CN116037134A - Maleic anhydride hydrogenation catalyst, preparation method thereof and method for preparing succinic anhydride by liquid-phase hydrogenation of maleic anhydride - Google Patents
Maleic anhydride hydrogenation catalyst, preparation method thereof and method for preparing succinic anhydride by liquid-phase hydrogenation of maleic anhydride Download PDFInfo
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Abstract
The invention relates to the technical field of catalysts, and provides a maleic anhydride hydrogenation catalyst, a preparation method thereof and a method for preparing succinic anhydride by liquid phase hydrogenation of maleic anhydride. The maleic anhydride hydrogenation catalyst comprises a carrier and an active component loaded on the carrier; the active component comprises NiO and SnO 2 And CeO 2 . Dispersing an active nickel precursor, an active tin precursor and an active cerium precursor in water, adding a precipitator, uniformly stirring, performing hydrothermal reaction, and performing aftertreatment to obtain an active component; mixing the active components with a carrier, ball milling and roasting to obtain the catalyst. The catalyst has the advantages of high catalytic activity, high selectivity, simple preparation process and low price, and has the potential of industrial application.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a maleic anhydride hydrogenation catalyst, a preparation method thereof and a method for preparing succinic anhydride by liquid phase hydrogenation of maleic anhydride.
Background
Maleic anhydride is a common important basic organic chemical raw material, and C=C double bond in molecules can be synthesized into succinic anhydride through selective hydrogenation. Succinic anhydride has wide application in the fields of food, surfactant, paint, medicine, agriculture, plastics, etc. Particularly, with the development of the industry of poly (butylene succinate) which is a biodegradable material, the market demand of succinic acid which is a hydrolysate of succinic anhydride is growing year by year. Therefore, maleic anhydride is used as a raw material, and succinic anhydride is synthesized through selective hydrogenation of C=C bonds, so that the method has important promotion significance for the development of petrochemical industry and material science.
The catalyst system for synthesizing succinic anhydride with maleic anhydride as material includes noble metal catalyst and non-noble metal catalyst. Wherein, the noble metals such as Pd, pt and the like are selected as main active components in the Chinese patents CN107473954A and CN102311332A, and the dosage of the noble metals accounts for 3.0-10.0wt% of the total weight of the catalyst. Although the catalyst has good activity and high selectivity for hydrogenation reaction, the production cost is greatly increased, and large-scale industrialization is difficult to realize.
On the other hand, nickel is often used as the main active component for non-noble metal catalyst systems, which, although having a stronger cost advantage compared to noble metal catalysts, also have some drawbacks in application. As disclosed in patent CN109529850A, a 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.
How to control the selectivity of hydrogenation reaction in the hydrogenation stage of c=c bond is the most important problem in the preparation of succinic anhydride by hydrogenating maleic anhydride, and a suitable catalyst needs to be found to improve the selectivity of succinic anhydride.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a maleic anhydride hydrogenation catalyst, a preparation method thereof and a method for preparing succinic anhydride by liquid phase hydrogenation of maleic anhydride. The catalyst has the advantages of high catalytic activity, high selectivity, simple preparation process and low price, and has the potential of industrial application.
One of the purposes of the invention is to provide a maleic anhydride hydrogenation catalyst, which comprises a carrier and an active component supported on the carrier;
the active component comprises NiO and SnO 2 And CeO 2 ；
The loading of the active component is 5 to 50wt%, such as may be 5wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, 22wt%, 25wt%, 28wt%, 30wt%, 32wt%, 35wt%, 38wt%, 40wt%, 42wt%, 45wt%, 48wt%, 50wt%, and any range between any two values, based on 100% of the total weight of the catalyst; preferably 10 to 40wt%, more preferably 15 to 25wt%.
In the present invention, the catalyst may be added with other conventional active metal elements as required.
Preferably, the method comprises the steps of,
of the active ingredients in the composition of the present invention,
NiO and SnO 2 The molar ratio of (2) is 5-10:1; for example, can be 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, and any range between any two values; preferably 5 to 6:1;
NiO and CeO 2 The molar ratio of (2) is 20-50:1; for example, can be 20:1, 22:1, 25:1, 28:1, 30:1, 32:1, 35:1, 38:1, 40:1, 42:1, 45:1, 48:1, 50:1, and any range between any two values; preferably 30 to 40:1.
Preferably, the method comprises the steps of,
in the catalyst, the particle size range of the active component is 5-15 nm.
Preferably, the method comprises the steps of,
the carrier is selected from one or a combination of sepiolite, alumina, silicon dioxide or active carbon, preferably sepiolite, and in the invention, the sepiolite carrier has a fiber structure and an open porous network, so that the catalyst has good catalytic performance.
Another object of the present invention is to provide a method for preparing the maleic anhydride hydrogenation catalyst according to one of the objects of the present invention, comprising the steps of:
(1) Dispersing an active nickel precursor, an active tin precursor and an active cerium precursor in water, adding a precipitator, uniformly stirring, performing hydrothermal reaction, and performing aftertreatment to obtain an active component;
(2) And mixing the active components with a carrier, performing ball milling and roasting to obtain the catalyst.
In the present invention, the post-treatment is carried out by conventional post-treatment means such as centrifugation, washing, drying, etc.
Preferably, the method comprises the steps of,
in the step (1), the step of (a),
the active nickel precursor is selected from at least one of soluble nickel salts; preferably at least one of nickel nitrate, nickel sulfate, nickel chloride or nickel acetate; more preferably nickel nitrate; and/or, the number of the groups,
the active tin precursor is selected from at least one of soluble tin salts; preferably at least one of potassium stannate or sodium stannate; more preferably potassium stannate; and/or, the number of the groups,
the active cerium precursor is selected from at least one of soluble cerium salts; preferably at least one of cerium nitrate, cerium sulfate, cerium chloride or cerium acetate; more preferably cerium nitrate; and/or, the number of the groups,
the precipitant is selected from alkali soluble matter, preferably at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate or potassium hydroxide, preferably NaOH.
Preferably, the method comprises the steps of,
in the step (1), the step of (a),
the molar ratio of the active nickel precursor to the active tin precursor is 5-10:1; preferably 5 to 6:1;
the molar ratio of the active nickel precursor to the active cerium precursor is 20-50:1; preferably 30-40:1;
the mass ratio of the active nickel precursor to the precipitator is 1:2.5-1:5;
the mass ratio of the active nickel precursor to the water is 1:8-12.
Preferably, the method comprises the steps of,
in the step (1), the step of (a),
the temperature of the hydrothermal reaction is 150-200 ℃, preferably 160-190 ℃; the time is 4-12 hours.
In the invention, the existing common drying conditions are adopted for drying, and the drying temperature is preferably 80-120 ℃ and the drying time is 6-12 hours.
Preferably, the method comprises the steps of,
in the step (2), the step of (C),
the addition amount of the active component is 5 to 50wt percent, preferably 10 to 40wt percent, based on 100 percent of the total weight of the raw materials in the step (2);
the ball milling is carried out until the ball milling is carried out to 40-120 meshes;
the roasting temperature is 350-650 ℃ and the roasting time is 2-8 hours.
The invention further provides a method for preparing succinic anhydride by liquid-phase hydrogenation of maleic anhydride, which comprises the following steps:
and (3) carrying out contact reaction on the activated catalyst prepared by the method for preparing the succinic anhydride or the catalyst prepared by the method for preparing the succinic anhydride.
Preferably, the reaction pressure of the contact reaction is 1 to 5MPa, for example, can be 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa, 5MPa, and any range between any two values; preferably 1 to 3MPa, more preferably 1 to 1.5MPa.
In the present invention, the catalyst may be activated by conventional activation methods, preferably by hydrogen reduction.
In the invention, succinic anhydride is prepared by adopting the conventional process conditions, and the catalyst and the maleic anhydride solution are preferably added into a slurry bed or a suspension bed reactor for reaction at the same time; the maleic anhydride solution is formed by dissolving maleic anhydride in an organic solvent; preferably, the organic solvent is selected from at least one of tetrahydrofuran, 1, 4-dioxane or gamma-butyrolactone;
the concentration of the maleic anhydride solution is 10-30wt%; and/or the number of the groups of groups,
the mass ratio of the catalyst to the maleic anhydride is 0.01-0.05:1; and/or the number of the groups of groups,
the temperature of the contact reaction is 60-150 ℃ and the time is 1-6 h.
Compared with the prior art, the invention has at least the following advantages:
1. the active component of the catalyst of the invention comprises NiO and SnO 2 And CeO 2 The catalytic effect of the catalyst is further improved through the special proportion of the three components, and the active components are low in price and beneficial to industrial application.
2. The preparation method of the traditional catalyst is improved, active components are prepared by a hydrothermal method, then the active components are ball-milled with a specific carrier, and the novel Ni-Sn-Ce/carrier catalyst is prepared, wherein active component grains of the supported catalyst are nano-sized, uniformly distributed, have better catalytic active centers with better polydispersity, and have good coking resistance, and the preparation process is simple and practical.
3. The catalyst of the invention has good catalytic performance in the preparation of succinic anhydride by maleic anhydride hydrogenation, can react under lower pressure, can realize continuous large-scale succinic anhydride production, and is a novel nano catalyst with industrial application potential.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The raw materials used in the following examples and comparative examples are all commercially available.
The particle size range of the active component in the catalyst is mainly calculated by XRD, and the size is rechecked by SEM and TEM tests.
Example 1
Weighing appropriate amount of Ni (NO) 3 ) 2 ·6H 2 O、K 2 Sn(OH) 6 、Ce(NO 3 ) 3 ·6H 2 O was dissolved in 500mL deionized water, wherein Ni (NO 3 ) 2 ·6H 2 The addition amount of O was 50g, ni (NO 3 ) 2 ·6H 2 O and K 2 Sn(OH) 6 Is 6:1, ni (NO) 3 ) 2 ·6H 2 O and Ce (NO) 3 ) 3 ·6H 2 The molar ratio of O is 40:1, stirring and dissolving are carried out, 125g of NaOH is added after the O is completely dispersed, stirring is continued for 10 minutes, then the O is transferred into a reaction kettle, and the reaction is carried out for 10 hours after the temperature is programmed and the temperature is increased to 170 ℃. After the reaction is finished, centrifugally separating the product, then washing the product with deionized water until the pH value of the filtrate is neutral, and drying the product at 110 ℃ for 12 hours to obtain the active component.
Adding 25g of active component into 75g of sepiolite carrier, mixing the active component with sepiolite, ball-milling, mixing to 40 meshes, roasting at 500 ℃ for 4 hours, and forming to obtain the catalyst.
In the catalyst prepared by the method, the loading of the active component is 25wt% based on 100% of the total weight of the catalyst, and the sepiolite component accounts for 75wt% of the total weight of the catalyst after roasting. Wherein NiO/SnO in the active component 2 The molar ratio of NiO/CeO is 6:1 2 The molar ratio of (2) was 40:1. In the catalyst, the grain size corresponding to the active component is 5-15 nm.
After the catalyst was prepared, the activity of the catalyst was evaluated by the following method: 1.2g of the activated catalyst and 500g of tetrahydrofuran solution with 15wt% of maleic anhydride content are simultaneously added into a slurry bed reactor, and the conversion rate of maleic anhydride and the selectivity of succinic anhydride are shown in table 1 under the conditions that the reaction temperature is 70 ℃, the reaction pressure is 1.5MPa and 2.5MPa respectively and the reaction time is 2 hours.
Example 2
Weighing appropriate amount of Ni (NO) 3 ) 2 ·6H 2 O、K 2 Sn(OH) 6 、Ce(NO 3 ) 3 ·6H 2 O was dissolved in 500mL deionized water, wherein Ni (NO 3 ) 2 ·6H 2 The addition amount of O was 50g, ni (NO 3 ) 2 ·6H 2 O and K 2 Sn(OH) 6 Is 5:1, ni (NO) 3 ) 2 ·6H 2 O and Ce (NO) 3 ) 3 ·6H 2 The molar ratio of O is 30:1, stirring and dissolving are carried out, 250g of sodium carbonate is added after the sodium carbonate is completely dispersed, stirring is continued for 10 minutes, then the mixture is transferred into a reaction kettle, and the mixture is heated to 160 ℃ for reaction for 10 hours through programmed heating. After the reaction is finished, centrifugally separating the product, then washing the product with deionized water until the pH value of the filtrate is neutral, and drying the product at 110 ℃ for 12 hours to obtain the active component.
15g of active component is added into 85g of sepiolite carrier, the active component is mixed with sepiolite, ball-milled and mixed to 80 meshes, the product is roasted for 4 hours at 500 ℃, and the catalyst is obtained after molding.
In the catalyst prepared by the method, the loading of the active component is 15wt% based on 100% of the total weight of the catalyst, and the sepiolite component accounts for 85wt% of the total weight of the catalyst after roasting. Wherein NiO/SnO in the active component 2 The molar ratio of NiO/CeO is 5:1 2 The molar ratio of (2) was 30:1. In the catalyst, the grain size corresponding to the active component is 5-15 nm.
After the catalyst was produced, the catalyst evaluation method was the same as that of example 1 under 2.5 MPa. The conversion of maleic anhydride and the selectivity of succinic anhydride were examined and are shown in Table 1.
Example 3
Weighing appropriate amount of Ni (NO) 3 ) 2 ·6H 2 O、K 2 Sn(OH) 6 、Ce(NO 3 ) 3 ·6H 2 O was dissolved in 500mL deionized water, wherein Ni (NO 3 ) 2 ·6H 2 The addition amount of O was 50g, ni (NO 3 ) 2 ·6H 2 O and K 2 Sn(OH) 6 Is 8:1, ni (NO) 3 ) 2 ·6H 2 O and Ce (NO) 3 ) 3 ·6H 2 Molar ratio of OStirring and dissolving the mixture at a ratio of 20:1, adding 150g of sodium carbonate after the mixture is completely dispersed, continuously stirring the mixture for 10 minutes, transferring the mixture into a reaction kettle, and heating the mixture to 180 ℃ for reaction for 10 hours by programming. After the reaction is finished, centrifugally separating the product, then washing the product with deionized water until the pH value of the filtrate is neutral, and drying the product at 110 ℃ for 12 hours to obtain the active component.
Adding 30g of active component into 70g of silicon dioxide carrier, mixing the active component and silicon dioxide, ball-milling, mixing to 100 meshes, roasting at 500 ℃ for 4 hours, and forming to obtain the catalyst.
In the catalyst prepared by the method, the loading of the active component is 30wt% based on 100% of the total weight of the catalyst, and the silicon dioxide component accounts for 70wt% of the total weight of the catalyst after roasting. Wherein NiO/SnO in the active component 2 The molar ratio of NiO/CeO is 8:1 2 The molar ratio of (2) was 20:1. In the catalyst, the grain size corresponding to the active component is 5-15 nm.
After the catalyst was produced, the catalyst evaluation method was the same as that of example 1 under 2.5 MPa. The conversion of maleic anhydride and the selectivity of succinic anhydride were examined and are shown in Table 1.
Example 4
Weighing a proper amount of NiSO 4 ·6H 2 O、Na 2 Sn(OH) 6 、Ce 2 (SO 4 ) 3 ·8H 2 O is dissolved in 500mL deionized water, wherein NiSO 4 ·6H 2 The addition amount of O was 62.5g, niSO 4 ·6H 2 O and Na 2 Sn(OH) 6 In a molar ratio of 10:1, niSO 4 ·6H 2 O and Ce 2 (SO 4 ) 3 ·8H 2 The molar ratio of O is 50:1, stirring and dissolving are carried out, 187.5g of potassium hydroxide is added after the mixture is completely dispersed, stirring is continued for 10 minutes, then the mixture is transferred into a reaction kettle, and the mixture is heated to 170 ℃ for reaction for 4 hours through programmed heating. After the reaction is finished, centrifugally separating the product, then washing the product with deionized water until the pH value of the filtrate is neutral, and drying the product at 110 ℃ for 12 hours to obtain the active component.
Adding 40g of active component into 60g of sepiolite carrier, mixing the active component and sepiolite, ball-milling, mixing to 90 meshes, roasting at 350 ℃ for 8 hours, and forming to obtain the catalyst.
In the catalyst prepared by the method, the loading of the active component is 40wt% based on 100% of the total weight of the catalyst, and the sepiolite component accounts for 60wt% of the total weight of the catalyst after roasting. Wherein NiO/SnO in the active component 2 Molar ratio of NiO/CeO of 10 2 The molar ratio of (2) was 50. In the catalyst, the grain size corresponding to the active component is 5-15 nm.
After the catalyst was produced, the catalyst evaluation method was the same as that of example 1 under 2.5 MPa. The conversion of maleic anhydride and the selectivity of succinic anhydride were examined and are shown in Table 1.
Example 5
Weighing a proper amount of NiCl 2 ·6H 2 O、K 2 Sn(OH) 6 、CeCl 3 ·6H 2 O is dissolved in 500mL deionized water, wherein NiCl 2 ·6H 2 The addition amount of O is 42g, niCl 2 ·6H 2 O and K 2 Sn(OH) 6 In a molar ratio of 9:1, niCl 2 ·6H 2 O and CeCl 3 ·6H 2 The molar ratio of O is 40:1, stirring and dissolving are carried out, 168g of sodium carbonate is added after the mixture is completely dispersed, stirring is continued for 10 minutes, then the mixture is transferred into a reaction kettle, and the mixture is heated to 200 ℃ for reaction for 12 hours through programmed heating. After the reaction is finished, centrifugally separating the product, then washing the product with deionized water until the pH value of the filtrate is neutral, and drying the product at 110 ℃ for 12 hours to obtain the active component.
Adding 10g of active component into 90g of alumina carrier, mixing the active component with alumina, ball milling, mixing to 120 meshes, roasting at 650 ℃ for 2 hours, and forming to obtain the catalyst.
In the catalyst prepared by the method, the loading of the active component is 10wt% based on 100% of the total weight of the catalyst, and the alumina component accounts for 90wt% of the total weight of the catalyst after roasting. Wherein NiO/SnO in the active component 2 The molar ratio of NiO/CeO is 9:1 2 The molar ratio of (2) was 40:1. In the catalyst, the grain size corresponding to the active component is 5-15 nm.
After the catalyst was produced, the catalyst evaluation method was the same as that of example 1 under 2.5 MPa. The conversion of maleic anhydride and the selectivity of succinic anhydride were examined and are shown in Table 1.
Example 6
Weighing a proper amount of Ni (CH) 3 COO) 2 、K 2 Sn(OH) 6 、Ce(Ac) 3 ·nH 2 O was dissolved in 500mL deionized water, wherein Ni (CH 3 COO) 2 The addition amount of (C) is 50g, ni (NO) 3 ) 2 ·6H 2 O and K 2 Sn(OH) 6 Is 7:1, ni (CH) 3 COO) 2 And Ce (Ac) 3 ·nH 2 The molar ratio of O is 30:1, stirring and dissolving are carried out, 150g of sodium carbonate is added after the sodium carbonate is completely dispersed, stirring is continued for 10 minutes, then the mixture is transferred into a reaction kettle, and the mixture is heated to 170 ℃ for reaction for 8 hours through programmed heating. After the reaction is finished, centrifugally separating the product, then washing the product with deionized water until the pH value of the filtrate is neutral, and drying the product at 110 ℃ for 12 hours to obtain the active component.
Adding 20g of active components into 80g of active carbon carrier, mixing the active components with active carbon, ball-milling, mixing to 60 meshes, roasting at 500 ℃ for 4 hours, and forming to obtain the catalyst.
In the catalyst prepared by the method, the loading of the active component is 20wt% based on 100% of the total weight of the catalyst, and the active carbon component accounts for 80wt% of the total weight of the catalyst after roasting. Wherein NiO/SnO in the active component 2 The molar ratio of NiO/CeO is 7:1 2 The molar ratio of (2) was 30:1. In the catalyst, the grain size corresponding to the active component is 5-15 nm.
After the catalyst was produced, the catalyst evaluation method was the same as that of example 1 under 2.5 MPa. The conversion of maleic anhydride and the selectivity of succinic anhydride were examined and are shown in Table 1.
Comparative example 1
This comparative example is for illustration of a reference catalyst for the liquid phase hydrogenation of maleic anhydride to succinic anhydride and a method for preparing succinic anhydride.
Nickel nitrate (Ni (NO) 3 ) 2 ·3H 2 O) 290.79g and acidic silica sol (SiO 2 About 25% by mass) of 1165.48g was dissolved in 2000mL of deionized water to obtain a mixed solution. Firstly, putting the mixed solution into a reaction kettle, adding ammonium bicarbonate solution with the mass concentration of 10wt% into the mixed solution under continuous stirring, simultaneously raising the temperature of the reaction solution to 70 ℃ until the pH value reaches 7.2, continuously preserving heat and stirring for 1 hour after the addition is finished, filtering, washing, drying at 120 ℃ for 12 hours, and then mixing with CaCO (CaCO) 3 7.47g of the catalyst powder is mixed and molded, and then the mixture is roasted in a muffle furnace at 550 ℃ for 4 hours to obtain the catalyst powder. The catalyst contains NiO 20wt%, siO 2 78wt％、CaCO 3 2wt％。
After the catalyst was produced, the catalyst evaluation method was the same as that of example 1 under 2.5 MPa. The conversion of maleic anhydride and the selectivity of succinic anhydride were examined and are shown in Table 1.
Comparative example 2
This comparative example is for illustration of a reference catalyst for the liquid phase hydrogenation of maleic anhydride to succinic anhydride and a method for preparing succinic anhydride.
Nickel nitrate (Ni (NO) 3 ) 2 ·6H 2 O) 290.79g, acidic silica Sol (SiO) 2 1060.88g of the mixture is mixed and dissolved in 2000mL of deionized water to obtain a first mixed solution; potassium stannate (K) 2 Sn(OH) 6 ) 54.63g was dissolved in 250mL deionized water; firstly, putting a first mixed solution into a reaction kettle, adding a potassium stannate aqueous solution into the first mixed solution under continuous stirring, simultaneously raising the temperature of a reaction solution to 70 ℃, continuously adding an ammonium bicarbonate solution with the mass concentration of 10wt% after the addition is finished until the pH value reaches 7.2, and carrying out heat preservation and stirring for 1 hour after the addition is finished again to obtain a precipitate; filtering, washing, drying at 120 ℃ for 12 hours, and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain a catalyst; the catalyst contains NiO 20wt% and SnO based on the total weight of the catalyst 2 9wt％、SiO 2 71wt％。
After the catalyst was produced, the catalyst evaluation method was the same as that of example 1 under 2.5 MPa. The maleic anhydride conversion was determined to be the same as succinic anhydride selectivity as shown in Table 1.
Comparative example 3
This comparative example is for illustration of a reference catalyst for the liquid phase hydrogenation of maleic anhydride to succinic anhydride and a method for preparing succinic anhydride.
Nickel nitrate (Ni (NO) 3 ) 2 ·6H 2 O) 290.79g, acidic silica Sol (SiO) 2 1060.88g of the mixture is mixed and dissolved in 2000mL of deionized water to obtain a first mixed solution; potassium stannate (Ce (NO) 3 ) 3 ·6H 2 O) 88.24g are dissolved in 250mL deionized water; firstly, putting a first mixed solution into a reaction kettle, adding a potassium stannate aqueous solution into the first mixed solution under continuous stirring, simultaneously raising the temperature of a reaction solution to 70 ℃, continuously adding an ammonium bicarbonate solution with the mass concentration of 10wt% after the addition is finished until the pH value reaches 7.2, and carrying out heat preservation and stirring for 1 hour after the addition is finished again to obtain a precipitate; filtering, washing, drying at 120 ℃ for 12 hours, and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain a catalyst; the catalyst contains NiO 20wt% and CeO based on the total weight of the catalyst 2 9wt％、SiO 2 71wt％。
After the catalyst was produced, the catalyst evaluation method was the same as that of example 1 under 2.5 MPa. The maleic anhydride conversion was determined to be the same as succinic anhydride selectivity as shown in Table 1.
Table 1 comparative catalyst performance table
As can be seen from Table 1, the catalyst prepared in the example of the present invention has better maleic anhydride conversion rate and succinic anhydride selectivity than the catalyst prepared in the comparative example, and particularly, the sepiolite and alumina composite carrier of the present invention has the best performance under the specific Pd and Ni ratios.
The catalyst prepared by the embodiment of the invention has the advantages of small reaction pressure, low requirement on production equipment and production safety.
Compared with the catalyst prepared in the comparative example, the catalyst prepared in the embodiment of the invention has the advantages that the maleic anhydride conversion rate and the succinic anhydride selectivity are improved, and particularly, the succinic anhydride selectivity is improved, so that the catalyst has important significance in industrial production. Firstly, the yield of succinic anhydride can be improved, and the benefit is increased; secondly, the purity of the succinic anhydride product can be improved by improving the selectivity of the succinic anhydride, the subsequent purification process of the succinic anhydride product can be saved, and the cost is effectively saved.
Therefore, the maleic anhydride liquid phase catalytic hydrogenation catalyst has good industrial application value.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
Claims (11)
1. A maleic anhydride hydrogenation catalyst is characterized in that:
the catalyst comprises a carrier and an active component loaded on the carrier;
the active component comprises NiO and SnO 2 And CeO 2 ；
The loading of the active component is 5 to 50wt%, preferably 10 to 40wt%, more preferably 15 to 25wt%, based on 100% total weight of the catalyst.
2. The maleic anhydride hydrogenation catalyst according to claim 1, characterized in that:
of the active ingredients in the composition of the present invention,
NiO and SnO 2 The molar ratio of (2) is 5-10:1; preferably 5 to 6:1;
NiO and CeO 2 The molar ratio of (2) is 20-50:1; preferably 30 to 40:1.
3. The maleic anhydride hydrogenation catalyst according to claim 1, characterized in that:
in the catalyst, the particle size range of the active component is 5-15 nm.
4. The maleic anhydride hydrogenation catalyst according to claim 1, characterized in that:
the carrier is selected from one or a combination of sepiolite, alumina, silica or activated carbon.
5. The method for preparing a maleic anhydride hydrogenation catalyst according to any one of claims 1 to 4, characterized in that said method comprises the steps of:
(1) Dispersing an active nickel precursor, an active tin precursor and an active cerium precursor in water, adding a precipitator, uniformly stirring, performing hydrothermal reaction, and performing aftertreatment to obtain an active component;
(2) And mixing the active components with a carrier, performing ball milling and roasting to obtain the catalyst.
6. The method for preparing the maleic anhydride hydrogenation catalyst according to claim 5, wherein,
in the step (1), the step of (a),
the active nickel precursor is selected from at least one of soluble nickel salts; preferably at least one of nickel nitrate, nickel sulfate, nickel chloride or nickel acetate; and/or, the number of the groups,
the active tin precursor is selected from at least one of soluble tin salts; preferably at least one of potassium stannate or sodium stannate; and/or, the number of the groups,
the active cerium precursor is selected from at least one of soluble cerium salts; preferably at least one of cerium nitrate, cerium sulfate, cerium chloride or cerium acetate; and/or, the number of the groups,
the precipitant is selected from alkali soluble matter, preferably at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate or potassium hydroxide.
7. The method for preparing the maleic anhydride hydrogenation catalyst according to claim 5, wherein,
in the step (1), the step of (a),
the molar ratio of the active nickel precursor to the active tin precursor is 5-10:1; preferably 5 to 6:1;
the molar ratio of the active nickel precursor to the active cerium precursor is 20-50:1; preferably 30-40:1;
the mass ratio of the active nickel precursor to the precipitator is 1:2.5-1:5;
the mass ratio of the active nickel precursor to the water is 1:8-12.
8. The method for preparing the maleic anhydride hydrogenation catalyst according to claim 5, wherein,
in the step (1), the step of (a),
the temperature of the hydrothermal reaction is 150-200 ℃, preferably 160-190 ℃; the time is 4-12 hours.
9. The method for preparing the maleic anhydride hydrogenation catalyst according to claim 5, wherein,
in the step (2), the step of (C),
the addition amount of the active component is 5 to 50wt percent, preferably 10 to 40wt percent, based on 100 percent of the total weight of the raw materials in the step (2);
the ball milling is carried out until the ball milling is carried out to 40-120 meshes;
the roasting temperature is 350-650 ℃ and the roasting time is 2-8 hours.
10. A method for preparing succinic anhydride by maleic anhydride liquid phase hydrogenation, which is characterized by comprising the following steps:
the catalyst of any one of claims 1-4 or the catalyst prepared by the preparation method of any one of claims 5-9 after activation, hydrogen and maleic anhydride solution are subjected to contact reaction to prepare succinic anhydride.
11. The method for preparing succinic anhydride by liquid-phase hydrogenation of maleic anhydride according to claim 10, wherein the method comprises the following steps:
the pressure of the contact reaction is 1 to 5MPa, preferably 1 to 3MPa, more preferably 1 to 1.5MPa.
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