CN111604041B - Gamma-alumina modified catalyst, preparation method thereof and application thereof in synthesizing 1, 3-trichloropropene - Google Patents
Gamma-alumina modified catalyst, preparation method thereof and application thereof in synthesizing 1, 3-trichloropropene Download PDFInfo
- Publication number
- CN111604041B CN111604041B CN202010562033.0A CN202010562033A CN111604041B CN 111604041 B CN111604041 B CN 111604041B CN 202010562033 A CN202010562033 A CN 202010562033A CN 111604041 B CN111604041 B CN 111604041B
- Authority
- CN
- China
- Prior art keywords
- gamma
- alumina
- trichloropropene
- catalyst
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 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
- HIILBTHBHCLUER-IWQZZHSRSA-N (z)-1,2,3-trichloroprop-1-ene Chemical compound ClC\C(Cl)=C\Cl HIILBTHBHCLUER-IWQZZHSRSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 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
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 230000004913 activation Effects 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 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
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 description 12
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- 230000009467 reduction Effects 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
Landscapes
- 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, 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, 3-tetrachloropropane under a heating state, so that 1, 3-trichloropropene can be continuously obtained at the end of the reaction tube. The modified gamma-alumina catalyst has the advantages of high efficiency and good stability when used for preparing 1, 3-trichloropropene from 1, 3-tetrachloropropane, can be continuously used for a long time, and has 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, 3-trichloropropene.
Background
1, 3-trichloropropene is an important pesticide intermediate, and a typical application is for synthesizing trifluropyl ether (see: CN 1169147). Triflufen 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).
The method for synthesizing 1, 3-trichloropropene is reported to mainly use 1, 3-tetrachloropropane as a raw material, and remove 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, since the 1, 3-trichloropropene contains double bonds in the structure, a partial polymerization reaction inevitably occurs by a conventional batch or semi-continuous reaction in a kettle type.
The case of 1, 3-trichloropropene production using a tubular reactor has also been reported in recent years (see: CN102177116, JP 2012097017), 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, 3-trichloropropene. The mixture is filled into a tubular reactor, after being activated by nitrogen, 1, 3-tetrachloropropane is continuously introduced under a heating state, and 1, 3-trichloropropene can be continuously obtained at the end of the reaction tube. The modified gamma-alumina catalyst has the advantages of high preparation efficiency and good stability when being used for 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 solutions, further, the method for preparing the catalyst has an effective gamma-alumina content of > 99.9% and a specific surface area of 100-200m 2 G, the diameter of the spherical particles is 3-4mm.
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.
In the technical solution described above, further, in the method for preparing the catalyst, the γ -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 with 1.0 to 2.0 times of the mass of gamma-alumina is used for washing.
A second aspect of the present invention is to protect the catalyst obtained by the preparation method described above.
The third aspect of the present invention is to protect the use of the catalyst obtained by the above preparation method in the synthesis of 1, 3-trichloropropene.
For the above-mentioned application, further, the catalyst was packed in a tubular reactor, activated by introducing nitrogen gas in a heated state, then adjusted to a reaction temperature, and 1, 3-trichloropropene was continuously obtained at the end of the reaction tube by continuously introducing 1, 3-tetrachloropropane. The reaction equation is:
for the above applications, further, the method for synthesizing 1, 3-trichloropropene comprises the steps of filling the modified gamma-alumina catalyst into a tubular reactor, introducing nitrogen, and controlling the space velocity to be 1000.0-2000.0h -1 The first stage activation temperature is 50-70 ℃, the second stage activation temperature is 100-200 ℃, and then the temperature of the reaction tube is adjusted to the reaction temperature of 100-200 ℃. Further preferably, the first stage or the second stageThe activation time of the stage was 1.0h.
For the above applications, further, the method for synthesizing 1, 3-trichloropropene comprises continuously introducing 1, 3-tetrachloropropane after the reaction tube is adjusted to 100-200 ℃, and the weight hourly space velocity is controlled to be 80-120h -1 And collecting the generated 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, and does not need to be activated at 300-500 ℃ 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 -1 The 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 will allow one of ordinary skill in the art to more fully understand the present invention, but will not limit the invention in any way.
Example 1
Preparing a catalyst: to a 500mL beaker was added 50g (100-200 m) of gamma-alumina 2 And the content is more than 99.9 percent, ferrous chloride (5.0 g), polyethylene glycol 400 (5.0 g) and solution prepared by ethanol (90.0 g) are added into the mixture, the mixture is put into a constant-temperature water bath, the temperature is raised to 40 to 45 ℃ in a beaker, and the temperature is kept for 3 hours. And pouring the mixture into a centrifuge for centrifugation, and leaching the mixture by using 50g of ethanol to obtain 56g of modified gamma-alumina.
And (2) filling 20g of the modified catalyst into a reaction tube (with the length of 25cm and the diameter of 1.5 cm), filling glass beads on two sides of the tube, which are not filled with the catalyst, and plugging two ends of the tube by using steel wire meshes. After the catalyst is filled, nitrogen is introduced, and the space velocity is controlled at 1500h -1 Heating 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, 3-tetrachloropropane is pumped in by using a flow pump to ensure that the weight hourly space velocity reaches 100h -1 And 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 continuously operating for 54h without obvious reduction. In the method for preparing the 1, 3-trichloropropene in the tubular continuous reaction mode, the catalyst prepared by the method has the highest comprehensive efficiency of treating raw materials and product quality. Therefore, the technical scheme of the invention has the potential of further amplifying production.
Example 2
Referring to the operation 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, 3-trichloropropene are both 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 (7)
1. The application of a gamma-alumina modified catalyst in the synthesis of 1, 3-trichloropropene is characterized in that: filling the modified gamma-alumina catalyst into a tubular reactor, introducing nitrogen for activation in a heating state, then adjusting to a reaction temperature, and continuously introducing 1, 3-tetrachloropropane to continuously obtain 1, 3-trichloropropene at the tail end of the reaction tube;
the preparation method of the modified gamma-alumina catalyst comprises 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 heated state, and centrifuging to obtain the modified gamma-alumina catalyst.
2. Use according to claim 1, characterized in that: the effective content of the gamma-alumina is more than 99.9 percent, and the specific surface area is 100-200m 2 G, the diameter of the spherical particles is 3-4mm.
3. Use according to claim 1, characterized in that: 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).
4. Use according to claim 1, characterized in that: the average molecular weight of the polyethylene glycol is 400-800.
5. Use according to claim 1, characterized in that: the soaking temperature in the heating state is 30-45 ℃.
6. Use according to claim 1, characterized in that: the condition of introducing nitrogen for activation is that the airspeed is controlled to be 1000.0-2000.0h -1 The first stage activation temperature is 50-70 deg.C, the second stage activation temperature is 100-200 deg.C, and the reaction tube temperature is adjusted to 100-200 deg.C.
7. Use according to claim 1, characterized in that: after the temperature of the reaction tube is adjusted to be between 100 and 200 ℃,1, 3-tetrachloropropane is continuously introduced, and the weight hourly space velocity is controlled to be between 80 and 120h -1 And collecting the generated 1, 3-trichloropropene crude product at the tail end of the reaction tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111604041A CN111604041A (en) | 2020-09-01 |
| CN111604041B true CN111604041B (en) | 2023-04-07 |
Family
ID=72197379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010562033.0A Active CN111604041B (en) | 2020-06-18 | 2020-06-18 | Gamma-alumina modified catalyst, preparation method thereof and application thereof in synthesizing 1, 3-trichloropropene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111604041B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009085862A1 (en) * | 2007-12-19 | 2009-07-09 | Occidental Chemical Corporation | Methods of making chlorinated hydrocarbons |
| CN102614893A (en) * | 2012-03-04 | 2012-08-01 | 浙江建业化工股份有限公司 | Method for combining tributylamine and used catalyst |
| CN104549512A (en) * | 2014-12-31 | 2015-04-29 | 温州大学 | Supported chiral iron complex catalyst, and preparation method and application thereof |
| CN104888802A (en) * | 2015-05-21 | 2015-09-09 | 中国科学院青岛生物能源与过程研究所 | Catalyst for preparing butyric acid and preparation method and application of catalyst |
| CN107001190A (en) * | 2014-10-16 | 2017-08-01 | 化学和冶金生产联合体股份公司 | Method |
| CN107001195A (en) * | 2014-10-16 | 2017-08-01 | 化学和冶金生产联合体股份公司 | Method |
| CN109311785A (en) * | 2016-06-23 | 2019-02-05 | 蓝立方知识产权有限责任公司 | The dehydrochlorination method of chloralkane |
| CN110563547A (en) * | 2019-09-24 | 2019-12-13 | 浙江三美化工股份有限公司 | preparation method of 1,1,1,4,4, 4-hexafluoro-2-butene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8889930B2 (en) * | 2013-01-22 | 2014-11-18 | Axiall Ohio, Inc. | Process for producing chlorinated hydrocarbons |
-
2020
- 2020-06-18 CN CN202010562033.0A patent/CN111604041B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009085862A1 (en) * | 2007-12-19 | 2009-07-09 | Occidental Chemical Corporation | Methods of making chlorinated hydrocarbons |
| CN102614893A (en) * | 2012-03-04 | 2012-08-01 | 浙江建业化工股份有限公司 | Method for combining tributylamine and used catalyst |
| CN107001190A (en) * | 2014-10-16 | 2017-08-01 | 化学和冶金生产联合体股份公司 | Method |
| CN107001195A (en) * | 2014-10-16 | 2017-08-01 | 化学和冶金生产联合体股份公司 | Method |
| CN104549512A (en) * | 2014-12-31 | 2015-04-29 | 温州大学 | Supported chiral iron complex catalyst, and preparation method and application thereof |
| CN104888802A (en) * | 2015-05-21 | 2015-09-09 | 中国科学院青岛生物能源与过程研究所 | Catalyst for preparing butyric acid and preparation method and application of catalyst |
| CN109311785A (en) * | 2016-06-23 | 2019-02-05 | 蓝立方知识产权有限责任公司 | The dehydrochlorination method of chloralkane |
| CN110563547A (en) * | 2019-09-24 | 2019-12-13 | 浙江三美化工股份有限公司 | preparation method of 1,1,1,4,4, 4-hexafluoro-2-butene |
Non-Patent Citations (1)
| Title |
|---|
| 朱洪法主编，.催化剂手册.《催化剂手册》.金盾出版社,2008,第70-72页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111604041A (en) | 2020-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1437590A (en) | Process for operating the epoxidation of ethylene | |
| CN103275096B (en) | A kind of method preparing Isosorbide based on Mierocrystalline cellulose | |
| CN101544538B (en) | Method for preparing isopentenol from 3-methyl-3-butenol | |
| CN111604041B (en) | Gamma-alumina modified catalyst, preparation method thereof and application thereof in synthesizing 1, 3-trichloropropene | |
| CN113087697A (en) | Synthetic method of nicotine | |
| CN114957193B (en) | Method for green synthesis of vinylene carbonate | |
| CN111659426B (en) | Gamma-alumina modified catalyst, preparation method thereof and application thereof in synthesizing 2, 5-dihydrofuran | |
| CN110893348B (en) | High-stability catalyst for preparing ethylene from bioethanol, and preparation and application thereof | |
| CN104557454A (en) | Method for preparing high-quality ethanol through hydrogenating acetic acid | |
| CN104557455A (en) | Method for preparing ethanol through hydrogenating acetic acid | |
| CN102001930B (en) | Method for purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production and application thereof | |
| CN114950505B (en) | Catalyst for preparing beta-phenethyl alcohol by hydrogenation of styrene oxide, and preparation method and application thereof | |
| CN100575349C (en) | The method of preparing epichlorohydrin by chloropropene epoxidation | |
| CN101993353A (en) | Method for preparing 3-methyl-3-butene-1-alcohol | |
| CN116020580A (en) | Regeneration method of iron-based catalyst in phenol alkylation synthesis | |
| CN105523915B (en) | A kind of method that high yield gas phase catalysis cracking prepares two fluoracyl fluorides | |
| CN110743586B (en) | Na salt modified Cu/SiO2Preparation method and application of catalyst | |
| CN111346668A (en) | Preparation and application of modified beta molecular sieve catalyst | |
| CN111151291A (en) | Preparation method and application of mesoporous molecular sieve catalyst | |
| CN102001912A (en) | Method for synthesizing 3,3,3-trifluoropropene | |
| JP2010241790A (en) | Method for producing olefin | |
| CN115770594B (en) | Preparation method and application of hydrophobic catalyst | |
| CN109970635B (en) | Preparation method and application of aminopyridine derivative | |
| CN1676501A (en) | Method for preparing difluoromethane by stage continuous fluorination | |
| CN111484415B (en) | Preparation method of diisopropylethylamine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |