CN101913989B - Production method of 2,3,3,3-tetrafluoropropene - Google Patents
Production method of 2,3,3,3-tetrafluoropropene Download PDFInfo
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Abstract
The invention provides a production method of 2,3,3,3-tetrafluoropropene, in which 2-chloro-2,3,3,3-tetrafluoropropane is taken as a raw material for thermal cracking in the presence of diluents such as nitrogen, water vapour or HF (Hydrogen Fluoride) to prepare the 2,3,3,3-tetrafluoropropene. The method comprises the steps of: heating the diluents and preheating HCFC-244bb; mxing the diluents and the HCFC-244bb according to the mole ratio of 1-20 to 1; performing thermal cracking reaction at the reaction temperature of 450 to 900 DEG C and under the contact time of 0.01 to 60 seconds; and quenching, separating, disacidifying and rectificating to obtain the 2,3,3,3-tetrafluoropropene product. The preparation method provided by the invention needs no catalyst in the reaction process, thereby overcoming the defects that the catalyst in the prior art is easy to coke and inactivated and the continuous production period is short.
Description
Technical field
The present invention relates to a kind ofly 2,3,3, the production method of 3-tetrafluoeopropene (HFO-1234yf) relates in particular to a kind of 2-chloro-2,3,3, and 3-tetrafluoropropane (HCFC-244bb) thermo-cracking obtains the production method of 2,3,3,3-tetrafluoeopropene.
Background technology
The latent value of the ozone depletion of 2,3,3,3-tetrafluoeopropene is zero, and greenhouse gases is lower, is considered to the ideal substitute of HFC-134a.US Patent No. 20090043136 discloses the preparation method of a kind of HFO-1234yf, and the method is taken off HCl synthetic HFO-1234yf in 200 ℃～600 ℃ take HCFC-244bb as raw material under the effect of catalyzer.Because catalyzer is solid acid catalyst, and target product is alkene, catalyzer coking and deactivation very easily in reaction process, and the life-span is shorter, and catalyzer needs frequent regeneration, causes the continuous production cycle shorter.
Summary of the invention
The object of the invention is to overcome the deficiency that exists in background technology, provide need not in a kind of reaction process catalyzer, continuously the production cycle long 2,3,3, the production method of 3-tetrafluoeopropene.
Solution of the present invention is take HCFC-244bb as raw material, prepares HFO-1234yf by high temperature pyrolysis, mainly comprises following reaction:
The present invention need not to use catalyzer, has overcome the easy coking and deactivation of background technology catalyzer, and the life-span is shorter, causes shorter defective of continuous production cycle.The present invention adopts the diluent gass such as nitrogen, water vapor or HF that HCFC-244bb is diluted, and the coking when having suppressed the HCFC-244bb Pintsch process has extended the continuous production cycle.
Of the present invention a kind of 2,3,3, the production method of 3-tetrafluoeopropene comprises the following steps:
A, diluent gas nitrogen, water vapor or HF are heated to 600 ℃～1100 ℃; Simultaneously HCFC-244bb is preheated to 200 ℃～300 ℃;
B, be 1～20 with the diluent gas of above-mentioned preheating and HCFC-244bb according to the mol ratio of diluent gas and HCFC-244bb: 1 mixes;
The mixture that C, step B obtain diluent gas and HCFC-244bb enters tubular reactor, 450 ℃～900 ℃ of temperature of reaction, carries out heat scission reaction under 0.01 second～60 seconds residence time condition;
D, cleavage reaction product are chilled to 50 ℃～150 ℃;
The product that E, step D obtain obtains 2,3,3,3-tetrafluoeopropene product through separation, deacidification, rectifying aftertreatment.
Preferred 600 ℃～750 ℃ of the temperature of reaction of step C of the present invention, preferred 0.1 second～5 seconds of the residence time.Improve the selectivity that temperature of reaction and the residence time are conducive to improve transformation efficiency and the HFO-1234yf of HCFC-244bb.
Diluent gas and 2-chloro-2,3,3 that the present invention adopts, the mol ratio of 3-tetrafluoropropane preferred 5～10: 1.
The preferred HF of diluent gas that the present invention adopts.HF can make the reaction (2) that generates by product 2-chloro-3,3,3 ,-trifluoropropene (HFO-1233xf) to mobile in the other direction as diluent gas, suppresses the generation of HFO-1233xf, improves the selectivity of target product HFO-1234yf.
The difference of the diluent gas that adopts, the last handling process of thermal cracking products is different.When diluent gas was nitrogen, last handling process was as follows:
E-a, deacidification: with the product that step D obtains wash, alkali cleaning, remove HCl and HF in product;
E-b, denitrogenation: the mixture after deacidification is compressed to 1.5MPa～2.0MPa, separates through denitrification column, and tower top is nitrogen, recycles, and tower reactor is the HFO-1234yf crude product;
E-c, the refining further rectifying of HFO-1234yf:HFO-1234yf crude product, overhead fraction is the HFO-1234yf product, the tower reactor cut enters the HFC-244bb recovery tower further to be separated;
E-d, recovery HFC-244bb:HFC-244bb recovery tower tower top are unreacted HFC-244bb, are circulated to the scission reaction part, and the tower reactor residue is discharged as waste material.
When diluent gas was water vapor, last handling process was as follows:
E-a, dehydration, deacidification: the product that step D is obtained carries out low pressure condensation dehydration, and HCl and HF are soluble in water to be removed in the lump;
The further rectifying of mixture after the dehydration that E-b, refining HFO-1234yf: step e-a obtain, deacidification, overhead fraction is the HFO-1234yf product, the tower reactor cut enters the HFC-244bb recovery tower further to be separated
E-c, recovery HFC-244bb:HFC-244bb recovery tower tower top are unreacted HFC-244bb, are circulated to the scission reaction part, and the tower reactor residue is discharged as waste material.
When diluent gas was HF, last handling process was as follows:
E-a, separation, deacidification: the product that at first step D is obtained carries out rectifying separation, and the knockout tower overhead fraction is HCl and HFO-1234yf, obtains the HFO-1234yf crude product after washing, alkali cleaning, and the tower reactor cut enters recovery tower further to be separated;
E-b: the further rectifying of HFO-1234yf crude product that refining HFO-1234yf: step e-a obtains, overhead fraction is the HFO-1234yf product, the tower reactor cut is circulated to knockout tower.
E-c, recovery HF and HFC-244bb: the recovery tower overhead fraction is unreacted HFC-244bb and HF, is circulated to the scission reaction part, and the tower reactor residue is discharged as waste material.
Reactor of the present invention adopts tubular reactor, both external heat reactors, also adiabatic reactor.The preferred nickel material of the material of tubular reactor.
The present invention does not do further restriction to the operating parameters of reaction pressure and aftertreatment rectifying tower, and operating parameters is selected according to the working pressure of reaction product separation system.
Of the present invention 2,3,3, the preparation method of 3-tetrafluoeopropene, compared with prior art, its useful effect is: reaction process need not catalyzer, does not have the problem of catalyst deactivation, has extended the continuous production cycle, is conducive to industrial applications.
Description of drawings
Fig. 1 represents process flow diagram of the present invention.
Fig. 2,3,4 expression diluent gass are respectively the aftertreatment technology schematic flow sheet of nitrogen, water vapor and HF.
In figure: 1, diluent gas primary heater unit; 2, HFC-244bb primary heater unit; 3, material mixing device; 4, pyrolysis reactor; 5, quenching device; 6, after-treatment device; 6-1, scale eccysis acid device; 6-2, denitrification column; 6-3, HFO-1234yf rectifying tower; 6-4, HFC-244bb recovery tower; 6-5, low pressure condensation dewatering unit; 6-6, knockout tower; 6-7, HF and HFC-244bb recovery tower.
Embodiment
Embodiment 1
It is the external heat reactor of ∮ 19 * 2mm that the present embodiment pyrolysis reactor 4 adopts caliber, and diluent gas is nitrogen.Its technical process is:
A, nitrogen is preheated to 600 ℃ by diluent gas primary heater unit 1; Simultaneously HCFC-244bb is preheated to 200 ℃ by HCFC-244bb primary heater unit 2;
After B, preheating, nitrogen and HCFC-244bb enter material mixing device 3, are to mix at 20: 1 according to nitrogen and the mol ratio of HCFC-244bb;
The mixture that C, step B obtain nitrogen and HCFC-244bb enters tubular type pyrolysis reactor 4,450 ℃ of temperature of reaction, carries out heat scission reaction under 60 seconds residence time condition;
D, cleavage reaction product are through quenching device to 50 ℃;
E, aftertreatment
The product that E-a, deacidification: step D obtains enters that scale eccysis acid device 6-1 washes, alkali cleaning, removes HCl and HF in product;
E-b, denitrogenation: the mixture after deacidification is compressed to 1-5MPa～2.0MPa, separates through denitrification column, and tower top is nitrogen, is circulated to diluent gas primary heater unit 1 and continues to use, and tower reactor is the HFO-1234yf crude product;
E-c, refining HFO-1234yf:HFO-1234yf crude product enter the further rectifying of HFO-1234yf rectifying tower 6-3, and overhead fraction is the HFO-1234yf product, and the tower reactor cut enters HFC-244bb recovery tower 6-4 further to be separated;
E-d, recovery HFC-244bb:HFC-244bb recovery tower 6-4 tower top are unreacted HFC-244bb, are circulated to HCFC-244bb primary heater unit 2, and the tower reactor residue is discharged as waste material.
The transformation efficiency 90.8% of the present embodiment HCFC-244bb, the selectivity 65.6% of HFO-1234yf, the purity of the HFO-1234yf that rectifying makes is greater than 99.5%.
It is the external heat reactor of ∮ 19 * 2mm that the present embodiment pyrolysis reactor 4 adopts caliber, and diluent gas is water vapor.Its technical process is:
A, water vapor is preheated to 1100 ℃ by diluent gas primary heater unit 1; Simultaneously HCFC-244bb is preheated to 300 ℃ by HCFC-244bb primary heater unit 2;
After B, preheating, water vapor and HCFC-244bb enter material mixing device 3, are to mix at 5: 1 according to water vapor and the mol ratio of HCFC-244bb;
The mixture that C, step B obtain water vapor and HCFC-244bb enters tubular type pyrolysis reactor 4,900 ℃ of temperature of reaction, carries out heat scission reaction under 0.01 second residence time condition;
D, cleavage reaction product are through quenching device to 150 ℃;
E, aftertreatment
The product that E-a, dehydration, deacidification: step D obtains carries out low pressure condensation dehydration by low pressure condensation dewatering unit 6-5, and HCl and HF are soluble in water to be removed in the lump
E-b, refining HFO-1234yf:HFO-1234yf crude product enter the further rectifying of HFO-1234yf rectifying tower 6-3, and overhead fraction is the HFO-1234yf product, and the tower reactor cut enters HFC-244bb recovery tower 6-4 further to be separated;
E-c, recovery HFC-244bb:HFC-244bb recovery tower 6-4 tower top are unreacted HFC-244bb, are circulated to HCFC-244bb primary heater unit 2, and the tower reactor residue is discharged as waste material.
The transformation efficiency 99.8% of the present embodiment HCFC-244bb, the selectivity 60.0% of HFO-1234yf, the purity of the HFO-1234yf that rectifying makes is greater than 99.5%.
It is the external heat reactor of ∮ 19 * 2mm that the present embodiment pyrolysis reactor 4 adopts caliber, and diluent gas is HF.Its technical process is:
A, HF is preheated to 900 ℃ by diluent gas primary heater unit 1; Simultaneously HCFC-244bb is preheated to 300 ℃ by HCFC-244bb primary heater unit 2;
After B, preheating, HF and HCFC-244bb enter material mixing device 3, are to mix at 1: 1 according to HF and the mol ratio of HCFC-244bb;
The mixture that C, step B obtain HF and HCFC-244bb enters tubular type pyrolysis reactor 4,600 ℃ of temperature of reaction, carries out heat scission reaction under 0.5 second residence time condition;
D, cleavage reaction product are through quenching device to 100 ℃;
E, aftertreatment
E-a, separation, deacidification: the product that at first step D is obtained separates by knockout tower 6-6, the knockout tower overhead fraction is HCl and HFO-1234yf, through scale eccysis acid device 6-1 wash, alkali cleaning, obtain the HFO-1234yf crude product after removing the HCl in product, the tower reactor cut enters HF further to be separated with HFC-244bb recovery tower 6-7;
E-b: refining HFO-1234yf:HFO-1234yf crude product enters the further rectifying of HFO-1234yf rectifying tower 6-3, and overhead fraction is the HFO-1234yf product, and the tower reactor cut is circulated to knockout tower 6-6.
E-c, recovery HF and HFC-244bb:HF and HFC-244bb recovery tower 6-7 overhead fraction are unreacted HFC-244bb and HF, are circulated to the scission reaction part, and the tower reactor residue is discharged as waste material.
The transformation efficiency 95.2% of the present embodiment HCFC-244bb, the selectivity 73.4% of HFO-1234yf, the purity of the HFO-1234yf that rectifying makes is greater than 99.5%.
The operation identical with embodiment 3, difference is 750 ℃ of temperature of reaction, 5 seconds residence time, and the mol ratio of HF and HCFC-244bb is 10: 1, the transformation efficiency 98.5% of HCFC-244bb, the selectivity 94.5% of HFO-1234yf, the purity of the HFO-1234yf that rectifying makes is greater than 99.5%.
Claims (3)
1. one kind 2,3,3, the production method of 3-tetrafluoeopropene, the method are with 2-chloro-2,3,3, and the 3-tetrafluoropropane is raw material, comprises the following steps:
A, diluent gas is heated to 600 ℃～1100 ℃, HCFC-244bb is preheated to 200 ℃～300 ℃, and wherein diluent gas is water vapor or HF;
B, with diluent gas and the HCFC-244bb of steps A preheating, be 1～20 according to the mol ratio of diluent gas and HCFC-244bb: 1 mixes;
C, step B obtain mixture and enter tubular reactor, 450 ℃～900 ℃ of temperature of reaction, carry out heat scission reaction under 0.01 second～60 seconds residence time condition;
D, the cleavage reaction product that step C is obtained are chilled to 50 ℃～150 ℃, obtain 2,3,3,3-tetrafluoeopropene product through separation, deacidification, rectifying aftertreatment.
2. according to claim 12,3,3, the preparation method of 3-tetrafluoeopropene is characterized in that diluent gas and 2-chloro-2,3,3 in step B, and the mol ratio of 3-tetrafluoropropane is 5～10: 1; Temperature of reaction described in step C is 600 ℃～750 ℃, and the residence time is 0.1 second～5 seconds.
3. according to claim 22,3,3, the preparation method of 3-tetrafluoeopropene is characterized in that diluent gas is HF.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4212500A1 (en) * | 2018-06-06 | 2023-07-19 | Honeywell International Inc. | Method for dehydrochlorination of hcfc-244bb to manufacture hfo-1234yf |
| EP4055112A4 (en) * | 2019-11-06 | 2023-12-13 | Honeywell International Inc. | Azeotrope or azeotrope-like compositions of 2-chloro-1,1,1,2-tetrafluoropropane (hcfc-244bb) and water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5201284B1 (en) * | 2012-03-14 | 2013-06-05 | 旭硝子株式会社 | Method for producing 2,3,3,3-tetrafluoropropene |
| CN102675038B (en) * | 2012-04-23 | 2014-05-21 | 山东东岳高分子材料有限公司 | Preparation method of 2, 3, 3, 3-tetrafluoropropene |
| CN103833511B (en) * | 2012-11-26 | 2016-01-20 | 山东东岳高分子材料有限公司 | The preparation method of 2,3,3,3-tetrafluoeopropene |
| CN104744210A (en) * | 2013-12-25 | 2015-07-01 | 中化近代环保化工(西安)有限公司 | 2,3,3,3-tetrafluoropropene preparation technology |
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| CN101479219A (en) * | 2006-06-27 | 2009-07-08 | 纳幕尔杜邦公司 | Tetrafluoropropene production processes |
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| US8058486B2 (en) * | 2004-04-29 | 2011-11-15 | Honeywell International Inc. | Integrated process to produce 2,3,3,3-tetrafluoropropene |
| US9040759B2 (en) * | 2007-07-06 | 2015-05-26 | Honeywell International Inc. | Preparation of fluorinated olefins via catalytic dehydrohalogenation of halogenated hydrocarbons |
| US8203022B2 (en) * | 2008-10-27 | 2012-06-19 | E I Du Pont De Nemours And Company | Conversion of 2-chloro-1,1,1,2-tetrafluoropropane to 2,3,3,3-tetrafluoropropene |
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| CN101479219A (en) * | 2006-06-27 | 2009-07-08 | 纳幕尔杜邦公司 | Tetrafluoropropene production processes |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4212500A1 (en) * | 2018-06-06 | 2023-07-19 | Honeywell International Inc. | Method for dehydrochlorination of hcfc-244bb to manufacture hfo-1234yf |
| EP4055112A4 (en) * | 2019-11-06 | 2023-12-13 | Honeywell International Inc. | Azeotrope or azeotrope-like compositions of 2-chloro-1,1,1,2-tetrafluoropropane (hcfc-244bb) and water |
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Effective date of registration: 20160519 Address after: 255300 Zhoucun City, Shandong province constant access road, No. 979, Patentee after: Shandong Huaan Modern Environmental Protection Technology Co., Ltd. Address before: 710065 Shaanxi province Xi'an Yanta District Zhang eight road No. 168 Patentee before: Xi'an Inst. of Modern Chemistry |