CN104892353A - Method for increasing conversion ratio of 1,1,1,2-tetrafluoroethane prepared by gas phase fluorination - Google Patents
Method for increasing conversion ratio of 1,1,1,2-tetrafluoroethane prepared by gas phase fluorination Download PDFInfo
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Abstract
The invention discloses a method for increasing the conversion ratio of 1,1,1,2-tetrafluoroethane. The method is characterized in that a third-order reaction kettle as same as a second-order reaction kettle is added in the original gas phase fluorination method preparation process; the third-order reaction kettle is also provided with a third-order heater as same as a second-order electric heater; and the third-order reaction kettle and the second-order reaction kettle are connected in series or in parallel. The method has the actual gain that the third-order reaction kettle as same as the second-order reaction kettle is added and connected with the second-order reaction kettle in series or in parallel, so that reaction materials are heated uniformly, the contact area of a catalyst is enlarged on the premise of guaranteeing a certain second-order reaction retention time, and the conversion ratio of the second-order reaction is greatly increased.
Description
Technical field
The present invention relates to a kind of method improving gas phase fluorination and prepare HFA 134a transformation efficiency, belong to hydrofluorocarbon class field.
Background technology
In recent years, CFCs is day by day serious to the destruction of ozonosphere, and HFA 134a (HFC-134a) is a kind of colourless, nontoxic, incombustible chemical substance, and be a kind of HFC type refrigeration agent, ozone depletion latent energy value (ODP) value is zero.Thermomechanical property and the CFC-12 of HFC-134a are quite similar, safety can compare favourably with CFC-12, be acknowledged as the best substitute of CFC-12.
HFC-134a is generally prepared by trieline and anhydrous hydrogen fluoride, there are liquid phase method and vapor phase process two kinds of preparation methods at present.Liquid phase method generally adopts the halogenide of antimony as catalyzer, but the method exists low conversion rate, and the shortcoming such as reactor corrosion condition is serious.Industrial general use vapor phase process prepares HFC-134a.The reaction process of vapor phase process is main in two steps: the first step, and trieline and hydrogen fluoride fluoridize synthesis 1,1,1-trifluoro-2-chloroethane (HCFC-133a); Second step, 1,1,1-trifluoro-2-chloroethane and hydrogen fluoride gas phase fluorination synthesize Tetrafluoroethane.Current gas phase process display, uses effective catalyzer, conservative control temperature of reaction, pressure, feed ratio, and the transformation efficiency of the first step reaction trieline can reach more than 98% substantially.But the reaction that HCFC-133a and hydrogen fluoride gas phase fluorination synthesize Tetrafluoroethane is disadvantageous thermo-negative reaction on a thermodynamics, has considerable influence for HCFC-133a transformation efficiency, general second order reaction HCFC-133a transformation efficiency only has 20-30%.Although can improve HCFC-133a transformation efficiency by improving temperature of reaction, temperature raises and causes catalyzer coking to be accelerated simultaneously, shortens the work-ing life of catalyzer.
In publication, in order to improve reaction conversion ratio in US patent 5395889, require when reacting, with to reaction being the nitrogen of inertia or argon-dilution trieline and hydrogen fluoride, also require three reactors being applicable to this technique, although this technique is improved reaction conversion ratio, produce numerous and diverse, facility investment is large.US patent 4158675 by preparing HFC-134a with hydrogen fluoride gas phase catalytic fluorination HCFC-133a in the first reactor, but this reaction conditions can produce as undesirable 1, the 1-bis-chloro-2-vinylchlorid of impurity.These existing patents all do not control second order reaction temperature and there be any mentioning the residence time, the HFC-134a being issued to higher yields in the prerequisite not producing more by product for how becomes the problems of the prior art already.
Summary of the invention
Object of the present invention is exactly the deficiency overcoming background technology, designs a kind of simple technique and reaches the transformation efficiency improving second order reaction under as far as possible not producing the prerequisite of abnormal amount.
To achieve these goals, especially solve second order reaction low conversion rate and the problem of by product to be produced, the present invention adds a third order reaction still identical with second order reaction still in Primordial Qi phase fluorination method preparation technology, simultaneously third order reaction still is also furnished with three grade well heaters identical with secondary electric heater, and third order reaction still and second order reaction still serial or parallel connection use.
When third order reaction still is connected with second order reaction still, the first step: first order reaction still crude product is out sent into after secondary electric heater is warming up to certain temperature and sends into second order reaction still.Second step: second order reaction occurs in described second order reaction still and makes HCFC-133a and hydrogen fluoride reaction generate HFC-134a.3rd step: send into third order reaction still after described second order reaction still crude product is out warming up to certain temperature by three grades of electric heaters and proceed second order reaction.Described second order reaction still and third order reaction still are all equipped with identical fluorination catalyst, and control temperature is at 300-350 DEG C simultaneously, and reaction pressure is at 0.3-0.6MPa.A third order reaction still because connected, substantially increase the second order reaction residence time, add catalytic reaction contact area, carry out under making second order reaction remain on stable temperature by electric heater heated material simultaneously always, second order reaction transformation efficiency is improved, but the HFC-134a product produced due to second order reaction still can enter third order reaction still together with material, the accumulation of HFC-134a significantly reduces the positive reaction speed of second order reaction, makes series connection third order reaction still can only reach limited raising for secondary transformation efficiency.
When third order reaction still is in parallel with second order reaction still, the first step: divide two-way simultaneously to send into secondary electric heater crude product out in first order reaction still and three grades of electric heaters are warming up to certain temperature.Second step: the one-level crude product after described secondary electric heater and described three grades of electric heaters being heated sends into second order reaction still respectively and third order reaction still carries out second order reaction simultaneously.Second order reaction occurs in second order reaction still makes HCFC-133a and hydrogen fluoride reaction generate HFC-134a.Described second order reaction still and third order reaction still are all equipped with identical fluorination catalyst, and control temperature is at 300-350 DEG C simultaneously, and reaction pressure is at 0.3-0.6MPa.Because second order reaction still and third order reaction still independently carry out second order reaction, so the product of second order reaction still can not have influence on the reaction of described third order reaction still.Shunt the crude product of a first order reaction still simultaneously with two reactors, increase catalytic reaction area, drastically increase secondary transformation efficiency.
Actual gain of the present invention is: by increase a third order reaction still identical with second order reaction still for second order reaction still serial or parallel connection, ensure that reaction mass is heated evenly, increasing the contact area with catalyzer when ensureing certain second order reaction residence time, drastically increasing the transformation efficiency of second order reaction.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that original gaseous fluoridizing method prepares HFC-134a.
Fig. 2 is the process flow sheet of an embodiment of the present invention.
Fig. 3 is the process flow sheet of the another kind of embodiment of the present invention.
Wherein: 1, mixing tank, 2, first order reaction still, 3, secondary electric heater, 4, second order reaction still, 5, three grades of electric heaters, 6, third order reaction still.
Embodiment
In following examples, embodiment 1-3 composition graphs 1 is described; Embodiment 4-6 composition graphs 2 is described; Embodiment 7-9 composition graphs 3 is described.
Embodiment 1
By TCE(tri-vinyl chloride) with AHF(anhydrous hydrogen fluoride) with 1:4(mol ratio) and charge ratio drop into first order reaction still, controlling first order reaction still makes TCE and AHF that fluoridation occur, crude product is sent into the heating of secondary electric heater, then second order reaction still is sent into, control second order reaction still temperature of reaction 300 DEG C, reaction pressure 0.3MPa, makes HCFC-133a and hydrogen fluoride reaction generate HFC-134a.To reacting coarse product sampling analysis, the content of HFC-134a is in table 1.
Embodiment 2
By TCE and AHF with 1:4(mol ratio) charge ratio drop into first order reaction still, controlling first order reaction still makes TCE and AHF that fluoridation occur, crude product is sent into the heating of secondary electric heater, then second order reaction still is sent into, control second order reaction still temperature of reaction 330 DEG C, reaction pressure 0.4MPa, makes HCFC-133a and hydrogen fluoride reaction generate HFC-134a.To reacting coarse product sampling analysis, the content of HFC-134a is in table 1.
Embodiment 3
By TCE and AHF with 1:4(mol ratio) charge ratio drop into first order reaction still, controlling first order reaction still makes TCE and AHF that fluoridation occur, crude product is sent into the heating of secondary electric heater, then second order reaction still is sent into, control second order reaction still temperature of reaction 350 DEG C, reaction pressure 0.6MPa, makes HCFC-133a and hydrogen fluoride reaction generate HFC-134a.To reacting coarse product sampling analysis, the content of HFC-134a is in table 1.
Embodiment 4
By TCE and AHF with 1:4(mol ratio) charge ratio drop into first order reaction still, controlling first order reaction still makes TCE and AHF that fluoridation occur, crude product is sent into the heating of secondary electric heater, then second order reaction still is sent into, control second order reaction still temperature of reaction 300 DEG C, reaction pressure 0.3MPa, makes HCFC-133a and hydrogen fluoride reaction generate HFC-134a.Send into third order reaction still after described second order reaction still crude product is out warming up to 300 DEG C by three grades of electric heaters and proceed second order reaction.Control third order reaction still temperature of reaction 300 DEG C, reaction pressure 0.3MPa.Residue HCFC-133a and hydrogen fluoride is made to continue to react and generate HFC-134a.To reacting coarse product sampling analysis, the content of HFC-134a is in table 1.
Embodiment 5
By TCE and AHF with 1:4(mol ratio) charge ratio drop into first order reaction still, controlling first order reaction still makes TCE and AHF that fluoridation occur, crude product is sent into the heating of secondary electric heater, then second order reaction still is sent into, control second order reaction still temperature of reaction 330 DEG C, reaction pressure 0.4MPa, makes HCFC-133a and hydrogen fluoride reaction generate HFC-134a.Send into third order reaction still after described second order reaction still crude product is out warming up to 330 DEG C by three grades of electric heaters and proceed second order reaction.Control third order reaction still temperature of reaction 330 DEG C, reaction pressure 0.4MPa.Residue HCFC-133a and hydrogen fluoride is made to continue to react and generate HFC-134a.To reacting coarse product sampling analysis, the content of HFC-134a is in table 1.
Embodiment 6
By TCE and AHF with 1:4(mol ratio) charge ratio drop into first order reaction still, controlling first order reaction still makes TCE and AHF that fluoridation occur, crude product is sent into the heating of secondary electric heater, then second order reaction still is sent into, control second order reaction still temperature of reaction 350 DEG C, reaction pressure 0.6MPa, makes HCFC-133a and hydrogen fluoride reaction generate HFC-134a.Send into third order reaction still after described second order reaction still crude product is out warming up to 350 DEG C by three grades of electric heaters and proceed second order reaction.Control third order reaction still temperature of reaction 350 DEG C, reaction pressure 0.6MPa.Residue HCFC-133a and hydrogen fluoride is made to continue to react and generate HFC-134a.To reacting coarse product sampling analysis, the content of HFC-134a is in table 1.
Embodiment 7
By TCE and AHF with 1:4(mol ratio) charge ratio drop into first order reaction still, control first order reaction still and make TCE and AHF that fluoridation occur, divided by the crude product of first order reaction two-way to send into secondary electric heater and three grades of electric heaters intensifications simultaneously.One-level crude product after secondary electric heater and three grades of electric heater heating is sent into control temperature respectively at 300 DEG C, the second order reaction still of reaction pressure under 0.3MPa and third order reaction still carry out second order reaction simultaneously, make HCFC-133a and hydrogen fluoride reaction generate HFC-134a.To reacting coarse product sampling analysis, the content of HFC-134a is in table 1.
Embodiment 8
By TCE and AHF with 1:4(mol ratio) charge ratio drop into first order reaction still, control first order reaction still and make TCE and AHF that fluoridation occur, divided by the crude product of first order reaction two-way to send into secondary electric heater and three grades of electric heaters intensifications simultaneously.One-level crude product after secondary electric heater and three grades of electric heater heating is sent into control temperature respectively at 330 DEG C, the second order reaction still of reaction pressure under 0.4MPa and third order reaction still carry out second order reaction simultaneously, make HCFC-133a and hydrogen fluoride reaction generate HFC-134a.To reacting coarse product sampling analysis, the content of HFC-134a is in table 1.
Embodiment 9
By TCE and AHF with 1:4(mol ratio) charge ratio drop into first order reaction still, control first order reaction still and make TCE and AHF that fluoridation occur, divided by the crude product of first order reaction two-way to send into secondary electric heater and three grades of electric heaters intensifications simultaneously.One-level crude product after secondary electric heater and three grades of electric heater heating is sent into control temperature respectively at 350 DEG C, the second order reaction still of reaction pressure under 0.6MPa and third order reaction still carry out second order reaction simultaneously, make HCFC-133a and hydrogen fluoride reaction generate HFC-134a.To reacting coarse product sampling analysis, the content of HFC-134a is in table 1.
Table 1:
When embodiment 1,2,3 illustrates and only has a second order reaction still as seen from Table 1, the transformation efficiency of second order reaction is lower, embodiment 4,5,6 illustrates and uses a novel process third order reaction still of connecting to increase to reaction conversion ratio, HFC-134a productive rate is made to improve about 30%, embodiment 7,8,9 illustrates the transformation efficiency using a novel process third order reaction still in parallel greatly can improve second order reaction, makes HFC-134a productive rate improve about 80%.
Claims (3)
1. one kind is improved 1,1,1, the method of 2-Tetrafluoroethane transformation efficiency, it is characterized in that: the third order reaction still that increase by is identical with second order reaction still in Primordial Qi phase fluorination method preparation technology, described third order reaction still is also furnished with three grade well heaters identical with secondary electric heater, and described third order reaction still and second order reaction still serial or parallel connection use.
2. a kind of method improving HFA 134a transformation efficiency according to claim 1, is characterized in that: when producing, described third order reaction still and second order reaction still are all equipped with identical fluorination catalyst.
3. one according to claim 1 and 2 improves 1,1,1, the method of 2-Tetrafluoroethane transformation efficiency, is characterized in that: when producing, described third order reaction still is all identical with the temperature and pressure of second order reaction still, namely control temperature W is at 300-350 DEG C, and reaction pressure is at 0.3-0.6MPa.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055534A (en) * | 1990-03-13 | 1991-10-23 | 大金工业株式会社 | Preparation 1,1,1-trifluoro-chloroethane and 1,1,1, the method for 2-Tetrafluoroethane |
| CN1153160A (en) * | 1995-12-27 | 1997-07-02 | 西安近代化学研究所 | Production process of 1, 1, 1, 2-tetrafluoroethane |
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- 2015-06-02 CN CN201510292658.9A patent/CN104892353A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055534A (en) * | 1990-03-13 | 1991-10-23 | 大金工业株式会社 | Preparation 1,1,1-trifluoro-chloroethane and 1,1,1, the method for 2-Tetrafluoroethane |
| CN1153160A (en) * | 1995-12-27 | 1997-07-02 | 西安近代化学研究所 | Production process of 1, 1, 1, 2-tetrafluoroethane |
Non-Patent Citations (1)
| Title |
|---|
| 陈科峰等: "1， 1， 1， 2 - 四氟乙烷的发展情况", 《有机氟工业》 * |
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Application publication date: 20150909 |