Two-stage reactor and use method thereof
By designing a two-stage reactor, the adsorption and catalytic reaction of carbonyl metal compounds is carried out using the wire mesh layer and porcelain balls, the problem of reducing catalyst activity in the synthesis gas is solved, and more efficient and stable synthesis of ethanol, methanol and methyl acetate is achieved.
Patent Information
- Application Number
- CN202411758375.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-02
- Publication Date
- 2025-04-25
AI Technical Summary
During the process of synthesis gas to ethanol or methanol, substances such as iron carbonyl carbonyl carbonyl and nickel carbonyl carbonyl will reduce the activity of the catalyst in the reactor, resulting in a shortening of the catalyst life, affecting product quality and yield, and being difficult to remove.
A two-stage reactor is designed, including reactor one and reactor two. By using a wire mesh layer and a porcelain ball in reactor one, the purified raw material gas is obtained, and then catalytic reaction is carried out in reactor two.
Effective treatment of iron carbonyl and nickel carbonyl in synthesis gas improves the stability and economy of the process of ethanol, methanol and methyl acetate in synthesis gas, extends the service life of the catalyst, and improves the purity and yield of the product.
Smart Images
Figure CN119869365A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to a two-stage reactor and a method for using the same, and belongs to the technical field of chemical engineering. Background Art
[0002] The production of ethanol or methanol from syngas is an important chemical process that usually includes multiple steps and reactions and requires suitable catalysts and conditions to achieve;
[0003] At present, in industry, when syngas is used to produce ethanol or methanol, the syngas often contains substances such as carbonyl iron (Fe(CO)5) and carbonyl nickel (Ni(CO)4). These substances will reduce the activity of the catalyst in the reactor, resulting in a shortened catalyst life, while affecting the quality and output of the ethanol or methanol products and the intermediate product methyl acetate. They are also difficult to remove from the product. When the content of carbonyl metal compounds in the product reaches more than 10 ppm, the product color will be affected. Summary of the invention
[0004] According to one aspect of the present application, a two-stage reactor is provided, comprising a reactor 1 and a reactor 2, wherein the reactor 1 is arranged on the top of the reactor 2, a grid plate is arranged between the two, and a plurality of porcelain balls are placed on the grid plate;
[0005] A manhole is provided on one side of the top of the outer wall of the reactor 1, and a raw gas inlet is provided on the other side;
[0006] The top of the interior of the reactor 1 is provided with a wire mesh layer, and the wire mesh layer is filled with porcelain balls;
[0007] The reactor 1 and the reactor 2 are both provided with thermocouples;
[0008] The bottom of the reactor 2 is filled with porcelain balls;
[0009] A reaction gas outlet is provided at the bottom center of the reactor 2, and discharge ports are symmetrically provided on both sides of the reaction gas outlet.
[0010] The present application also provides a method for using the two-stage reactor as described above, comprising the following steps:
[0011] S1: Introduce hot N2 from the raw gas inlet to dry, purge and replace the catalysts in reactor 1 and reactor 2;
[0012] After drying and replacement, the preheated raw gas is introduced into the reactor 1;
[0013] S2: The raw gas enters the reactor and undergoes an adsorption reaction of the metal carbonyl compound to obtain a purified pure raw gas;
[0014] S3: sending the purified raw gas into the second reactor for catalytic reaction to obtain a catalytic reaction product;
[0015] S4: sending the catalytic reaction product from the reaction gas outlet to the subsequent process section for condensation, distillation and separation to obtain a pure product.
[0016] Optionally, in step S1, the raw gas includes at least two of dimethyl ether, CO, H2 and N2.
[0017] Optionally, in step S1, the drying temperature is 120-250° C., and the purge replacement standard is O 2 concentration ≤ 0.2%.
[0018] Optionally, in step S2, the adsorption temperature is 20-250° C., and the adsorption pressure is 3-8 MPa.
[0019] Optionally, the catalytic reaction in step S3 is specifically:
[0020] Carry out carbonylation reaction with a carbonylation catalyst to obtain methyl acetate;
[0021] Or it can undergo carbonylation hydrogenation reaction with a modified catalyst to obtain methanol and ethanol.
[0022] Optionally, in step S3, the reaction temperature is 150-260° C. and the reaction pressure is 3-8 MPa.
[0023] Optionally, the modified catalyst is a carbonylation hydrogenation catalyst.
[0024] The beneficial effects of this application include:
[0025] The two-stage reactor and the method for using the same provided in the present application can effectively treat carbonyl iron and carbonyl nickel in synthesis gas without adding purification equipment, innovatively improving the stability and economy of the process of preparing ethanol, methanol and methyl acetate from synthesis gas; improving the catalyst utilization and efficiency of the ethanol, methanol and methyl acetate synthesis reaction; extending the service life of the catalyst, reducing replacement and maintenance costs; and improving the purity and output of ethanol, methanol and methyl acetate products.
[0026] Under the conventional industrial method, the space-time yields of methyl acetate and ethanol are about 0.3-0.33 and 0.45-0.58 respectively, and the content of carbonyl metal compounds in the products is 20-50ppm and 8-20ppm respectively. Under the same conditions, using a two-stage reactor, the space-time yields of methyl acetate and ethanol can be increased by 9% and 14% respectively, and the content of carbonyl metal compounds in the product is almost undetectable. BRIEF DESCRIPTION OF THE DRAWINGS
[0027] Figure 1A schematic diagram of the device structure of a two-stage reactor provided in one embodiment of the present application.
[0028] List of parts and reference numerals:
[0029] 1. Reactor 1; 2. Reactor 2; 3. Manhole; 4. Raw gas inlet; 5. Wire mesh layer; 6. Ceramic ball; 7. Thermocouple; 8. Grid plate; 9. Discharge port; 10. Reaction gas outlet. DETAILED DESCRIPTION
[0030] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.
[0031] Unless otherwise specified, the raw materials and catalysts in the examples of this application were purchased through commercial channels.
[0032] like Figure 1 As shown, according to one embodiment of the present application, a two-stage reactor is provided, comprising a reactor 1 and a reactor 2, wherein the reactor 1 is arranged on the top of the reactor 2, and a grid plate 8 is arranged between the two, and a plurality of porcelain balls 6 are placed on the grid plate 8;
[0033] A manhole 3 is provided on one side of the top of the outer wall of the reactor 1, and a raw gas inlet 4 is provided on the other side;
[0034] The top of the reactor 1 is provided with a wire mesh layer 5, and the wire mesh layer 5 is filled with porcelain balls 6;
[0035] The reactor 1 and the reactor 2 are both provided with thermocouples 7;
[0036] The bottom of the reactor 2 2 is filled with porcelain balls 6;
[0037] A reaction gas outlet 10 is provided at the bottom center of the reactor 2, and discharge ports 9 are symmetrically provided on both sides of the reaction gas outlet 10.
[0038] The present application also provides a method for using the two-stage reactor as described above, comprising the following steps:
[0039] S1: Introduce hot N2 from the raw gas inlet 4 to dry, purge and replace the catalysts in the reactor 1 and the reactor 2;
[0040] After drying and replacement, the preheated raw gas is introduced into the reactor 1;
[0041] The raw gas includes at least two of dimethyl ether, CO, H2 and N2;
[0042] Drying temperature: 120~250℃, purge replacement standard: O2 concentration ≤0.2%;
[0043] S2: The raw gas enters the reactor 1 and undergoes an adsorption reaction of the metal carbonyl compound to obtain a purified pure raw gas;
[0044] Adsorption temperature: 20~250℃, adsorption pressure: 3~8MPa;
[0045] S3: sending the purified raw gas into the reactor 2 for catalytic reaction to obtain a catalytic reaction product;
[0046] The catalytic reaction is specifically:
[0047] Carry out carbonylation reaction with a carbonylation catalyst to obtain methyl acetate;
[0048] Or it can undergo carbonylation hydrogenation reaction with modified catalyst to obtain methanol and ethanol;
[0049] The modified catalyst is a mixture of a carbonylation catalyst and hydrogen;
[0050] S4: sending the catalytic reaction product from the reaction gas outlet 10 to a subsequent process section for condensation, distillation, and separation to obtain a pure product;
[0051] Reaction temperature: 150-260°C; reaction pressure: 3-8MPa.
[0052] Example 1
[0053] Preparation of methyl acetate using an apparatus for processing carbonyl iron and carbonyl nickel:
[0054] Introduce hot N2 from the raw gas inlet to dry, purge and replace the catalysts in reactor 1 and reactor 2;
[0055] Drying temperature: 230℃, purge replacement standard: O2≤0.2%;
[0056] After drying and replacement, the preheated raw gas is introduced into the reactor 1;
[0057] The raw gas includes dimethyl ether, CO, H2 and N2;
[0058] The raw gas enters the reactor 1 and undergoes an adsorption reaction of the carbonyl metal compound to obtain a purified pure raw gas;
[0059] Adsorption temperature: 150℃; adsorption pressure: 4MPa;
[0060] The purified pure raw gas enters the reactor 2, and undergoes a carbonylation reaction with a carbonylation catalyst to generate methyl acetate; the reaction temperature is 180°C, and the reaction pressure is 4MPa;
[0061] The carbonylation reaction product, methyl acetate, is sent from the reaction gas outlet to the subsequent process section for condensation, distillation and separation to obtain a pure product.
[0062] Under the conventional industrial method, the space-time yield of methyl acetate is about 0.3 to 0.33, and the content of carbonyl metal compounds in the product is 20 to 50 ppm.
[0063] Under the same conditions, using the two-stage reactor provided in the present application, the space-time yield of methyl acetate can be increased by about 9% by calculation, and at the same time, the content of carbonyl metal compounds in the product is almost undetectable.
[0064] Example 2
[0065] Preparation of ethanol using a unit for processing carbonyl iron and carbonyl nickel:
[0066] Introduce hot N2 from the raw gas inlet to dry, purge and replace the catalysts in reactor 1 and reactor 2;
[0067] Drying temperature: 120℃, purge replacement standard: O2≤0.2%;
[0068] After drying and replacement, the preheated raw gas is introduced into the reactor 1;
[0069] The raw gas includes dimethyl ether, CO, and H2;
[0070] The raw gas enters the reactor 1 and undergoes an adsorption reaction of the carbonyl metal compound to obtain a purified pure raw gas;
[0071] Adsorption temperature: 20℃; adsorption pressure: 5MPa;
[0072] The purified raw gas enters the reactor 2, and undergoes carbonylation hydrogenation reaction with the modified catalyst at a reaction temperature of 210°C and a reaction pressure of 5MPa.
[0073] The carbonylation hydrogenation reaction products, methanol and ethanol, are sent from the reaction gas outlet to subsequent process sections for condensation, distillation and separation to obtain pure products.
[0074] Under the conventional industrial method, the space-time yield of ethanol is about 0.45 to 0.58, and the content of carbonyl metal compounds in the product is 8 to 20 ppm.
[0075] Under the same conditions, when the two-stage reactor provided in the present application is used, the space-time yield of ethanol can be increased by 14% by calculation, and at the same time, the content of carbonyl metal compounds in the product is almost undetectable.
[0076] The above description is only a partial embodiment of the present application and does not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the above disclosed technical content to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A two-stage reactor, characterized in that: It comprises a reactor 1 and a reactor 2, wherein the reactor 1 is arranged on the top of the reactor 2, a grid plate is arranged between the two, and a plurality of porcelain balls are placed on the grid plate; A manhole is provided on one side of the top of the outer wall of the reactor 1, and a raw gas inlet is provided on the other side; The top of the interior of the reactor 1 is provided with a wire mesh layer, and the wire mesh layer is filled with porcelain balls; The reactor 1 and the reactor 2 are both provided with thermocouples; The bottom of the reactor 2 is filled with porcelain balls; A reaction gas outlet is provided at the bottom center of the reactor 2, and discharge ports are symmetrically provided on both sides of the reaction gas outlet.
2. The method for using a two-stage reactor according to claim 1, characterized in that: The following steps are involved: S1: Introduce hot N2 from the raw gas inlet to dry, purge and replace the catalysts in reactor 1 and reactor 2; After drying and replacement, the preheated raw gas is introduced into the reactor 1; S2: The raw gas enters the reactor and undergoes an adsorption reaction of the metal carbonyl compound to obtain a purified pure raw gas; S3: sending the purified raw gas into the second reactor for catalytic reaction to obtain a catalytic reaction product; S4: sending the catalytic reaction product from the reaction gas outlet to the subsequent process section for condensation, distillation and separation to obtain a pure product.
3. The method for using a two-stage reactor according to claim 2, characterized in that: In step S1, the raw gas includes at least two of dimethyl ether, CO, H2 and N2.
4. The method for using a two-stage reactor according to claim 3, characterized in that: In the step S1, the drying temperature is 120-250°C, and the purge replacement standard is O2 concentration ≤ 0.2%.
5. The method for using a two-stage reactor according to claim 2, characterized in that: In the step S2, the adsorption temperature is 20 to 250°C, and the adsorption pressure is 3 to 8 MPa.
6. The method for using a two-stage reactor according to claim 2, characterized in that: The catalytic reaction in step S3 is specifically: Carry out carbonylation reaction with a carbonylation catalyst to obtain methyl acetate; Or it can undergo carbonylation hydrogenation reaction with a modified catalyst to obtain methanol and ethanol.
7. The method for using a two-stage reactor according to claim 6, characterized in that: In the step S3, the reaction temperature is 150-260° C. and the reaction pressure is 3-8 MPa.
8. The method for using a two-stage reactor according to claim 7, characterized in that: The modified catalyst is a carbonylation hydrogenation catalyst.