12 wt％、SiO 2 58wt％、CaO 3wt％。
Preparation example 3
(1) 210.2g Ni (NO) was weighed out 3 ) 2 ·6H 2 O and 888g of acidic silica sol are mixed and dissolved in 2000mL of deionized water to obtain a first mixed solution; 41.66 and 41.66g K 2 Sn(OH) 6 Dissolving in 250mL deionized water; the first mixed solution is put into a reaction kettle, and under the condition of stirring at 70 ℃, the potassium stannate aqueous solution is added into the first mixed solution, and stirring is carried out for 2 hours, so as to obtain a second mixed solution;
(2) Adding 10wt% ammonium bicarbonate solution into the second mixed solution in the step (1), controlling the pH value to be 7.2, and stirring for 1 hour at 65 ℃ to obtain a precipitate;
(3) Filtering, washing, drying at 120 ℃ for 12 hours, and then mixing with 5.35g CaCO 3 And (3) mixing and molding, and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain the hydrogenation catalyst S3.
Based on the total weight of the hydrogenation catalyst S3, the hydrogenation catalyst S3 contains 18wt% of NiO and 18wt% of SnO 2 7 wt％、SiO 2 74wt％、CaO1 wt％。
Preparation example 4
In the same manner as in preparation example 1, except that CaCO was used 3 Replaced by BaCO 3 Hydrogenation catalyst S4 is obtained.
The hydrogenation catalyst S4 comprises, based on the total weight of the hydrogenation catalyst S4: niO20wt% and SnO 2 9 wt％、SiO 2 68wt％、BaO 3wt％。
Preparation example 5
(1) 128.45g Ni (NO) 3 ) 2 ·6H 2 O, 984g of acidic silica sol are mixed and dissolved in 2000mL of deionized water to obtain a first mixed solution; 35.70g K 2 Sn(OH) 6 Dissolving in 250mL deionized water; the first mixed solution is put into a reaction kettle, and under the condition of stirring at 70 ℃, the potassium stannate aqueous solution is added into the first mixed solution, and stirring is carried out for 2 hours, so as to obtain a second mixed solution;
(2) Adding 10wt% ammonium bicarbonate solution into the second mixed solution in the step (1), controlling the pH value to be 7.2, and stirring for 1 hour at 65 ℃ to obtain a precipitate;
(3) Filtering, washing and drying the precipitate in the step (2) at 120 ℃ for 12 hours, and then mixing with 5.35g CaCO 3 And (5) mixing and molding, and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain the hydrogenation catalyst S5.
The hydrogenation catalyst S5 contains NiO 11wt% and SnO based on the total weight of the hydrogenation catalyst S5 2 6 wt％、SiO 2 82wt％、CaO1 wt％。
Preparation example 6
(1) 443.75g Ni (NO) 3 ) 2 ·6H 2 O, 516g of acidic silica sol is mixed and dissolved in 2000mL of deionized water to obtain a first mixed solution; 83.32g K 2 Sn(OH) 6 Dissolving in 250mL deionized water; the first mixed solution is put into a reaction kettle, and under the condition of stirring at 70 ℃, the potassium stannate aqueous solution is added into the first mixed solution, and stirring is carried out for 2 hours, so as to obtain a second mixed solution;
(2) Adding 10wt% ammonium bicarbonate solution into the second mixed solution in the step (1), controlling the pH value to be 7.2, and stirring for 1 hour at 65 ℃ to obtain a precipitate;
(3) Filtering, washing and drying the precipitate in the step (2) at 120 ℃ for 12 hours, and then mixing with 26.78g CaCO 3 And (3) mixing and molding, and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain the hydrogenation catalyst S6.
Based on the total weight of the hydrogenation catalyst S6, the hydrogenation catalyst S6 contains 38wt% of NiO and 38wt% of SnO 2 14 wt％、SiO 2 43wt％、CaCO 3 5wt％。
Preparation example 7
In accordance with preparation 1, except that in step (1), K was stirred at 50℃C 2 Sn(OH) 6 Adding the catalyst into the first mixed solution, stirring for 3 hours to obtain a second mixed solution, and preparing the hydrogenation catalyst S7 by other steps consistent with preparation example 1.
The hydrogenation catalyst S7 contains NiO 21wt% and SnO based on the total weight of the hydrogenation catalyst S7 2 10wt％、SiO 2 67wt％、CaO 2wt％。
Preparation example 8
The procedure was identical to that of preparation example 1, except that in step (3), the calcination conditions were changed to 450℃for 6 hours, and the other procedures were identical to that of preparation example 1, to prepare hydrogenation catalyst S8.
Based on the total weight of the hydrogenation catalyst S8, the hydrogenation catalyst S8 contains 19wt% of NiO and 19wt% of SnO 2 8wt％、SiO 2 69 wt％、CaO 2wt％。
Preparation example 9
In the same manner as in preparation example 1, except that CaCO was added in step (3) 3 Replaced by BaCO 3 And CaCO (CaCO) 3 Maintaining the same total amount of CaCO therein 3 With BaCO 3 The mass ratio was 1:1, and the other steps were identical to those of preparation example 1, to prepare hydrogenation catalyst S9.
The hydrogenation catalyst S9 contains NiO20wt% and SnO based on the total weight of the hydrogenation catalyst S9 2 9wt％、SiO 2 69 wt％、CaO 1wt％、BaO 1wt％
Comparative preparation example 1
(1) 233.55g Ni (NO) 3 ) 2 ·6H 2 O, 936g of acidic silica sol is mixed and dissolved in 2000mL of deionized water to obtain a first mixed solution;
(2) Placing the first mixed solution into a reaction kettle, adding 10wt% ammonium bicarbonate solution into the first mixed solution under stirring at 70 ℃, controlling the pH value to 7.2, and stirring for 1 hour at 65 ℃ to obtain a precipitate;
(3) Filtering, washing and drying the precipitate obtained in the step (2) at 120 ℃ for 12 hours, and then mixing with 10.71g CaCO 3 And (3) mixing and molding, and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain the hydrogenation catalyst CS1.
The hydrogenation catalyst CS1 contains NiO20wt% and SiO based on the total weight of the hydrogenation catalyst CS1 2 78wt％、CaO2 wt％。
Comparative preparation example 2
(1) 233.55g Ni (NO) 3 ) 2 ·6H 2 O, 852g of acidic silica sol is mixed and dissolved in 2000mL of deionized water to obtain a first mixed solution; 53.56g K 2 Sn(OH) 6 Dissolving in 250mL deionized water; the first mixed solution is put into a reaction kettle, and K is stirred at 70 DEG C 2 Sn(OH) 6 Adding the mixture into the first mixed solution, and stirring for 2 hours to obtain a second mixed solution;
(2) Adding 10wt% ammonium bicarbonate solution into the second mixed solution in the step (1), controlling the pH value to be 7.2, and stirring for 1 hour at 65 ℃ to obtain a precipitate;
(3) Filtering, washing and drying the precipitate in the step (2) at 120 ℃ for 12 hours, and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain the hydrogenation catalyst CS2.
The hydrogenation catalyst CS2 contains NiO20wt% and SnO based on the total weight of the hydrogenation catalyst CS2 2 9 wt％、SiO 2 71wt％。
Preparation of comparative example 3
(1) 93.42g Ni (NO) was weighed out 3 ) 2 ·6H 2 O, 984g of acidic silica sol are mixed and dissolved in 2000mL of deionized water to obtain a first mixed solution; 53.56g K 2 Sn(OH) 6 Dissolving in 250mL deionized water; the first mixed solution is put into a reaction kettle, and under the condition of stirring at 70 ℃, the potassium stannate aqueous solution is added into the first mixed solution, and stirring is carried out for 2 hours, so as to obtain a second mixed solution;
(2) Adding 10wt% ammonium bicarbonate solution into the second mixed solution in the step (1), controlling the pH value to be 7.2, and stirring for 1 hour at 65 ℃ to obtain a precipitate;
(3) Filtering, washing and drying the precipitate in the step (2) at 120 ℃ for 12 hours, and then mixing with 5.36g CaCO 3 Mixing, molding, and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain the additiveHydrogen catalyst CS3.
The hydrogenation catalyst CS3 contains NiO8wt% and SnO based on the total weight of the hydrogenation catalyst CS3 2 9wt％、SiO 2 82 wt％、CaO 1wt％。
The following examples are presented to illustrate the use of the hydrogenation catalyst of the present invention and the method of hydrogenating maleic anhydride to succinic anhydride
Example 1
(a) In a slurry bed reactor, 1.2g of the above hydrogenation catalyst was weighed out at 450℃with a mixture of nitrogen and hydrogen (the hydrogen content in the mixture was 50% by volume, the hydrogen space velocity was 400 h) -1 ) Reducing for 6h to activate to obtain an activated catalyst;
(b) In the presence of the activated catalyst, carrying out a second contact reaction between hydrogen and 500g of maleic anhydride solution (the solvent is tetrahydrofuran maleic anhydride solution with the concentration of 20 weight percent) at 60 ℃ and 2 MPa;
(c) Condensing the product obtained after the reaction in the step (b) to obtain a liquid product, and analyzing the content of each component in the liquid product through gas chromatography. The conversion of maleic anhydride and the selectivity of succinic anhydride were calculated by the following formulas, and the specific results are shown in table 1.
Wherein the maleic anhydride conversion and the succinic anhydride selectivity are calculated by the following formula:
maleic anhydride conversion = (Mo-Ma)/mo×100%
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 9
The procedure of example 1 was followed, except that the hydrogenation catalysts prepared in preparation examples 2 to 9 were used in place of the hydrogenation catalyst prepared in preparation example 1 described above, respectively, and the procedure was otherwise identical to that of example 1. The conversion of maleic anhydride and the selectivity of succinic anhydride are shown in Table 1.
Comparative examples 1 to 3
The procedure of example 1 was followed, except that the hydrogenation catalysts prepared in comparative preparation examples 1 to 3 were used in place of the hydrogenation catalyst prepared in preparation example 1 described above, respectively, and the procedure was otherwise identical to that of example 1. The conversion of maleic anhydride and the selectivity of succinic anhydride are shown in Table 1.
TABLE 1
| Maleic anhydride conversion (%) | Succinic anhydride selectivity (%) | |
| Example 1 | 100 | 99.6 |
| Example 2 | 100 | 96.8 |
| Example 3 | 99.5 | 97.5 |
| Example 4 | 100 | 98.3 |
| Example 5 | 96.7 | 95.1 |
| Example 6 | 100 | 92.8 |
| Example 7 | 100 | 98.9 |
| Example 8 | 100 | 99.2 |
| Example 9 | 100 | 99.3 |
| Comparative example 1 | 99.8 | 88.3 |
| Comparative example 2 | 99.5 | 88.9 |
| Comparative example 3 | 83.2 | 91.3 |
As shown in Table 1, the hydrogenation catalyst containing Ni-Sn-Si-Ca/Ba element of the invention has higher catalytic activity and succinic anhydride selectivity when applied to maleic anhydride liquid phase catalytic hydrogenation to prepare succinic anhydride.
As can be seen from comparison of the data of examples 1-3 and examples 5 and 6, the results of examples 1-3 are better than those of examples 5 and 6, and it is clear that the catalyst activity and succinic anhydride selectivity of the prepared hydrogenation catalyst are better when the content of the active components in the catalyst meets the preferred ranges of the present application.
As is apparent from example 1 and comparative example 1, comparative example 1 has significantly reduced succinic anhydride selectivity under the same reaction conditions as the present invention since Sn element is not introduced, whereas in example 1, succinic anhydride selectivity is as high as 99.6%.
As is clear from example 1 and comparative example 2, the comparative example has significantly reduced succinic anhydride selectivity under the same reaction conditions as the present invention because Ca or Ba is not introduced.
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 (12)
1. A hydrogenation catalyst comprising a support and an active component supported on the support, the active component comprising: a Ni element, a Sn element, a Ca element and/or a Ba element; the carrier contains SiO 2 ；
In the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, the content of Ni element is 10-40wt%, the content of Sn element is 5-15wt%, the content of Ca element and/or Ba element is 0.5-5wt%, and the content of carrier is 20-80wt% based on oxide.
2. The hydrogenation catalyst according to claim 1, wherein the hydrogenation catalyst has a Ni element content of 17 to 28wt%, a Sn element content of 7 to 12wt%, a Ca and/or Ba element content of 1 to 3wt%, and a carrier content of 40 to 75wt%, based on the total weight of the hydrogenation catalyst, on an oxide basis.
3. A process for preparing a hydrogenation catalyst, said process being a co-precipitation process comprising the steps of:
(1) Will contain Ni first mixing the precursor compound, the precursor compound of the carrier and the first solvent to obtain a first mixed solution, wherein the precursor compound of the carrier contains SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Carrying out second mixing on the Sn-containing precursor compound solution and the first mixed solution to obtain a second mixed solution;
(2) Carrying out a first contact reaction on the second mixed solution and the alkali solution to obtain a precipitate;
(3) Filtering, washing, drying and crushing the precipitate to obtain a powder matrix catalyst;
(4) Mixing and molding the powder matrix catalyst with a Ca-containing precursor compound and/or a Ba-containing precursor compound, and roasting to obtain a hydrogenation catalyst;
wherein, in the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, the content of Ni element is 10-40wt%, the content of Sn element is 5-15wt%, the content of Ca element and/or Ba element is 0.5-5wt%, and the content of carrier is 20-80wt% based on oxide.
4. The process according to claim 3, wherein the hydrogenation catalyst has a Ni element content of 17 to 28wt%, a Sn element content of 7 to 12wt%, a Ca and/or Ba element content of 1 to 3wt% and a carrier content of 40 to 75wt% in terms of oxides based on the total weight of the hydrogenation catalyst.
5. The method of claim 3 or 4, wherein the Ni-containing precursor compound is a soluble nickel salt, preferably at least one of nickel nitrate, nickel sulfate, nickel chloride and nickel acetate;
the Sn-containing precursor compound is a soluble tin salt, preferably potassium stannate and/or sodium stannate;
the precursor compound of the carrier is selected from acidic silica sol and/or basic silica sol, preferably acidic silica sol;
preferably, the Ca-containing precursor compound is CaCO 3 ；
Preferably, the Ba-containing precursor compound is BaCO 3 。
6. The method of any one of claims 3-5, wherein in step (1), the second mixing conditions comprise: the temperature is 40-90 ℃, and the stirring time is 0.5-10h.
7. The method according to any one of claims 3 to 6, wherein in the step (2), the pH of the first contact reaction system is controlled to be 5 to 8;
preferably, the alkaline solution is at least one of ammonia water, an ammonium carbonate solution and an ammonium bicarbonate solution.
8. The method according to any one of claims 3 to 7, wherein in step (2), the conditions of the first contact reaction include: the temperature is 40-90 ℃ and the reaction time is 0.5-10h;
and/or, in step (3), the drying conditions include: the temperature is 100-120 ℃ and the time is 10-20h;
and/or, in step (4), the firing conditions include: the temperature is 300-600deg.C, preferably 450-550deg.C, and the time is 10-20 hr, preferably 2-6 hr.
9. A hydrogenation catalyst prepared by the process of any one of claims 3-8.
10. Use of the hydrogenation catalyst of any one of claims 1, 2 and 9 and/or the method for preparing the hydrogenation catalyst of any one of claims 3-8 in the reaction of preparing succinic anhydride by liquid-phase hydrogenation of maleic anhydride.
11. A method for preparing succinic anhydride by maleic anhydride liquid phase hydrogenation is characterized by comprising the following steps: in the presence of an activated catalyst, carrying out a second contact reaction on hydrogen and maleic anhydride to obtain the succinic anhydride;
wherein the activated catalyst is obtained by reducing and activating the hydrogenation catalyst in any one of claims 1, 2 and 9 and/or the hydrogenation catalyst obtained by the preparation method in any one of claims 3 to 8 by a gas containing hydrogen;
the conditions of the reductive activation include: the temperature is 300-600 ℃ and the time is 0.5-20h.
12. The method of claim 11, wherein the maleic anhydride is present as a maleic anhydride solution and the concentration of the maleic anhydride solution is 10-30 wt.%;
the conditions of the second contact reaction include: the molar ratio of the hydrogen to the maleic anhydride is 10-30:1, the temperature is 40-70 ℃, the time is 1-6h, and the pressure is 1-5MPa;
and/or the mass ratio of the activated catalyst to the maleic anhydride is 0.01-0.05:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111248934.3A CN116020474A (en) | 2021-10-26 | 2021-10-26 | Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic anhydride by maleic anhydride hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111248934.3A CN116020474A (en) | 2021-10-26 | 2021-10-26 | Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic anhydride by maleic anhydride hydrogenation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116020474A true CN116020474A (en) | 2023-04-28 |
Family
ID=86069597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111248934.3A Pending CN116020474A (en) | 2021-10-26 | 2021-10-26 | Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic anhydride by maleic anhydride hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116020474A (en) |
-
2021
- 2021-10-26 CN CN202111248934.3A patent/CN116020474A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102617518B (en) | One-step preparation method for tetrahydrofuran by employing maleic anhydride gas phase hydrogenation | |
| CN101927168B (en) | Nickel-based catalyst for preparing isopropyl alcohol by acetone hydrogenation and application thereof | |
| CN102659724B (en) | A kind of preparation method of succinyl oxide | |
| CN114433100B (en) | Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic anhydride by maleic anhydride hydrogenation | |
| CN110947382B (en) | Catalyst for preparing methanol and co-producing ethylene glycol by ethylene carbonate hydrogenation and preparation method thereof | |
| CN102091624A (en) | Catalyst for preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol and preparation method thereof | |
| US20230174714A1 (en) | Supported catalyst used for synthesizing polyether amine, preparation method, and application | |
| CN113426457A (en) | Catalyst for preparing alcohol by ketone hydrogenation and preparation method and application thereof | |
| CN106232559A (en) | The hydrogenation catalyst comprising mixed oxide and the method producing ethanol | |
| CN104923218A (en) | Catalyst for itaconic acid hydrogenation as well as preparation method and use of catalyst, and method for preparing high value-added products from itaconic acid | |
| CN102500382A (en) | Catalyst for synthesizing methanol and preparation method thereof | |
| CN116020474A (en) | Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic anhydride by maleic anhydride hydrogenation | |
| CN114471638B (en) | Catalyst for synthesizing succinic acid (anhydride), preparation method and application | |
| CN101138726A (en) | Catalyst for industrial production of 1, 6-hexanediol and preparation method thereof | |
| CN114433127B (en) | Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic acid by maleic anhydride hydrogenation | |
| CN108947851B (en) | Synthesis method of 5-amino-1-pentanol | |
| CN103920502B (en) | The Catalysts and its preparation method of ethyl acetate gas phase hydrogenation ethanol and application under a kind of temperate condition | |
| CN111097427A (en) | Catalyst for preparing gamma-butyrolactone through maleic anhydride liquid-phase hydrogenation, preparation method and application thereof, and method for preparing gamma-butyrolactone | |
| CN101422732A (en) | Catalyst for producing 1,4-butylediol and preparation method and use thereof | |
| CN105727967B (en) | Catalyst for hydrogenation synthesis of 2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol, preparation method and application | |
| CN110845301A (en) | Production method of 1, 2-pentanediol | |
| CN114011421B (en) | Preparation method of hydrogenation catalyst for preparing succinic anhydride from maleic anhydride, and preparation method of succinic anhydride | |
| CN114539191B (en) | Method for preparing GBL by maleic anhydride hydrogenation and 1, 4-butanediol dehydrogenation coupling method | |
| CN116037134A (en) | Maleic anhydride hydrogenation catalyst, preparation method thereof and method for preparing succinic anhydride by liquid-phase hydrogenation of maleic anhydride | |
| CN102030727B (en) | Method for producing tetrahydrofuran |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |