CN1640860A - Method for preparing hydrofluoride hydrocarbon - Google Patents
Method for preparing hydrofluoride hydrocarbon Download PDFInfo
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- CN1640860A CN1640860A CN 200410002398 CN200410002398A CN1640860A CN 1640860 A CN1640860 A CN 1640860A CN 200410002398 CN200410002398 CN 200410002398 CN 200410002398 A CN200410002398 A CN 200410002398A CN 1640860 A CN1640860 A CN 1640860A
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Abstract
The liquid phase fluorination process of preparing fluorohydrocarbon with hydrogen-containing halogenated hydrocarbon and anhydrous hydrogen fluoride in the presence of catalyst has the fluoric reflux liquid collected from the fluorinating and separating tower heated externally to provide the reaction with required heat, and thus has reduced or even no heat transferred via the sandwiched jacket to the reactor, lowered reactor wall temperature, minimized corrosion of reaction liquid to the reactor and prolonged reactor life.
Description
Invention field
The present invention relates to the preparation method of hydrogen fluorohydrocarbon, particularly a kind of method for preparing the hydrogen fluorohydrocarbon by hydrogeneous halohydrocarbon through liquid-phase fluorination.
Background of invention
Because hydrogen fluorohydrocarbon (HFCs) does not damage the ozone layer, just progressively substitute Chlorofluorocarbons (CFCs) (CFCs), the Hydrochlorofluorocarbons (HCFCs) that damages the ozone layer and breathe out dragon, some have the hydrogen fluorohydrocarbon kind of applications well prospect as 1,1, and 1,3,3,3-HFC-236fa (HFC236fa), 1,1,1,3,3-pentafluoropropane (HFC245fa), 1,1,1,4,4-3-pentafluorobutane (HFC365mfc) etc., its preparation and production technique more and more come into one's own, usually, these products prepare through liquid-phase fluorination by corresponding chloroparaffin and anhydrous hydrogen fluoride mostly.
The portion of product of employed raw material of liquid phase fluorination reaction and generation as hydrogen fluoride, hydrogenchloride, lewis acid catalyst etc., has quite serious corrodibility to metallic reactors.When especially adopting antimony halides to make catalyzer, can form the extremely strong peracid of corrodibility, under High Temperature High Pressure, the structural integrity of meeting grievous injury fluorination reactor influences ordinary production.
For this reason, the person skilled in art has proposed many innovative approachs, propose employing fluorine resin lining as Chinese patent CN1261337A and solved the reactor corrosion problem, as everyone knows, fluorine resin has fine erosion resistance, but its heat conductivility is too poor, the heat that provides by reactor jacket very little, be difficult to satisfy the required heat of reaction, especially when preparation contains the product of more carbon atom as HFC236fa, HFC245fa etc., because of the heating of raw materials used halogenated alkane is easily decomposed, it is restricted that the method by preheating material provides heat.Chinese patent CN1308597 proposes a kind of liquid-phase fluorination system and method, this system comprises equipment such as a reactor, prewashing column, a cover water distilling apparatus, pretreatment system and vaporizer, the problem that is used to solve the corrosion of reactive system and promotes heat exchange, but this system is too complicated and loaded down with trivial details, and big difficulty is arranged during practical application.
Summary of the invention
Prepare the problem that exists in the hydrogen fluorohydrocarbon at liquid-phase fluorination, the inventor utilizes the technology of fluoridizing the outer heating of phegma dexterously, has satisfied the heat demand of liquid phase fluorination reaction, has alleviated the corrosion of reaction solution to reactor preferably, thereby in the extension reactor life-span, reduce production costs.
Hydrogen fluorohydrocarbon of the present invention be by hydrogeneous halohydrocarbon and anhydrous hydrogen fluoride in the presence of catalyzer, prepare through liquid phase fluorination reaction, its special character is the rectifying separation that the product of liquid phase fluorination reaction generation is flowed through and fluoridized knockout tower and fluoridize condenser, collect partially fluorinated phegma from fluoridizing the knockout tower body of the tower, through outside input reactor again after the heating, reaction institute heat requirement is provided; Obtain product hydrogen fluorohydrocarbon from fluoridizing condenser overhead.Even do not transmit heat to reactor thereby reduce, reduced the wall temperature of reactor, make reaction solution be reduced to minimum the corrosion of reactor by chuck.
The selection process flow process of preparation hydrogen fluorohydrocarbon of the present invention is as shown in drawings: add in the reactor [2] that catalyzer is arranged with hydrogeneous halohydrocarbon raw material with through the anhydrous hydrogen fluoride of heat exchanger [1] preheating and react, the product stream process that generates is fluoridized knockout tower [4] and is fluoridized the rectifying separation of condenser [5], collect the part phegma to ramp pan [8] from fluoridizing knockout tower [4] body of the tower by fluoridizing phegma collection device [3], phegma is imported heat exchanger [6] with pump [7], in the liquid phase reaction liquid of heating back input reactor [2], provide reaction institute heat requirement; From fluoridizing the reaction gas that condenser overhead obtains main hydrofluorocarbon, HCl and low amount of fluorinated hydrogen and by product, reaction gas obtains required hydrogen fluorohydrocarbon after washing, alkali cleaning.
Hydrogen fluorohydrocarbon of the present invention be meant comprise a hydrogen atom in the molecule at least, all the other are the aliphatic hydrocarbon of fluorine atom, its structural formula is C
xH
yF
z, wherein x is 1～5, y 〉=1, and y=2x+2-z, z 〉=1 is preferably x=3～4, and more preferably, when x=3, its chemical formula is CF
3CH
2CHF
2(HFC245fa) and CF
3CH
2CF
3(HFC236fa), when x=4, its chemical formula is CF
3CH
2CF
2CH
3(HFC365mfc).
Hydrogeneous halohydrocarbon raw material of the present invention is meant the synthetic corresponding halogenated alkane of above-mentioned hydrogen fluorohydrocarbon, requires to contain in its molecule the halohydrocarbon of the halogen atom that hydrogen and at least-individual can replace by fluorine, particularly contains the hydrogeneous chlorocarbon of 1～5 carbon atom, preferably 1,1,1,3,3,3-chlordene propane (HCC230), 1,1,1,3,3-pentachloropropane (HCC240), 1,1,1,4,4-pentachloro-butane (HCC450) etc.
Catalyzer of the present invention mainly refers to be used for fluorizated metal halide and two or more mixture thereof, and preferred catalyzer is muriate, fluorochemical, fluorochloride or their mixture, the more preferably SbCl of antimony and tin
5, because its active high, low price.Because catalyzer is easy to inactivation after a period of time, be favourable so feed periodically or continuously during reaction that a small amount of chlorine regenerates, per hour suitable chlorine feeding amount is 0.02～1.0% of a catalyst weight.
Catalyst concentration of the present invention is controlled at 5%～30% (weight ratio), and concentration is too low, and speed of response is slow; Concentration is too high, then easily produces side reaction, and preferably 10%～20%.
Reaction of the present invention institute heat requirement is preferably by raw material HF preheating with fluoridize the outer heating of phegma and provide, and the HF preheating temperature is controlled at 70～150 ℃, preferably 90～120 ℃; From fluoridizing the phegma of fluoridizing that the knockout tower body of the tower collects, main fluorinated hydrogen, hydrogen fluorohydrocarbon and fluorizated intermediate fully thereof, catalyst content is extremely low, to the corrosion of follow-up equipment seldom.The heating and temperature control of fluoridizing phegma is at 70～150 ℃, preferably 90～120 ℃.Reactor jacket can boosting or is not heated.Fluorination reaction temperature is mainly controlled by gathering speed and Heating temperature that phegma is fluoridized in adjusting, generally at 50～110 ℃, and preferably 60～90 ℃.
Reaction pressure can change, and working pressure is controlled at 0.5～1.5mpa easily, preferably 0.8～1.3Mpa.
In order to guarantee the transformation efficiency of raw material halohydrocarbon, the mole proportioning of anhydrous hydrogen fluoride and raw material halohydrocarbon will be higher than theoretical amount, and a mole proportioning generally is controlled at 1～2, preferably 1.05～1.3.
Liquid phase fluorination reaction of the present invention is depressed at band and is carried out, and used reactor is generally made by metallic substance, as carbon steel, stainless steel, Inconel(nickel alloys), Monel metal etc.Also can be lined with corrosion resistant fluoropolymer in the reactor, fluoropolymer can adopt tetrafluoroethylene, tetrafluoroethylene and hexafluoropropylene copolymer etc.
The knockout tower of fluoridizing of the present invention vertically is installed on the reactor top, filling material in the knockout tower, compare with the common knockout tower of fluoridizing, its special character is to have installed at its body of the tower fluoridizes the phegma collection device, liquid phase rewinding equipment class in this device and the traditional distillation system seemingly, be used for collection catalyst content low fluoridize phegma.
The present invention adopts and to fluoridize the outer heating process of phegma and carry out liquid-phase fluorination and prepare the hydrogen fluorohydrocarbon, has changed the input mode of reaction institute heat requirement, and the corrosion that has slowed down reactor has prolonged work-ing life of equipment.
Specific embodiment
At 2m
3Add 200kg catalyst S bCl in the carbon steel reactor
5, add the 300kg process again and be preheated to 100～110 ℃ HF, catalyst activation, drop into HCC230 then continuously and be preheated to 100～110 ℃ HF, feed rate is respectively 140kg/hr and 74kg/hr, and the Heating temperature of fluoridizing phegma is 100～110 ℃, and speed is 150～250kg/hr, chuck does not heat, control reaction temperature is between 60～75 ℃, and reaction pressure 1.0～1.2Mpa leads to a small amount of liquid chlorine between the reaction period, to keep catalyst activity, speed is 1kg/hr.
Reaction gas is collected after washing, alkali cleaning, and through stratographic analysis, the selectivity of HFC236fa is 98.3%, and yield is 90.2%.After reaction stops, checking reactor, do not see obvious corrosion.
Press the method for embodiment 1, adopt 2m
3The carbon steel reactor of inner liner polytetrafluoroethylene, the reactor jacket boosting, the control jacket temperature is the same with temperature of reaction, and the feed rate of HCC230 and HF is respectively 180kg/hr and 96kg/hr, and all the other conditions are with embodiment 1.Through stratographic analysis, the selectivity of HFC236fa is 99.1%, and yield is 90.4%.The reactor of inner liner polytetrafluoroethylene can prevent corrosion.
Claims (7)
- One kind by hydrogeneous halohydrocarbon and anhydrous hydrogen fluoride the method for prepared in reaction hydrogen fluorohydrocarbon in the presence of catalyzer, it is characterized in that reacting the rectifying separation that the product of generation is flowed through and fluoridized knockout tower and fluoridize condenser, collect partially fluorinated phegma from fluoridizing the knockout tower body of the tower, through outside input reactor again after the heating, reaction institute heat requirement is provided; Obtain product hydrogen fluorohydrocarbon from fluoridizing condenser overhead.
- 2. method according to claim 1, it is characterized in that described hydrogen fluorohydrocarbon be meant comprise a hydrogen atom in the molecule at least, all the other are the aliphatic hydrocarbon of fluorine atom, its structural formula is C xH yF z, x=1～5 wherein, y 〉=1, z 〉=1, y=2x+2-z.
- 3. method according to claim 1 is characterized in that described hydrogen fluorohydrocarbon is meant CF 3CH 2CF 3(HFC236fa), CF 3CH 2CHF 2(HFC245fa), CF 3CH 2CF 2CH 3(HFC365mfc).
- 4. method according to claim 1 is characterized in that the HF preheating temperature is controlled at 70～150 ℃; The heating and temperature control of fluoridizing phegma is at 70～150 ℃.Reactor jacket can boosting or is not heated.Temperature of reaction is controlled at 50～110 ℃.
- 5. method according to claim 4 is characterized in that the HF preheating temperature is controlled at 90～120 ℃; The heating and temperature control of fluoridizing phegma is at 90～120 ℃.Temperature of reaction is controlled at 60～90 ℃.
- 6. method according to claim 1 is characterized in that used catalyzer is muriate, fluorochemical, fluorochloride or their mixture of antimony and tin.
- 7. method according to claim 6 is characterized in that used catalyzer is SbCl 5
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410002398 CN1640860A (en) | 2004-01-15 | 2004-01-15 | Method for preparing hydrofluoride hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410002398 CN1640860A (en) | 2004-01-15 | 2004-01-15 | Method for preparing hydrofluoride hydrocarbon |
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| CN1640860A true CN1640860A (en) | 2005-07-20 |
Family
ID=34867379
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410002398 Pending CN1640860A (en) | 2004-01-15 | 2004-01-15 | Method for preparing hydrofluoride hydrocarbon |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100434166C (en) * | 2005-09-09 | 2008-11-19 | 北京宇极科技发展有限公司 | Producing art of hydroflurocarbon and producing method of special catalyst thereof |
| CN106146249A (en) * | 2015-04-09 | 2016-11-23 | 浙江蓝天环保高科技股份有限公司 | The process of HFC-245fa and HFC-236fa is prepared in a kind of coproduction |
| CN115043701A (en) * | 2022-08-12 | 2022-09-13 | 山东澳帆新材料有限公司 | Preparation method of cis-1-chloro-3, 3, 3-trifluoropropene |
-
2004
- 2004-01-15 CN CN 200410002398 patent/CN1640860A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100434166C (en) * | 2005-09-09 | 2008-11-19 | 北京宇极科技发展有限公司 | Producing art of hydroflurocarbon and producing method of special catalyst thereof |
| CN106146249A (en) * | 2015-04-09 | 2016-11-23 | 浙江蓝天环保高科技股份有限公司 | The process of HFC-245fa and HFC-236fa is prepared in a kind of coproduction |
| CN115043701A (en) * | 2022-08-12 | 2022-09-13 | 山东澳帆新材料有限公司 | Preparation method of cis-1-chloro-3, 3, 3-trifluoropropene |
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