CN111217695A - Method for continuously synthesizing cyclohexanecarboxylic acid - Google Patents
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Abstract
The invention relates to a method for continuously synthesizing cyclohexanecarboxylic acid, which belongs to the field of fine chemical synthesis and comprises the following steps: 1) mixing and preheating benzoic acid and a solvent, namely a cyclohexyl formic acid solvent; 2) preparing an emulsion; 3) preparing a mixture; 4) gas-liquid separation; the invention heats the screw conveyer with the jacket by the waste heat in the product of the cyclohexyl formic acid, the heated screw conveyer back feeds and preheats the mixture of the solid benzoic acid and the solvent cyclohexyl formic acid slowly, the preheating temperature of the solid benzoic acid and the solvent cyclohexyl formic acid is 80-135 ℃, the raw materials are preheated by the heat produced by the reaction, the activity of the raw materials is improved, the synthetic reaction is facilitated, and the synthetic reaction period is shortened; meanwhile, the heat in the synthesis reaction is reasonably recycled, thereby being beneficial to maximizing the enterprise benefit and meeting the current national environmental protection requirement.
Description
Technical Field
The invention relates to the field of fine chemical synthesis, in particular to a method for continuously synthesizing cyclohexanecarboxylic acid.
Background
The cyclohexyl formic acid is an important organic synthesis intermediate, is a good light curing agent per se, and can be used for synthesizing a new medicine praziquantel for treating schistosomiasis. The derivative such as trans-4-isopropyl methyl cyclohexanecarboxylate is an intermediate for producing a new medicine nateglinide for treating diabetes, so that the preparation of the cyclohexanecarboxylic acid plays an important role in organic synthesis. The preparation of the cyclohexanecarboxylic acid by selective hydrogenation of benzoic acid is difficult under the common conditions, the conversion rate is difficult to reach 100 percent even by using a palladium/carbon catalyst with high hydrogenation activity, and not only the carboxyl group of the benzoic acid is easy to remove by hydrogenation in the preparation of the cyclohexanecarboxylic acid by hydrogenation of the benzoic acid. And is difficult to industrialize due to catalyst stability and recovery problems.
With the increasing use amount of the cyclohexanecarboxylic acid, the continuous synthesis of the cyclohexanecarboxylic acid becomes more and more important, and the following technical problems exist in the preparation of the cyclohexanecarboxylic acid at present:
firstly, the conversion rate of the synthesis reaction is difficult to reach 100%, so that the raw materials are incompletely utilized and are not beneficial to enterprise production;
secondly, the raw materials are not preheated in the existing reaction, so that the synthesis reaction period is long;
thirdly, heat can be generated in the synthesis reaction, and the heat is not reasonably recycled in the existing synthesis method, so that the method is not beneficial to maximizing the enterprise benefit, and meanwhile, the method does not meet the current national environmental protection requirement.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for continuously synthesizing cyclohexanecarboxylic acid, so as to solve the technical problems.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for continuously synthesizing cyclohexanecarboxylic acid comprises the following steps:
1) mixing and preheating benzoic acid and a solvent, namely a cyclohexyl formic acid solvent: the benzoic acid is added through the front section of the flood dragon, then the solvent of the cyclohexanecarboxylic acid is added, the benzoic acid is conveyed forwards in the flood dragon, the hot cyclohexanecarboxylic acid product in a jacket of the flood dragon is heated to heat materials in the flood dragon and back feed the materials in the flood dragon to cool the cyclohexanecarboxylic acid product in the jacket, the hot benzoic acid and the solvent of the cyclohexanecarboxylic acid coming out of the flood dragon enter a raw material tank to obtain preheated benzoic acid and preheated cyclohexanecarboxylic acid, the temperature of the preheated benzoic acid and the preheated cyclohexanecarboxylic acid is controlled to be 80-135 ℃, and meanwhile, the cooled cyclohexanecarboxylic acid product enters a finished product tank;
2) preparing an emulsion: mixing the preheated benzoic acid and the preheated cyclohexanecarboxylic acid in the step (1), feeding the mixture and hydrogen into an umbrella-shaped microchannel mixer at a certain flow rate, mixing for 10-30s, and preparing an emulsion after mixing;
3) preparing a mixture: feeding the emulsion obtained in the step (2) into a tubular reactor for preheating, preheating a tubular reactor to the reaction temperature of 90-180 ℃, filling a fixed bed catalyst in the tubular reactor, carrying out reduction reaction of benzoic acid and hydrogen through the catalyst, and switching to cooling after heat release along with the reaction to obtain a mixture;
4) gas-liquid separation: enabling the mixture discharged from the tubular reactor in the step 3 to enter a gas-liquid separator for gas-liquid separation, compressing hydrogen in the mixture to a specified pressure by a hydrogen compressor after the hydrogen enters a buffer tank, controlling the pressure of the compressor to be 3-4Mpa, and using the compressed hydrogen as raw material hydrogen after passing through the buffer tank; and part of the cyclohexanecarboxylic acid from the bottom of the gas-liquid separator enters a flood dragon mixer to be used as a solvent, and part of the cyclohexanecarboxylic acid enters a jacket of the flood dragon to be heated and dissolved in the benzoic acid, meanwhile, the hot cyclohexanecarboxylic acid product is cooled and then enters a finished product tank, and part of the hot cyclohexanecarboxylic acid enters the flood dragon to be used as a solvent to be mixed with the benzoic acid.
Preferably, the molar ratio of preheated benzoic acid, preheated cyclohexanecarboxylic acid and hydrogen in step 2 is from 1:1 to 2: 3.8-4.8.
Preferably, the temperature after cooling in step 3 is the same as the reaction temperature.
Preferably, the pressure in the tubular reactor in the step 3 is 1-2.5MPa, and the temperature is controlled at 100-250 ℃.
Preferably, the tubular reactor is formed by connecting a plurality of tubular reactors in parallel.
Preferably, the umbrella-shaped microchannel mixer is provided with a plurality of umbrella-shaped microchannel mixers, and the umbrella-shaped microchannel mixers are arranged in series.
Has the advantages that:
(1) heating a jacketed auger by waste heat in a cyclohexyl formic acid product, reversely preheating the heated auger to slowly mix and preheat solid benzoic acid and solvent cyclohexyl formic acid, preheating the solid benzoic acid and the solvent cyclohexyl formic acid at 80-135 ℃, and preheating the raw materials by heat generated by reaction, so that the activity of the raw materials is improved, the synthetic reaction is facilitated, and the synthetic reaction period is shortened; meanwhile, the heat in the synthesis reaction is reasonably recycled, thereby being beneficial to maximizing the enterprise benefit and meeting the current national environmental protection requirement;
(2) the umbrella-shaped microchannel mixer has the function of fully mixing, so that benzoic acid, solvent cyclohexyl formic acid and hydrogen reach the effect of opacification, and meanwhile, the heat transfer efficiency of the tubular reactor is high, hot spots cannot be formed, the conversion rate of raw materials can be greatly improved, the conversion rate can be improved by 100%, the selectivity of products is improved, the safety can be ensured, and the industrial production is easy to carry out;
(3) the tubular reactor is a continuous flow reactor, the reaction time can be shortened to several seconds to dozens of seconds, the production efficiency can be greatly improved, and the productivity can be improved.
(4) The tubular reactor is composed of a plurality of tubular pipes, the size of the tubular reactor is consistent with that of a single pipe test, the tubular reactor has no amplification effect, the capacity can be infinitely amplified, and redundant hydrogen can be completely recycled after the tubular reactor comes out and enters the gas-liquid separator.
(5) The tubular reactor greatly reduces the temperature, pressure and time of hydrogenation reduction reaction and improves the safety of the reaction.
(6) The invention has no gas discharge and completely meets the requirement of clean production.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow diagram of the continuous synthesis of cyclohexanecarboxylic acid in the present invention;
FIG. 2 is a schematic structural view of an umbrella-shaped microchannel mixer according to the present invention;
FIG. 3 is a schematic view of the structure of a shell and tube reactor of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a method for continuously synthesizing cyclohexanecarboxylic acid comprises the following steps:
1) mixing and preheating benzoic acid and a solvent, namely a cyclohexyl formic acid solvent: the benzoic acid is added through the front section of the flood dragon, then the solvent of the cyclohexanecarboxylic acid is added, the benzoic acid is conveyed forwards in the flood dragon, the hot cyclohexanecarboxylic acid product in a jacket of the flood dragon is heated to heat materials in the flood dragon and back feed the materials in the flood dragon to cool the cyclohexanecarboxylic acid product in the jacket, the hot benzoic acid and the solvent of the cyclohexanecarboxylic acid coming out of the flood dragon enter a raw material tank to obtain preheated benzoic acid and preheated cyclohexanecarboxylic acid, the temperature of the preheated benzoic acid and the preheated cyclohexanecarboxylic acid is controlled at 80 ℃, and meanwhile, the cooled cyclohexanecarboxylic acid product enters a finished product tank;
2) preparing an emulsion: mixing the preheated benzoic acid and the preheated cyclohexanecarboxylic acid in the step 1, and then feeding the mixture and hydrogen into an umbrella-shaped micro-channel mixer for mixing according to a certain flow rate, wherein the umbrella-shaped micro-channel mixer is provided with a plurality of umbrella-shaped micro-channel mixers which are arranged in series, and the molar ratio of the preheated benzoic acid to the preheated cyclohexanecarboxylic acid to the hydrogen is 1: 3.8, mixing for 22s to obtain emulsion after mixing;
3) and (3) feeding the emulsion obtained in the step (2) into a tubular reactor for preheating, wherein the tubular reactor is formed by connecting a plurality of tubular reactors in parallel, the pressure in the tubular reactor is 1MPa, and the temperature is controlled at 250 ℃. Preheating a tube array to the reaction temperature of 90 ℃ in advance, wherein a fixed bed catalyst is filled in the tube array, the reduction reaction of benzoic acid and hydrogen is realized through the catalyst, heat is released along with the reaction, then the tube array is switched to be cooled, and the temperature after cooling is the same as the reaction temperature, so that a mixture is obtained;
4) enabling the mixture discharged from the tubular reactor in the step 3 to enter a gas-liquid separator for gas-liquid separation, compressing hydrogen in the mixture to a specified pressure by a hydrogen compressor after the hydrogen enters a buffer tank, controlling the pressure of the compressor to be 4Mpa, and using the compressed hydrogen as raw material hydrogen after passing through the buffer tank; and part of the cyclohexanecarboxylic acid from the bottom of the gas-liquid separator enters a flood dragon mixer as a solvent, and part of the cyclohexanecarboxylic acid enters a jacket of the flood dragon to be heated and dissolved in the benzoic acid, meanwhile, the hot cyclohexanecarboxylic acid product is cooled and then enters a finished product tank, part of the hot cyclohexanecarboxylic acid enters the flood dragon as the solvent and is mixed with the benzoic acid, the conversion rate of the benzoic acid reaches 100%, and the selectivity reaches more than 99.8%.
Example 2:
a method for continuously synthesizing cyclohexanecarboxylic acid comprises the following steps:
1) mixing and preheating benzoic acid and a solvent, namely a cyclohexyl formic acid solvent: the benzoic acid is added through the front section of the flood dragon, then the solvent of the cyclohexanecarboxylic acid is added, the benzoic acid is conveyed forwards in the flood dragon, the hot cyclohexanecarboxylic acid product in a jacket of the flood dragon is heated to heat materials in the flood dragon and back feed the materials in the flood dragon to cool the cyclohexanecarboxylic acid product in the jacket, the hot benzoic acid and the solvent of the cyclohexanecarboxylic acid coming out of the flood dragon enter a raw material tank to obtain preheated benzoic acid and preheated cyclohexanecarboxylic acid, the temperature of the preheated benzoic acid and the preheated cyclohexanecarboxylic acid is controlled at 95 ℃, and the cooled cyclohexanecarboxylic acid product enters a finished product tank;
2) preparing an emulsion: mixing the preheated benzoic acid and the preheated cyclohexanecarboxylic acid in the step 1, and then feeding the mixture and hydrogen into an umbrella-shaped micro-channel mixer for mixing according to a certain flow rate, wherein the umbrella-shaped micro-channel mixer is provided with a plurality of umbrella-shaped micro-channel mixers which are arranged in series, and the molar ratio of the preheated benzoic acid to the preheated cyclohexanecarboxylic acid to the hydrogen is 1: 1.3: 4.2, mixing for 16s to obtain emulsion after mixing;
3) and (3) feeding the emulsion obtained in the step (2) into a tubular reactor for preheating, wherein the tubular reactor is formed by connecting a plurality of tubular reactors in parallel, the pressure in the tubular reactor is 2.5MPa, and the temperature is controlled at 100 ℃. Preheating a tube array to the reaction temperature of 135 ℃, wherein a fixed bed catalyst is filled in the tube array, the reduction reaction of benzoic acid and hydrogen is realized through the catalyst, heat is released along with the reaction, then the tube array is switched to be cooled, and the temperature after cooling is the same as the reaction temperature, so that a mixture is obtained;
4) enabling the mixture discharged from the tubular reactor in the step 3 to enter a gas-liquid separator for gas-liquid separation, compressing hydrogen in the mixture to a specified pressure by a hydrogen compressor after the hydrogen enters a buffer tank, controlling the pressure of the compressor to be 3Mpa, and using the compressed hydrogen as raw material hydrogen after passing through the buffer tank; and part of the cyclohexanecarboxylic acid from the bottom of the gas-liquid separator enters a flood dragon mixer as a solvent, and part of the cyclohexanecarboxylic acid enters a jacket of the flood dragon to be heated and dissolved in the benzoic acid, meanwhile, the hot cyclohexanecarboxylic acid product is cooled and then enters a finished product tank, part of the hot cyclohexanecarboxylic acid enters the flood dragon as the solvent and is mixed with the benzoic acid, the conversion rate of the benzoic acid reaches 100%, and the selectivity reaches more than 99.9%.
Example 3:
a method for continuously synthesizing cyclohexanecarboxylic acid comprises the following steps:
1) mixing and preheating benzoic acid and a solvent, namely a cyclohexyl formic acid solvent: the benzoic acid is added through the front section of the flood dragon, then the solvent of the cyclohexanecarboxylic acid is added, the benzoic acid is conveyed forwards in the flood dragon, the hot cyclohexanecarboxylic acid product in a jacket of the flood dragon is heated to heat materials in the flood dragon and back feed the materials in the flood dragon to cool the cyclohexanecarboxylic acid product in the jacket, the hot benzoic acid and the solvent of the cyclohexanecarboxylic acid coming out of the flood dragon enter a raw material tank to obtain preheated benzoic acid and preheated cyclohexanecarboxylic acid, the temperature of the preheated benzoic acid and the preheated cyclohexanecarboxylic acid is controlled at 110 ℃, and the cooled cyclohexanecarboxylic acid product enters a finished product tank;
2) preparing an emulsion: mixing the preheated benzoic acid and the preheated cyclohexanecarboxylic acid in the step 1, and then feeding the mixture and hydrogen into an umbrella-shaped micro-channel mixer for mixing according to a certain flow rate, wherein the umbrella-shaped micro-channel mixer is provided with a plurality of umbrella-shaped micro-channel mixers which are arranged in series, and the molar ratio of the preheated benzoic acid to the preheated cyclohexanecarboxylic acid to the hydrogen is 1: 2: 4.8, mixing for 10s to obtain emulsion after mixing;
3) and (3) feeding the emulsion obtained in the step (2) into a tubular reactor for preheating, wherein the tubular reactor is formed by connecting a plurality of tubular reactors in parallel, the pressure in the tubular reactor is 2.1MPa, and the temperature is controlled at 180 ℃. Preheating a tube array to the reaction temperature of 155 ℃ in advance, wherein a fixed bed catalyst is filled in the tube array, the reduction reaction of benzoic acid and hydrogen is realized through the catalyst, heat is released along with the reaction, then the tube array is switched to be cooled, and the temperature after cooling is the same as the reaction temperature, so that a mixture is obtained;
4) enabling the mixture discharged from the tubular reactor in the step 3 to enter a gas-liquid separator for gas-liquid separation, compressing hydrogen in the mixture to a specified pressure by a hydrogen compressor after the hydrogen enters a buffer tank, controlling the pressure of the compressor to be 4Mpa, and using the compressed hydrogen as raw material hydrogen after passing through the buffer tank; and part of the cyclohexanecarboxylic acid from the bottom of the gas-liquid separator enters a flood dragon mixer as a solvent, and part of the cyclohexanecarboxylic acid enters a jacket of the flood dragon to be heated and dissolved in the benzoic acid, meanwhile, the hot cyclohexanecarboxylic acid product is cooled and then enters a finished product tank, and part of the hot cyclohexanecarboxylic acid enters the flood dragon as the solvent and is mixed with the benzoic acid, so that the conversion rate of the benzoic acid reaches 100%, and the selectivity reaches more than 99.1%.
Example 4:
a method for continuously synthesizing cyclohexanecarboxylic acid comprises the following steps:
1) mixing and preheating benzoic acid and a solvent, namely a cyclohexyl formic acid solvent: the benzoic acid is added through the front section of the flood dragon, then the solvent of the cyclohexanecarboxylic acid is added, the benzoic acid is conveyed forwards in the flood dragon, the hot cyclohexanecarboxylic acid product in a jacket of the flood dragon is heated to heat materials in the flood dragon and back feed the materials in the flood dragon to cool the cyclohexanecarboxylic acid product in the jacket, the hot benzoic acid and the solvent of the cyclohexanecarboxylic acid coming out of the flood dragon enter a raw material tank to obtain preheated benzoic acid and preheated cyclohexanecarboxylic acid, the temperature of the preheated benzoic acid and the preheated cyclohexanecarboxylic acid is controlled at 135 ℃, and the cooled cyclohexanecarboxylic acid product enters a finished product tank;
2) preparing an emulsion: mixing the preheated benzoic acid and the preheated cyclohexanecarboxylic acid in the step 1, and then feeding the mixture and hydrogen into an umbrella-shaped micro-channel mixer for mixing according to a certain flow rate, wherein the umbrella-shaped micro-channel mixer is provided with a plurality of umbrella-shaped micro-channel mixers which are arranged in series, and the molar ratio of the preheated benzoic acid to the preheated cyclohexanecarboxylic acid to the hydrogen is 1: 1.6: 4.6, mixing for 30s to obtain emulsion after mixing;
3) and (3) feeding the emulsion obtained in the step (2) into a tubular reactor for preheating, wherein the tubular reactor is formed by connecting a plurality of tubular reactors in parallel, the pressure in the tubular reactor is 1.7MPa, and the temperature is controlled at 210 ℃. Preheating a tube array to the reaction temperature of 180 ℃ in advance, wherein a fixed bed catalyst is filled in the tube array, the reduction reaction of benzoic acid and hydrogen is realized through the catalyst, heat is released along with the reaction, then the tube array is switched to be cooled, and the temperature after cooling is the same as the reaction temperature, so that a mixture is obtained;
4) enabling the mixture discharged from the tubular reactor in the step 3 to enter a gas-liquid separator for gas-liquid separation, compressing hydrogen in the mixture to a specified pressure by a hydrogen compressor after the hydrogen enters a buffer tank, controlling the pressure of the compressor to be 3Mpa, and using the compressed hydrogen as raw material hydrogen after passing through the buffer tank; and part of the cyclohexanecarboxylic acid from the bottom of the gas-liquid separator enters a flood dragon mixer to serve as a solvent, and part of the cyclohexanecarboxylic acid enters a jacket of the flood dragon to be heated and dissolved in the benzoic acid, meanwhile, the hot cyclohexanecarboxylic acid product is cooled and then enters a finished product tank, part of the hot cyclohexanecarboxylic acid enters the flood dragon to serve as the solvent and is mixed with the benzoic acid, the conversion rate of the benzoic acid reaches 100%, and the selectivity reaches 99.5.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (6)
1. A method for continuously synthesizing cyclohexanecarboxylic acid is characterized by comprising the following steps:
1) mixing and preheating benzoic acid and a solvent, namely a cyclohexyl formic acid solvent: the benzoic acid is added through the front section of the flood dragon, then the solvent of the cyclohexanecarboxylic acid is added, the benzoic acid is conveyed forwards in the flood dragon, the hot cyclohexanecarboxylic acid product in a jacket of the flood dragon is heated to heat materials in the flood dragon and back feed the materials in the flood dragon to cool the cyclohexanecarboxylic acid product in the jacket, the hot benzoic acid and the solvent of the cyclohexanecarboxylic acid coming out of the flood dragon enter a raw material tank to obtain preheated benzoic acid and preheated cyclohexanecarboxylic acid, the temperature of the preheated benzoic acid and the preheated cyclohexanecarboxylic acid is controlled to be 80-135 ℃, and meanwhile, the cooled cyclohexanecarboxylic acid product enters a finished product tank;
2) preparing an emulsion: mixing the preheated benzoic acid and the preheated cyclohexanecarboxylic acid in the step (1), feeding the mixture and hydrogen into an umbrella-shaped microchannel mixer at a certain flow rate, mixing for 10-30s, and preparing an emulsion after mixing;
3) preparing a mixture: feeding the emulsion obtained in the step (2) into a tubular reactor for preheating, preheating a tubular reactor to the reaction temperature of 90-180 ℃, filling a fixed bed catalyst in the tubular reactor, carrying out reduction reaction of benzoic acid and hydrogen through the catalyst, and switching to cooling after heat release along with the reaction to obtain a mixture;
4) gas-liquid separation: enabling the mixture discharged from the tubular reactor in the step 3 to enter a gas-liquid separator for gas-liquid separation, compressing hydrogen in the mixture to a specified pressure by a hydrogen compressor after the hydrogen enters a buffer tank, controlling the pressure of the compressor to be 3-4Mpa, and using the compressed hydrogen as raw material hydrogen after passing through the buffer tank; and part of the cyclohexanecarboxylic acid from the bottom of the gas-liquid separator enters a flood dragon mixer to be used as a solvent, and part of the cyclohexanecarboxylic acid enters a jacket of the flood dragon to be heated and dissolved in the benzoic acid, meanwhile, the hot cyclohexanecarboxylic acid product is cooled and then enters a finished product tank, and part of the hot cyclohexanecarboxylic acid enters the flood dragon to be used as a solvent to be mixed with the benzoic acid.
2. The continuous synthesis method of cyclohexanecarboxylic acid as claimed in claim 1, wherein: the molar ratio of the preheated benzoic acid, preheated cyclohexanecarboxylic acid and hydrogen in the step 2 is 1: 1-2: 3.8-4.8.
3. The continuous synthesis method of cyclohexanecarboxylic acid as claimed in claim 1, wherein: the temperature after cooling in step 3 is the same as the reaction temperature.
4. The continuous synthesis method of cyclohexanecarboxylic acid as claimed in claim 1, wherein: in the step 3, the pressure in the tubular reactor is 1-2.5MPa, and the temperature is controlled at 100-250 ℃.
5. The continuous synthesis method of cyclohexanecarboxylic acid as claimed in claim 3, wherein: the shell and tube reactor is formed by connecting a plurality of shell and tube in parallel.
6. The continuous synthesis method of cyclohexanecarboxylic acid as claimed in claim 3, wherein: the umbrella-shaped micro-channel mixer is provided with a plurality of umbrella-shaped micro-channel mixers which are arranged in series.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569816A (en) * | 2020-06-30 | 2020-08-25 | 江苏京控装备有限公司 | Solid-liquid homogeneous mixing pump matched multi-tube reactor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450010A (en) * | 2013-08-28 | 2013-12-18 | 大连理工大学 | Method for preparing cyclohexanecarboxylic acid |
| CN103599795A (en) * | 2013-11-25 | 2014-02-26 | 江苏清泉化学有限公司 | Catalyst for preparing cyclohexane carboxylic acid through benzoic acid hydrogenation and preparation method and application thereof |
| CN105251482A (en) * | 2015-10-14 | 2016-01-20 | 南京大学连云港高新技术研究院 | Ruthenium palladium/carbon catalyst of cyclohexanecarboxylic acid synthesized through benzoic acid hydrogenation and preparation method and application thereof |
| CN108358778A (en) * | 2018-04-26 | 2018-08-03 | 黑龙江鑫创生物科技开发有限公司 | A kind of method of micro passage reaction synthetic hydrochloric acid cinacalcet intermediate |
| US20190084918A1 (en) * | 2015-10-07 | 2019-03-21 | Council Of Scientific & Industrial Research | An eco-friendly process for hydrogenation or/and hydrodeoxygenation of organic compound using hydrous ruthenium oxide catalyst |
-
2020
- 2020-02-21 CN CN202010108402.9A patent/CN111217695A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450010A (en) * | 2013-08-28 | 2013-12-18 | 大连理工大学 | Method for preparing cyclohexanecarboxylic acid |
| CN103599795A (en) * | 2013-11-25 | 2014-02-26 | 江苏清泉化学有限公司 | Catalyst for preparing cyclohexane carboxylic acid through benzoic acid hydrogenation and preparation method and application thereof |
| US20190084918A1 (en) * | 2015-10-07 | 2019-03-21 | Council Of Scientific & Industrial Research | An eco-friendly process for hydrogenation or/and hydrodeoxygenation of organic compound using hydrous ruthenium oxide catalyst |
| CN105251482A (en) * | 2015-10-14 | 2016-01-20 | 南京大学连云港高新技术研究院 | Ruthenium palladium/carbon catalyst of cyclohexanecarboxylic acid synthesized through benzoic acid hydrogenation and preparation method and application thereof |
| CN108358778A (en) * | 2018-04-26 | 2018-08-03 | 黑龙江鑫创生物科技开发有限公司 | A kind of method of micro passage reaction synthetic hydrochloric acid cinacalcet intermediate |
Non-Patent Citations (1)
| Title |
|---|
| 张龙等: "《绿色化学》", 31 August 2014 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569816A (en) * | 2020-06-30 | 2020-08-25 | 江苏京控装备有限公司 | Solid-liquid homogeneous mixing pump matched multi-tube reactor |
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