CN116037151A - Selective hydrogenation catalyst and its preparation method and application - Google Patents

Selective hydrogenation catalyst and its preparation method and application Download PDF

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Publication number
CN116037151A
CN116037151A CN202111264834.XA CN202111264834A CN116037151A CN 116037151 A CN116037151 A CN 116037151A CN 202111264834 A CN202111264834 A CN 202111264834A CN 116037151 A CN116037151 A CN 116037151A
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catalyst
carrier
active
selective hydrogenation
hydrogenation catalyst
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朱跃辉
冯海强
赵开径
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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • 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
    • 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

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the technical field of catalysts, and provides a selective hydrogenation catalyst, a preparation method and application thereof. The selective hydrogenation catalyst comprises a carrier and an active component loaded on the carrier; the active component comprises Ni element and Pd element. Dispersing an active nickel precursor in water, adding a precipitator, uniformly stirring, performing hydrothermal reaction, and performing post-treatment to obtain a centrifugal separation product; mixing the centrifugal separation product with a carrier, ball milling, forming and roasting to obtain a roasted product; dispersing an active palladium precursor in water to obtain an active palladium precursor solution, immersing a calcined substance in the active palladium precursor solution, and drying to obtain the catalyst. The catalyst has the advantages of high catalytic activity and selectivity, simple preparation process and low price, and has the potential of industrial application.

Description

Selective hydrogenation catalyst and its preparation method and application
Technical Field
The invention relates to the technical field of catalysts, in particular to a selective hydrogenation catalyst, a preparation method and application thereof.
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.
The hydrolysate succinic acid of the succinic anhydride is the 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. Accordingly, the demand for succinic anhydride is also increasing year by year, and particularly high-purity succinic anhydride has high external dependence.
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, high product purity and the like, 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 selectivity of 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, and a proper catalyst needs to be searched for to improve the selectivity of the succinic anhydride.
Patent US5616730A discloses a process for preparing succinic anhydride, the catalyst being prepared as SiO 2 Nickel is loaded, pd or Pt is added as an auxiliary agent, and in the process conditions, the reaction conditions are more severe, the reaction pressure is up to 15MPa, and the process is neededSpecial requirements are imposed on the arrangement and the materials of the reactor, which limits the large-scale application of the reactor.
In the method disclosed in patent EP0691335B1, noble metal Pd is selected as a main active component to prepare the catalyst, and the hydrogenation selectivity is higher, but the dosage of the noble metal accounts for 3.0-10.0wt% of the total weight of the catalyst, so that the production cost is greatly increased, and industrialization is difficult to realize.
Patent CN109529850A discloses 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 in continuous mass production.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a selective hydrogenation catalyst, a preparation method and application thereof. The catalyst has the advantages of high catalyst activity and selectivity, simple preparation process and low catalyst price, and has the potential of industrial application.
It is an object of the present invention to provide a selective hydrogenation catalyst comprising a support and an active component supported on the support;
the active component comprises Ni element and Pd element;
the loading of the Ni element and the Pd element is 1.1 to 16wt%, such as 1.1wt%, 1.5wt%, 2wt%, 3wt%, 4wt%, 5wt%, 5.1wt%, 6wt%, 7wt%, 8wt%, 9wt%, 9.2wt%, 10wt%, 11wt%, 12wt%, 12.3wt%, 13wt%, 14wt%, 15wt%, 15.5wt%, 16wt%, and any range between any two values, based on 100% of the total weight of the catalyst; preferably 5.1 to 15.5wt%, more preferably 9.2 to 12.3wt%.
In the present invention, the catalyst may be added with other conventional active metal elements as required.
Preferably, the method comprises the steps of,
based on 100% of the total weight of the catalyst,
pd is supported in an amount of 0.1 to 1.0wt%, for example, may be 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, and any range between any two values; preferably 0.1 to 0.5wt%; more preferably 0.2 to 0.3wt%; and/or the number of the groups of groups,
the Ni loading is 1-15 wt%, such as 1wt%, 1.5wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, and any range between any two values; preferably 5 to 15wt%, more preferably 9 to 12wt%.
Preferably, the method comprises the steps of,
the carrier comprises a first carrier and a second carrier;
the carrier one is selected from sepiolite; and/or the number of the groups of groups,
the carrier II is at least one selected from alumina, silica and active carbon;
preferably, the mass ratio of the first carrier to the second carrier is 5:1-1:5. For example, can be 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, and any range between any two values.
In the invention, the sepiolite carrier has a fiber structure and an open porous network, so that the catalyst has good catalytic performance, especially the composite carrier formed by the sepiolite carrier and the alumina carrier, and the catalyst performance is better.
It is a second object of the present invention to provide a process for preparing a selective hydrogenation catalyst according to one of the objects of the present invention, comprising the steps of:
(1) Dispersing active nickel precursor in water, adding precipitant, stirring, hydrothermal reaction, post-treatment to obtain centrifugal separation product;
(2) Mixing the centrifugal separation product with a carrier, performing ball milling, forming and roasting to obtain a roasted product;
(3) Dispersing an active palladium precursor in water to obtain an active palladium precursor solution, immersing the calcined substance in the active palladium precursor solution, and drying 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.
The molding adopts the conventional common molding means, and the extrusion molding mode is adopted in the invention.
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 and nickel acetate; more preferably nickel nitrate; and/or, the number of the groups,
the precipitant is selected from alkali soluble matter, preferably at least one of sodium hydroxide, sodium bicarbonate, sodium carbonate, ammonium carbonate or potassium hydroxide.
Preferably, the method comprises the steps of,
in the step (1), the step of (a),
the mass ratio of the active nickel precursor to the precipitator is 1:2-1:3; and/or, the number of the groups,
the mass ratio of the active nickel precursor to water is 8-12:1.
Preferably, the method comprises the steps of,
in the step (1), the step of (a),
the temperature of the hydrothermal reaction is 150-220 ℃, preferably 150-180 ℃; the time is 6-12 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 mass ratio of the carrier to the centrifugal separation product is 1:5-15;
ball milling to 20-100 meshes;
the roasting temperature is 350-650 ℃ and the roasting time is 2-8 hours.
Preferably, the method comprises the steps of,
in the step (3), the step of (c),
the active palladium precursor is soluble palladium salt, preferably Na 2 PdCl 4 、PdCl 2 At least one of (a)The method comprises the steps of carrying out a first treatment on the surface of the And/or, the number of the groups,
the concentration of the active palladium precursor solution is 0.5-5g/L.
In the invention, the existing conventional impregnation conditions are adopted in the impregnation process of the active palladium precursor solution and the roasted product, and the volume ratio of the active palladium precursor solution to the roasted product is preferably 1:1;
in the present invention, the drying after impregnation adopts the conventional drying conditions, preferably the drying temperature is 80-120 ℃ and the time is 6-12 hours.
The invention further provides a method for preparing succinic anhydride by liquid-phase hydrogenation of maleic anhydride, which comprises the following steps:
the activated catalyst of one of the purposes of the invention or the catalyst prepared by the preparation method of the second of the purposes of the invention, hydrogen and maleic anhydride solution are subjected to contact reaction to prepare 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 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 components of the catalyst comprise Ni and Pd, and the catalytic effect of the catalyst is further improved through the special proportion of the two components.
2. The noble metal Pd of the catalyst of the invention has small dosage, so that the catalyst has low overall price and is beneficial to industrial application.
3. The invention changes the traditional catalyst preparation process, firstly prepares NiO active components by a hydrothermal method, then ball-mills with a specific composite carrier, and then loads PdO active components by an impregnation method to prepare the novel Pd-Ni/carrier catalyst, wherein active component grains of the supported catalyst are nano-sized, are uniformly distributed, have better catalytic active centers with better polydispersity, and have good coking resistance, and the preparation process is simple and practical.
4. 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.
Example 1
100 g of Ni (NO) was weighed out 3 ) 2 ·6H 2 O is dissolved in 1000mL deionized water, stirred and dissolved, 250 g KOH is completely dispersed, the mixture is continuously stirred for 10 minutes and then transferred into a reaction kettle, and the mixture is heated to 180 ℃ for reaction for 10 hours by programming. After the reaction is finished, centrifugal separation is carried out, deionized water is used for washing until the pH value of the filtrate is neutral, and the product is dried at 110 ℃ for 12 hours, thus obtaining a centrifugal separation product.
Mixing 50 g of the centrifugal separation product and 341.99 g of sepiolite (Spt)/alumina (mixed carrier, the mass ratio of sepiolite to alumina is 2:1), grinding to 6And (3) forming by 0 meshes, and roasting at 500 ℃ for 4 hours for later use to obtain a roasted product. Another 0.42L Na 2 PdCl 4 Soaking the prepared solution with the concentration of 2g/L into the roasted material, and drying at constant temperature after 3 hours to finally obtain the Pd-Ni/Spt-Al catalyst.
Pd in the obtained catalyst accounts for 0.2wt% of the catalyst; ni accounts for 10wt% of the catalyst; the rest is sepiolite (Spt)/alumina mixed carrier.
After the catalyst was prepared, the catalyst activity 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 a proper amount of 125 g Ni (NO) 3 ) 2 ·6H 2 O is dissolved in 1000mL of deionized water, stirred and dissolved, 250 g of NaOH is added after the O is completely dispersed, the mixture is continuously stirred for 10 minutes and then transferred into a reaction kettle, and the mixture is heated to 170 ℃ for reaction for 10 hours through programmed heating. After the reaction is finished, centrifugal separation is carried out, deionized water is used for washing until the pH value of the filtrate is neutral, and the product is dried at 110 ℃ for 12 hours, thus obtaining a centrifugal separation product.
Mixing 50 g of the centrifugal separation product and 276.34 g of sepiolite (Spt)/alumina (mixed carrier, mass ratio of sepiolite to alumina is 1:1), grinding to 40 meshes, molding, roasting at 500 ℃ for 4 hours for later use, and obtaining a roasted product. Weighing 0.50L of Na 2 PdCl 4 Preparing a solution with the concentration of 3g/L, immersing the solution into the roasted product, and drying the roasted product at constant temperature after 3 hours to finally obtain the Pd-Ni/Spt-Al catalyst.
Pd in the obtained catalyst accounts for 0.3wt% of the catalyst; ni accounts for 12wt% of the catalyst; the rest is sepiolite (Spt)/alumina mixed carrier.
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.
Example 3
100 g of Ni (CH) was weighed out 3 COO) 2 Dissolving in 1000mL deionized water, stirring for dissolving, adding 300 g of sodium carbonate after the sodium carbonate is completely dispersed, continuously stirring for 10 minutes, transferring to a reaction kettle, and heating to 150 ℃ for reaction for 12 hours by programming. After the reaction is finished, centrifugal separation is carried out, deionized water is used for washing until the pH value of the filtrate is neutral, and the product is dried at 110 ℃ for 12 hours, thus obtaining a centrifugal separation product.
Mixing 50 g of the centrifugal separation product and 785.57.9 g of sepiolite (Spt)/alumina (mixed carrier, the mass ratio of sepiolite to alumina is 5:1), grinding to 80 meshes, molding, roasting at 500 ℃ for 4 hours, and obtaining a roasted product. Weighing 0.80L of Na 2 PdCl 4 Preparing a solution with the concentration of 5g/L, immersing the solution into the roasted product, and drying the roasted product at constant temperature after 3 hours to finally obtain the Pd-Ni/Spt-Al catalyst.
Pd in the obtained catalyst accounts for 0.5wt% of the catalyst; ni accounts for 5wt% of the catalyst; the rest is sepiolite (Spt)/alumina mixed carrier.
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.
Example 4
Weigh 83 grams of NiCl 2 ·6H 2 O is dissolved in 1000mL of deionized water, stirred and dissolved, 200 g of sodium bicarbonate is added after the O is completely dispersed, the mixture is continuously stirred for 10 minutes and then transferred into a reaction kettle, and the mixture is heated to 180 ℃ for reaction for 10 hours through programmed heating. After the reaction is finished, centrifugal separation is carried out, deionized water is used for washing until the pH value of the filtrate is neutral, and the product is dried at 110 ℃ for 12 hours, thus obtaining a centrifugal separation product.
Mixing 50 g of the centrifugal separation product and 490.98 g of sepiolite (Spt)/alumina (mixed carrier, the mass ratio of sepiolite to alumina is 1:3), grinding to 20 meshes, molding, and roasting at 500 ℃ for 5 hours for later use to obtain a roasted product. Weighing 0.50L of Na 2 PdCl 4 Preparing a solution with the concentration of 4g/L, immersing the solution into the roasted product, and drying the soaked solution at constant temperature for 3 hours to finally obtain the Pd-Ni/Spt-Al catalyst.
Pd in the obtained catalyst accounts for 0.4 weight percent of the catalyst; ni accounts for 8wt% of the catalyst; the rest is sepiolite (Spt)/alumina mixed carrier.
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.
Example 5
Weigh 100 grams of NiSO 4 ·6H 2 O is dissolved in 1000mL of deionized water, stirred and dissolved, 225 g of KOH is added after the O is completely dispersed, the mixture is continuously stirred for 10 minutes and then transferred into a reaction kettle, and the mixture is heated to 180 ℃ for reaction for 10 hours through programmed heating. After the reaction is finished, centrifugal separation is carried out, deionized water is used for washing until the pH value of the filtrate is neutral, and the product is dried at 110 ℃ for 12 hours, thus obtaining a centrifugal separation product.
Mixing 50 g of the centrifugal separation product and 211.6 g of sepiolite (Spt)/alumina (mixed carrier, the mass ratio of the sepiolite to the alumina is 1:5), grinding to 60 meshes, molding, and roasting at 500 ℃ for 4 hours for later use to obtain a roasted product. Weighing 0.27L of Na 2 PdCl 4 Preparing a solution with the concentration of 1g/L, immersing the solution into the roasted product, and drying the roasted product at constant temperature after 3 hours to finally obtain the Pd-Ni/Spt-Al catalyst.
Pd in the obtained catalyst accounts for 0.1 weight percent of the catalyst; ni accounts for 15wt% of the catalyst; the rest is sepiolite (Spt)/alumina mixed carrier.
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.
Example 6
100 g of Ni (NO) was weighed out 3 ) 2 ·6H 2 O is dissolved in 1000mL of deionized water, stirred and dissolved, 250 g of KOH is added after the O is completely dispersed, the mixture is continuously stirred for 10 minutes and then transferred into a reaction kettle, and the mixture is heated to 220 ℃ for reaction for 6 hours by programming. After the reaction is finished, centrifugal separation is carried out, deionized water is used for washing until the pH value of the filtrate is neutral, and the product is dried at 110 ℃ for 12 hours, thus obtaining a centrifugal separation product.
Mixing 50 g of the centrifugal separation product and 385.56 g of sepiolite (Spt)/alumina (mixed carrier, the mass ratio of sepiolite to alumina is 1:2), grinding to 60 meshes, molding, and roasting at 500 ℃ for 4 hours for later use to obtain a roasted product. Weighing 0.46L of Na 2 PdCl 4 Preparing a solution with the concentration of 2g/L, immersing the solution into the roasted product, and drying the roasted product at constant temperature after 3 hours to finally obtain the Pd-Ni/Spt-Al catalyst.
Pd in the obtained catalyst accounts for 0.2wt% of the catalyst; ni accounts for 9wt% of the catalyst; the rest is sepiolite (Spt)/alumina mixed carrier.
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.
Example 7
100 g of Ni (NO) was weighed out 3 ) 2 ·6H 2 O is dissolved in 1000mL of deionized water, stirred and dissolved, 250 g of KOH is added after the O is completely dispersed, the mixture is continuously stirred for 10 minutes and then transferred into a reaction kettle, and the mixture is heated to 180 ℃ for reaction for 4 hours through programmed heating. After the reaction is finished, centrifugal separation is carried out, deionized water is used for washing until the pH value of the filtrate is neutral, and the product is dried at 110 ℃ for 12 hours, thus obtaining a centrifugal separation product.
Mixing 50 g of the centrifugal separation product and 276.34 g of sepiolite (Spt)/active carbon (mixed carrier, the mass ratio of sepiolite to active carbon is 1:1), grinding to 100 meshes, molding, and roasting at 650 ℃ for 2 hours for later use to obtain a roasted product. Weighing 0.50L of Na 2 PdCl 4 Preparing a solution with the concentration of 3g/L, immersing the solution into the roasted product, and drying the roasted product at constant temperature after 3 hours to finally obtain the Pd-Ni/Spt-S catalyst.
Pd in the obtained catalyst accounts for 0.3wt% of the catalyst; ni accounts for 12wt% of the catalyst; the rest is sepiolite (Spt)/active carbon mixed carrier.
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.
Example 8
100 g of Ni (NO) was weighed out 3 ) 2 ·6H 2 O is dissolved in 1000mL of deionized water, stirred and dissolved, 250 g of KOH is added after the O is completely dispersed, the mixture is continuously stirred for 10 minutes and then transferred into a reaction kettle, and the mixture is heated to 180 ℃ for reaction for 4 hours through programmed heating. After the reaction is finished, centrifugal separation is carried out, deionized water is used for washing until the pH value of the filtrate is neutral, and the product is dried at 110 ℃ for 12 hours, thus obtaining a centrifugal separation product.
Mixing 50 g of the centrifugal separation product and 276.34 g of sepiolite (Spt)/silicon dioxide (mixed carrier, the mass ratio of the sepiolite to the silicon dioxide is 1:1), grinding to 80 meshes, molding, and roasting at 450 ℃ for 5 hours for later use to obtain a roasted product. Weighing 0.50L of Na 2 PdCl 4 Preparing a solution with the concentration of 3g/L, immersing the solution into the roasted product, and drying the roasted product at constant temperature after 3 hours to finally obtain the Pd-Ni/Spt-S catalyst.
Pd in the obtained catalyst accounts for 0.3wt% of the catalyst; ni accounts for 12wt% of the catalyst; the rest is sepiolite (Spt)/silicon dioxide mixed carrier.
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 1
The carrier of example 1 was replaced with pure aluminum powder, the nickel precursor precipitation temperature was changed to 60 ℃, and the remaining parameters were unchanged.
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 2
The carrier in example 2 was replaced with pure silicon powder, the nickel precursor precipitation temperature was changed to 60 ℃, and the remaining parameters were unchanged.
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
The nickel precursor precipitation temperature in example 1 was changed to 60 ℃ and the remaining parameters were unchanged.
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 4
The alumina support in example 1 was replaced with sepiolite of equal mass, the remaining parameters being unchanged.
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
Catalyst Maleic anhydride conversion (%) Succinic anhydride selectivity (%)
Example 1 (2.5 MPa) 100 99.60
Example 1 (1.5 MPa) 100 99.30
Example 2 (2.5 MPa) 100 98.50
Example 3 (2.5 MPa) 99.20 99.00
Example 4 (2.5 MPa) 100 98.90
Example 5 (2.5 MPa) 98.60 98.50
Example 6 (2.5 MPa) 99.60 99.10
Example 7 (2.5 MPa) 99.30 99.00
Example 8 (2.5 MPa) 98.90 99.10
Comparative example 1 (2.5 MPa) 97.10 95.60
Comparative example 2 (2.5 MPa) 98.60 97.60
Comparative example 3 (2.5 MPa) 97.60 98.00
Comparative example 4 (2.5 MPa) 98.30 98.10
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 catalyst prepared in the example 1 of the present invention has the best performance under the specific Pd and Ni ratio of sepiolite and alumina composite carrier.
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.
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 selective hydrogenation catalyst characterized by:
the catalyst comprises a carrier and an active component loaded on the carrier;
the active component comprises Ni element and Pd element;
the loading of the Ni element and Pd element is 1.1 to 16wt%, preferably 5.1 to 15.5wt%, more preferably 9.2 to 12.3wt%, based on 100% of the total weight of the catalyst.
2. The selective hydrogenation catalyst of claim 1, wherein:
based on 100% of the total weight of the catalyst,
pd is supported in an amount of 0.1 to 1.0wt%, preferably 0.1 to 0.5wt%; more preferably 0.2 to 0.3wt%; and/or the number of the groups of groups,
the Ni loading is 1 to 15wt%, preferably 5 to 15wt%, more preferably 9 to 12wt%.
3. The selective hydrogenation catalyst of claim 1, wherein:
the carrier comprises a first carrier and a second carrier;
the carrier one is selected from sepiolite; and/or the number of the groups of groups,
the carrier II is at least one selected from alumina, silica and active carbon;
preferably, the mass ratio of the first carrier to the second carrier is 5:1-1:5.
4. A process for the preparation of a selective hydrogenation catalyst according to any of claims 1-3, characterized in that said process comprises the steps of:
(1) Dispersing active nickel precursor in water, adding precipitant, stirring, hydrothermal reaction, post-treatment to obtain centrifugal separation product;
(2) Mixing the centrifugal separation product with a carrier, performing ball milling, forming and roasting to obtain a roasted product;
(3) Dispersing an active palladium precursor in water to obtain an active palladium precursor solution, immersing the calcined substance in the active palladium precursor solution, and drying to obtain the catalyst.
5. The process for preparing a selective hydrogenation catalyst according to claim 4, 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 and nickel acetate; more preferably nickel nitrate; and/or, the number of the groups,
the precipitant is selected from alkali soluble matter, preferably at least one of sodium hydroxide, sodium bicarbonate, sodium carbonate, ammonium carbonate or potassium hydroxide.
6. The process for preparing a selective hydrogenation catalyst according to claim 4, wherein,
in the step (1), the step of (a),
the mass ratio of the active nickel precursor to the precipitator is 1:2-1:3; and/or, the number of the groups,
the mass ratio of the active nickel precursor to water is 8-12:1.
7. The process for preparing a selective hydrogenation catalyst according to claim 4, wherein,
in the step (1), the step of (a),
the temperature of the hydrothermal reaction is 150-220 ℃, preferably 150-180 ℃; the time is 6-12 hours.
8. The process for preparing a selective hydrogenation catalyst according to claim 4, wherein,
in the step (2), the step of (C),
the mass ratio of the carrier to the centrifugal separation product is 1:5-15;
ball milling to 20-100 meshes;
the roasting temperature is 350-650 ℃ and the roasting time is 2-8 hours.
9. The process for preparing a selective hydrogenation catalyst according to claim 4, wherein,
in the step (3), the step of (c),
the active palladium precursor is soluble palladium salt, preferably Na 2 PdCl 4 、PdCl 2 At least one of (a) and (b); and/or, the number of the groups,
the concentration of the active palladium precursor solution is 0.5-5g/L.
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 1-3 or the catalyst prepared by the preparation method of any one of claims 4-9 after activation, hydrogen and maleic anhydride solution are subjected to contact reaction to prepare succinic anhydride.
11. The method for preparing succinic anhydride by maleic anhydride liquid-phase hydrogenation according to claim 10, wherein,
the pressure of the contact reaction is 1 to 5MPa, preferably 1 to 3MPa, more preferably 1 to 1.5MPa.
CN202111264834.XA 2021-10-28 2021-10-28 Selective hydrogenation catalyst and its preparation method and application Pending CN116037151A (en)

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