CN111205155A - Method for synthesizing adamantane from tetrahydrodicyclopentadiene - Google Patents
Method for synthesizing adamantane from tetrahydrodicyclopentadiene Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/29—Rearrangement of carbon atoms in the hydrocarbon skeleton changing the number of carbon atoms in a ring while maintaining the number of rings
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/52—Isomerisation reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
A process for synthesizing adamantane from tetrahydro-dicyclopentadiene features use of anhydrous AlCl3Reacting with alkyl tertiary amine, alkyl imidazole and alkyl pyridine to prepare chloroaluminate type room temperature ionic liquid as a catalyst. The catalyst with reduced activity is activated and then used continuously. The catalyst and the bridged tetrahydrodicyclopentadiene are respectively pumped into a micro-tube reactor by a metering pump, and are partially converted into the adamantane. And (3) allowing the material discharged from the reactor to enter a cylindrical separation container for standing and layering, transferring the upper oil phase material into a crystallizer, cooling to separate and separate adamantane crystals, returning the mother liquor to be used as the initial raw material continuously, and returning the lower catalyst to be used continuously. The invention has the characteristics of simplified process links, high product yield, continuous production and the like.
Description
Technical Field
The invention relates to a synthesis method of adamantane, in particular to a reaction method for synthesizing a target product adamantane from a starting material tetrahydrodicyclopentadiene through a catalytic isomerization reaction.
Background
Adamantane (Adamantane) chemical name is tricyclo [ 3,3,1,13,7 ] decane, a cyclic tetrahedral hydrocarbon consisting of 10 carbon atoms and 16 hydrogen atoms. Adamantane has symmetry and rigidity characteristics, so that the adamantane is relatively stable in property, and hydrogen atoms in molecules of the adamantane are easy to generate SN1 type nucleophilic substitution reaction and SE2 type electrophilic substitution reaction to generate various derivatives, so that the adamantane has wide application in the aspects of medicines, functional polymer materials, lubricants, surfactants, catalysts and the like.
At present, the industrial synthesis method of adamantane at home and abroad takes bridge type tetrahydro dicyclopentadiene as an initial raw material, and generates the target product adamantane by a zeolite molecular sieve catalytic isomerization method or an aluminum trichloride catalytic isomerization method.
The zeolite molecular sieve catalytic isomerization method is a patent method (CN1221501C, CN1398246A and CN1398245A) developed by Nippon Kyohima petrochemical company, and the method uses Y-type zeolite exchanged by rare earth metal ions as a catalyst carrier and loads a plurality of metals to prepare a zeolite-based bifunctional catalyst, and the zeolite-based bifunctional catalyst is prepared by adding a small amount of H into the catalyst carrier2Under the existence of HCl mixed gas and at the temperature of 250 ℃ and the pressure of 1-2 MPa, bridge type tetrahydro dicyclopentadiene gas is isomerized into adamantane through a zeolite catalyst, side reaction tar generated in the reaction of the method is little, and the environmental protection problems that the side reaction tar generated by the common aluminum trichloride catalytic isomerization method is large in amount and residual aluminum trichloride is difficult to treat are solved. But the side reaction of bond breaking of the initial raw material decomposition of the zeolite molecular sieve catalysis method is obvious, the yield of the target product adamantane is only about 31 percent, and the production cost is high.
The anhydrous aluminum trichloride catalytic isomerization method is the most mature industrial synthesis method of adamantane at present. The method uses anhydrous aluminum trichloride as a catalyst, and carries out a strong stirring reaction with an initial raw material of bridge type tetrahydro-dicyclopentadiene in a reaction kettle at a temperature of not higher than 100 ℃ to generate a target product adamantane. The traditional aluminum trichloride catalysis method generates a large amount of side reaction tar, and the residual aluminum trichloride with more inclusions is difficult to separate and treat, so that the environmental pollution is serious. A two-step one-circulation method developed by Luzhou Dazhou chemical industry limited company for producing adamantane (a new process ZL200810045391.3 for producing adamantane by the two-step one-circulation method) improves an aluminum trichloride catalytic isomerization method, and an isomerization reaction is carried out in two stages, wherein the first stage is to convert bridge type tetrahydrodicyclopentadiene into hanging type tetrahydrodicyclopentadiene, the second stage is to isomerize the hanging type tetrahydrodicyclopentadiene into adamantane, the conversion rate of the hanging type tetrahydrodicyclopentadiene is controlled, the generation of the adamantane is stopped when 15% -30% of the total material is reached, and a mother solution (the hanging type tetrahydrodicyclopentadiene) is recycled after cooling and separating adamantane crystals. The method generates less side reaction tar and less decomposition side reaction of the initial raw material, so that the inactivated aluminum trichloride is easy to treat, the environmental protection problem is partially solved, and the production cost is obviously reduced. However, the method still directly uses the aluminum trichloride as the catalyst, and still has the problems that a large amount of hydrogen chloride gas released in the treatment process of large amount of deactivated aluminum trichloride needs to be absorbed and disposed, the reaction operation is intermittently carried out in a reaction kettle, and the operation process is complicated.
Disclosure of Invention
The invention aims to provide a method for synthesizing adamantane from tetrahydrodicyclopentadiene, which has high product yield and simpler operation process, aiming at adopting improved chloroaluminate type room temperature ionic liquid as a catalyst and continuously using the catalyst with reduced activity after activation treatment, so that the reaction process is continuously carried out in a reactor.
The purpose of the invention is realized as follows: a method of synthesizing adamantane from tetrahydrodicyclopentadiene, comprising the steps of:
1) catalyst preparation
The chloroaluminate type room-temperature ionic liquid is prepared from anhydrous AlCl3Reacting with alkyl tertiary amine, alkyl imidazole and alkyl pyridine, wherein the chloroaluminate type room temperature ionic liquid used as a catalyst is used for a period of time, after the activity is reduced, 10-30% of anhydrous aluminum trichloride is additionally added into the chloroaluminate type room temperature ionic liquid, the chloroaluminate type room temperature ionic liquid is stirred and reacts for 2-3 hours at the temperature of 30-60 ℃, then the chloroaluminate type room temperature ionic liquid is kept stand overnight, then the upper part of liquid is separated, and the lower part of solid is separated and then treated by adding clear water for hydrolysis;
2) reaction equipment
Using a micro-reactor as isomerization reaction equipment to implement continuous reaction operation;
the reaction diameter of the micro-reactor is 0.5 mm-1.5 mm, and the length of the reactor is 5 m-20 m;
3) operation process of isomerization reaction
3-1) pumping a catalyst chloroaluminate type room temperature ionic liquid into a microreactor by using a micro-metering pump, and simultaneously heating to control the reaction temperature of the reactor to be 60-90 ℃;
3-2) pumping bridge type tetrahydro dicyclopentadiene which is preheated to 60-70 ℃ and is in a flowing liquid state into a reactor by a micro-metering pump, mixing the bridge type tetrahydro dicyclopentadiene with a catalyst and passing the mixture through the reactor, wherein the bridge type tetrahydro dicyclopentadiene generates hanging type tetrahydro dicyclopentadiene firstly by isomerization reaction in the process of passing through the reactor and then is isomerized into adamantane;
3-3) controlling the weight ratio of bridge type tetrahydro dicyclopentadiene to a catalyst to be passed through the reactor to be 1: 5-25, controlling the total flow rate of materials to be 5L/min-15L/min and the reaction temperature of the materials to be 60-90 ℃, controlling the bridge type tetrahydro to be completely converted into hanging type tetrahydro dicyclopentadiene and adamantane after the materials are passed through the reactor, wherein the content of the adamantane is 18-25%, and the condition that no adamantane is crystallized and separated out is met;
3-4) after the materials pass through the reactor, entering a cylindrical separation container, keeping the temperature at 60-90 ℃, standing and layering, wherein the catalyst is arranged at the lower layer, and the hanging type tetrahydrodicyclopentadiene-adamantane oil phase liquid is arranged at the upper layer;
3-5) transferring the upper oil phase liquid material into a crystallizer, cooling to separate out adamantane crystals, separating the adamantane crystals, returning the mother liquor of the hanging type tetrahydrodicyclopentadiene dissolved with a small amount of adamantane to be mixed with the bridge type tetrahydrodicyclopentadiene to be used as an initial raw material;
3-6), returning the lower catalyst for continuous use, and when the catalyst is used for a period of time and the activity of the catalyst is reduced, carrying out retreatment and activation on the catalyst for use;
3-7), in the production implementation, a continuous reaction operation process is adopted, namely, the catalyst is continuously recycled, the bridge type tetrahydrodicyclopentadiene and the returned mother liquor are mixed and then are used as initial raw materials to be continuously fed, the oil phase liquid after the reaction is cooled and crystallized through a continuous crystallizer, the adamantane crystal is separated and taken out, and the mother liquor is returned for reuse.
The catalyst is prepared by using anhydrous AlCl3Mixing with alkyl tertiary amine (trimethylamine, triethylamine, tri-n-propylamine, tri-n-octylamine, etc.), alkyl imidazole (3-methyl-1-butyl imidazole chloride, etc.) or alkyl pyridine, etc. according to the preparation process of the common Lewis acid type room temperature ionic liquid, wherein the molar ratio of the alkyl macromolecular compound to the anhydrous aluminum trichloride is 1: 1.8-2; the reaction diameter of the micro-reactor is 0.5 mm-1.5 mm, and the length of the reactor is 5 m-20 m.
The invention has the beneficial effects that:
1. solid anhydrous aluminum trichloride is not directly used as a catalyst, so that the trouble caused by the generation of a large amount of hydrogen chloride gas during hydrolysis treatment of inactivated aluminum trichloride is avoided, and the production operation is more environment-friendly.
2. The catalyst chloroaluminate ionic liquid can be repeatedly used, after the activity of the chloroaluminate ionic liquid is reduced after the chloroaluminate ionic liquid is used for a period of time, the activity recovery treatment can be conveniently carried out, waste solid materials in the catalyst recovery operation process are mainly aluminum hydroxide, the aluminum hydroxide can be simply recovered and treated, and hydrogen chloride gas cannot be generated.
3. The chloroaluminate ionic liquid can be repeatedly used for a long time, so that the consumption of the catalyst is reduced, and the production cost is obviously reduced. The dosage of the aluminum trichloride is reduced to 1/4-1/3 of the aluminum trichloride catalysis process.
4. The isomerization reaction can adopt a continuous production mode, and the production operation process of the isomerization reaction is simplified.
Detailed Description
A method of synthesizing adamantane from tetrahydrodicyclopentadiene, comprising the steps of:
1) catalyst preparation
The chloroaluminate type room-temperature ionic liquid is prepared from anhydrous AlCl3Reacting with alkyl tertiary amine, alkyl imidazole and alkyl pyridine, wherein the chloroaluminate type room temperature ionic liquid used as a catalyst is used for a period of time, after the activity is reduced, 10-30% of anhydrous aluminum trichloride is additionally added into the chloroaluminate type room temperature ionic liquid, the chloroaluminate type room temperature ionic liquid is stirred and reacts for 2-3 hours at the temperature of 30-60 ℃, then the chloroaluminate type room temperature ionic liquid is kept stand overnight, then the upper part of liquid is separated, and the lower part of solid is separated and then treated by adding clear water for hydrolysis;
2) reaction equipment
Using a micro-reactor as isomerization reaction equipment to implement continuous reaction operation;
the reaction diameter of the micro-reactor is 0.5 mm-1.5 mm, and the length of the reactor is 5 m-20 m;
3) operation process of isomerization reaction
3-1) pumping a catalyst chloroaluminate type room temperature ionic liquid into the microreactor by using a micrometering pump, and simultaneously heating and controlling the reaction temperature of the reactor to be 60-90 ℃ (actually controlling the temperature of the reactor to be lower at the front section and gradually increasing at the rear section within the temperature range);
3-2) pumping bridge type tetrahydro dicyclopentadiene which is preheated to about 60 ℃ and is in a flowing liquid state into a reactor by a micro-metering pump, mixing the bridge type tetrahydro dicyclopentadiene with a catalyst and passing the catalyst through the reactor, wherein the bridge type tetrahydro dicyclopentadiene generates exo type tetrahydro dicyclopentadiene during isomerization reaction in the process of passing through the reactor and then is isomerized into adamantane;
3-3) controlling the weight ratio of bridge type tetrahydrodicyclopentadiene to a catalyst to pass through the reactor to be 1: 5-25, controlling the total flow rate of materials to be 5L/min-15L/min, gradually increasing the reaction temperature of the materials at 60-90 ℃, and controlling the bridge type tetrahydro to be completely converted into hanging type tetrahydrodicyclopentadiene and adamantane after the materials pass through the reactor, wherein the content of the adamantane is 18-25%, but no adamantane crystal is separated out;
3-4) after the materials pass through the reactor, entering a cylindrical separation container, keeping the temperature at 80-90 ℃, standing and layering, wherein the catalyst is arranged at the lower layer, and the hanging type tetrahydrodicyclopentadiene-adamantane oil phase liquid is arranged at the upper layer;
3-5) transferring the upper oil phase liquid material into a crystallizer, cooling to separate out adamantane crystals, separating the adamantane crystals, returning the mother liquor of the hanging type tetrahydrodicyclopentadiene dissolved with a small amount of adamantane to be mixed with the bridge type tetrahydrodicyclopentadiene to be used as an initial raw material;
3-6), returning the lower catalyst for continuous use, and when the catalyst is used for a period of time and the activity of the catalyst is reduced, carrying out retreatment and activation on the catalyst for use;
3-7), in the production implementation, a continuous reaction operation process is adopted, namely, the catalyst is continuously recycled, the bridge type tetrahydrodicyclopentadiene and the returned mother liquor are mixed and then are used as initial raw materials to be continuously fed, the oil phase liquid is continuously cooled and crystallized after the reaction, the adamantane crystal is separated and taken out, and the mother liquor is returned for reuse.
Example (b):
about 50Kg of catalyst (chloroaluminate room temperature ionic liquid synthesized by 3-methyl-1-butylimidazole chloride and anhydrous aluminum trichloride according to a molar ratio of 1: 1.8-2) is filled in a catalyst storage tank protected by nitrogen in advance, and bridge type tetrahydrodicyclopentadiene is filled in a starting material storage tank protected by nitrogen in an initial loading amount of 120Kg, and is heated to 60-65 ℃ in advance to be in a liquid state. Sequentially starting a micro-metering pump to respectively pump the catalyst chloroaluminate room temperature ionic liquid and the starting material bridge type tetrahydro dicyclopentadiene into the microreactor, and simultaneously heating to control the reaction temperature of the reactor so as to gradually increase the temperature of the reaction tube from the front section to the rear section within the range of 60-90 ℃.
The micro-reactor reaction tube is a special-shaped inner channel, the diameter (inner diameter) of the reaction tube is in the range of 0.5 mm-1.5 mm, and the total length of the reaction tube is about 7 m. The flow rate of the catalyst in the microreactor is controlled to be about 9Kg/min, and the flow rate of the bridge type tetrahydro dicyclopentadiene in the microreactor is controlled to be about 1.2 Kg/min. After passing through the microreactor, the material enters a heat-preservation separator, the material slowly rotates in the separator and is quickly layered, wherein the catalyst sinks to the lower layer and is continuously pumped back to the catalyst storage tank for continuous recycling (the catalyst can be repeatedly recycled for the reaction of multiple batches of materials). The upper hanging tetrahydro dicyclopentadiene-adamantane oil phase liquid continuously flows out from the top of the separator and is transferred to a small continuous crystallizer, and the temperature is cooled to 5-10 ℃ to separate and crystallize adamantane. The mother liquor (hanging tetrahydrodicyclopentadiene solution containing a small amount of adamantane) after the adamantane crystallization is separated out is pumped back to the initial raw material storage tank to be mixed with the residual raw materials in the tank and then continuously participate in the reaction. The reaction is continuously carried out until the content of the tetrahydrodicyclopentadiene in the mixed oil phase material in the raw material storage tank is reduced to below 15 percent, and the reaction is stopped. Washing the separated and collected adamantane crystal with water to remove residual mother liquor, and drying to obtain the target product.
In this example, 85.7Kg of adamantane crystals were collected, and the product appearance was white crystal particles with a purity of 99.6% by inspection. In addition, about 32Kg of oil phase mother liquor (mainly composed of thermal decomposition products of raw materials, exo-tetrahydrodicyclopentadiene and a small amount of adamantane) after the crystallization of the separated product is collected, and can be used for preparing raw material components of boiler fuel oil. The calculated yield of the target product adamantane is about 71%, the raw material yield of the fuel oil component is 26.7%, and the total utilization yield of the starting raw material is 97.7%.
Claims (3)
1. A method for synthesizing adamantane from tetrahydrodicyclopentadiene, comprising the steps of:
1) catalyst preparation
The chloroaluminate type room-temperature ionic liquid is prepared from anhydrous AlCl3Reacting with alkyl tertiary amine, alkyl imidazole and alkyl pyridine, wherein the chloroaluminate type room temperature ionic liquid used as a catalyst is used for a period of time, after the activity is reduced, 10-30% of anhydrous aluminum trichloride is additionally added into the chloroaluminate type room temperature ionic liquid, the chloroaluminate type room temperature ionic liquid is stirred and reacts for 2-3 hours at the temperature of 30-60 ℃, then the chloroaluminate type room temperature ionic liquid is kept stand overnight, then the upper part of liquid is separated, and the lower part of solid is separated and then treated by adding clear water for hydrolysis;
2) reaction equipment
Using a micro-reactor as isomerization reaction equipment to implement continuous reaction operation;
the reaction diameter of the micro-reactor is 0.5 cm-1.5 cm, and the length of the reactor is 5 m-20 m;
3) operation process of isomerization reaction
3-1) pumping a catalyst chloroaluminate type room temperature ionic liquid into a microreactor by using a micro-metering pump, and simultaneously heating to control the reaction temperature of the reactor to be 60-90 ℃;
3-2) pumping bridge type tetrahydro dicyclopentadiene which is preheated to 60-70 ℃ and is in a flowing liquid state into a reactor by a micro-metering pump, mixing the bridge type tetrahydro dicyclopentadiene with a catalyst and passing the mixture through the reactor, wherein the bridge type tetrahydro dicyclopentadiene generates hanging type tetrahydro dicyclopentadiene firstly by isomerization reaction in the process of passing through the reactor and then is isomerized into adamantane;
3-3) controlling the weight ratio of bridge type tetrahydro dicyclopentadiene to a catalyst to be passed through the reactor to be 1: 5-25, controlling the total flow rate of materials to be 5L/min-15L/min and the reaction temperature of the materials to be 60-90 ℃, controlling the bridge type tetrahydro to be completely converted into hanging type tetrahydro dicyclopentadiene and adamantane after the materials are passed through the reactor, wherein the content of the adamantane is 18-25%, and the condition that no adamantane is crystallized and separated out is met;
3-4) after the materials pass through the reactor, entering a cylindrical separation container, keeping the temperature at 80-90 ℃, standing and layering, wherein the catalyst is arranged at the lower layer, and the hanging type tetrahydrodicyclopentadiene-adamantane oil phase liquid is arranged at the upper layer;
3-5) transferring the upper oil phase liquid material into a crystallizer, cooling to separate out adamantane crystals, separating the adamantane crystals, returning the mother liquor of the hanging type tetrahydrodicyclopentadiene dissolved with a small amount of adamantane to be mixed with the bridge type tetrahydrodicyclopentadiene to be used as an initial raw material;
3-6), returning the lower catalyst for continuous use, and when the catalyst is used for a period of time and the activity of the catalyst is reduced, carrying out retreatment and activation on the catalyst for use;
3-7), in the production implementation, a continuous reaction operation process is adopted, namely, the catalyst is continuously recycled, the bridge type tetrahydrodicyclopentadiene and the returned mother liquor are mixed and then are used as initial raw materials for continuous feeding, the oil phase liquid is cooled and separated after the reaction, the adamantane crystal is taken out, and the mother liquor is returned for reuse.
2. The method for synthesizing adamantane from tetrahydrodicyclopentadiene as claimed in claim 1, wherein the catalyst is anhydrous AlCl3And alkyl tertiary amine (trimethylamine, triethylamine, tri-n-propylamine, tri-n-octylamine, etc.), alkyl imidazole (3-methyl-1-butyl imidazole chloride, etc.), alkyl pyridine, etc. according to the general preparation process of Lewis acid type room temperature ionic liquid, wherein the molar ratio of the alkyl macromolecular compound to the anhydrous aluminum trichloride is 1: 1.8-2.
3. The microreactor of claim 1 is a shaped internal channel structure with a channel diameter, i.e., internal diameter, in the range of 0.5mm to 1.5mm and a reactor length of 5m to 20 m.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200829536A (en) * | 2007-01-12 | 2008-07-16 | Chinese Petroleum Corp | Method for preparing adamantane by using acidic ionic liquid |
| CN101234945A (en) * | 2007-02-01 | 2008-08-06 | 北京化工大学 | Method for on-line producing alkymer from regenerative ionic liquid catalyst |
| US20100249475A1 (en) * | 2009-03-24 | 2010-09-30 | Ming-Yu Huang | Process for isomerization of tetrahydrodicyclopentadiene using supported acidic ionic liquid as a catalyst |
| TWI473784B (en) * | 2013-10-18 | 2015-02-21 | Nat Inst Chung Shan Science & Technology | Method for producing high yield adamantane |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200829536A (en) * | 2007-01-12 | 2008-07-16 | Chinese Petroleum Corp | Method for preparing adamantane by using acidic ionic liquid |
| CN101234945A (en) * | 2007-02-01 | 2008-08-06 | 北京化工大学 | Method for on-line producing alkymer from regenerative ionic liquid catalyst |
| US20100249475A1 (en) * | 2009-03-24 | 2010-09-30 | Ming-Yu Huang | Process for isomerization of tetrahydrodicyclopentadiene using supported acidic ionic liquid as a catalyst |
| TWI473784B (en) * | 2013-10-18 | 2015-02-21 | Nat Inst Chung Shan Science & Technology | Method for producing high yield adamantane |
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