CN109529906A - A kind of catalyst and preparation method thereof synthesizing 1,1,2,3,3,3- hexafluoro propyl methyl ether - Google Patents
A kind of catalyst and preparation method thereof synthesizing 1,1,2,3,3,3- hexafluoro propyl methyl ether Download PDFInfo
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- CN109529906A CN109529906A CN201811588779.8A CN201811588779A CN109529906A CN 109529906 A CN109529906 A CN 109529906A CN 201811588779 A CN201811588779 A CN 201811588779A CN 109529906 A CN109529906 A CN 109529906A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
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Abstract
The invention discloses a kind of catalyst and preparation method thereof for synthesizing 1,1,2,3,3,3- hexafluoro propyl methyl ether.The catalyst is made of carrier and cobalt-nitrogen-doped carbon, and the carrier is carbon dust or Ce-Al2O3, by Cobalt Phthalocyanine, high-temp in-situ pyrolysis generates cobalt-nitrogen-doped carbon in a nitrogen atmosphere, and wherein the quality of cobalt element is the 1%~9% of catalyst gross mass.By the way that Cobalt Phthalocyanine, carrier and auxiliary agent are placed in abundant ball milling in ball mill, then 1~10h of roasting temperature in nitrogen atmosphere at 400~1000 DEG C is made.The catalyst is applied to catalyze and synthesize in the reaction of 1,1,2,3,3,3- hexafluoro propyl methyl ether, has very high catalytic activity and selectivity of product, and preparation method is simple and environmentally-friendly, and catalyst is easily isolated, recyclable, has good industrial applications prospect.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method thereof for synthesizing 1,1,2,3,3,3- hexafluoro propyl methyl ether, belong to and urge
Agent field.
Background technique
With the development of science and technology, the integrated level of electronic product is higher and higher, in order to ensure its stable function and longer
Service life, carrying out efficiently cleaning to it becomes of crucial importance.Past electronics industry it is usually used be CFC (CFC-113)
Class cleaning agent, but because it has serious destruction and stronger greenhouse effects to ozone layer, it has been prohibited from using at present.Its
Substitute HCFC (HCFC-141b, HCFC-225) class cleaning agent is also because its higher consumption ozone latent energy value (ODP) and the whole world become
It warms up latent energy value (GWP) and longer atmosphere residence time and will be eliminated and limit use.Hydrofluoroether serial cleaning agent tool
There are preferable cleaning ability, good material compatibility, ODP value is 0, and GWP value is relatively low, and atmospheric lifetime is short, therefore beautiful
State and European Environment protection office regard as the ideal alternative solution of HCFC class cleaning agent jointly.1,1,2,3,3,3- hexafluoro propyl first
Ether is as one of serial hydrofluoroether, and recent domestic synthesizes it and has conducted extensive research, but document report is less.
United States Patent (USP) US 20030209685A1 discloses a kind of method for synthesizing 1,1,2,3,3,3- hexafluoro propyl methyl ether,
This method is catalyst using the KOH solution that mass fraction is 45% using hexafluoropropene and methanol as raw material, though using this method
So available 1,1,2,3,3,3- higher yield of hexafluoro propyl methyl ether (85%), but this method is unsatisfactory, there are the shortcomings that
Mainly have: the KOH solution of high concentration has stronger corrosivity, corrosive equipment；Highly basic is not easy to point as homogeneous catalyst
From, it is difficult to recycling and reusing, moreover, the salkali waste of generation also will cause serious environmental pollution；In addition, the heavy constituent generated
Content is also higher (9%), to bring difficulty to further purification, product quality is difficult to guarantee.The scientist of Japan also reports
A kind of method (Angew.Chem.Int.Ed.2005,44,1128- synthesizing 1,1,2,3,3,3- hexafluoro propyl methyl ether
1130), this method is also to use hexafluoropropene and methanol for raw material, the difference is that it is with Pd (PPh3)4For catalyst, experiment knot
Fruit shows that using the yield of 1,1,2,3,3,3- hexafluoro propyl methyl ether of this method, up to 83% although this method avoids highly basic
Use, will not generation environment pollution problem, but using precious metals pd as catalyst, catalyst higher cost, and homogeneous Pd catalysis
Agent is not readily separated, it is difficult to which recycling and reusing, this makes the preparation cost of 1,1,2,3,3,3- hexafluoro propyl methyl ether higher.
Environmental pollution is serious there is equipment burn into for the above method, and catalyst is at high cost, and product quality, which is difficult to guarantee, etc. asks
Topic.
Summary of the invention
In order to solve shortcomings and deficiencies of the prior art, it is corrosion-free, environment friendly and pollution-free that the present invention provides a kind of pair of equipment, urges
Agent is at low cost, is easily isolated, and catalytic activity is high, selectivity is high for synthesizing urging for 1,1,2,3,3,3- hexafluoro propyl methyl ether
Agent and preparation method thereof.
The catalyst of 1,1,2,3,3,3- hexafluoro propyl methyl ether of synthesis of the invention is made of carrier and cobalt-nitrogen-doped carbon,
The carrier is carbon dust or Ce-Al2O3One of, by Cobalt Phthalocyanine, high-temp in-situ is pyrolyzed cobalt-nitrogen-doped carbon in a nitrogen atmosphere
It generates, wherein the quality of cobalt element is the 1%~9% of catalyst gross mass.
Preferably, the carrier is Ce-Al2O3。
Preferably, the quality of the cobalt element is the 5%~9% of catalyst gross mass.
The present invention also provides the preparation methods of the catalyst of 1,1,2,3,3,3- hexafluoro propyl methyl ether of synthesis, including following step
It is rapid:
(1) Cobalt Phthalocyanine, carrier and auxiliary agent are separately added into the ball grinder equipped with zirconium pearl, the auxiliary agent is nitrogenous chemical combination
Object, wherein the quality of cobalt element is the 1%~9% of catalyst gross mass, and the molar ratio of Cobalt Phthalocyanine and auxiliary agent is 1:1~5, mixing
It is placed on abundant ball milling in ball mill, 0.5~12h of Ball-milling Time；
(2) gained mixture in step (1) is roasted into 1~10h in nitrogen atmosphere stove at 400~1000 DEG C
Obtain the catalyst of synthesis 1,1,2,3,3,3- hexafluoro propyl methyl ether.
Preferably, auxiliary agent described in step (1) is one in urea, 1,10- phenanthroline, dicyanodiamine and melamine
Kind is several.
Preferably, the molar ratio of Cobalt Phthalocyanine described in step (1) and auxiliary agent is 1:2~5.
Preferably, Ball-milling Time described in step (1) is 0.5~8h.
Preferably, maturing temperature described in step (2) is 500~900 DEG C, and calcining time is 2~6h.
Catalyst involved in the present invention is suitable for hexafluoropropene and methanol-fueled CLC 1,1,2,3,3,3- hexafluoro propyl methyl ether
Reaction.Catalyst can be separated using the methods of centrifugation or standing decantation with reaction solution after reaction.
Compared with prior art, catalyst of the invention has the advantage that
(1) it is different from traditional KOH or precious metals pd catalyst, this catalyst is not only non-corrosive to equipment but also honest and clean
Valence is easy to get, and will not pollute to environment, and catalyst preparation process does not use any organic solvent yet, belongs to cheap, green
Color, environment-friendly type catalyst；
(2) catalyst is present in catalyst system in solid form, passes through simple solid-liquid separation means after the reaction was completed
It can realize the separation and recycling of catalyst, and catalyst does not have metal precipitation, the quality of product is higher；
(3) 1,1,2,3,3,3- hexafluoro propyl methyl ether being synthesized using the catalyst, selectivity of product is high, and 1,1,2,3,
The selectivity of 3,3- hexafluoro propyl methyl ether is up to 99.9%.
Specific embodiment
It is as described below to be merely preferred embodiments of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art within the technical scope of the present disclosure, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
The model VXC-72R of carbon dust involved in the present invention, from Shanghai, Kai Yin Chemical Co., Ltd. is bought.
Ce-Al involved in the present invention2O3Preparation method can refer to document Int.J.Hydrogen Energy.2016,41,
10473-10482.
Embodiment 1
Cobalt element content is the preparation of 1% catalyst
It is separately added into 1g Cobalt Phthalocyanine, 8.58g carbon dust into the ball grinder equipped with zirconium pearl, 0.42g urea is subsequently placed in ball milling
Gained mixture, is then placed in nitrogen atmosphere stove by abundant ball milling 2h in machine, in 600 DEG C of roasting temperature 10h, Temperature fall
It is taken out after to room temperature, that is, obtains 1,1,2,3,3,3- hexafluoro propyl methyl ether catalyst C1 of synthesis.
Embodiment 2
Cobalt element content is the preparation of 9% catalyst
9g Cobalt Phthalocyanine, 0.06gCe-Al are separately added into the ball grinder equipped with zirconium pearl2O3, 0.94g urea is subsequently placed in
Gained mixture, is then placed in nitrogen atmosphere stove by abundant ball milling 6h in ball mill, natural in 700 DEG C of roasting temperature 8h
It is taken out after being cooled to room temperature, that is, obtains 1,1,2,3,3,3- hexafluoro propyl methyl ether catalyst C2 of synthesis.
Embodiment 3
Cobalt element content is the preparation of 5% catalyst
It is separately added into 5g Cobalt Phthalocyanine, 4.26g carbon dust into the ball grinder equipped with zirconium pearl, 0.74g dicyanodiamine is subsequently placed in
Gained mixture, is then placed in nitrogen atmosphere stove by abundant ball milling 5h in ball mill, natural in 800 DEG C of roasting temperature 3h
It is taken out after being cooled to room temperature, that is, obtains 1,1,2,3,3,3- hexafluoro propyl methyl ether catalyst C3 of synthesis.
Embodiment 4
Cobalt element content is the preparation of 2% catalyst
2g Cobalt Phthalocyanine, 5.8gCe-Al are separately added into the ball grinder equipped with zirconium pearl2O3, then 2.2g melamine sets
Gained mixture, is then placed in nitrogen atmosphere stove by abundant ball milling 0.5h in ball mill, in 900 DEG C of roasting temperature 6h,
It is taken out after being naturally cooling to room temperature, that is, obtains 1,1,2,3,3,3- hexafluoro propyl methyl ether catalyst C4 of synthesis.
Embodiment 5
Cobalt element content is the preparation of 6% catalyst
6g Cobalt Phthalocyanine is separately added into the ball grinder equipped with zirconium pearl, 0.22g carbon dust, 3.78g1,10- phenanthroline, then
It is placed in ball mill abundant ball milling 12h, then gained mixture is placed in nitrogen atmosphere stove, in 400 DEG C of roasting temperature 9h,
It is taken out after being naturally cooling to room temperature, that is, obtains 1,1,2,3,3,3- hexafluoro propyl methyl ether catalyst C5 of synthesis.
Embodiment 6
Cobalt element content is the preparation of 8% catalyst
8g Cobalt Phthalocyanine, 0.23gCe-Al are separately added into the ball grinder equipped with zirconium pearl2O3, 1.77g melamine, then
It is placed in ball mill abundant ball milling 8h, then gained mixture is placed in nitrogen atmosphere stove, in 1000 DEG C of roasting temperature 1h,
It is taken out after being naturally cooling to room temperature, that is, obtains 1,1,2,3,3,3- hexafluoro propyl methyl ether catalyst C6 of synthesis.
The evaluation method of the catalyst of synthesis 1,1,2,3,3,3- hexafluoro propyl methyl ether of the invention: it is stirred one with machinery
It mixes, sequentially add catalyst, methanol and acetonitrile, control stirring in the stainless steel autoclave that electric heating, thermocouple and pressure are shown
Speed is 600r/min, and stirring is warming up to 80 DEG C, is passed through 100g hexafluoro into kettle by gas mass flow meter to being uniformly mixed
Propylene is cooled to room temperature after reacting 10h, and gained reaction solution is centrifuged in centrifuge high speed, clear liquid is poured out, using gas-chromatography
Analysis.Example 1-6 prepared catalyst C1, C2, C3, C4, C5, C6 is evaluated respectively.Reaction result is shown in Table 1.Table 1 is anti-
Answer result.
| Catalyst | Conversion ratio % | Selective % |
| C1 | 84.6 | 99.9 |
| C2 | 91.9 | 99.9 |
| C3 | 87.5 | 99.9 |
| C4 | 89.7 | 99.9 |
| C5 | 91.6 | 99.9 |
| C6 | 93.5 | 99.9 |
Claims (3)
1. a kind of catalyst for synthesizing 1,1,2,3,3,3- hexafluoro propyl methyl ether, it is characterised in that the catalyst is by carrier and cobalt-
Nitrogen-doped carbon composition, the carrier are carbon dust or Ce-Al2O3, high temperature is former in a nitrogen atmosphere by Cobalt Phthalocyanine for cobalt-nitrogen-doped carbon
Position pyrolysis generates, and wherein the quality of cobalt element is the 1%~9% of catalyst gross mass.
2. a kind of preparation method for the catalyst for synthesizing 1,1,2,3,3,3- hexafluoro propyl methyl ether, comprising the following steps:
(1) Cobalt Phthalocyanine, carrier and auxiliary agent are separately added into the ball grinder equipped with zirconium pearl, the auxiliary agent is nitrogenous compound,
Wherein the quality of cobalt element is the 1%~9% of catalyst gross mass, and the molar ratio of Cobalt Phthalocyanine and auxiliary agent is 1:1~5, after mixing
It is placed in abundant ball milling in ball mill, 0.5~12h of Ball-milling Time；
(2) gained mixture in step (1) is roasted at 400~1000 DEG C in nitrogen atmosphere stove 1~10h, can be obtained
Synthesize the catalyst of 1,1,2,3,3,3- hexafluoro propyl methyl ether.
3. the preparation method of the catalyst of 1,1,2,3,3,3- hexafluoro propyl methyl ether of synthesis according to claim 2, special
Sign is that auxiliary agent described in step (1) is one or more of urea, 1,10- phenanthroline, dicyanodiamine and melamine.
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| CN201811588779.8A CN109529906B (en) | 2018-12-25 | 2018-12-25 | Catalyst for synthesizing 1,1,2,3,3, 3-hexafluoropropyl methyl ether and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024140169A1 (en) * | 2022-12-29 | 2024-07-04 | 蔚来电池科技(安徽)有限公司 | Composite material, preparation method, negative pole piece, lithium ion battery and electronic apparatus |
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| WO2024140169A1 (en) * | 2022-12-29 | 2024-07-04 | 蔚来电池科技(安徽)有限公司 | Composite material, preparation method, negative pole piece, lithium ion battery and electronic apparatus |
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