CN115010650A - Low-carbon-green synthesis process method for preparing tetramethyl piperidinol by continuous flow hydrogenation of triacetonamine - Google Patents

Low-carbon-green synthesis process method for preparing tetramethyl piperidinol by continuous flow hydrogenation of triacetonamine Download PDF

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CN115010650A
CN115010650A CN202210674006.1A CN202210674006A CN115010650A CN 115010650 A CN115010650 A CN 115010650A CN 202210674006 A CN202210674006 A CN 202210674006A CN 115010650 A CN115010650 A CN 115010650A
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triacetonamine
continuous flow
hydrogen
liquid
tetramethylpiperidinol
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项瞻波
张超
胡新利
王晶
苏波
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Suqian Unitechem Co ltd
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Suqian Unitechem Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/40—Oxygen atoms
    • C07D211/44—Oxygen atoms attached in position 4
    • C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/02—Crystallisation from solutions
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/001—Controlling catalytic processes
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
    • B01J8/025—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical shaped bed
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0278—Feeding reactive fluids
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0285—Heating or cooling the reactor
    • 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

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a continuous synthesis method of tetramethyl piperidinol, which comprises the steps of feeding triacetonamine raw material liquid into a continuous flow packed bed reaction zone, namely a catalyst layer; the temperature of the hydrogenation reduction reaction is 80-150 ℃, the pressure is 0.8-2.0 MPa, the mass percentage of triacetonamine in the feeding liquid is 10-40 wt%, and the triacetonamine is contacted with the catalyst layer of the continuous flow packed bed reactor for hydrogenation reduction to generate tetramethyl piperidinol, so that the continuous preparation of the tetramethyl piperidinol is realized; carrying out gas-liquid separation on the obtained reaction liquid, recycling redundant hydrogen, and collecting a liquid-phase product by a receiver and then carrying out crystallization treatment to obtain high-purity tetramethyl piperidinol; the process scheme overcomes the series defects of large potential safety hazard of the intermittent process, incapability of recycling hydrogen, more byproducts and small capacity in unit production time, realizes the continuous preparation of the tetramethyl piperidinol, and has the characteristics of high capacity, safety and green manufacture.

Description

Low-carbon-green synthesis process method for preparing tetramethyl piperidinol by continuous flow hydrogenation of triacetonamine
Technical Field
The invention belongs to the field of clean, green and low-carbon synthesis of fine chemicals with high added values, and particularly relates to a continuous synthesis method of tetramethyl piperidinol.
Background
Tetramethyl-piperidinol is an extremely important synthetic material intermediate in the high-end fine chemical industry field, and is widely used for preparing important intermediates of various Hindered Amine Light Stabilizers (HALS) with excellent performance. Hindered amine light stabilizers are widely used in synthetic materials, and due to their excellent performance, the development of HALS has been remarkably rapid in recent years abroad, and the HALS accounts for about 69% of the whole light stabilizer market by the end of 2010. The piperidone is subjected to hydrogenation reduction to obtain the tetramethyl piperidinol. Tetramethyl piperidinol is not only an important intermediate for synthesizing HALS, but also can be used as a bleaching agent, a lubricant, a medicine, a polymerization inhibitor, an epoxy resin cross-linking agent and the like, and has wide application and large market capacity in the field of synthesis of fine chemicals and intermediates thereof. According to incomplete statistics, the capacity of the tetramethylpiperidinol in the world is over 50 ten thousand tons at present. With the development of fine chemical engineering in China, the market demand of domestic tetramethyl piperidinol is also rapidly increased, and the annual capacity is about more than 20 ten thousand tons, which accounts for about 40% of the world capacity.
The industrial production process of tetramethyl piperidinol is still a batch reaction kettle type hydrogenation method using Raney Ni as a main catalyst. Other new methods have also been reported: chemical reduction of a ketocarbonyl group with aluminum isopropoxide, sodium borohydride, etc. as a reducing agent produces tetramethylpiperidinol (proceedings of Yanbian university, 1994,20(3):7576) and tetramethylpiperidinol by reduction of piperidone in a methanol solution of sodium hydroxide in an electrolytic cell with zinc as a cathode (Elektrokhimiya,1984,20(3): 404407). The influence rule of the structure and the property of the aluminum oxide loaded copper and chromium doped catalyst on the reaction performance of preparing the tetramethylpiperidinol by hydrogenating triacetonamine is researched on a microflow reactor by the standing work (Chin.J.Catal.,2012,33: 605-609). To date, there have been no patent reports and no industrial production examples of continuous flow preparation of tetramethylpiperidinol.
Although the batch operation reaction process has the advantage of flexible operation, the method has a plurality of byproducts and lower product yield. In particular, the batch still reaction process method has the problems that the operation process is complicated because unreacted residual hydrogen in the autoclave needs to be discharged and replaced by nitrogen every time, material leakage, overflow, dripping and leakage exist in each link of production operation, potential safety hazards are great, and the batch still reaction process method does not meet the safety standard and environmental requirements of China for the chemical industry at present. In the aspect of capacity, the batch kettle type reaction process has small capacity, and the equipment required for enlarging the capacity has extremely large volume, so that the requirement on the material strength of the equipment is extremely high and difficult to realize. And the intermittent operation cannot realize automatic control due to the limitation of the process technology. Therefore, the process for synthesizing the tetramethyl piperidinol by the batch kettle type reaction process is an extremely uneconomical, unsafe and non-green technology and cannot meet the requirements of high efficiency, greenness, safety and low carbon in the fine chemical industry of China at present. The development of safe, continuous and green process technology capable of realizing automatic control is a key for solving the problems of industrial preparation and capacity expansion of the existing tetramethyl piperidinol.
Disclosure of Invention
The invention discloses a novel method for synthesizing tetramethylpiperidinol by triacetonamine, which aims to solve the problems that the existing industrial batch kettle type reaction process is discontinuous, difficult to control safely, generates more byproducts, has low energy utilization rate, does not conform to the current purpose of green-low carbon chemical manufacture in China and the raw material hydrogen can not be recycled.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention aims to provide a method for synthesizing tetramethyl piperidinol by hydrogenation reduction of triacetonamine, which specifically comprises the following steps: isopropanol which takes triacetonamine as a solute is used as a solvent to prepare a raw material liquid for reaction according to a certain mass proportion, the raw material liquid enters a continuous flow packed bed reactor, the reaction is carried out at the reaction temperature of 80-150 ℃ and the pressure of 0.8-2.0 Mpa, and the obtained reaction liquid is collected by a receiver and then is crystallized to obtain the high-purity tetramethyl piperidinol. Preferably, the reaction temperature is 110-130 ℃ and the pressure is 1.2-1.5 MPa. The process adopts a continuous feeding and continuous discharging method, avoids the discontinuous defects of the traditional batch kettle type hydrogenation process and the great unsafe factors of operations of backfilling nitrogen, replacing air and the like in the reactor in each operation.
As a further improvement of the invention, the Weight Hourly Space Velocity (WHSV) of the raw material liquid feed is 3.51-10.24 h -1 (ii) a Preferably, the Weight Hourly Space Velocity (WHSV) of the feed solution is 4.73-9.46 h -1 。
As a further improvement of the invention, after the hydrogenation reduction reaction, unreacted hydrogen is compressed by a compressor and then enters a hydrogen storage tank for recycling, so that not only is the waste of hydrogen avoided, but also potential safety hazards caused by the fact that redundant hydrogen is directly discharged to the atmosphere by an intermittent reaction process are avoided.
As a further improvement of the invention, the solvent is a gas-liquid mixed phase at the temperature and pressure of the reaction, and does not react with the reactants triacetonamine, which is a liquid phase, and the product tetramethylpiperidinol.
In a further improvement of the present invention, the mass percent of triacetonamine in the raw material liquid is 10 to 40 wt.%, and preferably, the mass percent of triacetonamine in the raw material liquid is 15 to 30 wt.%.
As a further improvement of the present invention, the molar ratio of triacetonamine to hydrogen is in the range of 1: 1-5; preferably, the molar ratio of triacetonamine to hydrogen is 1: 1 to 3.
As a further improvement of the invention, a catalyst is arranged in the packed bed reactor, and the catalyst is a solid particle catalyst of porous aluminum material assembled metallic nickel. The synthesis method of the solid particle catalyst of the porous aluminum material assembled metallic nickel comprises the following steps: the metal Ni catalyst is assembled by adopting a commercially available clover strip-shaped alumina as a carrier and an impregnation method. Namely, nickel nitrate is used as a metal source to prepare impregnation liquid, and a catalyst precursor after being impregnated with metal is dried for 10 hours at 120 ℃ and then calcined for 3 hours at 400 ℃; the bed of the packed bed reactor is loaded with calcined solid particulate catalyst.
The invention also aims to provide a synthesis process for preparing tetramethylpiperidinol by continuous flow hydrogenation of triacetonamine, and the synthesis process device comprises a raw material tank, a metering pump, a check valve, a flowmeter, a preheater, a pressure stabilizing valve, a gas-liquid mixer, a packed bed reactor, a hydrogen compressor, a crystallization tank, a centrifuge, a compressed hydrogen tank and a discharge pump.
As a further improvement of the invention, the packed bed reactor has a cavity structure for supporting and filling solid catalyst particles, so that the reaction liquid and hydrogen can be in sufficient contact reaction in pores among the particles in the catalyst layer.
As a further improvement of the invention, the raw material liquid and hydrogen enter the packed bed reactor after being preheated by the preheater; the raw material liquid and the hydrogen can reach the target temperature of 80-150 ℃ when passing through the preheater, a heating device is not needed to be provided for the reactor, and the temperature of a catalyst layer in the reactor can be kept within a controllable reaction temperature range.
Compared with the prior art, the invention has the beneficial effects that:
(1) the technical scheme realizes continuous flow reaction, each component of the process fluid in the packed bed reactor is fully mixed in the catalyst layer and fully contacted with the catalyst, and the effective retention time of reactants in the packed bed of the reactor is long. Therefore, compared with a kettle type reactor, the reactor has the advantages of extremely high mixing efficiency, extremely high heat exchange capacity, extremely narrow residence time distribution, small occupied area of equipment and extremely high safety of equipment operation;
(2) the feeding of the continuous flow packed bed reactor can be accurately controlled in feeding temperature and flow through a raw material preheater and a feeding pump, so that a continuous and green production process is realized;
(3) in the process technology, the unreacted excessive hydrogen is compressed by a compressor and then enters a raw material hydrogen storage tank for recycling, so that potential safety hazards of directly discharging into the atmosphere and waste of raw materials are avoided;
(4) the technology is convenient for automatic control to carry out continuous feeding and discharging, and improves the production efficiency.
Drawings
FIG. 1 is a schematic diagram of a process for preparing tetramethylpiperidinol by continuous flow hydrogenation of triacetonamine;
FIG. 2 shows the conversion of triacetonamine as the reaction raw material for preparing tetramethylpiperidinol by continuous flow hydrogenation;
FIG. 3 is the stability of selectivity of tetramethylpiperidinol, a product of continuous flow hydrogenation of triacetonamine in accordance with the present invention;
FIG. 4 is a comparison of main technical and economic indicators of a batch reactor process and a packed bed continuous process for producing 2000 tons of tetramethylpiperidinol per year (in the indicators, 100% of the indicators of a batch reactor is used as a comparative reference);
description of reference numerals:
1. metering pump, 2, check valve, 3, flowmeter, 4, preheater, 5, gas-liquid mixer, 6, preheater, 7, pressure stabilizing valve, 8, compressed hydrogen tank, 9, packed bed reactor, 10, hydrogen compressor, 11, raw material tank, 12, reaction liquid receiver, 13, pressure stabilizing valve, 14, crystallizing tank, 15 and centrifuge.
Detailed Description
The present invention will be further illustrated with reference to the accompanying drawings and specific embodiments, which are to be understood as merely illustrative of the invention and not as limiting the scope of the invention.
Raw material liquid prepared from triacetonamine and isopropanol is stored in a raw material tank 11 and enters a gas-liquid mixer 5 through a preheater 4; hydrogen in a compressed hydrogen tank 8 enters a gas-liquid mixer 5 through a preheater 6 to be mixed with a raw material liquid, and then flows into a packed bed reactor 9 to carry out hydrogenation reduction reaction. The obtained reaction solution is collected by a receiver 12, crystallized in a crystallizing tank 14, and centrifuged in a centrifuge 15 to obtain the tetramethylpiperidinol. After the hydrogenation reduction reaction, unreacted hydrogen is compressed by a hydrogen compressor 10 and then enters a hydrogen storage tank 8 for recycling.
Example 1
As shown in the technical scheme of figure 1, the raw material liquid contains 15 mass percent of triacetonamine, the flow rate of the raw material liquid is 94.56kg/h, the raw material liquid and hydrogen with the flow rate of 1.83kg/h are mixed in a gas-liquid mixer, the mixture enters a continuous flow packed bed reactor under the conditions that the reaction temperature is 110 ℃ and the reaction pressure is 1.5MPa, the reaction period is 12 weeks, and the mixture and Ni/Al are reacted 2 O 3 The catalyst is contacted with hydrogenation and reduction to produce tetramethyl piperidinol and 2, 6-dimethyl-4-heptanone and other by-products. The weight hourly space velocity of the raw material liquid is 4.73h -1 The molar ratio of triacetonamine to hydrogen is 1: 1.5, GC detects that the product content in the reaction liquid is 99.1 percent.
Ni/Al 2 O 3 The preparation method of the catalyst comprises the following steps: the metal Ni catalyst is assembled by adopting a commercially available clover strip-shaped alumina as a carrier and an impregnation method. Namely, nickel nitrate is used as a metal source to prepare impregnation liquid, and a catalyst precursor after being impregnated with metal is dried for 10 hours at 120 ℃ and then calcined for 3 hours at 400 ℃; calcined Ni/Al 2 O 3 The catalyst is filled into the bed layer of the packed bed reactor.
Example 2
Other conditions were the same as in example 1, except that the reactor temperature was changed: the reactor temperature was 120 ℃. The weight hourly space velocity of the raw material liquid is 4.73h -1 The molar ratio of triacetonamine to hydrogen is 1: 1.5, GC detects that the product content in the reaction liquid is 99.7 percent.
Example 3
Other conditions were the same as in example 1, except that the reactor temperature was changed: the reactor temperature was 130 ℃. The weight hourly space velocity of the raw material liquid is 4.73h -1 The molar ratio of triacetonamine to hydrogen is 1: 1.5, GC detects that the product content in the reaction liquid is 99.0 percent.
Example 4
Other conditions were the same as in example 1, except that the mass percentage of triacetonamine in the starting material liquid was changed: triacetonamine mass percent in the feed solution was 20 wt.%. The weight hourly space velocity of the raw material liquid is 4.73h -1 The molar ratio of triacetonamine to hydrogen is 1: 1.5, GC detects that the content of the product in the reaction liquid is 99.0 percent.
Example 5
Other conditions were the same as in example 1 except that only tripropylene in the raw material solution was changedAnd (2) ketoamine mass percent: triacetonamine mass percent in the feed solution was 30 wt.%. The weight hourly space velocity of the raw material liquid is 4.73h -1 The molar ratio of triacetonamine to hydrogen is 1: 1.5, GC detects that the content of the product in the reaction liquid is 98.5 percent.
Example 6
Other conditions were the same as in example 1, except that the hydrogen flow rate was changed: the hydrogen flow rate was 2.44 kg/h. The weight hourly space velocity of the raw material liquid is 4.73h -1 The molar ratio of triacetonamine to hydrogen is 1: 2, GC detects that the content of the product in the reaction liquid is 99.3 percent.
Example 7
Other conditions were the same as in example 1, except that the hydrogen flow rate was changed: the hydrogen flow rate was 3.65 kg/h. The weight hourly space velocity of the raw material liquid is 4.73h -1 The molar ratio of triacetonamine to hydrogen is 1: 3, GC detects that the content of the product in the reaction liquid is 99.3 percent.
Example 8
Other conditions were the same as in example 1, except that the feed liquid weight hourly space velocity was changed: the liquid weight hourly space velocity of the raw material is 7.10h -1 . The molar ratio of triacetonamine to hydrogen is 1: 1.5, GC detects that the product content in the reaction liquid is 98.5 percent.
Example 9
Other conditions were the same as in example 1, except that the feed liquid weight hourly space velocity was changed: the liquid weight hourly space velocity of the raw material is 9.46h -1 . The molar ratio of triacetonamine to hydrogen is 1: 1.5, GC detects that the product content in the reaction liquid is 98.0 percent.
Example 10
Other conditions were the same as in example 1, except that the reactor pressure was changed: the reactor pressure was 1.0 MPa. The weight hourly space velocity of the raw material liquid is 4.73h -1 The molar ratio of triacetonamine to hydrogen is 1: 1.5, GC detects that the content of the product in the reaction liquid is 98.5 percent.
Example 11
Other conditions were the same as in example 1, with only the reactor pressure being varied: the reactor pressure was 2.0 MPa. The weight hourly space velocity of the raw material liquid is 4.73h -1 The molar ratio of triacetonamine to hydrogen is 1: 1.5, GC detects that the product content in the reaction liquid is 99.3 percent.
Example 12
Under the same conditions as in example 1, after 12 weeks of continuous feeding and continuous discharging, the reaction solution was analyzed and detected for the product content from the next day, the reaction solution was sampled 1 time at intervals every day, and the analysis results per day in one week (7 days) were used as an average value to give the stability of the high process technology, as can be seen from fig. 2, the reaction under the process conditions had a high triacetonamine conversion rate; as can be seen from FIG. 3, the selectivity of the product tetramethylpiperidinol is high, and the content of tetramethylpiperidinol in the reaction solution is 99.0-99.4%, which indicates that the technology has good stability. After the cost calculation, the packed bed continuous process adopted by the process has more advantages compared with the traditional batch kettle process, and as can be seen from fig. 4, the consumption of the catalyst, the cost of the catalyst, the consumption of hydrogen and the final product cost of the process are obviously lower than those of the traditional batch kettle process, and the carbon neutralization contribution is higher.
It should be noted that the above-mentioned contents only illustrate the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and it is obvious to those skilled in the art that several modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations fall within the protection scope of the claims of the present invention.

Claims (10)

1. The synthesis process method for preparing tetramethyl piperidinol by continuous flow hydrogenation of triacetonamine is characterized by comprising the following steps of: taking triacetonamine as a solute and isopropanol as a solvent to prepare a raw material solution, mixing and preheating the raw material solution and hydrogen, continuously feeding the raw material solution and the hydrogen into a packed bed reactor, carrying out hydrogenation reduction reaction at the temperature of 80-150 ℃ and the pressure of 0.8-2.0 Mpa, collecting the obtained reaction solution by a receiver, and carrying out crystallization treatment to obtain the tetramethyl piperidinol.
2. The synthesis process method for preparing tetramethylpiperidinol by continuous flow hydrogenation of triacetonamine as claimed in claim 1, wherein the Weight Hourly Space Velocity (WHSV) of the raw material liquid feed is 3.51-10.24 h -1 。
3. The synthesis process of triacetonamine with continuous flow hydrogenation to tetramethylpiperidinol as claimed in claim 1, wherein after the hydrogenation reduction reaction, unreacted hydrogen is compressed by a compressor and then enters a hydrogen storage tank for recycling.
4. The method for synthesizing tetramethylpiperidinol by continuous flow hydrogenation of triacetonamine as claimed in claim 1, wherein the solvent is a gas-liquid mixed phase during the hydrogenation reduction reaction, and the triacetonamine and the reaction product are liquid phases.
5. The synthesis process for preparing tetramethylpiperidinol by continuous flow hydrogenation of triacetonamine as claimed in claim 1, wherein the mass percent of triacetonamine in the raw material liquid is 10-40 wt.%.
6. The synthesis process of triacetonamine with continuous flow hydrogenation to tetramethylpiperidinol as claimed in claim 1, wherein the molar ratio of triacetonamine to hydrogen is in the range of 1: 1 to 5 under the condition of the following reaction.
7. The method for synthesizing tetramethylpiperidinol by continuous flow hydrogenation of triacetonamine according to claim 1, wherein a solid particulate catalyst of metallic nickel is assembled with a porous aluminum material in advance in the packed bed reactor.
8. The apparatus for preparing tetramethylpiperidinol by continuous flow hydrogenation of triacetonamine as claimed in any of claims 1 to 7, wherein the apparatus for synthesizing process comprises a raw material tank, a metering pump, a check valve, a flow meter, a preheater, a pressure maintaining valve, a gas-liquid mixer, a packed bed reactor, a hydrogen compressor, a crystallizing tank, a centrifuge, a compressed hydrogen tank, and a discharge pump.
9. The apparatus for preparing tetramethylpiperidinol by the continuous flow hydrogenation of triacetonamine as claimed in claim 8, wherein the packed bed reactor has a cavity structure for supporting and packing the solid particle catalyst.
10. The apparatus for preparing tetramethylpiperidinol by continuous flow hydrogenation of triacetonamine according to claim 8, wherein the feed liquid and hydrogen gas are preheated by a preheater and then fed into the packed bed reactor.
CN202210674006.1A 2022-06-15 2022-06-15 Low-carbon-green synthesis process method for preparing tetramethyl piperidinol by continuous flow hydrogenation of triacetonamine Pending CN115010650A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103274991A (en) * 2013-06-11 2013-09-04 衡水凯亚化工有限公司 Method and device for producing 2, 2, 6, 6-Tetramethyl-4-piperidinol through continuous catalytic hydrogenation
CN110317162A (en) * 2019-07-26 2019-10-11 宿迁联盛科技股份有限公司 Tetramethyl piperidine amine is continuously synthesizing to method and synthesizer
TW202210459A (en) * 2020-09-03 2022-03-16 台灣中油股份有限公司 Preparation method of tetramethylpiperidol wherein the catalyst has high conversion rate and high selectivity to reduce the cost of subsequent purification and improve the economic benefit of the overall process
CN114702434A (en) * 2022-05-11 2022-07-05 宿迁联盛科技股份有限公司 Continuous synthesis method of tetramethyl piperidinol

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103274991A (en) * 2013-06-11 2013-09-04 衡水凯亚化工有限公司 Method and device for producing 2, 2, 6, 6-Tetramethyl-4-piperidinol through continuous catalytic hydrogenation
CN110317162A (en) * 2019-07-26 2019-10-11 宿迁联盛科技股份有限公司 Tetramethyl piperidine amine is continuously synthesizing to method and synthesizer
TW202210459A (en) * 2020-09-03 2022-03-16 台灣中油股份有限公司 Preparation method of tetramethylpiperidol wherein the catalyst has high conversion rate and high selectivity to reduce the cost of subsequent purification and improve the economic benefit of the overall process
CN114702434A (en) * 2022-05-11 2022-07-05 宿迁联盛科技股份有限公司 Continuous synthesis method of tetramethyl piperidinol

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