CN111604041A - Gamma-alumina modified catalyst, preparation method thereof and application thereof in synthesis of 1,1, 3-trichloropropene - Google Patents
Gamma-alumina modified catalyst, preparation method thereof and application thereof in synthesis of 1,1, 3-trichloropropene Download PDFInfo
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- CN111604041A CN111604041A CN202010562033.0A CN202010562033A CN111604041A CN 111604041 A CN111604041 A CN 111604041A CN 202010562033 A CN202010562033 A CN 202010562033A CN 111604041 A CN111604041 A CN 111604041A
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- gamma
- alumina
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- trichloropropene
- polyethylene glycol
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- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 26
- JFEVIPGMXQNRRF-UHFFFAOYSA-N 1,1,3-trichloroprop-1-ene Chemical compound ClCC=C(Cl)Cl JFEVIPGMXQNRRF-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 11
- 229960002089 ferrous chloride Drugs 0.000 claims abstract description 11
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 11
- UTACNSITJSJFHA-UHFFFAOYSA-N 1,1,1,3-tetrachloropropane Chemical compound ClCCC(Cl)(Cl)Cl UTACNSITJSJFHA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 230000004913 activation Effects 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 2
- 239000012798 spherical particle Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 241000256244 Heliothis virescens Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241000500437 Plutella xylostella Species 0.000 description 1
- 239000005927 Pyriproxyfen Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- NHDHVHZZCFYRSB-UHFFFAOYSA-N pyriproxyfen Chemical compound C=1C=CC=NC=1OC(C)COC(C=C1)=CC=C1OC1=CC=CC=C1 NHDHVHZZCFYRSB-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a gamma-alumina modified catalyst, a preparation method thereof and application thereof in synthesizing 1,1, 3-trichloropropene, belonging to the field of catalyst preparation and organic synthesis. The catalyst takes gamma-alumina as a carrier, and is modified by ferrous chloride and polyethylene glycol to obtain the gamma-alumina modified catalyst. The mixture is filled into a tubular reactor, activated by nitrogen, and continuously introduced with 1,1,1, 3-tetrachloropropane in a heating state, so that 1,1, 3-trichloropropene can be continuously obtained at the tail end of the reaction tube. The modified gamma-alumina catalyst has the advantages of high efficiency and good stability when used for preparing 1,1, 3-trichloropropene from 1,1,1, 3-tetrachloropropane, and can be continuously used for a long time, thereby having the potential of further amplified production.
Description
Technical Field
The invention belongs to the field of catalyst preparation and organic synthesis, and particularly relates to a gamma-alumina modified catalyst, a preparation method thereof and application thereof in synthesis of 1,1, 3-trichloropropene.
Background
1,1, 3-trichloropropene is an important pesticide intermediate, and a typical application is used for synthesizing trifluromethyl pyriproxyfen (see: CN 1169147). Triflupirfen is a low-toxicity and high-efficiency pesticide, shows a good control effect on resistant tobacco budworm moth and diamond back moth, and has a good market development prospect (see: modern pesticides, 2014,13 and 28).
At present, the reported method for synthesizing 1,1, 3-trichloropropene mainly takes 1,1,1, 3-tetrachloropropane as a raw material, and removes one molecule of hydrogen chloride under the promotion of a catalyst to obtain a target product. Common catalysts are Lewis acid catalysts such as ferric chloride and ferrous chloride (see: CN101337940, CN105050989, WO 2020041731). In addition, because the 1,1, 3-trichloropropene structure contains double bonds, a part of polymerization reaction inevitably occurs by adopting a conventional kettle type batch or semi-continuous reaction.
The case of using a tubular reactor for the preparation of 1,1, 3-trichloropropene has also been reported in recent years (see: CN102177116, JP2012097017), but the reaction temperature is close to 500 ℃ and the reaction conditions are severe. Therefore, there is a need to develop a more efficient catalyst for tubular continuous reaction.
Disclosure of Invention
Aiming at the defects of the method, the invention provides a preparation method of a gamma-alumina modified catalyst, the catalyst prepared by the method and the application of the catalyst in the synthesis of 1,1, 3-trichloropropene. The mixture is filled into a tubular reactor, after being activated by nitrogen, 1,1,1, 3-tetrachloropropane is continuously introduced under a heating state, and 1,1, 3-trichloropropene can be continuously obtained at the tail end of the reaction tube. The modified gamma-alumina catalyst has the advantages of high preparation efficiency and good stability when used for preparing 1,1, 3-trichloropropene, can be continuously used for a long time, and has the potential of further enlarging production.
The technical scheme of the invention is as follows:
the first aspect of the invention is to protect a preparation method of a gamma-alumina modified catalyst, and the specific technical scheme is as follows: adding ferrous chloride and ethanol solution of polyethylene glycol into gamma-alumina as a carrier, soaking in a heating state, and centrifuging to obtain the modified gamma-alumina catalyst.
In the above technical solution, further, in the method for preparing the catalyst, the effective content of gamma-alumina is more than 99.9%, and the specific surface area is 100-2G, the diameter of the spherical particles is 3-4 mm.
In the above technical solution, further, in the method for preparing the catalyst, the total mass concentration of the ferrous chloride and the ethanol solution of polyethylene glycol is 5-10%, wherein the ratio of ferrous chloride: the mass ratio of the polyethylene glycol is 2: 1-1: 2, and the average molecular weight of the polyethylene glycol is 400-800.
In the technical scheme, further, in the method for preparing the catalyst, the gamma-alumina is soaked in the ethanol solution of ferrous chloride and polyethylene glycol for 5-10 hours; preferably, the soaking temperature is 30-45 ℃; preferably, after the centrifugation, ethanol of 1.0 to 2.0 times by mass of γ -alumina is used for washing.
A second aspect of the present invention is to protect the catalyst obtained by the above-described production method.
The third aspect of the invention is to protect the application of the catalyst obtained by the preparation method in the synthesis of 1,1, 3-trichloropropene.
For the above-mentioned application, further, the catalyst is packed in a tubular reactor, activated by introducing nitrogen gas in a heated state, then adjusted to a reaction temperature, and 1,1,1, 3-tetrachloropropane is continuously introduced to obtain 1,1, 3-trichloropropene continuously at the end of the reaction tube. The reaction equation is:
for the application, further, the method for synthesizing the 1,1, 3-trichloropropene is characterized in that the modified gamma-alumina catalyst is filled into a tubular reactor, nitrogen is introduced, and the space velocity is controlled to be 1000.0-2000.0h-1The first stage activation temperature is 50-70 ℃, the second stage activation temperature is 100-. Further preferably, the activation time of the first stage or the second stage is 1.0 h.
For the above applications, further, in the method for synthesizing 1,1, 3-trichloropropene, after the reaction tube is adjusted to 100-200 ℃,1,1, 1, 3-tetrachloropropane is continuously introduced, and the weight hourly space velocity is controlled to be 80-120h-1And collecting the generated 1,1, 3-trichloropropene crude product at the tail end of the reaction tube.
The invention has the following advantages:
1. the catalyst carrier is cheap and easy to obtain, the preparation process is simple, and the loaded catalyst only needs to be activated at 60-200 ℃ under the condition of nitrogen flow without the high-temperature activation at 500 ℃ in a muffle furnace.
2. The catalyst prepared by the method has high efficiency, and the weight hourly space velocity of the feed end reaches 100h-1The product purity reaches 99 percent, the yield reaches 98 percent, the continuous operation lasts for 54 hours, the yield and the purity are not obviously reduced, and the method has the potential of further amplification production.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
Preparing a catalyst: 50g (100-2Per g, content > 99.9%), ferrous chloride (5.0g), polyethylene glycol 400: (5.0g) and 90.0g of ethanol, putting the solution into a constant-temperature water bath, heating the solution to 40-45 ℃ in a beaker, and continuing to keep the temperature for 3 hours. And pouring the mixture into a centrifuge for centrifugation, and leaching the mixture with 50g of ethanol to obtain 56g of modified gamma-alumina.
20g of the modified catalyst is filled into a reaction tube (with the length of 25cm and the diameter of 1.5cm), two side parts of the pipeline, which are not filled with the catalyst, are filled with glass beads, and two ends of the pipeline are plugged with steel wire meshes. After the catalyst is filled, nitrogen is introduced, and the space velocity is controlled at 1500h-1Heating to raise the temperature inside the reaction tube to 60 deg.c, maintaining the temperature and nitrogen flow rate to activate for 1.0 hr, raising the temperature to 150 deg.c and activating for 1.0 hr.
Then 1,1,1, 3-tetrachloropropane is pumped in by using a flow pump to ensure that the weight hourly space velocity reaches 100h-1And collecting fractions produced at the tail end of the reaction tube in different time periods after passing through a condenser, and absorbing the produced tail gas (hydrogen chloride) by using a sodium hydroxide solution. The fractions produced each hour were collected separately, starting from the end condenser distillate production.
The summary data of time and yield are given in table 1:
TABLE 1
| Time/h | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| Yield/% | 94.0 | 97.2 | 97.8 | 98.1 | 98.3 | 98.1 | 98.2 | 98.0 | 98.1 |
| GC purity/%) | 96.0 | 98.5 | 98.9 | 99.1 | 99.2 | 99.0 | 99.4 | 99.2 | 99.3 |
| Time/h | 10-14 | 15-19 | 20-24 | 25-29 | 30-34 | 35-39 | 40-44 | 45-49 | 50-54 |
| Yield/% | 98.4 | 98.2 | 98.0 | 98.0 | 98.5 | 98.3 | 98.0 | 98.4 | 98.2 |
| GC purity/%) | 99.2 | 99.3 | 99.1 | 99.1 | 99.4 | 99.3 | 99.1 | 99.4 | 99.0 |
According to the analysis of the results in table 1, it can be seen that: the gamma-alumina modified catalyst prepared by the invention can keep stable product yield and purity after continuous operation for 54h, and is not obviously reduced. In the method for preparing the 1,1, 3-trichloropropene in the tubular continuous reaction mode, the catalyst prepared by the method has the highest comprehensive efficiency of raw material processing capacity and product quality. Therefore, the technical scheme of the invention has the potential of further enlarging production.
Example 2
Referring to the procedure of example 1, the reaction conditions were changed to obtain the results of Table 2.
TABLE 2
According to the analysis of the results in Table 2, it can be seen that: the ferrous chloride and the polyethylene glycol 400 are loaded on the gamma-alumina carrier, and the effect that the yield and the purity of the 1,1, 3-trichloropropene are more than 90 percent can be realized under the condition of the reaction temperature of 150 ℃.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A preparation method of a gamma-alumina modified catalyst is characterized by comprising the following steps: and (2) taking gamma-alumina as a carrier, adding an ethanol solution prepared from ferrous chloride and polyethylene glycol, soaking in a heating state, and centrifuging to obtain the modified gamma-alumina catalyst.
2. The method of claim 1, wherein: the effective content of the gamma-alumina is more than 99.9 percent, and the specific surface area is 100-2G, the diameter of the spherical particles is 3-4 mm.
3. The method of claim 1, wherein: the total mass concentration of the ferrous chloride and the ethanol solution prepared from polyethylene glycol is 5-10%, wherein the weight ratio of the ferrous chloride to the polyethylene glycol is as follows: the mass ratio of the polyethylene glycol is 2: 1-1: 2.
4. The method of claim 1, wherein: the average molecular weight of the polyethylene glycol is 400-800.
5. The method of claim 1, wherein: the soaking temperature in the heating state is 30-45 ℃.
6. A gamma-alumina modified catalyst prepared according to the process of claim 1.
7. Use of a gamma-alumina modified catalyst prepared according to the process of claim 1 for the synthesis of 1,1, 3-trichloropropene.
8. Use according to claim 7, characterized in that: the modified gamma-alumina catalyst is filled into a tubular reactor, nitrogen is introduced for activation in a heating state, then the reaction temperature is adjusted, and 1,1,1, 3-tetrachloropropane is continuously introduced to obtain the 1,1, 3-trichloropropene at the tail end of the reaction tube.
9. Use according to claim 7, characterized in that: the condition of introducing nitrogen for activation is that the space velocity is controlled to be 1000.0-2000.0h-1The first stage activation temperature is 50-70 ℃, the second stage activation temperature is 100-.
10. Use according to claim 9, characterized in that: after the reaction tube is regulated to 100-200 ℃,1,1, 1, 3-tetrachloropropane is continuously introduced, and the weight hourly space velocity is controlled to be 80-120h-1And collecting the generated 1,1, 3-trichloropropene crude product at the tail end of the reaction tube.
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| CN202010562033.0A CN111604041B (en) | 2020-06-18 | 2020-06-18 | Gamma-alumina modified catalyst, preparation method thereof and application thereof in synthesizing 1, 3-trichloropropene |
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