CN106542959A - The preparation method of one fluoromethane - Google Patents
The preparation method of one fluoromethane Download PDFInfo
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- CN106542959A CN106542959A CN201610942390.3A CN201610942390A CN106542959A CN 106542959 A CN106542959 A CN 106542959A CN 201610942390 A CN201610942390 A CN 201610942390A CN 106542959 A CN106542959 A CN 106542959A
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- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/30—Tungsten
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/56—Platinum group metals
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- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
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Abstract
The present invention relates to a kind of preparation method of a fluoromethane, belongs to the field of chemical synthesis.The present invention is with monochloro methane as raw material, under conditions of fluorination catalyst is present, there is gas phase catalytic fluorination reaction with fluohydric acid gas and obtain a fluoromethane, and unreacted monochloro methane and fluohydric acid gas in product stream are recycled in the reactor for be filled with hydrogen fluoride catalyst continue reaction, and the method using the adsorbing chlorinated hydrogen of water solves hydrogen chloride and the easy azeotropic of a fluoromethane, is difficult to detached technical barrier.The present invention is easy to get with initiation material, fluorination catalyst activity is high, long service life the characteristics of, using the Technology of continuous circulation, whole system only produces one fluoromethane of primary product and by-product HCl, methane, has reached zero-emission standard.
Description
Technical field
The present invention relates to a kind of preparation method of a fluoromethane (HFC-41).More particularly to monochloro methane (HCC-40) be
, gas phase fluorination in raw material in the presence of fluorination catalyst, the method for preparing HFC-41 there is, while taking circulation technology continuous
Extraction generate HFC-41, unreacted HCC-40 and HF continue in system interior circulation, till HFC-41 is converted into from
Produce in system.
Background technology
One fluoromethane (HFC-41), with the latent value (GWP of relatively low greenhouse effect100The latent value of=116) He zero ozone depletion
(ODP) it is, that few in number European Union that meets uses standard (GWP100<150) saturated hydrofluorocarbons, are sieved by international major company
Elect one of ideal working substance of hot pump in low temp as.With the signing and enforcement of the Kigali's agreement on the 15th of October in 2016, including HFC-
41 in interior GWP100<150 HFC will more and more be studied and be applied.
At present, the synthetic route with regard to HFC-41 mainly has two kinds of gas phase hydrodechlorination method and gaseous fluoridizing method.
Chinese patent CN201310065184.5 is reported with monofluorodichloromethane (HCFC-21) or a fluorine monochloro methane
(HCFC-31) it is raw material, hydrogenation-dechlorination reaction occurs with hydrogen in the presence of noble metal catalyst, HFC-41 is obtained.When 250 DEG C
When, catalyst is 2%Pd/C, H2/ HCFC-21=6/1 (mol/mol), HCFC-21 conversion ratios are 62.5%, and selectivity is
65.4%.
Chinese patent CN200580031247.9 is disclosed with monochloro methane as raw material, and fluorination catalyst is trivalent chromium oxide
With at least one selected from the elementary composition of In, Zn, Ni, Co, Mg and Al, as 300 DEG C of temperature, pressure 0.25MPa, HF/HCC-40
=12, total air speed is 1000h-1, there is gas phase fluorination synthesis HFC-41 in monochloro methane and HF, the conversion ratio of monochloro methane is
19.1%, the selectivity of a fluoromethane is 99.2%, then catalyst is 22.07g to the space-time yield of a fluoromethane-HFC-41/
(L-cat.h)。
At present, there is following defect in the above-mentioned prior art with regard to a fluoromethane preparation technology：First, gas phase catalysis adds
The raw material HCFC-21 or HCFC-31 of hydrogen dechlorination route will be as international community be to Ozone depletion material and hot room effect
Gas (GWP100>150) banning the production and be difficult to obtain, and the catalyst of the route is costly, and selectivity is relatively low；Again
Secondly, the fluorination catalyst activity of gas phase fluorination route is poor, causes the space-time yield of a fluoromethane relatively low, cause high energy consumption,
The bad situation of low output.
The content of the invention
The technical problem to be solved is to overcome not enough present in background technology, there is provided a kind of continuous circulation industrial
Skill, is capable of achieving the preparation method of the HFC-41 of no pollution production.
Present invention also offers the fluorination catalyst suitable for gas phase fluorination of a kind of high activity, long service life.
Present invention also offers it is a kind of by HCl from HFC-41 safe separating method.
The preparation method of one fluoromethane HFC-41, in the presence of fluorination catalyst, monochloro methane (HCC-40) and fluohydric acid gas
Generation gas phase catalytic fluorination reacts, and product stream includes methane, a fluoromethane, monochloro methane, fluohydric acid gas and hydrogen chloride, passes through
Rectification obtains a fluoromethane, and the rectification step includes：(1) distill for the first time, the first distillation column tower reactor component be a fluoromethane,
Monochloro methane, fluohydric acid gas and hydrogen chloride, overhead components are methane, and tower reactor component can be separated into after-fractionating tower, tower
Top component extraction system；(2) distill for second, after-fractionating tower tower reactor component is monochloro methane, fluohydric acid gas, and overhead components are one
Fluoromethane, hydrogen chloride, overhead components are separated into hydrogen chloride absorption tower, and hydrogen chloride is absorbed, and collect a fluoromethane gas,
Tower reactor component is then recycled to gas phase catalytic fluorination reactor and continues reaction.
The tower reactor of the hydrogen chloride absorption tower is equipped with water, and the tower reactor component after hydrogen chloride is absorbed is hydrochloric acid, and tower top group
It is a fluoromethane to divide.
System is produced when the hydrogen cloride concentration of the absorption tower tower reactor component reaches 30%-36% and obtains byproduct hydrochloric acid,
Overhead components are then obtained one fluoromethane of target product by deacidification, dehydration, rectification.
The fluorination catalyst is obtained by presoma high-temperature roasting, and the presoma is for trivalent chromium compound and at least
A kind of metal powder blending selected from tungsten powder, molybdenum powder, rhenium powder, technetium powder, osmium powder, iridium powder, ruthenium powder is constituted, and its quality percentage composition is
80%～99.9%：20%～0.1%.
It is preferred that：The presoma is trivalent chromium compound and a kind of blending composition, its quality hundred in tungsten powder, molybdenum powder, osmium powder
It is grouped into 85%～95%：15%～5%.
Wherein, trivalent chromium compound is chromic oxide or chromic oxide gel.
Gas phase catalytic fluorination reaction condition is：0.1～1.5MPa of reaction pressure, monochloro methane and anhydrous hydrogen fluoride mole
Ratio is 1:1～20, reaction temperature is 250～450 DEG C, and time of contact is 0.5～50s.
The preparation method of the fluorination catalyst is：
It is by trivalent chromium compound and metal powder mix homogeneously by mass percentage, compressing, obtain catalyst precursor；
Gained catalyst precursor, carries out roasting 6～15 hours in 300 DEG C～500 DEG C, under nitrogen atmosphere then at 60 DEG C～450 DEG C
It is 1 in mol ratio：Activate 6～15 hours under 10 fluorine gas and the mixed gas atmosphere of nitrogen composition, fluorination catalyst is obtained.
It is a discovery of the invention that obtaining a fluoromethane using monochloro methane gas phase fluorination, its selectivity is higher, this experiment
As a result, from the point of view of, its primary product is a fluoromethane, and the content of byproduct methane is then very low, the product stream be include methane, one
Fluoromethane, monochloro methane, fluohydric acid gas and hydrogen chloride, by the isolated fluoromethane of rectification, the rectification adopts following steps
Suddenly：The operation of first distillation column obtains side-product methane；Product stream is divided into monochloro methane/fluorination hydrogen system by after-fractionating tower operation
With one fluoromethane/system of chlorination hydrogen system two, monochloro methane/fluorination hydrogen system is recycled to gas phase catalytic fluorination reactor to be continued
Reaction；The operation of hydrogen chloride absorption tower is obtained the byproduct hydrochloric acid of one fluoromethane of target product and various concentration.Therefore, it is above-mentioned
Continuous circulation process, product are good for one fluoromethane selectivity of target product, and target product be easy to other by-products and
Raw material is separated, and raw material recoverable reaches zero-emission purpose.
In order to realize the purpose of the present invention, the W-response design thinking of the present invention is：The present invention with monochloro methane for
Beginning raw material, prepares a fluoromethane using the continuous circulation process that gas phase catalytic fluorination reacts, and the dominant response of generation is as follows：
The present invention prepares a fluoromethane using continuous circulation process, and first step reaction is substantially carried out the gas of HF and monochloro methane
Phase catalytic fluorination reacts, and product is a fluoromethane, methane and HCl.
The present invention provides a kind of preparation method of a fluoromethane, including step in detailed below：In the presence of fluorination catalyst,
There is gas phase catalytic fluorination reaction with anhydrous hydrogen fluoride in monochloro methane, obtain one fluoromethane of target product, and its reaction condition is：Instead
0.1～1.5MPa of pressure is answered, monochloro methane is 1 with the molar ratio of anhydrous hydrogen fluoride:1～20, reaction temperature is 250～450
DEG C, time of contact is 0.5～50s, and product stream includes methane, a fluoromethane, monochloro methane, fluohydric acid gas and hydrogen chloride, logical
Cross rectification and obtain a fluoromethane, wherein fluorination catalyst is obtained by presoma high-temperature roasting, the presoma is trivalent chromium
Compound and at least one metal powder blending composition selected from tungsten powder, molybdenum powder, rhenium powder, technetium powder, osmium powder, iridium powder, ruthenium powder, its matter
Amount percentage composition is 80%～99.9%：0.1%～20%.Wherein, trivalent chromium compound is chromic oxide or chromic oxide gel.
The reaction condition of the present invention is preferably：0.1～1.5MPa of reaction pressure, monochloro methane and anhydrous hydrogen fluoride mole
Ratio is 1:2～10, reaction temperature is 290～370 DEG C, and time of contact is 4～30s.
The fluorination catalyst that the present invention is used is that by being obtained by presoma high-temperature roasting, the presoma is trivalent chromaking
Compound and at least one metal powder blending composition selected from tungsten powder, molybdenum powder, rhenium powder, technetium powder, osmium powder, iridium powder, ruthenium powder, its quality
Percentage composition is 80%～99.9%：0.1%～20%.Wherein, trivalent chromium compound is chromic oxide or chromic oxide gel.Its
Preparation method is as follows：It is by trivalent chromium compound and metal powder mix homogeneously by mass percentage, compressing, before obtaining catalyst
Drive body；Gained catalyst precursor, carry out roasting 6～15 hours in 300 DEG C～500 DEG C under nitrogen atmosphere, then at 60 DEG C～
450 DEG C is 1 in mol ratio：Activate 6～15 hours under 10 fluorine gas and the mixed gas atmosphere of nitrogen composition, fluorination catalyst is obtained
Agent.In addition to above-mentioned catalyst, fluorination catalyst can also be chromium oxide, the chromium oxide of fluorination, aluminium fluoride, the oxidation of fluorination
Aluminum, the chromium oxide being carried on activated carbon, aluminium fluoride, Afluon (Asta), the oxygen containing various metals (such as Zn, Co, Ni, Ge, In etc.)
Change chromium etc..Using fluorination catalyst it is different, then reaction condition is different, including reaction temperature, reaction pressure, time of contact and
The mol ratio of material.
The present invention prepares fluorination catalyst using blending method, and trivalent chromium compound and metal powder are mixed according to certain ratio
Close be obtained catalyst precursor, when catalyst precursor Jing high-temperature roastings, trivalent chromium compound in the form of chromium oxide, and
Metal powder then continues with simple substance form presence, subsequently into the activation stage of the mixed gas being made up of nitrogen and fluorine gas, in oxygen
The fluorination of change chromium is charomic fluoride up to after producing without steam, the metal such as tungsten powder, molybdenum powder, rhenium powder, technetium powder, osmium powder, iridium powder or ruthenium powder
Powder is reacted with fluorine gas, obtain the relatively low hexafluoride of boiling point for example tungsten hexafluoride, molybdenum hexafluoride, rhenium hexafluoride, lithium technetium,
Osmium Hexafluoride, lithium iridium or lithium ruthenium, above-mentioned hexafluoride depart from catalyst structure mostly in the way of gas, so not
Only duct can be provided for catalyst, while increasing the specific surface area and pore volume of catalyst, improve the activity of catalyst, and be not lost in
Metallic element then mainly stayed in the catalyst in the form of simple substance or a small amount of hexafluoride, be catalyzed when can effectively suppress high temperature
The carbon distribution of agent.Whole effect sees that the fluorination catalyst prepared by such scheme is not only high using temperature, and catalysis activity
It is high.
The present invention is not crucial for the type of reactor of gas phase catalytic fluorination reaction, it is possible to use tubular reactor, stream
Fluidized bed reactor etc..In addition, adiabatic reactor or isothermal reactor also can use.
The present invention is not limited to the operating condition of distillation column, can be according to equipment, the level of public work, response system
Operating pressure and the factor such as composition to be separated suitably selected.Operating pressure is 0.1MPa～1.0MPa, preferably
0.3MPa～0.6MPa.Generally, in order to easy to operate, the operating pressure of distillation column is consistent with response system.Tower top temperature
Degree and bottom temperature are determined by operating pressure and its material component.Wherein, methane (boiling point be -161.5 DEG C/760mmHg), anhydrous
Fluohydric acid gas (boiling point be 19.5 DEG C/760mmHg), monochloro methane (boiling point is -24.2 DEG C/760mmHg), hydrogen chloride (boiling point for -
85.05 DEG C/760mmHg), a fluoromethane (boiling point be -78.2 DEG C/760mmHg).Due to hydrogen chloride and a fluoromethane boiling point it is suitable
It is close to, easy azeotropic, the present invention carries out separating hydrogen chloride and a fluoromethane using hydrogen chloride absorption tower.
Hydrogen chloride absorption tower in the present invention is equipped with water, the hydrogen chloride in a fluoromethane is absorbed, suitable charging
Amount is the 43%-56% that hydrogen chloride weight is preferably water weight, so that tower reactor component is hydrogen chloride concentrated acid is 30%-36%'s
Hydrochloric acid, overhead components are a fluoromethane, and now, in below 0.1ppm, overhead components are then produced the hydrogen chloride content of overhead components
System, through one fluoromethane of target product is obtained by deacidification, dehydration, rectification；Tower reactor component then produces system and is configured
The hydrochloric acid of various concentration is sold or is used.
Advantages of the present invention：
(1) raw material monochloro methane of the invention is easy to get, and cheap；
(2) the characteristics of fluorination catalyst in the present invention has little pollution, active high, long service life, to a fluoromethane
Space-time yield be up to 53.43g-HFC-41/(L-cat.h) (see embodiment 1), than the 22.07g of prior art-HFC-41/(L-cat.h)
(see CN200580031247.9 embodiments 4)；
(3) used in the present invention, water absorbs the hydrogen chloride in organic materials, realizes peace of the hydrogen chloride from a fluoromethane
Fully separating, not only in efficiency high, and the organic faciess for processing, hydrogen chloride content is less than 0.1ppm, while obtain can direct marketing
Or the byproduct hydrochloric acid for using, there is no the hidden danger for producing trade effluent.
(6) the achievable no pollution of the present invention produces a fluoromethane, and gas phase fluorination can be made by continuous circulation system
Material reaction completely, realizes making full use of for material, so as to greatly reduce pollution, realizes the no pollution of production.
Description of the drawings
Fig. 1 is the preparation technology flow chart of a fluoromethane.
Label meaning in FIG is as follows.1st, 2,3,4,6,8,9,11,13,14 and 15 is pipeline；5 is gas phase catalysis fluorine
Change reactor；7 is the first distillation column；10 is after-fractionating tower；12 is hydrogen chloride adsorption tower.
Specific embodiment
Illustrate below in conjunction with the accompanying drawings to be described in further details the present invention.
With reference to Fig. 1, the present invention is described in more detail.But it is not intended to limit the present invention.Fresh monochloro methane pipeline 1, with
The anhydrous hydrogen fluoride of Jing pipelines 2 and and Jing pipelines 4 recycle monochloro methane/fluohydric acid gas mixture together pass through pipeline
3 enter be filled with the gas phase catalytic fluorination reactor 5 of fluorination catalyst in reacted, product flows through pipeline 6 and enters the
One distillation column 7 is separated；The tower reactor component of the first distillation column 7 is a fluoromethane, monochloro methane, fluohydric acid gas and hydrogen chloride
Mixture, overhead components are methane (boiling point is -161.5 DEG C/760mmHg), and overhead components then produce system as side-product first
Alkane Jing pipelines 8 are collected and are sold or used (the raw material monochloro methane that the present invention can be obtained through simple chlorination reaction),
Tower reactor component Jing pipeline 9 is separated into after-fractionating tower 10；The tower reactor component of after-fractionating tower 10 is anhydrous hydrogen fluoride (boiling
Point is for 19.5 DEG C/760mmHg), the mixture of monochloro methane (boiling point is -24.2 DEG C/760mmHg), overhead components are hydrogen chloride
With a fluoromethane, tower reactor component be then recycled to gas phase catalytic fluorination reactor 5 continue reaction, overhead components Jing pipelines 11 enter dress
It is filled with the hydrogen chloride absorption tower 12 of water；Fresh water Jing pipelines 13 are inhaled into hydrogen chloride adsorption tower 12 by way of spray
Receive hydrogen chloride (boiling point be -85.05 DEG C/760mmHg), tower reactor component is hydrochloric acid, and overhead components be a fluoromethane (boiling point for -
78.2 DEG C/760mmHg), when the hydrogen cloride concentration of tower reactor component reaches 30%-36%, then 15 extraction system of Jing pipelines obtains pair
Product hydrochloric acid, then Jing pipelines 14 produce system to overhead components, by further deacidification, dehydration, distillation operation, are obtained high-purity
One fluoromethane of target product of degree.
Analytical tool：Glad chromatograph GC-930 in Shanghai sea, hydrogen flame detector, chromatographic column is capillary column Al2O3/S“50m×
0.320mm × 0.25 μm " (manufacture of chromatographic technique research and development centre of Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences).
Gas chromatography analysis method：Jing after washing, alkali cleaning and drying, take gaseous sample carries out gas chromatogram point to product
Analysis.High Purity Nitrogen and hydrogen are used as carrier gas.Testing conditions be 250 DEG C of temperature of vaporization chamber, 250 DEG C of 2 temperature of auxiliary furnace, detector temperature
250 DEG C, 50 DEG C of post stove initial temperature is kept for 2 minutes, 20 DEG C/min of heating rate, 280 DEG C of final temperature, is kept for 3 minutes.
The preparation of fluorination catalyst：Chromic nitrate is dissolved in water, precipitant ammonia is added at 60 DEG C, control solution
Between the scope of pH7.5～8.5 so as to fully precipitate under agitation, the slurry by filtration that will be formed, be washed with deionized to
Neutrality, then in 150 DEG C of dryings 12 hours, obtains chromic oxide gel.Gained chromic oxide gel and at least one are selected from into tungsten powder, molybdenum
Powder, rhenium powder, technetium powder, osmium powder, iridium powder, the metal powder of ruthenium powder are 80%～99.9% according to quality percentage composition：0.1%～20%
Mix homogeneously, it is compressing, obtain catalyst precursor；Above-mentioned catalyst precursor, under nitrogen atmosphere in 300 DEG C～500
DEG C carry out roasting 6～15 hours, be 1 in mol ratio then at 60 DEG C～450 DEG C：The mixed gas atmosphere that 10 fluorine gas is constituted with nitrogen
Lower activation 6～15 hours is enclosed, fluorination catalyst is obtained.
Embodiment 1
10 milliliters of fluorination catalysts are loaded in 1/2 inch of internal diameter, the tubular reactor because of Kang Hejin of long 30cm, should
The presoma of fluorination catalyst is according to quality percentage composition 90% by chromic oxide gel, tungsten powder：10% mixes, compacting is formed.Instead
Answer device to be warming up to 370 DEG C, monochloro methane and anhydrous hydrogen fluoride are passed through in gas phase catalytic fluorination reactor, control anhydrous hydrogen fluoride
Mol ratio with monochloro methane is 2：1, time of contact is 6 seconds, reaction pressure 0.1MPa, after reaction 20h, product Jing water
Wash, alkali cleaning, isolated Organic substance, after drying, eliminating water, with the composition of gas chromatographic analysiss Organic substance, the results are shown in Table 1.
Embodiment 2
Operation same as Example 1, except that the presoma of fluorination catalyst be by chromic oxide gel, tungsten powder according to
Quality percentage composition 80%：20% mixes, compacting forms, and reaction temperature is changed to 250 DEG C, the results are shown in Table 1.
Embodiment 3
Operation same as Example 1, except that the presoma of fluorination catalyst be by chromic oxide gel, tungsten powder according to
Quality percentage composition 99.9%：0.1% mixes, compacting forms, and reaction temperature is changed to 290 DEG C, the results are shown in Table 1.
Embodiment 4
Operation same as Example 1, except that the tungsten powder in the presoma of fluorination catalyst is changed to molybdenum powder, and will
Reaction temperature is changed to 450 DEG C, the results are shown in Table 1.
Embodiment 5
Operation same as Example 1, except that the tungsten powder in the presoma of fluorination catalyst is changed to rhenium powder, and will
It is changed to time of contact 0.5 second, the results are shown in Table 1.
Embodiment 6
Operation same as Example 1, except that the tungsten powder in the presoma of fluorination catalyst is changed to technetium powder, and will
It is changed to time of contact 4 seconds, the results are shown in Table 1.
Embodiment 7
Operation same as Example 1, except that the tungsten powder in the presoma of fluorination catalyst is changed to osmium powder, and will
It is changed to time of contact 30 seconds, the results are shown in Table 1.
Embodiment 8
Operation same as Example 1, except that the tungsten powder in the presoma of fluorination catalyst is changed to iridium powder, and will
It is changed to time of contact 50 seconds, the results are shown in Table 1.
Embodiment 9
Operation same as Example 1, except that the tungsten powder in the presoma of fluorination catalyst is changed to ruthenium powder, and will
The mol ratio of monochloro methane and anhydrous hydrogen fluoride is 1：1, the results are shown in Table 1.
Embodiment 10
Operation same as Example 1, except that being 10 by the mol ratio of anhydrous hydrogen fluoride and monochloro methane：1, knot
Fruit is shown in Table 1.
Embodiment 11
Operation same as Example 1, except that being 20 by the mol ratio of anhydrous hydrogen fluoride and monochloro methane：1, knot
Fruit is shown in Table 1.
Embodiment 12
Operation same as Example 1, except that reaction pressure is changed to 0.5MPa, the results are shown in Table 1.
Embodiment 13
Operation same as Example 1, except that reaction pressure is changed to 1MPa, the results are shown in Table 1.
Embodiment 14
Operation same as Example 1, except that reaction pressure is changed to 1.5MPa, the results are shown in Table 1.
Embodiment 15
Operation same as Example 1, except that chromic oxide gel roasting in 350 DEG C of nitrogen atmospheres is obtained for 6 hours
Chromic oxide, the presoma of fluorination catalyst is according to quality percentage composition 90% by chromic oxide with tungsten powder：10% mixes
Even, compacting is formed, and the results are shown in Table 1.
Its meaning is：Within the unit interval (1h), catalyst (1L) catalytic reaction of unit volume obtains target product
The grams of HFC-41.
Table 1
Claims (9)
1. the preparation method of a fluoromethane HFC-41, in the presence of fluorination catalyst, monochloro methane (HCC-40) is sent out with fluohydric acid gas
Raw gas phase catalytic fluorination reaction, product stream includes methane, a fluoromethane, monochloro methane, fluohydric acid gas and hydrogen chloride, by essence
Evaporate and obtain a fluoromethane, the rectification step includes：(1) distill for the first time, the first distillation column tower reactor component be a fluoromethane,
Monochloro methane, fluohydric acid gas and hydrogen chloride, overhead components are methane, and tower reactor component can be separated into after-fractionating tower, tower
Top component extraction system；(2) distill for second, after-fractionating tower tower reactor component is monochloro methane, fluohydric acid gas, and overhead components are one
Fluoromethane, hydrogen chloride, overhead components are separated into hydrogen chloride absorption tower, and hydrogen chloride is absorbed, and collect a fluoromethane gas,
Tower reactor component is then recycled to gas phase catalytic fluorination reactor and continues reaction.
2. preparation method according to claim 1, the tower reactor of the hydrogen chloride absorption tower are equipped with water, after hydrogen chloride is absorbed
Tower reactor component be hydrochloric acid, and overhead components are a fluoromethane.
3. preparation method according to claim 2, the hydrogen cloride concentration of the tower reactor component are produced when reaching 30%-36%
System obtains byproduct hydrochloric acid, and overhead components are then obtained one fluoromethane of target product by deacidification, dehydration, rectification.
4., according to the arbitrary described preparation method of claim 1-3, the fluorination catalyst is made by presoma high-temperature roasting
, the presoma is that trivalent chromium compound and at least one are selected from tungsten powder, molybdenum powder, rhenium powder, technetium powder, osmium powder, iridium powder, ruthenium powder
Metal powder blending composition, its quality percentage composition be 80%～99.9%：20%～0.1%.
5. preparation method according to claim 4, the presoma are trivalent chromium compounds and the blending of tungsten powder, molybdenum powder or osmium powder
Composition, its quality percentage composition are 85%～95%：15%～5%.
6. preparation method according to claim 5, wherein, trivalent chromium compound is chromic oxide or chromic oxide gel.
7. preparation method according to claim 4, the preparation method of the fluorination catalyst is：By trivalent chromium compound and
Metal powder mix homogeneously by mass percentage, it is compressing, obtain catalyst precursor；Gained catalyst precursor, in nitrogen
Roasting is carried out 6～15 hours in 300 DEG C～500 DEG C under atmosphere, fluorination catalyst is obtained.
8. preparation method according to claim 4, the fluorination catalyst need to be activated using before, the activation be in
60 DEG C～450 DEG C is 1 in mol ratio：Heat 6～15 hours under 10 fluorine gas and the mixed gas atmosphere of nitrogen composition.
9. preparation method according to claim 4, gas phase catalytic fluorination reaction condition is：0.1～1.5MPa of reaction pressure,
Monochloro methane is 1 with the molar ratio of anhydrous hydrogen fluoride:1～20, reaction temperature be 250～450 DEG C, time of contact be 0.5～
50s。
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110002947A (en) * | 2019-04-28 | 2019-07-12 | 北京宇极科技发展有限公司 | The preparation method of one fluothane hydrocarbon |
| CN110204414A (en) * | 2019-06-25 | 2019-09-06 | 福建省杭氟电子材料有限公司 | A kind of preparation method of a fluoromethane |
| CN110283041A (en) * | 2019-06-19 | 2019-09-27 | 浙江工业大学 | A method of one fluoromethane of synthesis |
| CN115485256A (en) * | 2020-05-29 | 2022-12-16 | 日本瑞翁株式会社 | Process for producing monofluoromethane |
| CN115838320A (en) * | 2023-02-28 | 2023-03-24 | 山东东岳化工有限公司 | Method for preparing monofluoromethane |
| WO2023206914A1 (en) * | 2022-04-28 | 2023-11-02 | 福建德尔科技股份有限公司 | Rectification control system and rectification control method for preparing electronic-grade methyl fluoride |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110002947A (en) * | 2019-04-28 | 2019-07-12 | 北京宇极科技发展有限公司 | The preparation method of one fluothane hydrocarbon |
| CN110283041A (en) * | 2019-06-19 | 2019-09-27 | 浙江工业大学 | A method of one fluoromethane of synthesis |
| CN110283041B (en) * | 2019-06-19 | 2021-08-31 | 浙江工业大学 | Method for synthesizing monofluoromethane |
| CN110204414A (en) * | 2019-06-25 | 2019-09-06 | 福建省杭氟电子材料有限公司 | A kind of preparation method of a fluoromethane |
| CN115485256A (en) * | 2020-05-29 | 2022-12-16 | 日本瑞翁株式会社 | Process for producing monofluoromethane |
| WO2023206914A1 (en) * | 2022-04-28 | 2023-11-02 | 福建德尔科技股份有限公司 | Rectification control system and rectification control method for preparing electronic-grade methyl fluoride |
| CN115838320A (en) * | 2023-02-28 | 2023-03-24 | 山东东岳化工有限公司 | Method for preparing monofluoromethane |
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