CN111420655A - Method for chemically plating metal catalyst on tube pass inner wall of continuous flow reaction module - Google Patents
Method for chemically plating metal catalyst on tube pass inner wall of continuous flow reaction module Download PDFInfo
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- CN111420655A CN111420655A CN202010308684.7A CN202010308684A CN111420655A CN 111420655 A CN111420655 A CN 111420655A CN 202010308684 A CN202010308684 A CN 202010308684A CN 111420655 A CN111420655 A CN 111420655A
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
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Abstract
The invention discloses a method for chemically plating a metal catalyst on the inner wall of a tube pass of a continuous flow reaction module, which comprises the steps of introducing a plating solution into the tube pass of the continuous flow reaction module by using a metering pump, heating to 75-95 ℃, and setting the flow of the metering pump; cooling the plating solution flowing out of the tube side of the continuous flow reaction module; performing cyclic chemical plating, closing the metering pump, and introducing compressed air into the tube pass of the continuous flow reaction module to exhaust liquid; keeping the temperature at 75-95 ℃ for 5-10 min, stopping introducing compressed air, cooling the continuous flow reaction module 1, introducing an ethanol water solution for cleaning, emptying by using the compressed air, and cooling to room temperature to ensure that the chemical plating metal catalyst is tightly adhered to the inner wall of the tube pass of the continuous flow reaction module. The method of the invention can lead the continuous flow reaction module to better carry out heterogeneous catalytic reaction, and broadens the application range of the continuous flow reaction module. The method has the advantages of simple operation, firm plating layer, uniform thickness and good catalytic effect.
Description
Technical Field
The invention relates to a method for chemically plating a metal catalyst on the inner wall of a tube side of a continuous flow reaction module.
Background
When a chemical reaction involving a metal catalyst such as silver, platinum, palladium, copper, cobalt, ruthenium, etc. is carried out in a continuous flow reactor, there are generally two approaches, i.e., feeding the material and catalyst particles into the continuous flow reactor, and then separating the product and recovering the catalyst. The method adopts micron-sized eggshell type catalyst, namely, a thin layer of noble metal is coated on the carrier, so that the consumption of the metal is reduced without reducing the catalytic efficiency. For example, patent CN106582826A discloses a method for coating the surface of a carrier such as alumina and silica particles by using an impregnation method, and a catalyst for producing vinyl acetate is prepared. The method of pumping the material and the catalyst particles into the continuous flow reactor has certain defects, the reaction flux is small, and the catalyst layer is easy to damage due to the friction between the catalyst particles and the wall surface of the reactor, so that the service life of the catalyst is short. The other idea is to plate a metal or metal oxide thin layer with catalytic activity on the inner wall of the continuous flow reactor and carry out heterogeneous catalytic reaction on the inner wall of the continuous flow reactor. The use of the continuous flow reactor is expanded through chemical modification of the inner wall of the reactor.
There are patents disclosing electroless plating of metal catalysts on tube side surfaces in a similar manner. For example, patent CN102605356A discloses a method for chemically plating metal catalyst on through holes of an insulating substrate, in which a colloid containing metal powder is adsorbed on the surface of the through holes after surface treatment, so that a metal catalyst layer is formed on the surface of the through holes. However, this method is complicated to produce a metal powder jelly and is only suitable for use in a case where the depth is shallow (0.1 to 0.5 cm). However, the tube side length of the reaction module of the continuous flow reactor is usually between 10 cm and 100cm, and a feeding pump is needed to pump the plating solution into the tube side, at this time, the colloidal solution described in the patent is extruded by the pump head and then agglomerated, which is likely to cause coating failure, and the tube side is likely to be blocked due to high pressure drop in the tube side.
Because the powder colloid is complicated to prepare and has the defects of easy agglomeration and easy blockage in the process of entering the continuous flow reactor, the powder chemical plating method is not suitable for plating the catalytic metallization agent on the inner wall of the module tube side of the continuous flow reactor.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for chemically plating metal catalyst on the inner wall of a tube side of a continuous flow reaction module.
The technical scheme of the invention is summarized as follows:
a method for chemically plating a metal catalyst on the inner wall of a tube pass of a continuous flow reaction module comprises the following steps of enabling plating solution J in a liquid storage tank 23 to enter the tube pass of the continuous flow reaction module 1 through a tee joint 26 by a metering pump 24, enabling the temperature to rise to 75-95 ℃, enabling the value of the flow of the metering pump calculated by m L/min to be 3-5 times of the total liquid holding capacity of the tube pass of the continuous flow reaction module 1 when m L is measured, enabling the plating solution flowing out of the tube pass of the continuous flow reaction module 1 to be cooled to 0-5 ℃ by a cooler 22 and then return to the liquid storage tank 23, conducting circulating chemical plating for 10-30 min, closing the metering pump 24, enabling compressed air or nitrogen K to enter the tube pass of the continuous flow reaction module 1 through a gas flowmeter 25 and the tee joint 26 to be discharged with liquid, keeping the temperature at 75-95 ℃ for 5-10 min, stopping introducing the compressed air or nitrogen K, enabling the temperature of the continuous flow reaction module 1 to be reduced to be below 60 ℃, introducing 50-75% of ethanol water solution to clean the tube pass of the continuous flow reaction module 1, washing the tube pass, washing metal residues, then cooling the inner wall of the continuous.
Preferably, the plating solution consists of L and M, wherein L is an inorganic salt aqueous solution, 5-10mg of inorganic salt is taken according to the surface area of the tube side inner wall of each square centimeter continuous flow reaction module, the inorganic salt aqueous solution is prepared by firstly preparing an inorganic salt saturated aqueous solution at normal temperature and normal pressure and then diluting the inorganic salt saturated aqueous solution by 5-20 times by volume with water, anions of the inorganic salt are chloride ions, nitrate radicals or sulfate radicals, cations of the inorganic salt are cation oxides corresponding to the cations and are insoluble in water and stable at normal temperature and normal pressure, the M is a hydrogen peroxide aqueous solution with the mass concentration of 5-20%, and the molar ratio of the inorganic salt to the hydrogen peroxide is 1: 3-5.
THE ADVANTAGES OF THE PRESENT INVENTION
The method can chemically coat metal catalyst on the inner wall of the tube pass of the continuous flow reaction module, so that the continuous flow reaction module can better perform heterogeneous catalytic reaction, and the application range of the continuous flow reaction module is widened. The method has the advantages of simple operation, firm plating layer and uniform thickness.
Drawings
FIG. 1 is a schematic diagram of an apparatus used in a method for chemically plating a metal catalyst on the inner wall of a tube side of a continuous flow reaction module.
FIG. 2A is a photograph of a continuous flow reaction module (material is glass) without metal-plated catalyst.
FIG. 2B is a photograph of a metal-coated catalyst continuous flow reaction module (glass in material).
FIG. 3 is a schematic diagram of an apparatus for continuously synthesizing vinyl acetate by using a metal catalyst chemically plated on the inner wall of a tube side of a continuous flow reaction module.
Detailed Description
The following terms described in the present invention have the following meanings.
The term "module" means the smallest unit that can be reacted as a continuous flow in a continuous flow reactor (e.g., the material can be glass, silicon carbide, etc., and the lumen of the microtube side is tubular or heart-shaped).
The term "metering pump" means a device capable of continuously supplying a material (e.g. a reciprocating pump, a syringe pump, etc.) with emphasis on metering.
The invention will be further described with reference to specific embodiments and the accompanying drawings.
Example 1
A method for chemically plating metal catalyst on the inner wall of tube pass of continuous flow reaction module (the adopted device is shown in figure 1) comprises the following steps of enabling plating solution J in a liquid storage tank 23 to enter the tube pass of the continuous flow reaction module 1 through a tee joint 26 by using a metering pump 24, enabling the temperature to rise to 75 ℃, setting the flow rate of the metering pump to be 24m L/min, taking a G1 type continuous flow reaction module of the Corning company of America as an example, enabling the module liquid-holding capacity to be 8m L, enabling the plating solution flowing out of the tube pass of the continuous flow reaction module 1 to return to the liquid storage tank 23 after being cooled to 0 ℃ through a cooler 22, conducting circulating chemical plating for 30min, closing the metering pump 24, enabling compressed air K to enter the tube pass of the continuous flow reaction module 1 through a gas flow meter 25 and the tee joint 26 to be emptied of liquid, keeping the temperature at 75 ℃ for 5min, stopping the compressed air K to enable the temperature of the continuous flow reaction module 1 to be reduced to be below 60 ℃, introducing 75% ethanol water solution to clean the tube pass of the continuous flow reaction module 1, washing residues, then naturally cooling the metal catalyst to be naturally cooled to room temperature, and emptying.
The plating solution is prepared by mixing L and M, wherein L is a palladium chloride aqueous solution, 5mg of palladium chloride (the internal surface area of the G1 type continuous flow reaction module is about 230 square centimeters and corresponds to 1150mg of palladium chloride) is taken according to the surface area of the tube side inner wall of each square centimeter of continuous flow reaction module, the palladium chloride aqueous solution is prepared by firstly preparing a saturated palladium chloride aqueous solution at normal temperature and normal pressure and then diluting the saturated palladium chloride aqueous solution by 20 volume times with water, palladium oxide is insoluble in water and stable at normal temperature and normal pressure, M is a hydrogen peroxide aqueous solution with the mass concentration of 5%, and the molar ratio of the palladium chloride to the hydrogen peroxide is 1: 3.
Example 2
A method for chemically plating metal catalyst on the inner wall of tube pass of continuous flow reaction module (the adopted device is shown in figure 1) comprises the following steps of enabling plating solution J in a liquid storage tank 23 to enter the tube pass of the continuous flow reaction module 1 through a tee joint 26 by using a metering pump 24, enabling the temperature to rise to 85 ℃, setting the flow rate of the metering pump to be 40m L/min, taking a G1 type continuous flow reaction module of the Corning company of America as an example, enabling the module liquid holding capacity to be 8m L, enabling the plating solution flowing out of the tube pass of the continuous flow reaction module 1 to return to the liquid storage tank 23 after being cooled to 5 ℃ through a cooler 22, conducting circulating chemical plating for 10min, closing the metering pump 24, enabling compressed nitrogen K to enter the tube pass of the continuous flow reaction module 1 through a gas flow meter 25 and the tee joint 26 to be emptied of liquid, keeping the temperature at 85 ℃ for 10min, stopping the compressed nitrogen K to enable the temperature of the continuous flow reaction module 1 to be reduced to be below 60 ℃, introducing 50% ethanol water solution to clean the tube pass of the reaction module 1, washing the tube pass, washing the residue, then plating metal by using the compressed nitrogen K, naturally cooling to room temperature, and enabling the inner wall of the continuous flow reaction.
The plating solution is prepared by mixing L and M, wherein L is a copper sulfate aqueous solution, 10mg of copper sulfate (the inner surface area of the G1 type continuous flow reaction module is about 230 square centimeters and the corresponding copper sulfate is 2300mg) is taken according to the surface area of the inner wall of the tube side of each square centimeter of continuous flow reaction module, the copper sulfate aqueous solution is prepared by firstly preparing a saturated copper sulfate aqueous solution at normal temperature and normal pressure and then diluting the saturated copper sulfate aqueous solution by 5 volume times with water, copper oxide is insoluble in water and stable at normal temperature and normal pressure, M is a hydrogen peroxide aqueous solution with the mass concentration of 10%, and the molar ratio of the copper sulfate to the hydrogen peroxide is 1.
Example 3
A method for chemically plating metal catalyst on the inner wall of tube pass of continuous flow reaction module (the adopted device is shown in figure 1) comprises the following steps of enabling plating solution J in a liquid storage tank 23 to enter the tube pass of the continuous flow reaction module 1 through a tee joint 26 by using a metering pump 24, enabling the temperature to rise to 95 ℃, enabling the flow rate of the metering pump to be 32m L/min, taking a G1 type continuous flow reaction module of the Corning company of America as an example, enabling the module liquid holding capacity to be 8m L, enabling the plating solution flowing out of the tube pass of the continuous flow reaction module 1 to return to the liquid storage tank 23 after being cooled to 3 ℃ through a cooler 22, conducting circulating chemical plating for 20min, closing the metering pump 24, enabling compressed nitrogen K to enter the tube pass of the continuous flow reaction module 1 through a gas flow meter 25 and the tee joint 26 to be emptied of liquid, keeping the temperature at 95 ℃ for 10min, stopping the compressed nitrogen K to enable the temperature of the continuous flow reaction module 1 to be reduced to be below 60 ℃, introducing 70% ethanol water solution to clean the tube pass of the reaction module 1, washing the tube pass, washing the residue, then plating metal by using the compressed nitrogen K, naturally cooling to room temperature, and enabling the inner wall of the continuous flow reaction.
The plating solution is prepared by mixing L and M, wherein L is a platinum nitrate aqueous solution, 5mg of platinum nitrate is taken according to the surface area of the inner wall of a tube side of a continuous flow reaction module per square centimeter, the (G1 type continuous flow reaction module has an inner surface area of about 230 square centimeters corresponding to 1150mg of platinum nitrate) platinum nitrate aqueous solution is prepared by firstly preparing a platinum nitrate saturated aqueous solution at normal temperature and normal pressure, then diluting the platinum nitrate saturated aqueous solution by 10 volume times with water, platinum dioxide is insoluble in water and stable at normal temperature and normal pressure, M is a hydrogen peroxide aqueous solution with the mass concentration of 20%, and the molar ratio of inorganic salt to hydrogen peroxide is 1: 5.
The continuous flow reaction modules are commercially available, for example, model G1, G2, G3, and G4 from corning, usa.
Example 4
The continuous flow reactor (the first reaction module 1 and the second reaction module 2 are both chemically plated by the method of example 1) for continuously synthesizing vinyl acetate by chemically plating metal catalyst on the inner wall of the tube side (see figure 3) comprises the following steps:
respectively introducing the ethylene A through a first metering pump 11 and the acetic acid B through a second metering pump 12 into a first tee joint 7 through pipelines, and then introducing into a first temperature control tube pass 9 of a first reaction module 1 of the continuous flow reactor 3, so that the temperature of the mixture of the A and the B is adjusted to a first set temperature of 80 ℃; respectively introducing nitrogen C passing through a third metering pump 13 and oxygen D passing through a fourth metering pump 14 into a second tee joint 8 through pipelines, and then introducing the mixture into a second temperature-controlled tube pass 10 of the first reaction module 1 of the continuous flow reactor 3, so that the temperature of the mixture of C and D is adjusted to a first set temperature of 80 ℃; two materials with the temperature of 80 ℃ are converged in the main tube side 15 of the first reaction module 1, react at the first set temperature of 80 ℃ for 10min and then are introduced into the tube side of the second reaction module 2 of the continuous flow reactor 3 through a pipeline; carrying out oxidation reaction at a second set temperature of 140 ℃ for 6min, introducing the oxidation product into a cooler 4 through a pipeline, cooling to room temperature, and introducing into a gas-liquid separator 5 through a pipeline to separate a gas phase E and a liquid phase F; and introducing the liquid phase F into an oil-water separator 6 through a pipeline, separating out a water phase H and vinyl acetate G, wherein the yield is 96 percent, and the purity is 99 percent.
Claims (2)
1. A method for chemically plating a metal catalyst on the inner wall of a tube pass of a continuous flow reaction module is characterized by comprising the following steps of enabling a plating solution (J) in a liquid storage tank (23) to enter the tube pass of the continuous flow reaction module (1) through a tee joint (26) by a metering pump (24), enabling the temperature to rise to 75-95 ℃, setting the flow of the metering pump to be 3-5 times of the total liquid holding capacity of the tube pass of the continuous flow reaction module (1) in terms of m L time according to the value of m L/min, enabling the plating solution flowing out of the tube pass of the continuous flow reaction module (1) to return to the tube pass through a cooler (22) after being cooled to 0-5 ℃, conducting circulating chemical plating for 10-30 min, closing the metering pump (24), enabling compressed air or nitrogen (K) to enter the tube pass of the continuous flow reaction module (1) through a gas flow meter (25) and the tee joint (26) to be discharged with liquid, keeping the temperature at 75-95 ℃ for 5-10 min, stopping introducing the compressed air or nitrogen (K) to enable the temperature of the continuous flow reaction module (1) to be reduced to be below 60 ℃, enabling the continuous flow reaction module (1) to be discharged with the residual metal catalyst, and enabling the ethanol to be tightly washed, and enabling the residual metal catalyst to be adhered to be washed, and enabling the continuous.
2. The method as claimed in claim 1, wherein the plating solution is composed of L and M, wherein L is an inorganic salt aqueous solution, 5-10mg of inorganic salt is taken according to the surface area of the inner wall of the tube pass of the continuous flow reaction module per square centimeter, the inorganic salt aqueous solution is prepared by preparing an inorganic salt saturated aqueous solution at normal temperature and normal pressure, and then diluting the inorganic salt saturated aqueous solution by 5-20 times by volume with water, anions of the inorganic salt are chloride ions, nitrate radicals or sulfate radicals, cations of the inorganic salt are cation oxides corresponding to the cations and are insoluble in water and stable at normal temperature and normal pressure, M is a hydrogen peroxide aqueous solution with a mass concentration of 5-20%, and the molar ratio of the inorganic salt to the hydrogen peroxide is 1: 3-5.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010308684.7A CN111420655A (en) | 2020-04-18 | 2020-04-18 | Method for chemically plating metal catalyst on tube pass inner wall of continuous flow reaction module |
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| CN202010308684.7A CN111420655A (en) | 2020-04-18 | 2020-04-18 | Method for chemically plating metal catalyst on tube pass inner wall of continuous flow reaction module |
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Citations (7)
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|---|---|---|---|---|
| CN1944709A (en) * | 2006-09-21 | 2007-04-11 | 复旦大学 | Method for depositing continuous metal layer on capillary tube inner wall |
| JP2008019457A (en) * | 2006-07-11 | 2008-01-31 | National Institute Of Advanced Industrial & Technology | Electroless gold-plating solution |
| US20090306414A1 (en) * | 2006-03-02 | 2009-12-10 | Yasuhiro Uozumi | Microchannel Reactor |
| CN103466955A (en) * | 2013-08-20 | 2013-12-25 | 秦皇岛玻璃工业研究设计院 | Manufacturing method for anti-reflection glass and coating equipment for implementation of manufacturing method |
| CN104911570A (en) * | 2015-05-14 | 2015-09-16 | 上海应用技术学院 | Plating solution carrying out chemical palladium plating on copper surface and preparation method therefor |
| CN105597641A (en) * | 2016-01-14 | 2016-05-25 | 重庆大学 | Preparation method of catalyst layer in microchannel reactor |
| CN110746296A (en) * | 2019-11-12 | 2020-02-04 | 云南正邦科技有限公司 | Method for preparing vinyl acetate by using microchannel reactor |
-
2020
- 2020-04-18 CN CN202010308684.7A patent/CN111420655A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090306414A1 (en) * | 2006-03-02 | 2009-12-10 | Yasuhiro Uozumi | Microchannel Reactor |
| JP2008019457A (en) * | 2006-07-11 | 2008-01-31 | National Institute Of Advanced Industrial & Technology | Electroless gold-plating solution |
| CN1944709A (en) * | 2006-09-21 | 2007-04-11 | 复旦大学 | Method for depositing continuous metal layer on capillary tube inner wall |
| CN103466955A (en) * | 2013-08-20 | 2013-12-25 | 秦皇岛玻璃工业研究设计院 | Manufacturing method for anti-reflection glass and coating equipment for implementation of manufacturing method |
| CN104911570A (en) * | 2015-05-14 | 2015-09-16 | 上海应用技术学院 | Plating solution carrying out chemical palladium plating on copper surface and preparation method therefor |
| CN105597641A (en) * | 2016-01-14 | 2016-05-25 | 重庆大学 | Preparation method of catalyst layer in microchannel reactor |
| CN110746296A (en) * | 2019-11-12 | 2020-02-04 | 云南正邦科技有限公司 | Method for preparing vinyl acetate by using microchannel reactor |
Non-Patent Citations (1)
| Title |
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