CN114471638B - Catalyst for synthesizing succinic acid (anhydride), preparation method and application - Google Patents

Catalyst for synthesizing succinic acid (anhydride), preparation method and application Download PDF

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CN114471638B
CN114471638B CN202210157513.8A CN202210157513A CN114471638B CN 114471638 B CN114471638 B CN 114471638B CN 202210157513 A CN202210157513 A CN 202210157513A CN 114471638 B CN114471638 B CN 114471638B
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CN114471638A (en
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李德宝
肖勇
张国权
贾丽涛
侯博
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Shanxi Institute of Coal Chemistry of CAS
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    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
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    • C07D307/60—Two oxygen atoms, e.g. succinic anhydride
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    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a catalyst for synthesizing succinic acid (anhydride), a preparation method and application thereof, and belongs to the technical field of catalyst synthesis. The acid and alkali properties of the catalyst surface are regulated by introducing solid alkali, and the synergistic effect of the components of the catalyst is promoted by introducing auxiliary agents. The catalyst preparation method of the invention adopts a method of liquid phase low temperature prereduction and then gas phase medium temperature phosphating to activate the metal compound of Ni, mo, co, W into metal phosphide, and uses alkali metal salt as solid alkali oxide and auxiliary salt as auxiliary oxide Nd 2 O 3 Or La (La) 2 O 3 Is supported on the catalyst. The synergistic effect of the metal phosphide, the solid alkali and the auxiliary agent in the catalyst ensures that the catalyst has the function of selective hydrogenation of C=C bonds at low temperature to generate succinic acid (anhydride). The succinic acid (anhydride) synthesized by the method has high purity and can be used as a raw material of C=C double bonds of degradable plastics.

Description

Catalyst for synthesizing succinic acid (anhydride), preparation method and application
Technical Field
The invention belongs to the technical field of catalyst synthesis, and particularly relates to a catalyst for synthesizing succinic acid (anhydride), a preparation method and application thereof.
Background
With the increasingly strict environmental protection requirements of China on the white pollution control of plastics, the development and the use of biodegradable plastics become the necessary requirements in the fields of plastic production and commerce. Along with the falling of various policy and regulations, the demands of biodegradable plastics such as polylactic acid, polycaprolactone, polybutylene succinate and the like are greatly increased. Compared with degradable plastics such as polylactic acid, the polybutylene succinate has excellent heat resistance, mechanical property and processing property, the demand of the polybutylene succinate is greatly increased, and the demand of the polybutylene succinate is expected to reach 300 ten thousand tons/year within five years.
Succinic acid is one of important raw materials for producing the poly (butylene succinate), and the demand quantity of the poly (butylene succinate) is greatly increased due to the pulling of the poly (butylene succinate) on the succinic acid demand, so that the annual demand quantity of the poly (butylene succinate) is expected to reach more than 100 ten thousand tons in the coming five years. With the development of economy and society, succinic acid and an extension product thereof are gradually applied to the fields of food, medicine, chemical industry and the like, but the consumption of succinic acid in China is only about 5 ten thousand tons/year at present, and the market gap is huge.
Industrial production methods of succinic acid include electrolytic synthesis, biological fermentation and catalytic hydrogenation. The electrolytic method has a plurality of production enterprises in China, but the electrolytic method has high power consumption, serious electrode corrosion, small production scale and high production cost, and is an obsolete production method. Although the biological fermentation method has a certain development prospect, the biological fermentation method has the problems of serious regional limitation, complex components of crude products, high separation cost, large wastewater quantity and the like. The hydro-synthesis method is the most common chemical synthesis method with the most economic advantage, and the technical route for synthesizing the succinic acid by hydrogenating the maleic acid (or synthesizing the succinic anhydride by hydrogenating the maleic anhydride and then hydrolyzing the succinic anhydride into the succinic acid) has the characteristics of high product purity and simple and efficient reaction process.
The key of the technology for synthesizing the succinic acid (anhydride) by hydrogenating the maleic acid (anhydride) is the development of a catalyst, and the noble metal catalyst has the characteristics of high hydrogenation activity and high product yield and is an important catalyst for synthesizing the succinic acid (anhydride). CN101844976a discloses a maleic acid aqueous hydrogenation catalyst containing noble metals such as Pd, pt, ru and the like and other transition metals as active components, CN111330580a discloses a maleic acid aqueous hydrogenation catalyst containing double active metal components such as noble metals Pt, pd and the like, CN102430404A discloses a maleic acid aqueous hydrogenation catalyst containing Ru and the like as active components, CN112479862A discloses a maleic acid aqueous hydrogenation catalyst containing noble metals such as Pt, pd, ir, ru and other metals as active components, CN101502802B discloses a maleic anhydride/gamma-butyrolactone aqueous hydrogenation catalyst containing noble metals such as Pt, pd, ru and the like and other metals as promoters, and CN103769105B discloses a maleic anhydride/gamma-butyrolactone aqueous hydrogenation catalyst containing noble metals such as Pt, pd, ir and the like and other metals as promoters.
Noble metal catalysts have high activity in maleic acid (anhydride) hydrogenation reactions, but the cost of the catalysts is high, so that the large-scale application of the catalysts is limited. The metal phosphide catalyst has noble metal-like properties and can be widely applied to the fields of oil product hydrofining, acetic acid hydrogenation to synthesize ethanol and the like. The key of the design and preparation of the metal phosphide catalyst for synthesizing the succinic acid (anhydride) by hydrogenating the maleic acid (anhydride) is to effectively control the hydrogenation selectivity of the active components of the catalyst, inhibit the generation of byproducts and improve the purity of the product, thereby simplifying the purification process and improving the economy of the whole process. The metal phosphide catalyst has two active sites, and the active sites of the metal phosphide have double bond hydrogenation capability on maleic acid (anhydride), so that succinic acid (anhydride) is selectively synthesized; the acid site on the surface of the catalyst and the metal phosphide cooperate to hydrogenate C=O bond of succinic acid (anhydride) to prepare gamma-butyrolactone, and the gamma-butyrolactone is further hydrogenated to prepare tetrahydrofuran, wherein the schematic diagram of the maleic anhydride hydrogenation reaction path is shown in figure 1. To synthesize succinic acid (anhydride) with high selectivity, the metal phosphide catalyst meets two basic requirements: firstly, the active components are highly dispersed, and succinic acid (anhydride) is efficiently synthesized; secondly, eliminating surface acid sites and inhibiting the generation of gamma-butyrolactone and tetrahydrofuran.
Disclosure of Invention
Aiming at the problems of high cost, difficult control of hydrogenation selectivity of catalyst active components and more byproducts in the process of synthesizing succinic acid (anhydride) by hydrogenating maleic acid (anhydride), the invention provides a metal phosphide catalyst, a preparation method and application thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the catalyst for synthesizing succinic acid (anhydride) consists of the following substances in parts by weight: transition metal phosphide, solid alkali metal oxide and auxiliary agent, wherein the carrier=0.057-0.177:0.045-0.083:0.006-0.026:0.750-0.892. The catalyst can synthesize the target product succinic acid (anhydride) with high selectivity, and meanwhile, the higher stability of the catalyst is ensured. The catalyst consists of a carrier, metal phosphide loaded on the carrier, solid alkali and an auxiliary agent. The carrier has the characteristic of high specific surface area, the phosphide has high double bond selective hydrogenation activity, the solid alkali can effectively inhibit C=O hydrogenation reaction, and the auxiliary agent has extremely high synergistic effect, so that the metal phosphide of the catalyst and the solid alkali are highly dispersed.
Further, the transition metal phosphide is one or a mixture of a plurality of Ni, co, mo, W phosphide in any proportion; the metal used for the solid alkali metal oxide is one of K, na, ca, mg; the auxiliary agent is one of Nd and La; the carrier is aluminum oxide, molecular sieve, silicon dioxide or zirconium oxide. Ni (Ni) 2 P、Co 2 The transition metal phosphide such as P has a noble metal-like effect and an excellent C=C double bond hydrogenation function; K. the effect of alkali metals such as Na is to form solid alkali, and inhibit the hydrogenation function of C=O bonds of the catalyst; the function of Nd and La is to form an auxiliary agent Nd 2 O 3 And La (La) 2 O 3 The dispersibility of the metal phosphide and the solid alkali can be obviously improved, the synergistic effect of each active component is enhanced, and the C=C double bond hydrogenation performance of the catalyst is effectively improved.
A method for preparing a catalyst for synthesizing succinic acid (anhydride), comprising the steps of:
step 1, adding a transition metal compound and diammonium phosphate into deionized water; then soaking the sample on a carrier in an equal volume, standing at room temperature, and drying for multiple times to obtain a sample 1;
step 2, adding the sample 1 into sodium borohydride solution, stirring for reduction, filtering, washing, standing at room temperature, and drying for multiple times to obtain a sample 2;
step 3, adding alkali metal salt and auxiliary agent salt into deionized water, immersing the mixture on the sample 2 in an equal volume, standing the mixture at room temperature, and drying the mixture for multiple times to obtain a sample 3;
step 4, sample 3 was taken at H 2 Heating up and reducing under atmosphere, then in H 2 After the atmosphere had cooled to room temperature, the mixture was cooled to room temperature with O 2 /N 2 And passivating to obtain the metal phosphide catalyst.
Further, the transition metal compound in the step 1 is one or a mixture of a plurality of nickel nitrate, cobalt nitrate, ammonium molybdate or ammonium metatungstate in any proportion; the mass ratio of the transition metal compound to the diammonium hydrogen phosphate in the step 1 is 0.034-0.115:0.0192-0.0750. The transition metal compound has good solubility and can provide excellent precursors for forming metal phosphide. The proportion of the transition metal compound and the diammonium phosphate can effectively form high-activity metal phosphide, and phosphide deviated from the proportion can cause incomplete formation of phosphide or excessively high phosphorus content of phosphide.
Further, the carrier in the step 1 is any one of aluminum oxide, molecular sieve, silicon dioxide or zirconium oxide.
Further, the concentration of the sodium borohydride solution in the step 2 is 0.2-0.4 mol/L; the dosage of the sodium borohydride is 2.6-25.4% of that of the transition metal compound; the reduction time of stirring reduction is 40-60 min. The low-temperature reduction of sodium borohydride can effectively pre-reduce the transition metal compound, the pre-reduction effect cannot be achieved if the dosage of sodium borohydride is too low or the stirring time is too short, and the active components are accumulated if the dosage of sodium borohydride is too high or the stirring time is too long.
Further, in the step 3, the alkali metal salt is any one of potassium nitrate, sodium nitrate, calcium nitrate and magnesium nitrate; the dosage of the alkali metal salt in the step 3 is 34.9-85.9% of that of the transition metal compound; the auxiliary salt in the step 3 is any one of neodymium nitrate or lanthanum nitrate; the dosage of the auxiliary salt is 5.6-21.1% of the transition metal compound. The proportion of the alkali metal salt, the auxiliary agent salt and the transition metal compound can effectively cooperate with the respective functions of the transition metal phosphide, the solid base and the auxiliary agent, thereby playing the comprehensive performance of the catalyst. The catalyst cannot effectively inhibit the hydrogenation reaction activity of the C=O bond if the alkali metal salt is used too low, and occupies the hydrogenation active site if the alkali metal salt is used too high, so that the comprehensive performance of the catalyst is reduced. The dosage of the auxiliary agent is required to be within the proper range, and the dispersity of the metal phosphide and the alkali metal cannot be effectively improved if the dosage is too low; if the dosage is too high, the alkali metal is agglomerated and cannot play a synergistic role.
Further, in step 4, at H 2 The specific operation of temperature rising reduction under atmosphere is as follows: heating to 340-420 ℃ at a speed of 0.5-2.0 ℃/min, and reducing for 5-8 h; h 2 Airspeed of 4000-6000 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The use of O 2 /N 2 The passivation specific operation is: with O 2 0.5 to 1.5 percent of O 2 /N 2 Passivating for 4-6 hours. The above reduction conditions are optimal conditions for efficient reduction of the metal phosphide precursor to metal phosphide. Exceeding the above reduction conditions may result in insufficient reduction to cause insufficient catalyst performance or excessive phosphating to cause a reduction in catalyst surface area. The passivation conditions are optimal conditions for effectively passivating the metal phosphide, and exceeding the conditions can lead to insufficient passivation of the catalyst, rapid oxidation after contacting air to generate combustion and excessive passivation activity reduction of the catalyst.
Further, the specific operation conditions of standing at room temperature and drying for multiple times in the step 1, the step 2 and the step 3 are that standing at room temperature for 3-6 hours, then drying at 30-60 ℃ for 2-5 hours, and then drying at 100-120 ℃ for 8-15 hours. The above conditions are optimal conditions for drying the catalyst, and exceeding the range can cause uneven distribution of active components in the drying process and cracking of the catalyst, and influence the effect of subsequent preparation conditions until the performance of the catalyst is affected.
The application of the catalyst for synthesizing succinic acid (anhydride) is applied to a fixed bed tubular reactor and the space velocity of hydrogen is 150-600 h -1 Pressure is 1.0 to the wholeUnder 5.0MPa, heating to a reaction temperature of 70-150 ℃ at a rate of 0.5-3 ℃/min, dissolving maleic acid with a concentration of 10-50% in water or a solvent to form a solution, and controlling the space velocity of maleic acid solution liquid to be 1.0-10.0 h -1 Is carried out in the presence of a catalyst; the solvent comprises any one of water, 1, 4-dioxane, dibutyl phthalate, gamma-butyrolactone, tetrahydrofuran or toluene. The fixed bed reactor can effectively exert the catalyst performance by adopting the reaction condition, reasonably match the hydrogenation performance and the isomerization performance of the catalyst, and achieve the best effect.
Compared with the prior art, the invention has the following advantages:
the invention applies metal phosphide to maleic acid (anhydride) hydrogenation dehydration to prepare succinic acid (anhydride), adjusts the acid-base on the surface of the catalyst by introducing solid base, and promotes the synergistic effect of the components of the catalyst by introducing auxiliary agents. The catalyst preparation method of the invention adopts a method of liquid phase low temperature prereduction and then gas phase medium temperature phosphating to activate the metal compound of Ni, mo, co, W into metal phosphide, and uses alkali metal salt as solid alkali oxide and auxiliary salt as auxiliary oxide Nd 2 O 3 Or La (La) 2 O 3 Is supported on the catalyst. The synergistic effect of the metal phosphide, the solid alkali and the auxiliary agent in the catalyst ensures that the catalyst has the function of selective hydrogenation of C=C bonds at low temperature to generate succinic acid (anhydride). The succinic acid (anhydride) synthesized by the method has high purity and can be used as a raw material of C=C double bonds of degradable plastics.
Drawings
FIG. 1 is a schematic diagram of the maleic anhydride hydrogenation reaction path.
Detailed Description
Example 1
The preparation method of the catalyst for synthesizing succinic anhydride by maleic anhydride hydrogenation comprises the following steps:
step 1, adding 4.18g of nickel nitrate and 2.84g of diammonium phosphate to 10mL of deionized water; then soaking the mixture on 14g of aluminum oxide in an equal volume, standing the mixture at room temperature for 4 hours, drying the mixture at 30 ℃ for 5 hours, and drying the mixture at 120 ℃ for 8 hours to obtain a sample 1;
step 2, adding the sample 1 into 20mL of 0.2mol/L sodium borohydride solution, stirring and reducing for 50min, filtering, washing, standing at room temperature for 5h, drying at 40 ℃ for 4h, and drying at 110 ℃ for 14h to obtain a sample 2;
step 3, adding 2.01g of sodium nitrate and 0.19g of neodymium nitrate into 10mL of deionized water, soaking the mixture on the sample 2 in an equal volume, standing the mixture at room temperature for 4 hours, drying the mixture at 50 ℃ for 5 hours, and drying the mixture at 110 ℃ for 9 hours to obtain a sample 3;
step 4, sample 3 was taken at H 2 Heating to 350 ℃ at a speed of 1.0 ℃/min under the atmosphere, reducing for 5h, and carrying out H 2 Space velocity of 5000h -1 Then at H 2 After the atmosphere had cooled to room temperature, the mixture was cooled to room temperature with O 2 O with a content of 0.5% 2 /N 2 Passivating for 4 hours to obtain the catalyst.
The obtained catalyst had a nickel phosphide content of 5.7wt%, a potassium sodium oxide content of 4.9wt%, a neodymium oxide content of 1.2wt% and a carrier aluminum oxide content of 88.2wt%.
2mL of the catalyst was packed in a fixed bed tubular reactor. The catalyst was used at a hydrogen space velocity of 200h -1 The pressure is 5.0MPa, the temperature is increased to 150 ℃ at 1.5 ℃/min, 30 percent maleic anhydride/tetrahydrofuran solution is used as the reaction raw material, and the airspeed is 1.0h -1 And (3) carrying out hydrogenation reaction. The reaction results are shown in Table 1.
Example 2
The preparation method of the catalyst for synthesizing succinic acid by maleic acid hydrogenation comprises the following steps:
step 1, 11.02g of cobalt nitrate and 7.50g of diammonium phosphate are added into 20mL of deionized water; then soaking the mixture on 13g of molecular sieve in an equal volume, standing the mixture at room temperature for 4 hours, drying the mixture at 50 ℃ for 4 hours, and drying the mixture at 110 ℃ for 8 hours to obtain a sample 1;
step 2, adding the sample 1 into 40mL of 0.4mol/L sodium borohydride solution, stirring and reducing for 60min, filtering, washing, standing at room temperature for 5h, drying at 30 ℃ for 5h, and drying at 120 ℃ for 15h to obtain a sample 2;
step 3, adding 5.32g of potassium nitrate and 1.34g of neodymium nitrate into 20mL of deionized water, soaking the mixture on the sample 2 in an equal volume, standing the mixture at room temperature for 4 hours, drying the mixture at 30 ℃ for 5 hours, and drying the mixture at 110 ℃ for 10 hours to obtain a sample 3;
step 4, sample 3 was taken at H 2 Heating to 420 ℃ at a speed of 0.5 ℃/min under the atmosphere, and reducing for 8h, H 2 Airspeed of 6000h -1 Then at H 2 After the atmosphere had cooled to room temperature, the mixture was cooled to room temperature with O 2 O with a content of 0.5% 2 /N 2 Passivating for 5h to obtain the catalyst.
The obtained catalyst contains 14.2wt% of cobalt phosphide, 8.3wt% of potassium oxide, 2.5wt% of neodymium oxide and 75.0wt% of carrier molecular sieve.
2mL of the catalyst was packed in a fixed bed tubular reactor. The catalyst was used at a hydrogen space velocity of 350h -1 The pressure is 3.0MPa, the temperature is increased to 70 ℃ at 1.0 ℃/min, 50 percent maleic acid/water solution is used as the reaction raw material, and the space velocity is 7.0h -1 And (3) carrying out hydrogenation reaction. The reaction results are shown in Table 1.
Example 3
The preparation method of the catalyst for synthesizing succinic anhydride by maleic anhydride hydrogenation comprises the following steps:
step 1, adding 3.40g of ammonium molybdate and 2.31g of diammonium phosphate to 14mL of deionized water; then soaking the mixture on 16g of silicon dioxide in an equal volume, standing the mixture at room temperature for 4 hours, drying the mixture at 40 ℃ for 5 hours, and drying the mixture at 100 ℃ for 11 hours to obtain a sample 1;
step 2, adding the sample 1 into 30mL of 0.2mol/L sodium borohydride solution, stirring and reducing for 50min, filtering, washing, standing at room temperature for 3h, drying at 60 ℃ for 4h, and drying at 110 ℃ for 8h to obtain a sample 2;
step 3, adding 4.93g of magnesium nitrate and 0.12g of lanthanum nitrate into 14mL of deionized water, soaking the mixture on the sample 2 in an equal volume, standing the mixture at room temperature for 5 hours, drying the mixture at 30 ℃ for 3 hours, and drying the mixture at 120 ℃ for 7 hours to obtain a sample 3;
step 4, sample 3 was taken at H 2 Heating to 360 ℃ at a speed of 2.0 ℃/min under the atmosphere, and reducing for 5h, H 2 Space velocity of 4000h -1 Then at H 2 After the atmosphere had cooled to room temperature, the mixture was cooled to room temperature with O 2 O with a content of 1.5% 2 /N 2 Passivating for 4 hours to obtain the catalyst.
The obtained catalyst had a molybdenum phosphide content of 10.7wt%, a magnesium oxide content of 6.2wt%, a lanthanum oxide content of 0.6wt%, and a carrier silicon dioxide content of 82.5wt%.
2mL of the catalyst was packed in a fixed bed tubular reactor. The catalyst was used at a hydrogen space velocity of 150h -1 The pressure is 2.0MPa, the temperature is increased to 90 ℃ at 1.5 ℃/min, 40 percent maleic anhydride/toluene solution is used as the reaction raw material, and the space velocity is 10.0h -1 And (3) carrying out hydrogenation reaction. The reaction results are shown in Table 1.
Example 4
The preparation method of the catalyst for synthesizing succinic anhydride by maleic anhydride hydrogenation comprises the following steps:
step 1, adding 5.15g of nickel nitrate, 6.39g of cobalt nitrate and 3.51g of diammonium hydrogen phosphate to 12mL of deionized water; then soaking the mixture on 12g of molecular sieve in an equal volume, standing the mixture at room temperature for 6 hours, drying the mixture at 30 ℃ for 5 hours, and drying the mixture at 100 ℃ for 8 hours to obtain a sample 1;
step 2, adding the sample 1 into 40mL of 0.3mol/L sodium borohydride solution, stirring and reducing for 40min, filtering, washing, standing at room temperature for 3h, drying at 60 ℃ for 3h, and drying at 110 ℃ for 10h to obtain a sample 2;
step 3, adding 3.92g of calcium nitrate and 1.20g of neodymium nitrate into 12mL of deionized water, soaking the mixture on the sample 2 in an equal volume, standing the mixture at room temperature for 3 hours, drying the mixture at 60 ℃ for 4 hours, and drying the mixture at 110 ℃ for 12 hours to obtain a sample 3;
step 4, sample 3 was taken at H 2 Heating to 400 ℃ at a speed of 1.5 ℃/min under the atmosphere, and reducing for 6h, H 2 Airspeed of 6000h -1 Then at H 2 After the atmosphere had cooled to room temperature, the mixture was cooled to room temperature with O 2 O with a content of 1.5% 2 /N 2 Passivating for 4 hours to obtain the catalyst.
The obtained catalyst contains 7.9wt% of nickel phosphide, 9.8wt% of cobalt phosphide, 4.5wt% of calcium oxide, 2.6wt% of neodymium oxide and 85.0wt% of carrier molecular sieve.
2mL of the catalyst was packed in a fixed bedIn the tubular reactor. The catalyst was used at a hydrogen space velocity of 600h -1 The pressure is 1.0MPa, the temperature is increased to 120 ℃ at 3.0 ℃/min, 20 percent of maleic anhydride/gamma-butyrolactone is used as the reaction raw material, and the space velocity is 7.0h -1 And (3) carrying out hydrogenation reaction. The reaction results are shown in Table 1.
Example 5
The preparation method of the catalyst for synthesizing succinic anhydride by maleic anhydride hydrogenation comprises the following steps:
step 1, adding 6.52g of cobalt nitrate and 1.77g of ammonium molybdate with 4.44g of diammonium phosphate to 20mL of deionized water; then soaking the mixture on 15g of aluminum oxide in an equal volume, standing the mixture at room temperature for 3 hours, drying the mixture at 50 ℃ for 6 hours, and drying the mixture at 100 ℃ for 10 hours to obtain a sample 1;
step 2, adding the sample 1 into 30mL of 0.3mol/L sodium borohydride solution, stirring and reducing for 50min, filtering, washing, standing for 4h at room temperature, drying for 5h at 60 ℃, and drying for 9h at 110 ℃ to obtain a sample 2;
step 3, adding 2.26g of potassium nitrate and 0.37g of lanthanum nitrate into 20mL of deionized water, soaking the mixture on the sample 2 in an equal volume, standing the mixture at room temperature for 4 hours, drying the mixture at 40 ℃ for 2 hours, and drying the mixture at 120 ℃ for 12 hours to obtain a sample 3;
step 4, sample 3 was taken at H 2 Heating to 340 ℃ at a speed of 2.0 ℃/min under the atmosphere, reducing for 5h, and carrying out H 2 Space velocity of 5000h -1 Then at H 2 After the atmosphere had cooled to room temperature, the mixture was cooled to room temperature with O 2 O with a content of 1.0% 2 /N 2 Passivating for 6 hours to obtain the catalyst.
The obtained catalyst comprises 8.1wt% of cobalt phosphide, 6.2wt% of molybdenum phosphide, 5.0wt% of potassium oxide, 0.8wt% of lanthanum oxide and 86.1wt% of alumina carrier.
2mL of the catalyst was packed in a fixed bed tubular reactor. The catalyst was used at a hydrogen space velocity of 400h -1 The pressure is 4.0MPa, the temperature is increased to 120 ℃ at 0.5 ℃/min, 10 percent maleic anhydride/dibutyl phthalate solution is used as the reaction raw material, and the space velocity is 6.0h -1 And (3) carrying out hydrogenation reaction. The reaction results are shown in Table 1.
Example 6
The preparation method of the catalyst for synthesizing succinic anhydride by maleic anhydride hydrogenation comprises the following steps:
step 1, adding 2.82g of ammonium metatungstate and 1.33g of ammonium molybdate and 1.92g of diammonium phosphate to 15mL of deionized water; then soaking the mixture on 11g of zirconia in an equal volume, standing the mixture at room temperature for 3 hours, drying the mixture at 50 ℃ for 3 hours, and drying the mixture at 110 ℃ for 10 hours to obtain a sample 1;
step 2, adding the sample 1 into 30mL of 0.4mol/L sodium borohydride solution, stirring and reducing for 40min, filtering, washing, standing for 5h at room temperature, drying for 3h at 40 ℃, and drying for 10h at 120 ℃ to obtain a sample 2;
step 3, adding 2.69g of sodium nitrate and 0.49g of lanthanum nitrate into 15mL of deionized water, soaking the mixture on the sample 2 in an equal volume, standing the mixture at room temperature for 3 hours, drying the mixture at 50 ℃ for 4 hours, and drying the mixture at 110 ℃ for 9 hours to obtain a sample 3;
step 4, sample 3 was taken at H 2 Heating to 390 ℃ at a speed of 1.0 ℃/min under the atmosphere, reducing for 6h, and obtaining H 2 Space velocity of 4000h -1 Then at H 2 After the atmosphere had cooled to room temperature, the mixture was cooled to room temperature with O 2 O with a content of 0.5% 2 /N 2 Passivating for 6 hours to obtain the catalyst.
The obtained catalyst comprises 3.4wt% of tungsten phosphide, 6.6wt% of molybdenum phosphide, 5.9wt% of sodium oxide, 1.5wt% of lanthanum oxide and 89.2wt% of carrier zirconium oxide.
2mL of the catalyst was packed in a fixed bed tubular reactor. The catalyst was used at a hydrogen space velocity of 300h -1 The pressure is 2.0MPa, the temperature is increased to 130 ℃ at 2.5 ℃/min, 30 percent maleic anhydride/1, 4-dioxane solution is used as the reaction raw material, and the airspeed is 5.0h -1 And (3) carrying out hydrogenation reaction. The reaction results are shown in Table 1.
The reaction results according to examples 1 to 6 are shown in Table 1. As can be seen from Table 1, the yield of succinic acid (anhydride) as catalyst was greater than 99.7%, and the product yield was extremely high.
TABLE 1 reaction results for examples 1-6
Examples Succinic acid (anhydride) yield (%) Yield of gamma-butyrolactone (%) Tetrahydrofuran yield (%)
Example 1 99.81 0.14 0.05
Example 2 99.71 0.16 0.13
Example 3 99.74 0.14 0.12
Example 4 99.79 0.19 0.02
Example 5 99.76 0.11 0.13
Example 6 99.80 0.09 0.11
What is not described in detail in the present specification belongs to the prior art known to those skilled in the art. While the foregoing describes illustrative embodiments of the present invention to facilitate an understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the embodiments, but is to be construed as protected by the accompanying claims insofar as various changes are within the spirit and scope of the present invention as defined and defined by the appended claims.

Claims (7)

1. The application of the catalyst in the synthesis of succinic anhydride is characterized in that: in the fixed bed tubular reactor, the hydrogen airspeed is 150-600 h -1 Under the pressure of 1.0-5.0 MPa, heating to the reaction temperature of 70-150 ℃ at the speed of 0.5-3 ℃/min, dissolving 10-50% maleic acid into the solvent to form a solution, and controlling the space velocity of the maleic acid solution to be 1.0-10.0 h -1 Is carried out in the presence of a catalyst; the solvent comprises any one of water, 1, 4-dioxane, dibutyl phthalate, gamma-butyrolactone, tetrahydrofuran or toluene;
the catalyst consists of the following substances in parts by weight: the transition metal phosphide comprises solid alkali metal oxide, auxiliary agent, carrier=0.057-0.177, 0.045-0.083, 0.006-0.026 and 0.750-0.892;
the transition metal phosphide is one or a mixture of a plurality of Ni, co, mo, W phosphides in any proportion; the metal used for the solid alkali metal or alkaline earth metal oxide is one of K, na, ca, mg; the auxiliary agent is one of Nd and La; the carrier is any one of aluminum oxide, molecular sieve, silicon dioxide or zirconium oxide.
2. Use of a catalyst according to claim 1 for the synthesis of succinic anhydride, characterized in that: the preparation method of the catalyst comprises the following steps:
step 1, adding a transition metal compound and diammonium phosphate into deionized water; then soaking the sample on a carrier in an equal volume, standing at room temperature, and drying for multiple times to obtain a sample 1;
step 2, adding the sample 1 into sodium borohydride solution, stirring for reduction, filtering, washing, standing at room temperature, and drying for multiple times to obtain a sample 2;
step 3, adding alkali metal or alkaline earth metal salt and auxiliary agent salt into deionized water, soaking the mixture on the sample 2 in an equal volume, standing the mixture at room temperature, and drying the mixture for multiple times to obtain a sample 3;
step 4, sample 3 was taken at H 2 Heating up and reducing under atmosphere, then in H 2 After the atmosphere had cooled to room temperature, the mixture was cooled to room temperature with O 2 /N 2 Passivating to obtain the metal phosphide catalyst;
the use of O 2 /N 2 The passivation specific operation is: with O 2 O with the content of 0.5-1.5% 2 /N 2 Passivating for 4-6 hours.
3. Use of a catalyst according to claim 2 for the synthesis of succinic anhydride, characterized in that: the transition metal compound in the step 1 is one or a mixture of a plurality of nickel nitrate, cobalt nitrate, ammonium molybdate or ammonium metatungstate in any proportion; in the step 1, the mass ratio of the transition metal compound to the diammonium hydrogen phosphate is 0.034-0.115:0.0192-0.0750.
4. Use of a catalyst according to claim 3 for the synthesis of succinic anhydride, characterized in that: the concentration of the sodium borohydride solution in the step 2 is 0.2-0.4 mol/L; the dosage of the sodium borohydride is 2.6% -25.4% of that of the transition metal compound; and the reduction time of stirring reduction is 40-60 min.
5. The use of a catalyst according to claim 4 for the synthesis of succinic anhydride, characterized in that: the alkali metal or alkaline earth metal salt in the step 3 is any one of potassium nitrate, sodium nitrate, calcium nitrate and magnesium nitrate; the dosage of the alkali metal or alkaline earth metal salt in the step 3 is 34.9% -85.9% of that of the transition metal compound; the auxiliary salt in the step 3 is any one of neodymium nitrate or lanthanum nitrate; the dosage of the auxiliary salt is 5.6% -21.1% of that of the transition metal compound.
6. The use of a catalyst according to claim 5 for the synthesis of succinic anhydride, characterized in that: in the step 4, at H 2 The specific operation of temperature rising reduction under atmosphere is as follows: heating to 340-420 ℃ at a speed of 0.5-2.0 ℃/min, and reducing for 5-8 h; h 2 Airspeed is 4000-6000 h -1 。
7. The use of a catalyst according to claim 6 for the synthesis of succinic anhydride, characterized in that: the specific operation conditions of standing at room temperature and drying for multiple times in the step 1, the step 2 and the step 3 are that standing at room temperature for 3-6 hours, then drying at 30-60 ℃ for 2-5 hours, and then drying at 100-120 ℃ for 8-15 hours.
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CN101502802A (en) * 2009-03-18 2009-08-12 山西大学 Catalyst for continuous production of succinic anhydride from hydrogenation of maleic anhydride and preparation method thereof
CN105251521A (en) * 2015-11-19 2016-01-20 中科合成油淮南催化剂有限公司 Loaded type transition metal phosphide catalyst as well as preparation method and application thereof
CN105709786A (en) * 2014-12-04 2016-06-29 中国石油化工股份有限公司 Catalyst for selective hydrogenation of butadiene and isomerization of 1-butylene, and preparation method and application thereof

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CN101502802A (en) * 2009-03-18 2009-08-12 山西大学 Catalyst for continuous production of succinic anhydride from hydrogenation of maleic anhydride and preparation method thereof
CN105709786A (en) * 2014-12-04 2016-06-29 中国石油化工股份有限公司 Catalyst for selective hydrogenation of butadiene and isomerization of 1-butylene, and preparation method and application thereof
CN105251521A (en) * 2015-11-19 2016-01-20 中科合成油淮南催化剂有限公司 Loaded type transition metal phosphide catalyst as well as preparation method and application thereof

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