CN106977366A - A kind of method for synthesizing monochlorodifluoromethane refrigerant - Google Patents
A kind of method for synthesizing monochlorodifluoromethane refrigerant Download PDFInfo
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- CN106977366A CN106977366A CN201710200240.XA CN201710200240A CN106977366A CN 106977366 A CN106977366 A CN 106977366A CN 201710200240 A CN201710200240 A CN 201710200240A CN 106977366 A CN106977366 A CN 106977366A
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- monochlorodifluoromethane
- mixed gas
- tfe
- synthesizing
- refrigerant
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/361—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms
Abstract
Field is made the invention belongs to refrigerant, specifically related to a kind of method for synthesizing monochlorodifluoromethane refrigerant, by the mixed gas containing TFE together with hydrogen by the bed for the hydrogenation catalyst being made up of porous carrier, obtain mixed gas A, mixed gas A is passed into hypochlorite solution again, the gas out from hypochlorite solution is collected, that is, synthesizes the mixed gas B containing monochlorodifluoromethane, mixed gas B is passed through in weak acid solution again and filtered, monochlorodifluoromethane refrigerant is obtained.Synthetic method stability of the present invention is good, building-up process safety, suitable for technology production.
Description
Technical field
Field is made the invention belongs to refrigerant, and in particular to a kind of method of synthesis monochlorodifluoromethane refrigerant.
Background technology
Refrigerant is also known as refrigeration working medium, and snow kind is commonly called as in some southern areas.It is constantly to circulate in refrigeration systems simultaneously
By the state change of itself to realize the operation material of refrigeration.Refrigerant absorbs cooled medium in evaporator（Water or
Air etc.）Heat and vaporize, surrounding air or water are transferred heat within the condenser and is condensed.
Ammonia be it is the most widely used at present it is a kind of in press middle temperature refrigerant.The setting temperature of ammonia is -77.7 DEG C, and standard is steamed
It is -33.3 DEG C to send out temperature, and condensing pressure is generally 1.1~1.3MPa at normal temperatures, even if when summer coolant water temperature is up to 30 DEG C
When must not also exceed 1.5MPa.The unit norm volume refrigerating capacity compressor of ammonia is about 520kcal/m3.Ammonia has good water suction
Property, it will not also separate out and freeze from ammoniacal liquor even if water at low temperature, therefore " ice berg " phenomenon will not occur in system.Ammonia is to steel
Do not rise in corrosiveness, but ammoniacal liquor and contain after moisture, have corrosiveness to copper and copper alloy, and evaporating temperature is slightly improved.
Therefore, water content in copper and Cu alloy material, and regulation ammonia can not be used to be not to be exceeded 0.2% in ammonia refrigerating installation.Pure ammonia is to profit
Lubricating oil has no adverse effects, but when having moisture, can reduce the lubrication of refrigeration oil.Ammonia is not readily dissolved in lubricating oil, therefore will be
Dress centers oil eliminator, reduces lubricating oil and enters condenser and evaporator, prevents heat exchange surface from being conducted heat after being polluted by the oil
Performance is reduced.
Liquefied ammonia clear, colorless, ammonia steam is colourless, there is strong impulse stink.Ammonia has larger toxicity to human body, works as ammoniacal liquor
Frostbite can be caused when being splashed on skin.It can set off an explosion when the volume of ammonia steam in air reaches 0.5-0.6%.Therefore computer room
The concentration of ammonia must not exceed 0.02mg/L in interior air.
Under Soviet citizen Ke Nuniyangci in 1958 proposes that tetrafluoroethene (TFE) is raw material normal temperature and pressure, Pd catalytic hydrogenation systems
Standby HFC-134, yield reaches 96%；Nineteen ninety Moore (EP365296) et al. proposes to use Al2O3Synthesized under supported palladium normal temperature
HFC-134；(Japanese Laid-Open Patent Publication, flat 2-129131) such as the rice fields of Japan proposes 100- under activated carbon loaded palladium normal pressure
150 DEG C of synthesis HFC-134, yield is 84%.Raw material TFE storages and transport used in these methods is more difficult, secondly, to obtain
Pure TFE is obtained as synthesis material, rectifying condition is more harsh, synthesis cost is higher.
Chinese patent (publication number CN1086802) proposes the method with mixing Fluorine containing olefine gas pressure synthesis HFC-134, living
Property charcoal or Al2O3Supported catalyst Pd synthesizes HFC-134 under the conditions of 100-170 DEG C.But the catalysis of carrier is used as using activated carbon
After agent inactivation, regeneration is more difficult, it is impossible to use oxygen recovery.During using aluminum oxide as carrier, produced in hydrogenation process
HF can be with oxidation reactive aluminum generation AlF3, reduce specific surface area of catalyst, and then influence the service life of catalyst.
The content of the invention
In view of the above-mentioned problems, the technical problem to be solved in the present invention is to provide a kind of synthesis monochlorodifluoromethane refrigerant
Method, its raw material sources facility, building-up process safety, the side of the synthesis monochlorodifluoromethane refrigerant produced suitable for technology
Method.
To achieve the above object, the technical scheme is that：A kind of method for synthesizing monochlorodifluoromethane refrigerant, will
Mixed gas containing TFE, by the bed for the hydrogenation catalyst being made up of porous carrier, obtains mixed gas together with hydrogen
A, then mixed gas A is passed into hypochlorite solution, collect the gas out from hypochlorite solution, i.e. synthesis and contain difluoro
The mixed gas B of monochloro methane, then mixed gas B is passed through into filtering in weak acid solution, obtain monochlorodifluoromethane refrigerant.
Preferably, the mixed gas containing TFE is TFE and the mixture of inert gas formation, the inert gas
Refer at reaction conditions with the nonreactive gas of TFE and hydrogen.
Preferably, the material of the porous carrier is fluorine-containing compound, and the fluorine-containing compound includes oxyfluoride
Or/and fluoride.
Preferably, the hydrogenation catalyst is Pt, at least one of Cr, or at least one of Pt, Cr and Fe,
The compound of at least one of Cu, Zn, Ni metal formation.
Preferably, the weight ratio of the hydrogenation catalyst and porous carrier is 0.2% ~ 5%.
Preferably, TFE molar content is 10% ~ 80% in the mixed gas.
Preferably, the inert gas is nitrogen, helium or HCFC-22.
Preferably, the reaction condition is 0.1 ~ 0.4MPa of pressure, 100 ~ 250 DEG C of temperature, mole of the TFE and hydrogen
Than for 1：1~10.
The beneficial effects of the present invention are：Because TFE easily gathers cruelly, pressurization is lower easily to be blocked, and therefore, it is difficult to realize under pressurization
Hydrogenation reaction, therefore the present invention using mixed gas hydrogenation, it is possible to achieve pressurization, improve hydrogenation efficiency, while being mixed with TFE
Gas be inert gas, even if so TFE and other gas mixings, will not also change TFE characteristic.What the present invention was used
Porous carrier is fluoride or oxyfluoride, porous carrier materials used not with the hydrogen fluoride reaction generated in course of reaction,
The service life of catalyst is not only increased, while recycling can also be regenerated.Synthetic method stability of the present invention is good, synthesis
Process safety, suitable for technology production.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, following examples, to present invention progress
It is further to describe in detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, this is not limited
Invention.
Embodiment 1
It is a kind of synthesize monochlorodifluoromethane refrigerant method, by the mixed gas containing TFE together with hydrogen by by porous
The bed for the hydrogenation catalyst that carrier is constituted, obtains mixed gas A, then mixed gas A is passed into hypochlorite solution, collects
Gas from hypochlorite solution out, that is, synthesize the mixed gas B containing monochlorodifluoromethane, then mixed gas B is passed through
Filtered in weak acid solution, obtain monochlorodifluoromethane refrigerant.
The mixed gas containing TFE is TFE and the mixture of inert gas formation, and the inert gas refers to anti-
With TFE and the nonreactive gas of hydrogen under the conditions of answering.
The material of the porous carrier is fluorine-containing compound, and the fluorine-containing compound includes oxyfluoride and fluorination
Thing.
The hydrogenation catalyst is Pt, at least one of Cr, or at least one of Pt, Cr and Cu, Zn, Ni metal
At least one of formed compound.
The weight ratio of the hydrogenation catalyst and porous carrier is 0.2%.
TFE molar content is 10% in the mixed gas.
The inert gas is nitrogen, helium or HCFC-22.
The reaction condition is pressure 0.1MPa, and 100 DEG C of temperature, the mol ratio of the TFE and hydrogen is 1：1.
Embodiment 2
It is a kind of synthesize monochlorodifluoromethane refrigerant method, by the mixed gas containing TFE together with hydrogen by by porous
The bed for the hydrogenation catalyst that carrier is constituted, obtains mixed gas A, then mixed gas A is passed into hypochlorite solution, collects
Gas from hypochlorite solution out, that is, synthesize the mixed gas B containing monochlorodifluoromethane, then mixed gas B is passed through
Filtered in weak acid solution, obtain monochlorodifluoromethane refrigerant.
The mixed gas containing TFE is TFE and the mixture of inert gas formation, and the inert gas refers to anti-
With TFE and the nonreactive gas of hydrogen under the conditions of answering.
The material of the porous carrier is fluorine-containing compound, and the fluorine-containing compound includes oxyfluoride or fluorination
Thing.
The hydrogenation catalyst be Pt, or at least one of Pt and Fe, Cu, Zn, Ni metal formation compound.
The weight ratio of the hydrogenation catalyst and porous carrier is 1.5%.
TFE molar content is 30% in the mixed gas.
The inert gas is nitrogen, helium or HCFC-22.
The reaction condition is pressure 0.2MPa, and 180 DEG C of temperature, the mol ratio of the TFE and hydrogen is 1：5.
Embodiment 3
It is a kind of synthesize monochlorodifluoromethane refrigerant method, by the mixed gas containing TFE together with hydrogen by by porous
The bed for the hydrogenation catalyst that carrier is constituted, obtains mixed gas A, then mixed gas A is passed into hypochlorite solution, collects
Gas from hypochlorite solution out, that is, synthesize the mixed gas B containing monochlorodifluoromethane, then mixed gas B is passed through
Filtered in weak acid solution, obtain monochlorodifluoromethane refrigerant.
The mixed gas containing TFE is TFE and the mixture of inert gas formation, and the inert gas refers to anti-
With TFE and the nonreactive gas of hydrogen under the conditions of answering.
The material of the porous carrier is fluorine-containing compound, and the fluorine-containing compound includes fluoride.
The hydrogenation catalyst be Cr, or at least one of Cr and Fe, Cu, Zn, Ni metal formation compound.
The weight ratio of the hydrogenation catalyst and porous carrier is 0.2%.
TFE molar content is 60% in the mixed gas.
The inert gas is nitrogen, helium or HCFC-22.
The reaction condition is pressure 0.3MPa, and 150 DEG C of temperature, the mol ratio of the TFE and hydrogen is 1：7.
Embodiment 4
It is a kind of synthesize monochlorodifluoromethane refrigerant method, by the mixed gas containing TFE together with hydrogen by by porous
The bed for the hydrogenation catalyst that carrier is constituted, obtains mixed gas A, then mixed gas A is passed into hypochlorite solution, collects
Gas from hypochlorite solution out, that is, synthesize the mixed gas B containing monochlorodifluoromethane, then mixed gas B is passed through
Filtered in weak acid solution, obtain monochlorodifluoromethane refrigerant.
The mixed gas containing TFE is TFE and the mixture of inert gas formation, and the inert gas refers to anti-
With TFE and the nonreactive gas of hydrogen under the conditions of answering.
The material of the porous carrier is fluorine-containing compound, and the fluorine-containing compound includes oxyfluoride.
The hydrogenation catalyst is Pt, at least one of Cr, or at least one of Pt, Cr and Fe, Ni metal
At least one formation compound.
The weight ratio of the hydrogenation catalyst and porous carrier is 5%.
TFE molar content is 80% in the mixed gas.
The inert gas is nitrogen, helium or HCFC-22.
The reaction condition is pressure 0.4MPa, and 250 DEG C of temperature, the mol ratio of the TFE and hydrogen is 1：10.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, although with reference to foregoing reality
Apply example the present invention is described in detail, for those skilled in the art, it still can be to foregoing each implementation
Technical scheme described in example is modified, or carries out equivalent substitution to which part technical characteristic.All essences in the present invention
God is with principle, and any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.
Claims (10)
1. a kind of method for synthesizing monochlorodifluoromethane refrigerant, it is characterised in that by the mixed gas containing TFE and hydrogen one
Rise by the bed for the hydrogenation catalyst being made up of porous carrier, obtain mixed gas A, then mixed gas A is passed into time chlorine
In acid solution, the gas out from hypochlorite solution is collected, that is, synthesizes the mixed gas B containing monochlorodifluoromethane, then will
Mixed gas B, which passes through in weak acid solution, to be filtered, and obtains monochlorodifluoromethane refrigerant.
2. a kind of method for synthesizing monochlorodifluoromethane refrigerant according to claim 1, it is characterised in that described to contain
TFE mixed gas is the mixture of TFE and inert gas formation, the inert gas refer at reaction conditions with TFE and
The nonreactive gas of hydrogen.
3. a kind of method for synthesizing monochlorodifluoromethane refrigerant according to claim 1, it is characterised in that described porous
The material of carrier is fluorine-containing compound, and the fluorine-containing compound includes oxyfluoride or/and fluoride.
4. a kind of method for synthesizing monochlorodifluoromethane refrigerant according to claim 1, it is characterised in that the hydrogenation
At least one of catalyst is at least one of Pt, Cr, or at least one of Pt, Cr and Fe, Cu, Zn, Ni metal
The compound of formation.
5. a kind of method for synthesizing monochlorodifluoromethane refrigerant according to claim 1, it is characterised in that the hydrogenation
The weight ratio of catalyst and porous carrier is 0.2% ~ 5%.
6. a kind of method for synthesizing monochlorodifluoromethane refrigerant according to claim 5, it is characterised in that the hydrogenation
The weight ratio of catalyst and porous carrier is 0.8% ~ 3%.
7. a kind of method for synthesizing monochlorodifluoromethane refrigerant according to claim 1, it is characterised in that the mixing
TFE molar content is 10% ~ 80% in gas.
8. a kind of method for synthesizing monochlorodifluoromethane refrigerant according to claim 2, it is characterised in that the inertia
Gas is nitrogen, helium or HCFC-22.
9. a kind of method for synthesizing monochlorodifluoromethane refrigerant according to claim 2, it is characterised in that the reaction
Condition is 0.1 ~ 0.4MPa of pressure, and 100 ~ 250 DEG C of temperature, the mol ratio of the TFE and hydrogen is 1：1~10.
10. a kind of method for synthesizing monochlorodifluoromethane refrigerant according to claim 9, it is characterised in that described anti-
Condition is answered for 0.2 ~ 0.3MPa of pressure, 120 ~ 200 DEG C of temperature, the mol ratio of the TFE and hydrogen are 1：1.5~9.
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| CN201710200240.XA CN106977366A (en) | 2017-03-30 | 2017-03-30 | A kind of method for synthesizing monochlorodifluoromethane refrigerant |
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| CN201710200240.XA CN106977366A (en) | 2017-03-30 | 2017-03-30 | A kind of method for synthesizing monochlorodifluoromethane refrigerant |
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| CN106977366A true CN106977366A (en) | 2017-07-25 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02129131A (en) * | 1988-11-08 | 1990-05-17 | Asahi Glass Co Ltd | Production of 1,1,2,2-tetrafluoroethane (r-134) |
-
2017
- 2017-03-30 CN CN201710200240.XA patent/CN106977366A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02129131A (en) * | 1988-11-08 | 1990-05-17 | Asahi Glass Co Ltd | Production of 1,1,2,2-tetrafluoroethane (r-134) |
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Application publication date: 20170725 |
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