CN114939413A - Catalyst for catalyzing methanol to directly synthesize dimethyl carbonate and preparation method and application thereof - Google Patents
Catalyst for catalyzing methanol to directly synthesize dimethyl carbonate and preparation method and application thereof Download PDFInfo
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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Abstract
The invention discloses a catalyst for catalyzing methanol to directly synthesize dimethyl carbonate, a preparation method and application thereof, wherein the catalyst comprises an active component, an auxiliary agent and a carrier; the weight ratio of each component in the catalyst is as follows according to 100 percent: 5-30% of active component, 0.1-10% of auxiliary agent and 68-93% of carrier; the active component is CuO, and the auxiliary agent is NiO and Fe 2 O 3 At least one of PdO; the carrier is cerium oxide and/or zirconium oxide. The catalyst provided by the invention is simple to prepare, environment-friendly in preparation process, and good in catalytic performance when used for preparing dimethyl carbonate by methanol gas-phase oxidation carbonylation, and has the advantages of raw material conversion rate and product selectionThe method has high performance and space-time yield, the reaction atom has high economy, and the byproduct is only water, thereby being green and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of dimethyl carbonate (DMC) preparation, and particularly relates to a catalyst for catalyzing methanol to directly synthesize dimethyl carbonate, and a preparation method and application thereof.
Background
Dimethyl carbonate (DMC) contains functional groups such as methyl, methoxy and carbonyl groups, is an important intermediate, and can be used as a methylating agent, a methoxylating agent and a carbonylating agent, and is also called a "new base block" in the field of organic green chemical synthesis. Because DMC has low toxicity, low viscosity characteristics, also used to replace organic volatile substances as green solvent, in the electronic chemicals, medicine, pesticide, dyes, synthetic materials, oil additives, food additives, vehicle fuel and other fields have wide application.
DMC has a high dielectric constant and the ability to dissolve lithium salts, making it useful as a battery electrolyte. The low viscosity of DMC allows ions to move more easily, resulting in a higher conductivity of the electrolyte, compared to other conventional solvents such as propylene carbonate, ethylene carbonate, and dimethyl sulfoxide. With the increasing expansion of the quantity of electronic products and the vigorous development of the new energy electric automobile industry, the lithium battery industry is growing, and the market of DMC must be stimulated.
The main production methods of DMC industry in China are ester exchange method and oxidative carbonylation method. The transesterification process is CO 2 And the propylene carbonate is generated with alkylene oxide, and then the propylene carbonate and methanol are subjected to ester exchange reaction to generate DMC, and a byproduct is dihydric alcohol. The alkylene oxide mostly takes petroleum cracking products as raw materials, so the DMC produced by the route is greatly influenced by the price fluctuation of crude oil and has higher cost. The methanol liquid phase oxidation carbonylation method adopts halide of Cu or Pd as a catalyst, so that equipment is corroded, and the service life is short; in the process of indirect gas-phase oxidation carbonylation of methanol, expensive nitrogen-containing oxide is used, thus polluting the environment.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a catalyst for catalyzing methanol to directly synthesize dimethyl carbonate, and simultaneously provides a preparation method and application of the catalyst.
A catalyst for catalyzing methanol to directly synthesize dimethyl carbonate comprises an active component, an auxiliary agent and a carrier; the weight ratio of each component in the catalyst is as follows according to 100 percent: 5-30% of active component, 0.1-10% of auxiliary agent and 68-93% of carrier; the active component is CuO, and the auxiliary agent is NiO and Fe 2 O 3 At least one of PdO; the carrier is cerium oxide and/or zirconium oxide.
The preparation method of the catalyst comprises the following steps:
(1) mixing precursor salt of the active component, precursor salt of the auxiliary agent and precursor salt of the carrier, then adding urea and water into the mixture, and stirring the mixture at the temperature of between 38 and 45 ℃ until the mixture is clear;
(2) transferring the mixture into a polytetrafluoroethylene lining, then placing the mixture into a microwave synthesis kettle, and reacting for 6-12h at the temperature of 130-;
(3) naturally cooling to room temperature, carrying out suction filtration, washing until filtrate is neutral, then drying and roasting;
(4) cooling, tabletting, crushing, screening and sieving by a 40-60 mesh sieve to obtain the target catalyst.
Preferably, the precursor salt of the active component is copper nitrate or copper acetate; the precursor salt of the carrier is nitrate of corresponding metal; the precursor salt of the auxiliary agent is at least one of nickel acetate, ferric nitrate and palladium chloride.
Preferably, the adding amount of the urea and the water in the step (1) is 2 times and 23-28 times of the mass of the target catalyst respectively. .
Preferably, in the step (3), the drying condition is drying at 80-120 ℃ for 12-15 h.
Preferably, in the step (3), the roasting condition is 2 o The C/min is raised to 500-600 ℃ and kept for 5-6.5 h.
The method for preparing the dimethyl carbonate by the gas-phase oxidative carbonylation of the methanol comprises the following steps:
(S1) uniformly mixing the catalyst and quartz sand, loading the mixture into a fixed bed reactor, and activating in an inert atmosphere;
(S2) adding CH 3 OH、CO、O 2 Introducing into a preheater to remove CH 3 OH is vaporized and then enters a reactor to react at the temperature of 120-170 ℃ and under the pressure of 0.1-1.0 MPa;
wherein the catalyst is the catalyst of the invention.
Preferably, the space velocity of the methanol liquid in the step (S2) is LHSV =3.75h -1 ，CH 3 OH:CO:O 2 The flow ratio was 1:1200: 120.
Preferably, in the step (S1), the mass ratio of the catalyst to the quartz sand is 0.4: 1.
Preferably, in the step (S1), the condition of activation is 2 o C/min is increased to 300 o C, and keeping for 1-1.5 h.
The invention has the advantages that:
the catalyst provided by the invention is simple to prepare, the preparation process is environment-friendly, and the prepared catalyst does not contain Cl, so that the problems of catalyst inactivation, equipment corrosion, environmental pollution and the like caused by Cl loss are fundamentally avoided; the catalyst has good catalytic performance when being used for preparing dimethyl carbonate by methanol gas phase oxidation carbonylation, the conversion rate of raw materials, the selectivity of products and the space-time yield are high, the reaction atom has high economy, and the byproduct is only water, thereby being green and environment-friendly.
Detailed Description
Example 1
1. A catalyst for catalyzing methanol to directly synthesize dimethyl carbonate comprises an active component, an auxiliary agent and a carrier; the weight ratio of each component in the catalyst is as follows according to 100 percent: 5% of active component, 2% of auxiliary agent and 93% of carrier; the active component is CuO, and the auxiliary agent is NiO; the carrier is CeO with equal mass ratio 2 And ZrO 2 A mixture of (a).
2. The preparation method of the catalyst comprises the following steps:
(1) weighing precursor salt Cu (NO) of active component according to the mass ratio of each component in the catalyst 3 ) 2 ·3H 2 O, precursor salt of auxiliary, and precursor salt Ce (NO) of carrier 3 ) 3 ·3H 2 O and Zr (NO) 3 ) 4 ·5H 2 O, mixing, according to the targetAdding urea and water into the precursor salt at a mass ratio of 1:2:25, and stirring at 40 ℃ until the precursor salt is clear;
(2) transferring the mixture into a polytetrafluoroethylene lining, then placing the polytetrafluoroethylene lining into a microwave synthesis kettle, and reacting for 12 hours at 140 ℃;
(3) naturally cooling to room temperature, suction filtering, washing until the filtrate is neutral, and oven drying at 120 deg.C for 12 hr to obtain filtrate with a volume of 2 o C/min is increased to 550 ℃ and kept for 6h for roasting;
(4) cooling, tabletting, crushing, screening and sieving by a 40-60 mesh sieve to obtain the target catalyst.
Example 2
The catalyst is prepared by the same method as in example 1, and Cu (CH) is selected as precursor salt of the active component 3 COO) 2 ·H 2 O, the same as example 1.
Example 3
The auxiliary agent is Fe 2 O 3 During preparation, the precursor salt of the auxiliary agent is Fe (NO) 3 ) 3 ·9H 2 O, the same as example 1.
Example 4
The auxiliary agent is PdO, and during preparation, PdCl is selected as precursor salt of the auxiliary agent 2 Otherwise, the same procedure as in example 1 was repeated.
Example 5
1. A catalyst for catalyzing methanol to directly synthesize dimethyl carbonate comprises an active component, an auxiliary agent and a carrier; the weight ratio of each component in the catalyst is as follows according to 100 percent: 30% of active component, 2% of auxiliary agent and 68% of carrier; the active component is CuO, and the auxiliary agent is NiO and Fe with equal mass ratio 2 O 3 (ii) a The carrier is CeO 2 。
2. The preparation method of the catalyst comprises the following steps:
(1) weighing precursor salt Cu (NO) of active component according to the mass ratio of each component in the catalyst 3 ) 2 ·3H 2 O, precursor salt Ni (CH) of auxiliary agent 3 COO) 2 ·4H 2 O and Fe (NO) 3 ) 3 ·9H 2 O, precursor salt of carrier Ce (NO) 3 ) 3 ·3H 2 O, adding urea and water into the precursor salt according to the mass ratio of the target catalyst to the urea to the water of 1:2:23, and stirring at 38 ℃ until the precursor salt is clear;
(2) transferring the mixture into a polytetrafluoroethylene lining, then placing the polytetrafluoroethylene lining into a microwave synthesis kettle, and reacting for 12 hours at 130 ℃;
(3) naturally cooling to room temperature, suction filtering, washing until the filtrate is neutral, and oven drying at 80 deg.C for 15 hr to obtain filtrate with a volume of 2 o C/min is increased to 500 ℃ and kept for 6.5h for roasting;
(4) cooling, tabletting, crushing, screening and sieving by a 40-60 mesh sieve to obtain the target catalyst.
Example 6
A catalyst for catalyzing methanol to directly synthesize dimethyl carbonate comprises an active component, an auxiliary agent and a carrier; the weight ratio of each component in the catalyst is as follows according to 100 percent: 9.9 percent of active component, 0.1 percent of auxiliary agent and 90 percent of carrier; the active component is CuO, and the auxiliary agent is NiO and PdO with equal mass ratio; the carrier is ZrO 2 。
The preparation method of the catalyst comprises the following steps:
(1) weighing precursor salt Cu (NO) of active component according to the mass ratio of each component in the catalyst 3 ) 2 ·3H 2 O, precursor salt Ni (CH) of auxiliary agent 3 COO) 2 ·4H 2 O and PdCl 2 Zr (NO) precursor salt of carrier 3 ) 4 ·5H 2 O, mixing to obtain a precursor salt mixture, adding urea and water into the precursor salt mixture according to the mass ratio of the target catalyst to the urea to the water of 1:2:28, and stirring at 45 ℃ until the mixture is clear;
(2) transferring the mixture into a polytetrafluoroethylene lining, then placing the polytetrafluoroethylene lining into a microwave synthesis kettle, and reacting for 6 hours at 150 ℃;
(3) naturally cooling to room temperature, suction filtering, washing until the filtrate is neutral, and oven drying at 100 deg.C for 13 hr to obtain filtrate with a volume of 2 ℃ o C/min is increased to 600 ℃ and kept for 5 hours for roasting;
(4) cooling, tabletting, crushing, screening and sieving by a 40-60 mesh sieve to obtain the target catalyst.
Example 7
One kind is usedThe catalyst for directly synthesizing the dimethyl carbonate by catalyzing the methanol comprises an active component, an auxiliary agent and a carrier; the weight ratio of each component in the catalyst is as follows according to 100 percent: 20% of active component, 10% of auxiliary agent and 70% of carrier; the active component is CuO, and the auxiliary agent is NiO and Fe with equal mass ratio 2 O 3 And PdO; the carrier is CeO with equal mass ratio 2 And ZrO 2 。
The preparation method of the catalyst comprises the following steps:
(1) weighing precursor salt Cu (NO) of active component according to the mass ratio of each component in the catalyst 3 ) 2 ·3H 2 O, precursor salt Ni (CH) of auxiliary agent 3 COO) 2 ·4H 2 O and PdCl 2 A precursor salt of Ce (NO) for carrier 3 ) 3 ·3H 2 O and Zr (NO) 3 ) 4 ·5H 2 O, adding urea and water into the precursor salt according to the mass ratio of the target catalyst to the urea to the water of 1:2:28, and stirring at 45 ℃ until the precursor salt is clear;
(2) transferring the mixture into a polytetrafluoroethylene lining, then placing the polytetrafluoroethylene lining into a microwave synthesis kettle, and reacting for 6 hours at 150 ℃;
(3) naturally cooling to room temperature, suction filtering, washing until the filtrate is neutral, and oven drying at 100 deg.C for 13 hr to obtain filtrate with a volume of 2 ℃ o C/min is increased to 600 ℃ and kept for 5h for roasting;
(4) cooling, tabletting, crushing, screening and sieving by a 40-60 mesh sieve to obtain the target catalyst.
Comparative example 1
In the catalyst, the carrier is activated carbon, and the rest is the same as the example 1, specifically as follows:
1. a catalyst for catalyzing methanol to directly synthesize dimethyl carbonate comprises an active component, an auxiliary agent and a carrier; the weight ratio of each component in the catalyst is as follows according to 100 percent: 5% of active component, 2% of auxiliary agent and 93% of carrier; the active component is CuO, and the auxiliary agent is NiO; the carrier is activated carbon.
2. The preparation method of the catalyst comprises the following steps:
(1) by the same volume immersion method according to each groupWeighing precursor salt Cu (NO) of active component according to the mass ratio of the active component to the catalyst 3 ) 2 ·3H 2 O, precursor salt Ni (CH) of auxiliary agent 3 COO) 2 ·4H 2 Dissolving O in deionized water to prepare a steeping fluid;
(2) slowly adding the impregnation liquid into carrier activated carbon, performing ultrasonic treatment for 0.5h, and then impregnating for 12 h;
(3) then drying at 120 ℃ for 12h under the condition of N 2 Under the atmosphere of 2 o C/min is increased to 550 ℃ and kept for 6h for roasting;
(4) cooling, tabletting, crushing, sieving, and sieving with 40-60 mesh sieve.
Comparative example 2
No auxiliary agent is added, and the concrete steps are as follows:
1. a catalyst for catalyzing methanol to directly synthesize dimethyl carbonate comprises an active component, an auxiliary agent and a carrier; the weight ratio of each component in the catalyst is as follows according to 100 percent: 5% of active component and 95% of carrier; the active component is CuO, and the carrier is CeO with equal mass ratio 2 And ZrO 2 A mixture of (a).
2. The preparation method of the catalyst comprises the following steps:
(1) weighing precursor salt Cu (NO) of active component according to the mass ratio of each component in the catalyst 3 ) 2 ·3H 2 O, precursor salt of carrier Ce (NO) 3 ) 3 ·3H 2 O and Zr (NO) 3 ) 4 ·5H 2 O, mixing, adding urea and water into the precursor salt according to the mass ratio of the target catalyst to the urea to the water of 1:2:25, and stirring at 40 ℃ until the precursor salt is clear;
(2) transferring the mixture into a polytetrafluoroethylene lining, then placing the polytetrafluoroethylene lining into a microwave synthesis kettle, and reacting for 12 hours at 140 ℃;
(3) naturally cooling to room temperature, vacuum filtering, washing until the filtrate is neutral, and oven drying at 120 deg.C for 12 hr to obtain filtrate o Raising the temperature to 550 ℃ per min, and keeping the temperature for 6 hours for roasting;
(4) cooling, tabletting, crushing, sieving, and sieving with 40-60 mesh sieve.
Detection of catalytic Performance
1. The catalyst provided by the invention is used for preparing dimethyl carbonate by methanol gas phase oxidation carbonylation, and comprises the following specific components:
(S1) uniformly mixing 0.4g of the catalyst provided by the invention and 1g of quartz sand, and filling the mixture into a fixed bed reactor, wherein the mixture is filled in an inert atmosphere by 2 o C/min is increased to 300 o C, keeping for 1-1.5h for activation;
(S2) controlling the liquid space velocity of methanol to be LHSV =3.75h -1 ，CH 3 OH:CO:O 2 The flow ratio is 1:1200:120, and CH is added 3 OH、CO、O 2 Introducing into a preheater to remove CH 3 OH is vaporized and then enters a reactor to react at the temperature of 120-170 ℃ and under the pressure of 0.1-1.0 MPa;
(S3) the product was analyzed for CO, O by gas chromatography of the whole components, TCD channel connected to Porapak Q and Molesieve 5A chromatography columns 2 And CO 2 (ii) a FID channel and HP-Innowax chromatographic column are connected to analyze CH 3 OH and DMC;
the reaction results are shown in Table 1.
TABLE 1 catalytic Performance reaction results
| Catalyst and process for preparing same | Reaction temperature/. degree.C | Reaction pressure/MPa | Methanol conversion/% | DMC selectivity/%) | Space-time yield/(mg/(g) cat ·h)) |
| Example 2 | 120 | 0.1 | 10.43 | 80.71 | 353.7 |
| Example 3 | 120 | 0.1 | 9.51 | 80.26 | 320.7 |
| Example 4 | 120 | 0.1 | 13.57 | 80.43 | 458.6 |
| Example 5 | 120 | 0.1 | 15.34 | 82.35 | 530.8 |
| Example 6 | 120 | 0.1 | 14.58 | 81.34 | 498.3 |
| Example 7 | 120 | 0.1 | 20.41 | 83.42 | 715.4 |
| Example 1 | 120 | 0.1 | 9.56 | 79.77 | 320.4 |
| Example 1 | 150 | 0.1 | 13.47 | 80.24 | 454.1 |
| Example 1 | 170 | 0.1 | 15.34 | 81.66 | 526.3 |
| Example 1 | 120 | 1 | 14.86 | 80.77 | 504.3 |
| Comparative example 1 | 120 | 0.1 | 5.31 | 70.32 | 156.9 |
| Comparative example 2 | 120 | 0.1 | 7.62 | 75.63 | 242.1 |
As can be seen from Table 1, the catalyst provided by the invention has good catalytic performance when used for preparing dimethyl carbonate by methanol gas phase oxidation carbonylation by using methanol, oxygen and CO as raw materials. In contrast, in comparative example 1, when activated carbon was used as a carrier, the methanol conversion of the catalyst was only 5%, and the catalyst of example 1 was better able to activate methanol. In comparative example 2, the methanol conversion was only 7.62% without the addition of promoter, indicating that the addition of promoter can improve the catalyst performance.
2. On the basis of the above Table 1, the catalyst provided in example 1 was used to replace the starting material with CH 3 OH and CO 2 And controlling the space velocity of the methanol liquid to be LHSV =3.75h -1 ，CH 3 OH:CO 2 The flow ratio is 1:1200, the catalytic performance of the catalyst is detected, and the results are shown in table 2 under the other experimental conditions as in the table above.
TABLE 2 catalytic performance reaction results after raw material change
| Catalyst and process for producing the same | Starting materials | Reaction temperature/. degree.C | Reaction pressure/MPa | Methanol conversion/% | DMC selectivity/%) | Space-time yield/(mg/(g) cat ·h)) |
| Example 1 | CH 3 OH、CO、O 2 | 120 | 0.1 | 9.56 | 79.77 | 320.4 |
| Example 1 | CH 3 OH、CO 2 | 120 | 0.1 | 2.34 | 40.15 | 39.5 |
As can be seen from Table 2, methanol and CO were used as catalysts in example 1 2 The conversion rate, product selectivity and yield of methanol are obviously reduced as raw materials. Because, methanol and CO are used 2 When used as a raw material, a reaction is difficult to proceed r G is between 0 and 800 o The range of C is positive value, and the reaction can not be carried out spontaneously; only when the temperature is 80 deg.C o C, pressure is more than or equal to 2.4 multiplied by 10 4 At MPa,. DELTA. r G<0, the reaction can be carried out in thermodynamics, but the pressure condition is too harsh, and the operation is difficult in practice; therefore, in actual production, if methanol and CO are used 2 When dimethyl carbonate is prepared as a raw material,it is required to be carried out under the conditions of high-voltage discharge, plasma, membrane reactor and the like. In Table 2, methanol and CO were used 2 When the methanol is used as a raw material, the reaction cannot be carried out thermodynamically, and the reaction is weak only under the kinetic factor, so that the conversion rate, the product selectivity and the yield of the methanol are remarkably reduced.
Therefore, the catalyst provided by the invention is prepared from methanol, CO and O 2 The raw material is prepared into the dimethyl carbonate without the conditions of high-voltage discharge and the like, and the reaction condition is mild.
Claims (10)
1. A catalyst for catalyzing methanol to directly synthesize dimethyl carbonate is characterized in that: the catalyst comprises an active component, an auxiliary agent and a carrier; the weight ratio of each component to the catalyst is as follows according to 100 percent: 5-30% of active component, 0.1-10% of auxiliary agent and 68-93% of carrier; the active component is CuO, and the auxiliary agent is NiO and Fe 2 O 3 At least one of PdO; the carrier is cerium oxide and/or zirconium oxide.
2. A process for preparing the catalyst of claim 1, wherein: the method comprises the following steps:
(1) mixing precursor salt of the active component, precursor salt of the auxiliary agent and precursor salt of the carrier, then adding urea and water into the mixture, and stirring the mixture at the temperature of between 38 and 45 ℃ until the mixture is clear;
(2) transferring the mixture into a polytetrafluoroethylene lining, then placing the mixture into a microwave synthesis kettle, stirring the mixture, and reacting the mixture for 6 to 12 hours at the temperature of 130-;
(3) naturally cooling to room temperature, carrying out suction filtration, washing until filtrate is neutral, then drying and roasting;
(4) cooling, tabletting, crushing, screening and sieving by a 40-60 mesh sieve to obtain the target catalyst.
3. The method for preparing the catalyst according to claim 2, wherein: the precursor salt of the active component is copper nitrate or copper acetate; the precursor salt of the carrier is nitrate of corresponding metal; the precursor salt of the auxiliary agent is at least one of nickel acetate, ferric nitrate and palladium chloride.
4. The method for preparing the catalyst according to claim 3, wherein: in the step (1), the adding amount of urea and water is 2 times and 23-28 times of the mass of the target catalyst respectively.
5. The method for preparing the catalyst according to claim 4, wherein: in the step (3), the drying condition is drying for 12-15h at 80-120 ℃.
6. The method for preparing the catalyst according to claim 5, wherein: in the step (3), the roasting condition is 2 o The C/min is raised to 500-600 ℃ and kept for 5-6.5 h.
7. The method for preparing dimethyl carbonate by methanol gas phase oxidation carbonylation is characterized in that: the method specifically comprises the following steps:
(S1) uniformly mixing the catalyst and quartz sand, loading the mixture into a fixed bed reactor, and activating in an inert atmosphere;
(S2) adding CH 3 OH、CO、O 2 Introducing into a preheater to remove CH 3 OH is vaporized and then enters a reactor to react at the temperature of 120-170 ℃ and the pressure of 0.1-1.0 MPa;
wherein the catalyst is the catalyst of claim 1.
8. The process for the vapor-phase oxidative carbonylation of methanol to dimethyl carbonate according to claim 7, wherein: the space velocity of the methanol liquid in the step (S2) is LHSV =3.75h -1 ，CH 3 OH:CO:O 2 The flow ratio was 1:1200: 120.
9. The process for the vapor-phase oxidative carbonylation of methanol to dimethyl carbonate according to claim 8, wherein: the mass ratio of the catalyst to the quartz sand is 0.4: 1.
10. According to claim 9The method for preparing the dimethyl carbonate by the gas-phase oxidative carbonylation of the methanol is characterized by comprising the following steps: the conditions for activation in step (S1) are 2 o C/min is increased to 300 o C, and keeping for 1-1.5 h.
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