CN107456972B - Dibutyl carbonate synthesizing catalyst, preparation method and application - Google Patents

Dibutyl carbonate synthesizing catalyst, preparation method and application Download PDF

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CN107456972B
CN107456972B CN201610389110.0A CN201610389110A CN107456972B CN 107456972 B CN107456972 B CN 107456972B CN 201610389110 A CN201610389110 A CN 201610389110A CN 107456972 B CN107456972 B CN 107456972B
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dibutyl carbonate
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CN107456972A (en
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贾庆龙
菅秀君
王申军
马瑞杰
孟宪谭
孙丛丛
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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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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    • B01J35/615—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • 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

Abstract

A dibutyl carbonate synthesizing catalyst, a preparation method and application thereof, belonging to the technical field of catalyst preparation. A dibutyl carbonate synthesizing catalyst comprising the following components: ZnO: NiO: alkaline earth metal oxide: alkali metal oxides: the weight ratio of the carrier is 100: 3-60: 0.1-40: 0.1-10: 2 to 50. The preparation method of the dibutyl carbonate synthesizing catalyst comprises 1) preparing filter cakes, 2) preparing catalyst slurry and 3) forming the catalyst. The synthetic dibutyl carbonate catalyst has high catalytic activity, long service life and higher mechanical strength, the preparation method is simple and feasible, and the synthetic dibutyl carbonate catalyst is suitable for preparing dibutyl carbonate by reacting n-butanol with urea.

Description

Dibutyl carbonate synthesizing catalyst, preparation method and application
Technical Field
The invention relates to a dibutyl carbonate synthesis catalyst, a preparation method and application thereof, and belongs to the technical field of catalyst preparation.
Background
Dibutyl carbonate is an organic synthesis intermediate with a long carbon chain, can be used for synthesizing diphenyl carbonate and further synthesizing polycarbonate, can also be used as a matrix material of lubricating oil, is used for industries such as metal oil removal, leather treatment and the like, and has wide application. The synthesis method of dibutyl carbonate mainly includes phosgene method, urea alcoholysis method, oxidation and carbonylation method and ester exchange method. Phosgene methods have the disadvantages of extremely toxic raw materials, long operation cycle, severe corrosion of equipment by-products and the like, and are being gradually eliminated. The oxidative carbonylation method generally uses noble metals such as palladium and compounds thereof as catalysts, and the catalysts are not easy to recycle. The transesterification method adopts dimethyl carbonate as a raw material, so that the raw material cost is high, and the reaction is a parallel series reaction, so that a reaction rectification method is required to improve the reaction yield.
The applicant is in the studyThe following are found: the urea alcoholysis method utilizes butanol and urea as reaction raw materials to produce dibutyl carbonate through one-step or several-step reaction, and ammonia gas generated in the reaction process can be recycled for the synthesis of urea. The main advantages of the synthetic route are: (1) the reaction raw materials (urea and butanol) are bulk chemical raw materials, the price is low, and the by-product ammonia gas can be circularly used as the raw material for synthesizing the urea; (2) the other raw material for synthesizing the urea is CO2, CO2 is not only a main greenhouse gas, but also a non-toxic, cheap, clean and abundant renewable carbon source, and the reaction indirectly utilizes CO2The method can solve the problems of resources and energy, relieves the environmental pressure, has very important economic significance and social significance, and is the specific implementation of the green low-carbon strategy in the technical development work. (3) The synthetic route does not generate three wastes, does not use (or generate) extremely toxic or strongly corrosive substances in the whole process, and is a real 'green' synthetic route with high potential. However, the applicant found that: the existing urea alcoholysis method has the problem that the molar ratio of butanol to urea is higher
CN102093221A discloses a method for synthesizing dibutyl carbonate, wherein butyl carbamate and n-butanol are used as raw materials, MgO is used as a catalyst, CO2 is used as a reaction promoter and an ammonia gas absorbent, the conversion rate of butyl carbamate reaches 99%, but the problem that the price of the butyl carbamate is higher than that of the dimethyl carbonate product is solved. Dun et al (CN 102557948A, CN 102464588A) adopts a reaction separation system composed of a tank reactor and a gas storage-condensation-carbamate trap, and adopts a two-stage heating mode to control the reaction temperature to obtain higher dibutyl carbonate yield, but still has the problems of complex process and high molar ratio of butanol to urea, 2mol of n-butyl alcohol and 1mol of urea are needed for generating 1mol of dibutyl carbonate by reaction according to a metering coefficient, the actual n-butyl alcohol is far excessive, and the addition of the excessive n-butyl alcohol increases the energy consumption of the system and simultaneously increases the load of the separation system.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the synthetic dibutyl carbonate catalyst has high catalytic activity, long service life and higher mechanical strength, and the preparation method is simple, convenient and feasible and is suitable for industrial large-scale production.
The technical scheme adopted by the invention for solving the technical problems is as follows: the dibutyl carbonate synthesizing catalyst comprises the following components: ZnO, NiO, alkaline earth metal oxide, alkali metal oxide and a carrier; the weight ratio of ZnO, NiO, alkaline earth metal oxide, alkali metal oxide and carrier is 100: 3-60: 0.1-40: 0.1-10: 2-50; the BET specific surface area of the catalyst is 209-270 m2The mass percentage of particles with the particle size distribution of 80-130 mu m is more than 91%; the carrier is silicon dioxide or aluminum oxide; the alkaline earth metal is element Be, Mg, Ca, Sr or Ba.
The weight ratio of ZnO, NiO, alkaline earth metal oxide, alkali metal oxide and carrier is 100: 5-35: 0.2-11: 1-7: 4 to 28.
The alkali metal is element sodium or potassium.
The preparation method of the synthetic dibutyl carbonate catalyst is characterized by comprising the following steps of:
1) preparing a filter cake, namely mixing a salt solution of Zn, Ni and alkaline earth metal with the concentration of 0.05-2.5 mol/L with an alkaline precipitator solution with the mass concentration of 2-25% to obtain a mixed solution, heating the mixed solution to form a precipitate, washing the mixed solution with distilled water until the pH value is 7-8, filtering the mixed solution to obtain the filter cake, wherein the precipitation conditions are that the mixed solution is heated to 40-95 ℃ in a water bath, the pH value is 7-13, and the precipitate is kept stand for 6-24 hours;
2) preparing catalyst slurry, namely mixing an alkali metal salt solution with the concentration of 0.01-2 mol/L and a sol carrier solution with the mass concentration of 15-40%, adding the filter cake obtained in the step 1), pulping and mixing for 2-30 h to obtain catalyst slurry;
3) and (3) catalyst molding: spray drying and forming are adopted, the rotating speed of an atomizer is 4000-18000 r/min, the dry gas is diesel oil combustion gas, the inlet temperature of the dry gas is controlled to be 120-350 ℃, and the outlet temperature of exhaust air is controlled to be 90-300 ℃, so that a catalyst precursor is obtained; and roasting the catalyst precursor in an inert atmosphere at the roasting temperature of 300-700 ℃ for 3-12 h to obtain the synthetic dibutyl carbonate catalyst.
The salt solution of Zn, Ni and alkaline earth metal in the step 1) is nitrate solution of Zn, Ni and alkaline earth metal, and the alkaline precipitator is sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium salt or ammonia water.
The precipitation conditions in the step 1) are as follows: heating the mixed solution in a water bath to 60-90 ℃, keeping the pH value at 8-11, and standing for 12-20 h.
The alkali metal salt in the step 2) is potassium carbonate, sodium carbonate, potassium nitrate, sodium nitrate, potassium oxalate or sodium oxalate.
The sol carrier in the step 2) is aluminum sol or silica sol.
The application of the dibutyl carbonate synthesizing catalyst is characterized in that: the method is used for preparing dibutyl carbonate by reacting n-butanol with urea.
The application of the dibutyl carbonate synthesizing catalyst is characterized by comprising the following steps: n-butyl alcohol and urea are mixed according to a molar ratio of 2.5-6: 1, mixing, adding a synthetic dibutyl carbonate catalyst to react to prepare dibutyl carbonate, wherein the mass ratio of the synthetic dibutyl carbonate catalyst to urea is (0.01-0.15): 1, carrying out reaction in a reaction kettle with magnetic stirring, and maintaining the reaction pressure by continuously flowing nitrogen at the nitrogen flow rate of 10-100 ml/min, the reaction temperature of 150-260 ℃, the reaction pressure of 0.03-0.8 MPa and the reaction time of 4-24 h.
The invention is described below:
the applicant determines that Zn and Ni elements are used as active components in the catalyst in a combined way through a large amount of researches, so that the best catalytic activity can be obtained, and the effect of the Zn and Ni elements in the combined way cannot be achieved by singly using Zn or Ni or selecting other metal elements. Preferably, the elements Zn and Ni are present in the catalyst in the form of oxides. The applicant verifies through research that the addition of the auxiliary agent alkaline earth metal can further improve the activity of the catalyst and improve the yield of dibutyl carbonate. The specific surface area of the catalyst can be improved by adding the alkali metal oxide. The applicant found in the study that: when BET ratio of catalystThe area is less than 209m2At the time of the reaction,/g, the yield of dibutyl carbonate is low; when the BET specific surface area of the catalyst is more than 270m2At/g, there was no significant increase in dibutyl carbonate yield. Therefore, the BET specific surface area of the catalyst is 209 to 270m2The best is/g, and higher dibutyl carbonate yield can be obtained. The applicant designs that the mass percentage of the particles with the catalyst particle size distribution of 80-130 μm is more than 91%, because the applicant considers that: when the catalyst is used as a slurry bed reaction catalyst, the particle size of the catalyst is too small, so that the subsequent separation difficulty is increased; the large particles reduce the contact area of the effective catalyst on the one hand, increase the abrasion of the stirring paddle and provide the energy consumption for stirring on the other hand, and experiments prove that the reaction has better reaction effect when the particle size distribution of the catalyst is 80-130 mu m.
In the step 1), the alkaline precipitant enables soluble active components and alkaline earth metal cations to generate precipitates which are changed into oxide forms after subsequent roasting. Preferably, the alkaline precipitant is ammonia water, and the ammonia water is used as a non-catalyst component of the precipitant and can be easily removed in the subsequent drying and roasting processes. The alkali metal salt in the step 2) is potassium carbonate, sodium carbonate, potassium nitrate, sodium nitrate, potassium oxalate or sodium oxalate, and the applicant considers that the catalyst needs corresponding metal oxide, and the carbonic acid, the nitric acid and the oxalate are easy to decompose to generate oxide in the subsequent roasting process, and meanwhile, acid radical decomposition is removed in a gaseous form, so that the preparation process obtained by catalysis is simplified, and the preparation process difficulty is reduced. The sol carrier used in the step 2) of the applicant is aluminum sol or silica sol, the catalyst of the invention mainly introduces SiO2 as the carrier, and the addition of the silica sol is a convenient way to introduce SiO 2. The silica sol may also be replaced by an aluminum sol, preferably a silica sol. Silica sols are dispersions of nanoscale silica particles in water or a solvent. The chemical formula of the aluminum sol is a (Al)2O3·nH2O)·bHx·cH2O, wherein: al (Al)2O3·nH2O is hydrated alumina, Hx is peptizing agent, and the coefficient is as follows: b<a. c, n; when the alumina sol is used, the alumina sol in the catalyst is Al2O3Exist in the form of (1).
Preferably, the specific operation of the step 1) is mixing a salt solution of Zn, Ni and an alkaline earth metal with the concentration of 0.1-1 mol/L with an alkaline precipitator solution with the mass concentration of 10-15% to obtain a mixed solution, heating the mixed solution to form a precipitate, washing the mixed solution with distilled water until the pH value is 7-8, filtering the mixed solution to obtain a filter cake, preferably, the specific operation of the step 2) is mixing an alkali metal salt solution with the concentration of 0.1-1 mol/L with a sol carrier solution with the mass concentration of 20-30%, adding the filter cake of the step 1), pulping and mixing for 5-12 h to obtain a catalyst slurry, preferably, the specific operation of the step 3) is 3) catalyst molding, namely, spray drying molding is adopted, the rotation speed of an atomizer is 8000-12000 r/min, the drying gas is diesel combustion gas, the inlet temperature of the drying gas is controlled to be 180-250 ℃, the exhaust outlet temperature is 120-200 ℃ to obtain a catalyst precursor, the catalyst is calcined in an inert atmosphere, the calcination temperature is 400-600 h, the calcination time is 5-10 h, the synthesis catalyst is preferably, the dibutyl carbonate catalyst is prepared by a magnetic reaction, the reaction is carried out in a nitrogen-dibutyl carbonate synthesis reaction kettle, the reaction is carried out at the reaction pressure of 0.1.1-30-0.06, the dibutyl carbonate synthesis reaction is preferably, the dibutyl carbonate synthesis reaction is carried out under the reaction, the reaction pressure of a dibutyl carbonate reaction kettle is maintained, the nitrogen-0.1-30-0.0.0.0-0-30-0..
Compared with the prior art, the dibutyl carbonate synthesizing catalyst and the preparation method thereof have the beneficial effects that:
1. the dibutyl carbonate synthesizing catalyst has higher catalytic activity, and the lower molar ratio of n-butanol to urea is as follows: under the condition of 3-5: 1, the conversion rate of urea reaches 100%, and the selectivity of dibutyl carbonate reaches 92%. In the catalyst, the active component contains Zn and Ni compounds, and the assistant is alkali metal and alkaline earth metal. Active components Zn and Ni and alkaline earth metal elements are prepared into multi-component slurry by a coprecipitation method through a mixed salt solution, and alkali metal and a carrier are added into the prepared precipitation slurry in a sol solution mode.
2. The dibutyl carbonate synthesizing catalyst has a large specific surface area, and the BET specific surface area is 200-280 m2/g。
3. The dibutyl carbonate synthesizing catalyst has long service life, high mechanical strength, continuous use for 20 times, no obvious decrease in urea converting rate and dibutyl carbonate selectivity, and catalyst recovering rate of 99.5%.
4. The dibutyl carbonate synthesizing catalyst is microspherical, and the diameter of the particles ranges from 80 to 130 mu m and reaches 96 percent.
5. The preparation method of the catalyst for synthesizing dibutyl carbonate is simple, the used raw materials are all commercial products, and the obtained slurry is formed by using a spray drying technology and is suitable for industrial large-scale production.
Detailed Description
Examples 1 to 9 are specific embodiments of the dibutyl carbonate synthesizing catalyst and the method for producing the same according to the present invention, and example 1 is the most preferred example.
Example 1
1) Preparing filter cakes, namely weighing 3654.7g, 311.5g and 21.1g of nickel nitrate, zinc nitrate and calcium nitrate respectively, preparing aqueous solutions of 1 mol/L, fully and uniformly mixing the aqueous solutions, putting the aqueous solutions in a mixed salt solution storage tank, preparing 3100g of ammonia water with the mass concentration of 15%, putting the ammonia water in a precipitator storage tank, pumping the mixed salt solution and the precipitator ammonia water into a precipitation tank with continuous stirring by using two pumps respectively in parallel, heating the precipitation tank in a water bath to keep the temperature of the precipitation tank at 60 ℃ and the pH =9, standing the solution for 12 hours after precipitation, repeatedly washing the solution in the precipitation tank by using distilled water until the pH =8, and then filtering the solution to obtain the filter cakes;
2) preparing catalyst slurry, namely weighing 24.9g of potassium carbonate to prepare 1 mol/L solution, adding 400g of silica sol solution with the mass concentration of 20% to obtain mixed solution of alkali metal and a carrier, adding the filter cake obtained in the previous step into the mixed solution of the alkali metal and the carrier, and pulping and fully mixing for 6 hours to obtain the catalyst slurry;
3) and (3) catalyst molding: the catalyst slurry is formed by spray drying, the rotating speed of an atomizer is 9000r/min, the dry gas is diesel combustion gas, and dry flue gas is controlledThe inlet temperature is 190 ℃, and the exhaust outlet temperature is 150 ℃ to obtain a catalyst precursor. And roasting the catalyst precursor in a nitrogen atmosphere at the roasting temperature of 450 ℃ for 6 h. The zinc/nickel catalyst added with various additives for preparing dibutyl carbonate by reacting n-butanol with urea is prepared, and the catalyst comprises the following components in percentage by weight in the form of metal oxide: ZnO: NiO: CaO: k2O ：SiO2=100：8：0.5：2：8。
The application method of the catalyst comprises the following steps:
the mass of reactants n-butanol and urea are 2223.6g and 600.6g respectively, the mass of catalyst is 12g, the reaction is carried out in a reaction kettle with magnetic stirring, the reaction pressure is maintained by continuously flowing nitrogen, the nitrogen flow rate is 40ml/min, the reaction temperature is 180 ℃, the reaction pressure is 0.1MPa, and the reaction time is 7 h. The main physical parameters of the catalyst and the reaction results are shown in Table 1.
Example 2
1) Preparing filter cakes, namely weighing 3654.7g, 389.4g and 63.3g of nickel nitrate, zinc nitrate and calcium nitrate respectively, preparing aqueous solutions of 1 mol/L respectively, fully and uniformly mixing the aqueous solutions, putting the aqueous solutions in a mixed salt solution storage tank, preparing 4723g of ammonia water with the mass concentration of 10%, putting the ammonia water in a precipitator storage tank, respectively pumping the mixed salt solution and the precipitator ammonia water into a precipitation tank with continuous stirring in a parallel way by using two pumps, heating the precipitation tank in a water bath to keep the temperature of the precipitation tank at 70 ℃ and the pH =9.8, standing the solution for 15 hours after precipitation, repeatedly washing the solution in the precipitation tank by using distilled water until the pH =8, and then filtering the solution to obtain the filter cakes;
2) preparing catalyst slurry, namely weighing 44.1g of potassium carbonate to prepare 0.8 mol/L solution, adding the solution into 500g of silica sol solution with the mass concentration of 20% to obtain mixed solution of alkali metal and a carrier, adding the filter cake obtained in the previous step into the mixed solution of the alkali metal and the carrier, and pulping and fully mixing for 9 hours to obtain the catalyst slurry;
3) and (3) catalyst molding: the catalyst slurry is formed by spray drying, the rotation speed of an atomizer is 10000r/min, the dry gas is diesel combustion gas, the inlet temperature of dry flue gas is controlled to be 200 ℃, and the outlet temperature of exhaust air is controlled to be 190 ℃, so that a catalyst precursor is obtained. Roasting the catalyst precursor in nitrogen atmosphere at the roasting temperatureThe roasting time is 8h at 490 ℃. The zinc/nickel catalyst added with various additives for preparing dibutyl carbonate by reacting n-butanol with urea is prepared, and the catalyst comprises the following components in percentage by weight in the form of metal oxide: ZnO: NiO: CaO: k2O：SiO2=100：10：1.5：3：10。
The application method of the catalyst comprises the following steps:
the mass of reactants n-butanol and urea are 2594.2g and 600.6g respectively, the mass of catalyst is 12g, the reaction is carried out in a reaction kettle with magnetic stirring, the reaction pressure is maintained by continuously flowing nitrogen, the nitrogen flow rate is 60ml/min, the reaction temperature is 200 ℃, the reaction pressure is 0.1MPa, and the reaction time is 9 h. The main physical parameters of the catalyst and the reaction results are shown in Table 1.
Example 3
1) Preparing filter cakes, namely weighing 3654.7g, 739.8g and 210.8g of nickel nitrate, zinc nitrate, calcium nitrate respectively, preparing aqueous solutions of 0.8 mol/L respectively, fully and uniformly mixing the aqueous solutions, putting the aqueous solutions in a mixed salt solution storage tank, preparing 4111g of 13 mass percent ammonia water, putting the ammonia water in a precipitator storage tank, respectively pumping the mixed salt solution and the precipitator ammonia water into a precipitation tank with continuous stirring in a parallel way by using two pumps, heating the precipitation tank in a water bath to keep the temperature of the precipitation tank at 70 ℃ and the pH =9.5, standing the solution for 24 hours after precipitation, repeatedly washing the slurry in the precipitation tank by using distilled water until the pH =8, and then filtering the solution to obtain the filter cakes;
2) preparing catalyst slurry, namely weighing 58.8g of potassium carbonate to prepare 0.9 mol/L solution, adding 666.7g of silica sol solution with the mass concentration of 30% to obtain mixed solution of alkali metal and a carrier, adding the filter cake obtained in the previous step into the mixed solution of the alkali metal and the carrier, and pulping and fully mixing for 12 hours to obtain the catalyst slurry;
3) and (3) catalyst molding: and (3) spray drying and forming the catalyst slurry, wherein the rotating speed of an atomizer is 12000r/min, the dry gas is diesel combustion gas, the inlet temperature of the dry flue gas is controlled to be 220 ℃, and the outlet temperature of the exhaust air is controlled to be 200 ℃ to obtain a catalyst precursor. And roasting the catalyst precursor in a nitrogen atmosphere at the roasting temperature of 580 ℃ for 7 hours. The zinc/nickel catalyst added with various additives and used for preparing dibutyl carbonate by reacting n-butanol with urea and the catalystThe composition of (A) is calculated in the form of metal oxide, and the weight ratio of the composition is as follows: ZnO: NiO: CaO: k2O：SiO2=100：19：5：4：20。
The application method of the catalyst comprises the following steps:
the mass of reactants n-butanol and urea are 3246g and 438g respectively, the mass of the catalyst is 26g, the reaction is carried out in a reaction kettle with magnetic stirring, continuously flowing nitrogen maintains the reaction pressure, the nitrogen flow rate is 80ml/min, the reaction temperature is 220 ℃, the reaction pressure is 0.15MPa, and the reaction time is 12 h. The main physical parameters of the catalyst and the reaction results are shown in Table 1.
Example 4
1) Preparing filter cakes, namely weighing 3654.7g, 1168.1g and 421.7g of nickel nitrate, zinc nitrate, calcium nitrate respectively, preparing aqueous solutions of 1 mol/L respectively, fully and uniformly mixing the aqueous solutions, putting the aqueous solutions in a mixed salt solution storage tank, preparing 3075g of ammonia water with the mass concentration of 20%, putting the ammonia water in a precipitator storage tank, respectively pumping the mixed salt solution and the precipitator ammonia water into a precipitation tank with continuous stirring by using two pumps in a parallel flow manner, heating the precipitation tank in a water bath to keep the temperature of the precipitation tank at 70 ℃ and the pH =9, standing the solution for 20 hours after precipitation, repeatedly washing the slurry in the precipitation tank by using distilled water until the pH =8, and then filtering the slurry to obtain the filter cakes;
2) preparing catalyst slurry, namely weighing 58.8g of potassium carbonate to prepare 1 mol/L solution, adding 666.7g of silica sol solution with the mass concentration of 30% to obtain mixed solution of alkali metal and a carrier, adding the filter cake obtained in the previous step into the mixed solution of the alkali metal and the carrier, and pulping and fully mixing for 10 hours to obtain the catalyst slurry;
3) and (3) catalyst molding: the catalyst slurry is formed by spray drying, the rotation speed of an atomizer is 10000r/min, the dry gas is diesel combustion gas, the inlet temperature of the dry flue gas is controlled to be 240 ℃, and the outlet temperature of the exhaust is controlled to be 130 ℃, so that a catalyst precursor is obtained. And roasting the catalyst precursor in a nitrogen atmosphere at the roasting temperature of 500 ℃ for 9 hours. The zinc/nickel catalyst added with various additives for preparing dibutyl carbonate by reacting n-butanol with urea is prepared, and the catalyst comprises the following components in percentage by weight in the form of metal oxide: ZnO: NiO: CaO: k2O：SiO2=100：30：10：4：20。
The application method of the catalyst comprises the following steps:
the mass of reactants n-butanol and urea are 3261g and 660g respectively, the mass of the catalyst is 33g, the reaction is carried out in a reaction kettle with magnetic stirring, the reaction pressure is maintained by continuously flowing nitrogen, the nitrogen flow rate is 80ml/min, the reaction temperature is 210 ℃, the reaction pressure is 0.1MPa, and the reaction time is 10 h. The main physical parameters of the catalyst and the reaction results are shown in Table 1.
Example 5
1) Preparing filter cakes, namely weighing 3654.7g, 856.6g and 316.3g of nickel nitrate, zinc nitrate, calcium nitrate respectively, preparing aqueous solutions of 1 mol/L respectively, fully and uniformly mixing the aqueous solutions, putting the aqueous solutions in a mixed salt solution storage tank, preparing 2817g of ammonia water with the mass concentration of 20%, putting the ammonia water in a precipitator storage tank, respectively pumping the mixed salt solution and the precipitator ammonia water into a precipitation tank with continuous stirring by using two pumps in a parallel flow manner, heating the precipitation tank in a water bath to keep the temperature of the precipitation tank at 90 ℃ and the pH =9, standing the solution for 15 hours after precipitation, repeatedly washing the slurry in the precipitation tank by using distilled water until the pH =8, and then filtering the slurry to obtain the filter cakes;
2) preparing catalyst slurry, namely weighing 36.8g of potassium carbonate to prepare 1 mol/L solution, adding 1080g of silica sol solution with the mass concentration of 25% to obtain mixed solution of alkali metal and a carrier, adding the filter cake obtained in the previous step into the mixed solution of the alkali metal and the carrier, and pulping and fully mixing for 10 hours to obtain the catalyst slurry;
3) and (3) catalyst molding: the catalyst slurry is formed by spray drying, the rotating speed of an atomizer is 9800r/min, the dry gas is diesel combustion gas, the inlet temperature of the dry flue gas is controlled to be 230 ℃, and the outlet temperature of the exhaust air is controlled to be 190 ℃, so that a catalyst precursor is obtained. And roasting the catalyst precursor in a nitrogen atmosphere at the roasting temperature of 540 ℃ for 8 h. The zinc/nickel catalyst added with various additives for preparing dibutyl carbonate by reacting n-butanol with urea is prepared, and the catalyst comprises the following components in percentage by weight in the form of metal oxide: ZnO: NiO: CaO: k2O：SiO2=100：22：7.5：2.5：27。
The application method of the catalyst comprises the following steps:
the mass of reactants n-butanol and urea are 3876g and 600g respectively, the mass of the catalyst is 18g, the reaction is carried out in a reaction kettle with magnetic stirring, continuously flowing nitrogen maintains the reaction pressure, the nitrogen flow rate is 80ml/min, the reaction temperature is 200 ℃, the reaction pressure is 0.3MPa, and the reaction time is 12 h. The main physical parameters of the catalyst and the reaction results are shown in Table 1.
Example 6
1) Preparing filter cakes, namely weighing 3654.7g, 1051.3g and 291g of nickel nitrate, zinc nitrate and calcium nitrate respectively, preparing aqueous solutions of 1 mol/L, fully and uniformly mixing the aqueous solutions, putting the aqueous solutions in a mixed salt solution storage tank, preparing 2912.5g of ammonia water with the mass concentration of 20%, putting the ammonia water in a precipitator storage tank, pumping the mixed salt solution and the precipitator ammonia water into a precipitation tank with continuous stirring by using two pumps respectively in parallel, heating the precipitation tank in a water bath to keep the temperature of the precipitation tank at 75 ℃ and the pH =9.2, standing the solution for 12 hours after precipitation, repeatedly washing the solution in the precipitation tank by using distilled water until the pH =7.5, and then filtering the solution to obtain the filter cakes;
2) preparing catalyst slurry, namely weighing 92.6g of potassium carbonate to prepare 1 mol/L solution, adding 1000g of 21 mass percent silica sol solution to obtain mixed solution of alkali metal and a carrier, adding the filter cake obtained in the previous step into the mixed solution of the alkali metal and the carrier, and pulping and fully mixing for 7 hours to obtain the catalyst slurry;
3) and (3) catalyst molding: and (3) spray drying and forming the catalyst slurry, wherein the rotating speed of an atomizer is 10100r/min, the dry gas is diesel combustion gas, the inlet temperature of the dry flue gas is controlled to be 240 ℃, and the outlet temperature of the exhaust air is controlled to be 190 ℃ to obtain a catalyst precursor. And roasting the catalyst precursor in a nitrogen atmosphere at the roasting temperature of 550 ℃ for 6 hours. The zinc/nickel catalyst added with various additives for preparing dibutyl carbonate by reacting n-butanol with urea is prepared, and the catalyst comprises the following components in percentage by weight in the form of metal oxide: ZnO: NiO: CaO: k2O ：SiO2=100：27：6.9：6.3：21。
The application method of the catalyst comprises the following steps:
the mass of reactants n-butanol and urea are 3102g and 780g respectively, the mass of catalyst is 40g, the reaction is carried out in a reaction kettle with magnetic stirring, the reaction pressure is maintained by continuously flowing nitrogen, the nitrogen flow rate is 80ml/min, the reaction temperature is 195 ℃, the reaction pressure is 0.3MPa, and the reaction time is 12 h. The main physical parameters of the catalyst and the reaction results are shown in Table 1.
Example 7
1) Preparing filter cakes, namely weighing 3654.7g, 973.4g and 400.6g of nickel nitrate, zinc nitrate and calcium nitrate respectively, preparing aqueous solutions of 1 mol/L respectively, fully and uniformly mixing the aqueous solutions, putting the aqueous solutions in a mixed salt solution storage tank, preparing 2946g of ammonia water with the mass concentration of 20%, putting the ammonia water in a precipitator storage tank, pumping the mixed salt solution and the precipitator ammonia water into a precipitation tank with continuous stirring by using two pumps respectively in parallel, heating the precipitation tank in a water bath to keep the temperature of the precipitation tank at 80 ℃ and the pH =9.2, standing the solution for 15 hours after precipitation, repeatedly washing the solution in the precipitation tank by using distilled water until the pH =7.5, and then filtering the solution to obtain the filter cakes;
2) preparing catalyst slurry, namely weighing 77.9g of potassium carbonate to prepare 1 mol/L solution, adding 826g of silica sol solution with the mass concentration of 23% to obtain mixed solution of alkali metal and a carrier, adding the filter cake obtained in the previous step into the mixed solution of the alkali metal and the carrier, and pulping and fully mixing for 11 hours to obtain the catalyst slurry;
3) and (3) catalyst molding: and (3) spray drying and forming the catalyst slurry, wherein the rotating speed of an atomizer is 11500r/min, the dry gas is diesel combustion gas, the inlet temperature of the dry flue gas is controlled to be 208 ℃, and the outlet temperature of the exhaust air is controlled to be 198 ℃, so that a catalyst precursor is obtained. And roasting the catalyst precursor in a nitrogen atmosphere at the roasting temperature of 510 ℃ for 7 h. The zinc/nickel catalyst added with various additives for preparing dibutyl carbonate by reacting n-butanol with urea is prepared, and the catalyst comprises the following components in percentage by weight in the form of metal oxide: ZnO: NiO: CaO: k2O ：SiO2=100：25：9.5：5.3：19。
The application method of the catalyst comprises the following steps:
the mass of reactants n-butanol and urea are 3903g and 756g respectively, the mass of the catalyst is 34g, the reaction is carried out in a reaction kettle with magnetic stirring, the reaction pressure is maintained by continuously flowing nitrogen, the nitrogen flow rate is 70ml/min, the reaction temperature is 228 ℃, the reaction pressure is 0.2MPa, and the reaction time is 10 h. The main physical parameters of the catalyst and the reaction results are shown in Table 1.
Example 8
1) Preparing filter cakes, namely weighing 3654.7g, 584g and 189.8g of nickel nitrate, zinc nitrate and calcium nitrate respectively, preparing aqueous solutions of 1 mol/L, fully and uniformly mixing the aqueous solutions, putting the aqueous solutions in a mixed salt solution storage tank, preparing 2566.5g of ammonia water with the mass concentration of 20%, putting the ammonia water in a precipitator storage tank, pumping the mixed salt solution and the precipitator ammonia water into a precipitation tank with continuous stirring by using two pumps respectively in parallel, heating the precipitation tank in a water bath to keep the temperature of the precipitation tank at 70 ℃ and the pH =8.9, standing the solution for 12 hours after precipitation, repeatedly washing the solution in the precipitation tank by using distilled water until the pH =7.5, and then filtering the solution to obtain the filter cakes;
2) preparing catalyst slurry, namely weighing 100g of potassium carbonate to prepare 1 mol/L solution, adding 1300g of silica sol solution with the mass concentration of 20% to obtain mixed solution of alkali metal and a carrier, adding the filter cake obtained in the previous step into the mixed solution of the alkali metal and the carrier, and pulping and fully mixing for 10 hours to obtain the catalyst slurry;
3) and (3) catalyst molding: the catalyst slurry is formed by spray drying, the rotational speed of an atomizer is 11700r/min, the dry gas is diesel combustion gas, the inlet temperature of the dry flue gas is controlled to be 228 ℃, and the outlet temperature of the exhaust air is controlled to be 190 ℃, so that a catalyst precursor is obtained. And roasting the catalyst precursor in a nitrogen atmosphere at the roasting temperature of 550 ℃ for 8 h. The zinc/nickel catalyst added with various additives for preparing dibutyl carbonate by reacting n-butanol with urea is prepared, and the catalyst comprises the following components in percentage by weight in the form of metal oxide: ZnO: NiO: CaO: k2O ：SiO2=100：15：4.5：6.8：26。
The application method of the catalyst comprises the following steps:
the mass of reactants n-butanol and urea are 4632g and 750g respectively, the mass of the catalyst is 40g, the reaction is carried out in a reaction kettle with magnetic stirring, the reaction pressure is maintained by continuously flowing nitrogen, the nitrogen flow rate is 70ml/min, the reaction temperature is 200 ℃, the reaction pressure is 0.15MPa, and the reaction time is 12 h. The main physical parameters of the catalyst and the reaction results are shown in Table 1.
Example 9
The catalyst was reused 20 times under the conditions of example 8, and the results of the 20 th use are shown in Table 1, and the recovery of the catalyst was 99.5%.
Performance testing
The specific surface and pore volume of the catalyst are measured by low-temperature nitrogen adsorption, and the specific surface area is the BET specific surface area. The particle size distribution in table 1 was determined using a laser particle size distribution instrument.
TABLE 1 Main physical property parameters and reaction results of the catalysts obtained in examples 1 to 9
Figure DEST_PATH_IMAGE001
。
As can be seen from Table 1, the dibutyl carbonate synthesizing catalyst has high catalytic activity, large specific surface area, long service life and high mechanical strength, and the recovery rate of the catalyst reaches 99.5%.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.

Claims (9)

1. The dibutyl carbonate synthesizing catalyst is characterized by comprising the following components: ZnO, NiO, alkaline earth metal oxide, alkali metal oxide and a carrier; the weight ratio of ZnO, NiO, alkaline earth metal oxide, alkali metal oxide and carrier is 100: 5-35: 0.2-11: 1-7: 4-28; the BET specific surface area of the catalyst is 209-270 m2The mass percentage of particles with the particle size distribution of 80-130 mu m is more than 91%; the carrier is silicon dioxide or aluminum oxide; the alkaline earth metal is element Be, Mg, Ca, Sr or Ba.
2. The dibutyl carbonate synthesizing catalyst according to claim 1, wherein: the alkali metal is element sodium or potassium.
3. The preparation method of the dibutyl carbonate synthesizing catalyst according to any one of claims 1 to 2, characterized by comprising the following steps:
1) preparing a filter cake, namely mixing a salt solution of Zn, Ni and alkaline earth metal with the concentration of 0.05-2.5 mol/L with an alkaline precipitator solution with the mass concentration of 2-25% to obtain a mixed solution, heating the mixed solution to form a precipitate, washing the mixed solution with distilled water until the pH value is 7-8, and filtering the mixed solution to obtain the filter cake, wherein the precipitation conditions are that the mixed solution is heated to 40-95 ℃ in a water bath, the pH value is 7-13, and the filter cake is kept stand for 6-24 hours;
2) preparing catalyst slurry, namely mixing an alkali metal salt solution with the concentration of 0.01-2 mol/L and a sol carrier solution with the mass concentration of 15-40%, adding the filter cake obtained in the step 1), pulping and mixing for 2-30 h to obtain catalyst slurry;
3) and (3) catalyst molding: spray drying and forming are adopted, the rotating speed of an atomizer is 4000-18000 r/min, the dry gas is diesel oil combustion gas, the inlet temperature of the dry gas is controlled to be 120-350 ℃, and the outlet temperature of exhaust air is controlled to be 90-300 ℃, so that a catalyst precursor is obtained; and roasting the catalyst precursor in an inert atmosphere at the roasting temperature of 300-700 ℃ for 3-12 h to obtain the synthetic dibutyl carbonate catalyst.
4. The method for preparing the dibutyl carbonate synthesizing catalyst according to claim 3, wherein: the salt solution of Zn, Ni and alkaline earth metal in the step 1) is nitrate solution of Zn, Ni and alkaline earth metal, and the alkaline precipitator is sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium salt or ammonia water.
5. The method for preparing the dibutyl carbonate synthesizing catalyst according to claim 3, wherein: the precipitation conditions in the step 1) are as follows: heating the mixed solution in a water bath to 60-90 ℃, keeping the pH value at 8-11, and standing for 12-20 h.
6. The method for preparing the dibutyl carbonate synthesizing catalyst according to claim 3, wherein: the alkali metal salt in the step 2) is potassium carbonate, sodium carbonate, potassium nitrate, sodium nitrate, potassium oxalate or sodium oxalate.
7. The method for preparing the dibutyl carbonate synthesizing catalyst according to claim 3, wherein: the sol carrier in the step 2) is aluminum sol or silica sol.
8. The use of the dibutyl carbonate synthesizing catalyst according to any one of claims 1 to 2, wherein: the method is used for preparing dibutyl carbonate by reacting n-butanol with urea.
9. The use of the dibutyl carbonate synthesizing catalyst according to claim 8, comprising the steps of: n-butyl alcohol and urea are mixed according to a molar ratio of 2.5-6: 1, mixing, adding a synthetic dibutyl carbonate catalyst to react to prepare dibutyl carbonate, wherein the mass ratio of the synthetic dibutyl carbonate catalyst to urea is (0.01-0.15): 1, carrying out reaction in a reaction kettle with magnetic stirring, and maintaining the reaction pressure by continuously flowing nitrogen at the nitrogen flow rate of 10-100 ml/min, the reaction temperature of 150-260 ℃, the reaction pressure of 0.03-0.8 MPa and the reaction time of 4-24 h.
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