CN114471638A - Catalyst for synthesizing succinic acid (anhydride) and preparation method and application thereof - Google Patents

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

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CN114471638A
CN114471638A CN202210157513.8A CN202210157513A CN114471638A CN 114471638 A CN114471638 A CN 114471638A CN 202210157513 A CN202210157513 A CN 202210157513A CN 114471638 A CN114471638 A CN 114471638A
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catalyst
anhydride
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succinic acid
drying
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CN114471638B (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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Abstract

The invention discloses a catalyst for synthesizing succinic acid (anhydride), a preparation method and application thereof, belonging to the technical field of catalyst synthesis. The acid-base property of the surface of the catalyst is adjusted by introducing solid base, and the synergistic effect of each component of the catalyst is promoted by introducing an auxiliary agent. The preparation method of the catalyst adopts the method of liquid-phase low-temperature pre-reduction and gas-phase medium-temperature carbonization to activate metal compounds of Ni, Mo, Co and W into metal phosphide, and uses solid alkali oxide as alkali metal salt and Nd as auxiliary agent oxide as auxiliary agent salt2O3Or La2O3Is immobilized on a catalyst. The synergistic effect of the metal phosphide, the solid alkali and the assistant in the catalyst of the invention enables the catalyst to have 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 for degradable plastics with C ═ C double bonds.

Description

Catalyst for synthesizing succinic acid (anhydride) and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalyst synthesis, and particularly relates to a catalyst for synthesizing succinic acid (anhydride), and a preparation method and application thereof.
Background
With the increasingly strict environmental protection requirements of our country on the treatment of white pollution of plastics, the development and use of biodegradable plastics become necessary requirements in the fields of plastic production and commerce. With the falling of various policy and regulations, the demand for biodegradable plastics such as polylactic acid, polycaprolactone, polybutylene succinate and the like will increase greatly. Compared with degradable plastics such as polylactic acid and the like, the poly (butylene succinate) has excellent heat resistance, mechanical properties and processability, the demand of the poly (butylene succinate) is greatly increased, and the demand of the poly (butylene succinate) in five years is expected to reach 300 ten thousand tons/year.
Succinic acid is one of important raw materials for producing polybutylene succinate, and the demand of the polybutylene succinate is greatly increased due to the pulling of the polybutylene succinate on the demand of the succinic acid, so that the annual demand of more than 100 million tons can be expected in the next five years. With the development of economic society, succinic acid and its extended products will be 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 million tons/year, and the market gap is huge.
The industrial production method of succinic acid includes electrolytic synthesis method, biological fermentation method and catalytic hydrogenation method. A plurality of electrolytic process production enterprises in China exist, but the electrolytic process has high power consumption, serious electrode corrosion, small production scale and high production cost, and is a production method which is being eliminated. Although the biological fermentation method has a certain development prospect, the problems of serious regional limitation, complex crude product components, high separation cost, large wastewater quantity and the like exist. The hydrogenation synthesis method is the most conventional and economically advantageous chemical synthesis method, and the technical route of the maleic acid hydrogenation synthesis of the succinic acid (or the maleic anhydride hydrogenation synthesis of the succinic anhydride and then the hydrolysis of 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 succinic acid (anhydride) by maleic acid (anhydride) hydrogenation 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 succinic acid (anhydride) synthesis catalyst. CN101844976A discloses a maleic acid aqueous solution hydrogenation catalyst containing noble metals such as Pd, Pt, Ru, etc. and other transition metals as active components, CN111330580A discloses a maleic acid aqueous solution hydrogenation catalyst containing noble metals such as Pt, Pd, etc. and other active metal components, CN102430404A discloses a maleic acid aqueous solution hydrogenation catalyst containing Ru as active components, CN112479862A discloses a maleic acid aqueous solution hydrogenation catalyst containing noble metals such as Pt, Pd, Ir, Ru, etc. and other metals as active components, CN101502802B discloses a maleic anhydride/γ -butyrolactone aqueous solution hydrogenation catalyst containing noble metals such as Pt, Pd, Ru, etc. and other metals as promoters, and CN103769105B discloses a maleic anhydride/γ -butyrolactone aqueous solution hydrogenation catalyst containing noble metals such as Pt, Pd, Ir, etc. and other metals as promoters.
The noble metal catalyst has higher activity in the hydrogenation reaction of maleic acid (anhydride), but the cost of the catalyst is high, so that the large-scale application of the catalyst is limited to a certain extent. The metal phosphide catalyst has the property of similar noble metal and can be widely applied to the fields of oil product hydrofining, acetic acid hydrogenation synthesis of ethanol and the like. The key points of the design and preparation of the maleic acid (anhydride) hydrogenation synthesis succinic acid (anhydride) metal phosphide catalyst lie in effectively controlling the hydrogenation selectivity of the active component of the catalyst, inhibiting the generation of byproducts and improving 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 the double bond hydrogenation capacity to maleic acid (anhydride) to selectively synthesize succinic acid (anhydride); the acid sites on the surface of the catalyst and the metal phosphide act synergistically to hydrogenate C ═ O bonds of succinic acid (anhydride) to synthesize gamma-butyrolactone, and the gamma-butyrolactone is further hydrogenated to synthesize tetrahydrofuran, as shown in FIG. 1, a schematic diagram of a maleic anhydride hydrogenation reaction path is shown in FIG. 1. For the high-selectivity synthesis of succinic acid (anhydride), the metal phosphide catalyst needs to meet two basic requirements: firstly, the active components are highly dispersed, and succinic acid (anhydride) is efficiently synthesized; and secondly, eliminating surface acid sites and inhibiting the generation of gamma-butyrolactone and tetrahydrofuran.
Disclosure of Invention
The invention provides a metal phosphide catalyst, a preparation method and application thereof, aiming at the problems of high cost of a catalyst for synthesizing succinic acid (anhydride) by maleic acid (anhydride) hydrogenation, difficult control of hydrogenation selectivity of active components of the catalyst and more byproducts.
In order to achieve the purpose, the invention adopts the following technical scheme:
a catalyst for synthesizing succinic acid (anhydride) is composed of the following substances in parts by weight: transition metal phosphide, solid alkali metal oxide, auxiliary agent, carrier and carrier, wherein the carrier is 0.057-0.177, 0.045-0.083, 0.006-0.026 and 0.750-0.892. The catalyst can synthesize the target product succinic acid (anhydride) with high selectivity, and simultaneously ensures higher stability of the catalyst. 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 assistant has extremely high synergistic effect and highly disperses the metal phosphide and the solid alkali of the catalyst.
Further, the transition metal phosphide is one or a mixture of more of Ni, Co, Mo and W phosphide in any proportion; the metal used by the solid alkali metal oxide is one of K, Na, Ca and Mg; the auxiliary agent is one of Nd and La; the carrier is aluminum oxide, molecular sieve, silicon dioxide or zirconium oxide. Ni2P、Co2P, etcThe transition metal phosphide has a noble metal-like effect and has an excellent C ═ C double bond hydrogenation function; K. the function of alkali metals such as Na is to form solid alkali and inhibit the C ═ O bond hydrogenation function of the catalyst; nd and La are used for forming auxiliary agent Nd2O3And La2O3The catalyst can obviously improve the dispersibility of metal phosphide and solid alkali, strengthen the synergistic effect of each active component and effectively improve the C-C double bond hydrogenation performance of the catalyst.
A preparation method of a catalyst for synthesizing succinic acid (anhydride) comprises the following steps:
step 1, adding a transition metal compound and diammonium hydrogen phosphate into deionized water; then soaking the carrier in the same volume, standing at room temperature, and drying for multiple times to obtain a sample 1;
step 2, adding the sample 1 into a sodium borohydride solution, stirring and reducing, 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, then soaking the deionized water on the sample 2 in the same volume, standing the sample at room temperature, and drying the sample for multiple times to obtain a sample 3;
step 4, sample 3 is placed in H2Reducing at elevated temperature under the atmosphere, and then carrying out reduction at H2After the atmosphere is cooled to room temperature, use O2/N2And passivating to obtain the metal phosphide catalyst.
Further, the transition metal compound in the step 1 is one or a mixture of several 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. The transition metal compound has good solubility and can provide an excellent precursor for forming metal carbide phosphide. The proportion of the transition metal compound and the diammonium hydrogen phosphate can effectively form high-activity metal phosphide, and phosphide deviating from the proportion can cause incomplete phosphide formation or overhigh phosphorus content of phosphide.
Further, in the step 1, the carrier 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 to 25.4 percent 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, if the dosage of sodium borohydride is too low or the stirring time is too short, the pre-reduction effect cannot be achieved, and if the dosage of sodium borohydride is too high or the stirring time is too long, the aggregation of the active component is caused.
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 to 85.9 percent of that of the transition metal compound; the auxiliary agent salt in the step 3 is any one of neodymium nitrate or lanthanum nitrate; the dosage of the auxiliary agent 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 alkali and the auxiliary agent, and the comprehensive performance of the catalyst is exerted. If the dosage of the alkali metal salt is too low, the alkaline site is insufficient, the catalyst can not effectively inhibit the hydrogenation reaction activity of C ═ O bonds, and if the dosage of the alkali metal salt is too high, the hydrogenation active site is occupied, so that the comprehensive performance of the catalyst is reduced. The dosage of the auxiliary agent needs to be within the proper range, and if the dosage is too low, the dispersibility of the metal phosphide and the alkali metal cannot be effectively improved; if the dosage is too high, the alkali metal is agglomerated, and the synergistic effect is not achieved.
Further, said step 4 is carried out at H2The specific operation of temperature-rising reduction under the atmosphere is as follows: heating to 340-420 ℃ at the speed of 0.5-2.0 ℃/min, and reducing for 5-8 h; h2The airspeed is 4000-6000 h-1(ii) a Said with O2/N2The passivation is specifically operated as: with O20.5 to 1.5% of O2/N2Passivating for 4-6 h. The above reduction conditions are the optimum conditions for efficiently reducing the metal phosphide precursor to metal phosphide. Exceeding the above reduction conditions may cause insufficient reduction to cause insufficient catalyst performance or excessive phosphating to cause a decrease in catalyst surface area. The passivating conditions are that the metal phosphide is provided withThe optimal conditions for effective passivation exceed the above conditions, which can cause insufficient passivation of the catalyst, rapid oxidation after air contact, combustion and excessive activity reduction of the catalyst passivation.
Further, the specific operation conditions of standing at room temperature in the step 1, the step 2 and the step 3 and drying for multiple times are that the mixture is placed at room temperature for 3-6 hours, then dried at 30-60 ℃ for 2-5 hours, and then dried at 100-120 ℃ for 8-15 hours. The above conditions are the optimum 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 influenced.
Application of catalyst for synthesizing succinic acid (anhydride) is applied to a fixed bed tubular reactor, and the air speed of hydrogen is 150-600 h-1Heating to 70-150 ℃ at a speed of 0.5-3 ℃/min under a pressure of 1.0-5.0 MPa, dissolving 10-50% maleic acid in water or solvent to form a solution, and allowing the liquid airspeed of the maleic acid solution to be 1.0-10.0 h-1The feed reaction of (1); the solvent comprises any one of water, 1, 4-dioxane, dibutyl phthalate, gamma-butyrolactone, tetrahydrofuran or toluene. The fixed bed reactor can effectively play the performance of the catalyst by adopting the reaction condition, and reasonably match the hydrogenation performance and the isomerization performance of the catalyst to achieve the best effect.
Compared with the prior art, the invention has the following advantages:
the invention uses metal phosphide for preparing succinic acid (anhydride) by maleic acid (anhydride) hydrogenation and dehydration, adjusts the surface acidity and alkalinity of the catalyst by introducing solid base, and promotes the synergistic effect of each component of the catalyst by introducing an auxiliary agent. The preparation method of the catalyst adopts the method of liquid-phase low-temperature pre-reduction and gas-phase medium-temperature carbonization to activate metal compounds of Ni, Mo, Co and W into metal phosphide, and uses solid alkali oxide as alkali metal salt and Nd as auxiliary agent oxide as auxiliary agent salt2O3Or La2O3Is immobilized on a catalyst. The synergistic effect of the metal phosphide, the solid alkali and the assistant in the catalyst of the invention ensures that the catalyst has the function ofThe C ═ C bond selective hydrogenation function at low temperature produces succinic acid (anhydride). The succinic acid (anhydride) synthesized by the method has high purity and can be used as a raw material for degradable plastics with C ═ C double bonds.
Drawings
FIG. 1 is a schematic diagram of a maleic anhydride hydrogenation reaction scheme.
Detailed Description
Example 1
A preparation method of a 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 hydrogen phosphate into 10mL of deionized water; soaking the sample in 14g of alumina in the same volume, standing at room temperature for 4h, drying at 30 ℃ for 5h, and drying at 120 ℃ for 8h 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, then soaking the sample 2 in an equal volume, standing the sample at room temperature for 4 hours, drying the sample at 50 ℃ for 5 hours, and drying the sample at 110 ℃ for 9 hours to obtain a sample 3;
step 4, sample 3 is placed in H2Heating to 350 deg.C at a rate of 1.0 deg.C/min under atmosphere, and reducing for 5H2The space velocity is 5000h-1Then at H2After the atmosphere is cooled to room temperature, use O2O content of 0.5%2/N2Passivating for 4h to obtain the catalyst.
The percentage content of the nickel phosphide of the obtained catalyst is 5.7 wt%, the percentage content of the sodium potassium oxide is 4.9 wt%, the percentage content of the neodymium oxide is 1.2 wt% and the percentage content of the aluminum oxide of the carrier is 88.2 wt%.
2mL of the catalyst was charged in a fixed bed tubular reactor. The catalyst is placed at a hydrogen space velocity of 200h-1The pressure is 5.0MPa, the temperature is increased to 150 ℃ at the rate of 1.5 ℃/min, 30 percent maleic anhydride/tetrahydrofuran solution is used as a reaction raw material, and the airspeed is 1.0h-1Hydrogenation reaction is carried out. The results are shown in the table1 in (c).
Example 2
A preparation method of a catalyst for synthesizing succinic acid by maleic acid hydrogenation comprises the following steps:
step 1, adding 11.02g of cobalt nitrate and 7.50g of diammonium phosphate into 20mL of deionized water; soaking the sample on a 13g molecular sieve in the same volume, standing at room temperature for 4h, drying at 50 ℃ for 4h, and drying at 110 ℃ for 8h 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 and washing, standing for 5h at room temperature, drying for 5h at 30 ℃, and drying for 15h at 120 ℃ to obtain a sample 2;
step 3, adding 5.32g of potassium nitrate and 1.34g of neodymium nitrate into 20mL of deionized water, then soaking the sample 2 in an equal volume, standing the sample at room temperature for 4h, drying the sample at 30 ℃ for 5h, and drying the sample at 110 ℃ for 10h to obtain a sample 3;
step 4, sample 3 is placed in H2Heating to 420 ℃ at the speed of 0.5 ℃/min under the atmosphere, and reducing for 8H, H2The space velocity is 6000h-1Then at H2After the atmosphere is cooled to room temperature, use O2O content of 0.5%2/N2Passivating for 5h to obtain the catalyst.
The percentage content of cobalt phosphide, potassium oxide, neodymium oxide and the percentage content of carrier molecular sieve are respectively 14.2 wt%, 8.3 wt%, 2.5 wt% and 75.0 wt%.
2mL of the catalyst was charged in a fixed bed tubular reactor. The catalyst is put at the space velocity of hydrogen of 350h-1The pressure is 3.0MPa, the temperature is increased to 70 ℃ at the speed of 1.0 ℃/min, 50 percent maleic acid/water solution is used as reaction raw material, and the airspeed is 7.0h-1Hydrogenation reaction is carried out. The reaction results are shown in Table 1.
Example 3
A preparation method of a 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 into 14mL of deionized water; then soaking the mixture on 16g of silicon dioxide in the same 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, then soaking the sample 2 in an equal volume, standing the sample at room temperature for 5 hours, drying the sample at 30 ℃ for 3 hours, and drying the sample at 120 ℃ for 7 hours to obtain a sample 3;
step 4, sample 3 is placed in H2Heating to 360 deg.C at a rate of 2.0 deg.C/min under atmosphere, and reducing for 5H2The space velocity is 4000h-1Then at H2After the atmosphere is cooled to room temperature, use O2O content of 1.5%2/N2Passivating for 4h to obtain the catalyst.
The percentage content of molybdenum phosphide, magnesium oxide, lanthanum oxide and silica in the catalyst is 10.7 wt%, 6.2 wt%, 0.6 wt% and 82.5 wt%.
2mL of the catalyst was charged in a fixed bed tubular reactor. The catalyst is placed at the space velocity of hydrogen of 150h-1The pressure is 2.0MPa, the temperature is increased to 90 ℃ at the speed of 1.5 ℃/min, 40 percent maleic anhydride/toluene solution is used as a reaction raw material, and the airspeed is 10.0h-1Hydrogenation reaction is carried out. The reaction results are shown in Table 1.
Example 4
A preparation method of a 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 phosphate into 12mL of deionized water; soaking the sample on a 12g molecular sieve in the same volume, standing at room temperature for 6h, drying at 30 ℃ for 5h, and drying at 100 ℃ for 8h 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, then soaking the sample 2 in an equal volume, standing the sample at room temperature for 3h, drying the sample at 60 ℃ for 4h, and drying the sample at 110 ℃ for 12h to obtain a sample 3;
step 4, sample 3 is placed in H2Heating to 400 ℃ at the speed of 1.5 ℃/min under the atmosphere, and reducing for 6H, H2The space velocity is 6000h-1Then at H2After the atmosphere is cooled to room temperature, use O2O content of 1.5%2/N2Passivating for 4h to obtain the catalyst.
The obtained catalyst contains 7.9 wt% of nickel phosphide, 9.8 wt% of cobalt phosphide, 4.5 wt% of calcium oxide, 2.6 wt% of neodymium oxide and 85.0 wt% of carrier molecular sieve.
2mL of the catalyst was charged in a fixed bed tubular reactor. The catalyst is put at the space velocity of hydrogen of 600h-1The pressure is 1.0MPa, the temperature is increased to 120 ℃ at the rate of 3.0 ℃/min, 20 percent maleic anhydride/gamma-butyrolactone is used as a reaction raw material, and the space velocity is 7.0h-1Hydrogenation reaction is carried out. The reaction results are shown in Table 1.
Example 5
A preparation method of a catalyst for synthesizing succinic anhydride by maleic anhydride hydrogenation comprises the following steps:
step 1, adding 6.52g of cobalt nitrate, 1.77g of ammonium molybdate and 4.44g of diammonium phosphate into 20mL of deionized water; soaking the sample in 15g of aluminum oxide in the same volume, standing at room temperature for 3h, drying at 50 ℃ for 6h, and drying at 100 ℃ for 10h 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 at room temperature for 4h, drying at 60 ℃ for 5h, and drying at 110 ℃ for 9h to obtain a sample 2;
step 3, adding 2.26g of potassium nitrate and 0.37g of lanthanum nitrate into 20mL of deionized water, then soaking the sample 2 in an equal volume, standing the sample at room temperature for 4h, drying the sample at 40 ℃ for 2h, and drying the sample at 120 ℃ for 12h to obtain a sample 3;
step 4, sample 3 is placed in H2The temperature is raised to 34 ℃ at the speed of 2.0 ℃/min under the atmosphereReduction at 0 ℃ for 5H, H2The space velocity is 5000h-1Then at H2After the atmosphere had cooled to room temperature, the reaction was carried out with O2O content of 1.0%2/N2Passivating for 6h to obtain the catalyst.
The obtained catalyst comprises 8.1 wt% of cobalt carbide, 6.2 wt% of molybdenum phosphide, 5.0 wt% of potassium oxide, 0.8 wt% of lanthanum oxide and 86.1 wt% of carrier aluminum oxide.
2mL of the catalyst was charged in a fixed bed tubular reactor. The catalyst is placed at the space velocity of hydrogen of 400h-1The pressure is 4.0MPa, the temperature is increased to 120 ℃ at the speed of 0.5 ℃/min, 10 percent maleic anhydride/dibutyl phthalate solution is used as reaction raw material, and the airspeed is 6.0h-1Hydrogenation reaction is carried out. The reaction results are shown in Table 1.
Example 6
A preparation method of a catalyst for synthesizing succinic anhydride by maleic anhydride hydrogenation comprises the following steps:
step 1, adding 2.82g of ammonium metatungstate, 1.33g of ammonium molybdate and 1.92g of diammonium phosphate into 15mL of deionized water; then soaking the mixture on 11g of zirconium oxide in the same 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 at room temperature for 5h, drying at 40 ℃ for 3h, and drying at 120 ℃ for 10h to obtain a sample 2;
step 3, adding 2.69g of sodium nitrate and 0.49g of lanthanum nitrate into 15mL of deionized water, then soaking the sample 2 in an equal volume, standing the sample at room temperature for 3h, drying the sample at 50 ℃ for 4h, and drying the sample at 110 ℃ for 9h to obtain a sample 3;
step 4, sample 3 is placed in H2Heating to 390 ℃ at the speed of 1.0 ℃/min under the atmosphere, and reducing for 6H, H2The space velocity is 4000h-1Then at H2After the atmosphere is cooled to room temperature, use O2O content of 0.5%2/N2Passivating for 6h to obtain the catalyst.
The obtained catalyst comprises 3.4 wt% of tungsten phosphide, 6.6 wt% of molybdenum phosphide, 5.9 wt% of sodium oxide, 1.5 wt% of lanthanum oxide and 89.2 wt% of carrier zirconium oxide.
2mL of the catalyst was charged in a fixed bed tubular reactor. The catalyst is placed at the space velocity of hydrogen of 300h-1The pressure is 2.0MPa, the temperature is raised to 130 ℃ at the speed of 2.5 ℃/min, 30 percent maleic anhydride/1, 4-dioxane solution is used as a reaction raw material, and the airspeed is 5.0h-1Hydrogenation reaction is carried out. The reaction results are shown in Table 1.
The results of the reactions according to examples 1 to 6 are shown in Table 1. As can be seen from Table 1, the yield of the catalyst succinic acid (anhydride) is more than 99.7%, and the product yield is extremely high.
TABLE 1 reaction results of examples 1 to 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
Those skilled in the art will appreciate that the invention may be practiced without these specific details. Although illustrative embodiments of the present invention have been described above to facilitate the 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, and various changes may be made apparent to those skilled in the art as long as they are within the spirit and scope of the present invention as defined and defined by the appended claims, and all matters of the invention which utilize the inventive concepts are protected.

Claims (10)

1. A catalyst for synthesizing succinic acid (anhydride) is characterized in that: the composition comprises the following substances in parts by weight: transition metal phosphide, solid alkali metal oxide, auxiliary agent, carrier and carrier, wherein the carrier is 0.057-0.177, 0.045-0.083, 0.006-0.026 and 0.750-0.892.
2. The catalyst for synthesizing succinic acid (anhydride) according to claim 1, characterized in that: the transition metal phosphide is one or a mixture of more of Ni, Co, Mo and W phosphide in any proportion; the metal used by the solid alkali metal oxide is one of K, Na, Ca and Mg; the auxiliary agent is one of Nd and La; the carrier is aluminum oxide, molecular sieve, silicon dioxide or zirconium oxide.
3. A preparation method of a catalyst for synthesizing succinic acid (anhydride) is characterized by comprising the following steps: the method comprises the following steps:
step 1, adding a transition metal compound and diammonium hydrogen phosphate into deionized water; then soaking the carrier in the same volume, standing at room temperature, and drying for multiple times to obtain a sample 1;
step 2, adding the sample 1 into a sodium borohydride solution, stirring and reducing, filtering, washing, standing at room temperature, and drying for multiple times to obtain a sample 2;
step 3, adding the alkali metal salt and the auxiliary agent salt into deionized water, then soaking the sample 2 in the same volume, standing the sample at room temperature, and drying the sample for multiple times to obtain a sample 3;
step 4, sample 3 is placed in H2Reducing at elevated temperature under atmosphere, then reducing at H2After the atmosphere is cooled to room temperature, use O2/N2And passivating to obtain the metal phosphide catalyst.
4. The method for preparing a catalyst for synthesizing succinic acid (anhydride) according to claim 3, characterized in that: the transition metal compound in the step 1 is one or a mixture of several 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.
5. The method for preparing a catalyst for synthesizing succinic acid (anhydride) according to claim 4, characterized in that: in the step 1, the carrier is any one of aluminum oxide, molecular sieve, silicon dioxide or zirconium oxide.
6. The method for preparing a catalyst for synthesizing succinic acid (anhydride) according to claim 5, 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 to 25.4 percent of the transition metal compound; the reduction time of stirring reduction is 40-60 min.
7. The method for preparing a catalyst for synthesizing succinic acid (anhydride) according to claim 6, characterized in that: 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 to 85.9 percent of that of the transition metal compound; the auxiliary agent salt in the step 3 is any one of neodymium nitrate or lanthanum nitrate; the dosage of the auxiliary agent salt is 5.6-21.1% of the transition metal compound.
8. The method for preparing a catalyst for synthesizing succinic acid (anhydride) according to claim 7, characterized in that: in said step 4 at H2The specific operation of temperature-rising reduction under the atmosphere is as follows: heating to 340-420 ℃ at the speed of 0.5-2.0 ℃/min, and reducing for 5-8 h; h2The airspeed is 4000-6000 h-1(ii) a Said with O2/N2The passivation is specifically operated as: with O20.5 to 1.5% of O2/N2Passivating for 4-6 h.
9. The method for preparing a catalyst for synthesizing succinic acid (anhydride) according to claim 8, characterized in that: standing at room temperature in the step 1, the step 2 and the step 3, and drying for multiple times under the specific operation conditions of 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.
10. The application of a catalyst for synthesizing succinic acid (anhydride) is characterized in that: applied to fixed bed pipeIn the reactor, the space velocity of hydrogen is 150-600 h-1Heating to 70-150 ℃ at the speed of 0.5-3 ℃/min under the pressure of 1.0-5.0 MPa, dissolving 10-50% maleic acid in water or solvent to form a solution, and keeping the liquid airspeed of the maleic acid solution for 1.0-10.0 h-1The feed reaction of (1); the solvent comprises any one of water, 1, 4-dioxane, dibutyl phthalate, gamma-butyrolactone, tetrahydrofuran or toluene.
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Publication number Priority date Publication date Assignee Title
CN114849688A (en) * 2022-05-23 2022-08-05 中国科学院山西煤炭化学研究所 Metal carbide catalyst for synthesizing succinic anhydride and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114849688A (en) * 2022-05-23 2022-08-05 中国科学院山西煤炭化学研究所 Metal carbide catalyst for synthesizing succinic anhydride and preparation method and application thereof

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