CN101050162A - Method for producing pentafluoropropane - Google Patents
Method for producing pentafluoropropane Download PDFInfo
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- CN101050162A CN101050162A CN 200610011726 CN200610011726A CN101050162A CN 101050162 A CN101050162 A CN 101050162A CN 200610011726 CN200610011726 CN 200610011726 CN 200610011726 A CN200610011726 A CN 200610011726A CN 101050162 A CN101050162 A CN 101050162A
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- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000006227 byproduct Substances 0.000 claims abstract description 9
- 239000011368 organic material Substances 0.000 claims abstract description 6
- VVWFZKBKXPXGBH-UHFFFAOYSA-N 1,1,1,3,3-pentachloropropane Chemical compound ClC(Cl)CC(Cl)(Cl)Cl VVWFZKBKXPXGBH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 55
- 238000000605 extraction Methods 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 238000003682 fluorination reaction Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 22
- 238000000926 separation method Methods 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 23
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 20
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 20
- 230000008569 process Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 9
- 239000007791 liquid phase Substances 0.000 description 8
- 241000282326 Felis catus Species 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000006200 vaporizer Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011552 falling film Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FFTOUVYEKNGDCM-OWOJBTEDSA-N (e)-1,3,3-trifluoroprop-1-ene Chemical compound F\C=C\C(F)F FFTOUVYEKNGDCM-OWOJBTEDSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- -1 if bad yield Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000012451 post-reaction mixture Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
This invention relates to a method for producing 1, 1, 1, 3, 3-pentafluoropropane (HFC-245fa). The method comprises: (1) reacting 1,1,1,3,3-pentachloropropane and anhydrous HF in the presence of Cr-based catalyst to obtain HCFC-1233zd, HFC-1234ze, a small amount of HFC-245fa, and byproduct HCl; (2) separating HCl through a HCl separation column, separating unreacted raw materials through a raw material separation column, returning to step 1, and introducing the residual organic materials to the next step. The method has such advantages as high selectivity of the final product, high yield, few byproducts, and high utility of raw materials and low energy consumption, and no pollution.
Description
Technical field
The present invention relates to the preparation field of Chemicals, it is a kind of 1,1,1,3 particularly to relate to compound, the preparation method of 3-pentafluoropropane (being HFC-245fa).
Background technology
The ozone depletion latent energy value (ODP) of HFC-245fa is zero, (GWP) is low for the Greenhouse effect value, do not fire, low toxicity, less to the environmental disruption effect, and have the physicochemical property close with CFC-11, HCFC-141b, as " third generation " whipping agent, CFC alternative-11 and HCFC-141b are used for the foaming of hard polyurethane foam material.
Prepare HFC-245fa generally through two to three reactions steps from HCC-240fa, at first generate 1-chloro-3,3, and the 3-trifluoro propene (HCFC-1233zd, TFCP), 1,3,3, and the 3-tetrafluoeopropene (HFC-1234ze, TFP) and the mix products of small amount of H FC-245fa, the former two further fluoridizes into expection product HFC-245fa in step subsequently, reaction formula is as follows:
The first step:
Second step:
Existing production HFC-245fa processing method can be divided into liquid phase method and vapor phase process two big classes.The liquid phase reaction catalyzer is made up of halogenide of IVb, Vb family element and composition thereof, for example SbCl
5, SbCl
3, TaCl
5, SnCl
4, NbCl
5, TiCl
4, MoCl
5And composition thereof (US 5,710,352, CN 1224410A, CN 1205682A).The advantage of liquid phaseization is that temperature of reaction is low, energy consumption is low, transformation efficiency and selectivity are high, but environmental pollution and equipment corrosion are serious.Vapor phase process is easy to realize continuous production, pollution is little, productive rate is high.
In existing patent, generally tend to the first step and adopt liquid phase method, be reflected at and carry out under lower temperature (80～150 ℃) and the high pressure that (1.5～2MPa), obvious, this helps the separation of by product HCl.In order to keep activity of such catalysts, also need intermittently to feed chlorine to reactive system; Second step was adopted vapor phase process, and temperature of reaction is 200～280 ℃.The flat 7-354118 of the special Willing of Japanese Patent discloses a kind of method that is prepared HFC-245fa by AHF and HCC-240fa via two step gas-phase reactions, but this second step of method generates the poor selectivity of HFC-245fa, this will cause a large amount of unreacted reactants to circulate in system, thereby the increase energy consumption, and this patent does not have detailed subsequent separation process.
Summary of the invention
The present invention is directed to the deficiency of above-mentioned Japanese Patent, utilize two step gas phase catalytic fluorination methods, the production method of a kind of HFC-245fa is provided, its selectivity of product height, the recycle of intermediate product energy makes that this process energy consumption is low, the yield rate height, product cost reduces.
1,1,1,3, the production method of 3-pentafluoropropane, be in the presence of chromium-based catalysts, with 1,1,1,3,3-pentachloropropane and anhydrous hydrogen fluoride are produced HFC-245fa by the gas phase catalytic fluorination reaction of two steps, and it is characterized in that: the first step resultant of reaction HCFC-1233zd, HFC-1234ze, a small amount of purpose product HFC-245fa, by product HCl and unreacted raw material are after " HCl knockout tower " removes HCl, tell HCC-240fa through the raw material knockout tower again and return the first step reaction, all the other organic materialss enter the reaction of second step.
The molar ratio of HF and HCC-240fa is 4～20: 1 in the described the first step reaction, 180～280 ℃ of temperature of reaction.
The molar ratio of preferred HF and HCC-240fa is for being 6～15: 1, and temperature of reaction is 200～250 ℃.
The molar ratio of HF and organic materials is 4～20: 1 in described second step reaction, and temperature of reaction is 160～250 ℃.
The molar ratio of preferred HF and organic materials is 6～15: 1, and temperature of reaction is 180～240 ℃.
Described chromium-based catalysts is at N
2Or be heated to 250 ℃～430 ℃ in other inert gas, then at N
2Pre-activated is handled in the HF air-flow of dilution.
HF gas in the second step reaction product absorbs by extraction agent, and all the other products obtain product HFC-245fa after washing, alkali cleaning, rectifying.
Described extraction agent is that concentration is hydrofluoric acid, the vitriol oil or the high boiling point fluorochlorohydrocarbon of 37%-47%.
The HF of described extraction agent and absorption thereof recycle after resolving.
The present invention adopts two step gas phase catalytic fluorination technologies, and two-step reaction carries out in two reactors packed with catalyst respectively, and reactor can be tubular fixed-bed reactor, fluidized-bed reactor.The catalyzer that is used for two-step reaction is chromium-based catalysts, can be the chrome catalysts of load, also can be DNAcarrier free chrome catalysts.The present invention is the improvement to the flat 7-354118 of the special Willing of Japanese Patent.Reaction product selectivity quality is the processing of intermediate product, if bad yield, product purity and the process economy that will directly influence the reaction of second step of the processing of intermediate product.The first step reaction of the present invention is fluorine chlorine permutoid reaction, and reaction generates HCFC-1233zd, HFC-1234ze, a small amount of purpose product HFC-245fa, by product HCl, has only HCl is removed, and reaction is carried out to useful direction; The same unreacted HCC-240fa of the first step also will influence the purity and the product yield of the second step reaction product, after removing by the raw material Analytic Tower, the present invention returns in the first step reaction, both reduce the reaction raw materials waste, alleviated the aftertreatment burden of back single step reaction again.Reaction and sepn process are as follows: (1) AHF and HCC-240fa are pumped in the reaction cycle logistics with measuring respectively, and the molar ratio of the two is 4～20: 1, and preferably 6～10: 1.Enter in " first reactor " 180～280 ℃ of temperature of reaction, preferably 200～250 ℃ after the vaporization of logistics process vaporizer, the preheater preheating.Reaction pressure does not have strict qualification, in order to help the separation of HCl, carries out under high slightly pressure usually.HCC-240 and AHF carry out fluorine chlorine permutoid reaction and eliminate reaction generating HCFC-1233zd, HFC-1234ze, a small amount of purpose product HFC-245fa, by product HCl under catalyst action.Reaction product is sent into " HCl knockout tower " in the lump together with unreacted raw material A HF and HCC-240fa and is carried out fractionation; (2) the HCl knockout tower is the partial condensation distillation tower, and the temperature of overhead condenser is decided by the pressure of tower, is generally-45～25 ℃, preferably-20～-40 ℃.With this understanding, pure HCl tells from cat head, adopts proper device, as " falling film absorbre ", hydrochloric acid is made in its absorption.The liquid phase material that HCl separates the extraction of Tata still enters " raw material knockout tower "; (3) raw material separates the Tata still and tells unreacted raw material HCC-240fa, returns first reactor, contains HCFC-1233zd, HFC-1234ze in the cat head extraction logistics, AHF all enters " second reactor " after preheating.Reaction of second step and separation: the ratio of HF and organic materials is 4～20: 1 in (4) second reactors, preferably 6～15: 1, temperature of reaction is 160～250 ℃, preferably 180～240 ℃, the logistics of coming out from second reactor comprises HFC-245fa, unreacted HF and HCFC-1233zd, HFC-1234ze, by product HCl etc.; (5) because the boiling point of HFC-245fa and HF ten minutes are approaching, be difficult to distillation method separation by routine.The present invention has adopted the solvent extration of knowing, and promptly uses appropriate solvent (extraction agent) that the dissolving of the HF in the logistics is absorbed.The extraction agent that is fit to has: concentration is 37～47% hydrofluoric acid (azeotropic acid), the vitriol oil and some high boiling point fluorochlorohydrocarbon.Post reaction mixture flows to into the extracting and separating system, and the extracting and separating system is made up of 2 placed in-line " extraction tower " He Yitai " desorption tower ".From the gaseous stream of extraction cat head extraction is crude product HFC-245fa, HCl and a spot of HFC-1234ze that does not contain HF, enters refining system after liquid phase washing, alkali cleaning deacidification; The liquid-phase extraction agent is through repeatedly circulation at the bottom of the extraction Tata, and HF concentration is delivered to desorption tower after increasing to certain value, reclaims HF, and azeotropic acid continues circulation.(6) normal reaction circulation time adds quantitative HF respectively in two reactors, guarantee that the HF and the mol ratio of raw material are about 10: 1; (7) after the raw product after the washing of process liquid phase, the alkali cleaning removed light constituent through degassing tower, material entered rectifying in the rectifying tower, cat head extraction finished product HFC-245fa.(8) rectifying Tata still material collection reclaims.
Catalyzer can carry out drying, pre-treatment before using.Pre-treatment is at N with catalyzer
2Or be heated to 250 ℃～430 ℃ in other inert gas; Then at N
2Activate in the HF air-flow of dilution, just obtain highly active catalyzer.
The present invention makes the selectivity of final product good, the yield height by the separating treatment to middle product, by product is few, simultaneously to the separating treatment of the second step reaction product, allows raw material recycle, this technology is more optimized, and production cost reduces, and meets the policy of China's less energy-consumption, environment protection clean production.
Description of drawings
Fig. 1. process flow diagram.
Wherein: 1. first reactor; 2. second reactor; 3. hydrogenchloride knockout tower; 4. raw material knockout tower; 5. HCl absorption system; 6. extraction tower; 7. Analytic Tower; 8. depickling system is refining system 9..
Embodiment
Following examples are described further above-mentioned technological process, but are not limited only to this.
Testing apparatus is built by flow process shown in Figure 1.2. 1. first reactor use making because of health 600 pipes of two φ 38 * 3 * 2000mm with second reactor, and about 1.6 liters of every volume is respectively charged into each one liter of chromium-based catalysts.4. 3. the hydrogenchloride knockout tower be packing tower with the raw material knockout tower, can be by the technical project of knowing, and the temperature of overhead condenser and tower bottom reboiler is decided with the working pressure of tower.6. extraction tower is packing tower, is used for removing the HF of logistics; 7. Analytic Tower is packing tower, is used for reclaiming the HF of extraction agent.As previously mentioned, it is 37～47% azeotropic hydrofluoric acid that extraction agent can be selected the vitriol oil or concentration for use, and these two towers can design with the technology of routine, but the material of tower must have enough erosion resistances to selected " extraction agent ".5. the HCl absorption system is made up of falling film absorbre, packed absorber.8. the depickling system is made up of liquid phase washing, alkali cleaning.9. refining system is made up of 2～3 rectifying tower and adsorbing tower with molecular sieve.Other equipment comprise: HF, HCC-240fa volume pump, vaporizer, preheater, mixing tank etc., all do not show among the figure, and can dispose as required.Be the reactivity worth of investigation catalyzer, but two equal independent operations of reactor.
Embodiment 1～3: the first step reaction
1. reactor packed with catalyst is warming up to 120 ℃,, keeps 8hr with the flow velocity feeding nitrogen of 15L/min.Temperature of reactor is risen to 200 ℃ subsequently, feed anhydrous hydrogen fluoride, carry out activation treatment with nitrogen dilution.Initial hydrofluoric volumetric concentration is 5%, and the adjustments of gas flow makes beds significantly " focus " not occur, and in venting process, reactor outlet has water vapour to overflow.Improve hydrogen fluoride concentration in reaction bed temperature and the gas gradually, final reaction bed temperature reaches 360 ℃, hydrogen fluoride concentration and reaches 100%, the outlet of question response device no longer includes water vapour and overflows, and promptly finishes " activation " of catalyzer, and this process needs 12hr～24hr approximately.Reaction bed temperature is adjusted to temperature of reaction, raw material HCC-240fa that feeding is gasified, preheating is good and the mixture of HF.Reaction product is collected in organic product with in the dry ice/acetone refrigerative cold-trap after the washing alkali cleaning.Composition with gas chromatograph analysis organic product the results are shown in table 1.
Table 1. the first step reaction experiment result
| Temperature of reaction ℃ | Material is than HF/HCC-240fa mol/mol | Duration of contact Sec. | HCC-240fa transformation efficiency .% | Selectivity, % | |||
| HFC-245fa | HCFC-1233zd | HFC-1234ze | |||||
| Embodiment 1 | 260 | 10∶1 | 1.5 | 100 | 0.8 | 97.8 | 1.4 |
| Embodiment 2 | 265 | 10∶1 | 2.7 | 100 | 1.3 | 97.2 | 1.5 |
| | 270 | 10∶1 | 4.2 | 100 | 0.6 | 98.7 | 0.7 |
Embodiment 1～3: the reaction of second step
With chromium-based catalysts pack into reactor 2. in, react described mode by the first step and carry out pre-treatment.With volume pump with HCFC-1233zd with send into second reactor 2. after HF mixes, temperature of reaction is controlled in 220～240 ℃ of scopes.Product is analyzed organic product with gas chromatograph and is formed through washing, alkali cleaning, the results are shown in table 2.
Second step of table 2. reaction experiment result
| Temperature of reaction ℃ | Material is than HF/HCFC-1233zd mol/mol | Duration of contact Sec. | Transformation efficiency, % | Selectivity, % | |||
| HFC-245fa | HFC-1234ze | Other | |||||
| Embodiment 1 | 220 | 10∶1 | 2.7 | 76.8 | 91.3 | 5.1 | 3.6 |
| Embodiment 2 | 225 | 10∶1 | 3.6 | 80.1 | 93.2 | 4.3 | 2.5 |
| | 230 | 10∶1 | 5.4 | 82.4 | 91.5 | 6.1 | 2.4 |
Embodiment 4～7
Each equipment is connected by flow process shown in Figure 1,1. 2. chromium-based catalysts is respectively charged into reactor, activate as stated above.With volume pump raw material HF and HCC-240fa are sent into vaporizer (mixing tank), preheater in proportion successively, be preheated to temperature of reaction, send into first reactor 1..1. 3. the gaseous mixture of output enters the hydrogenchloride knockout tower, and hydrogenchloride is delivered to chlorine hydride absorption system from the cat head extraction; Charging feed knockout towers such as organic product and unreacted HF, HCC-240 4., the first reactor vaporizer is delivered in unreacted HCC-240fa extraction at the bottom of the tower; 2. the cat head production sends into second reactor after replenishing section H F, and output object is delivered to extraction tower, removes HF in the logistics by extraction process, and cat head extraction material must be expected product through depickling, rectifying.Test-results is listed in table 3.
Table 3. continuous apparatus test-results
| Temperature of reaction, ℃ | Material compares mol/mol | The HFC-245fa yield, % | |||
| 1 is anti- | 2 is anti- | 1 is anti-, HF/HCC-240fa | 2 is anti-, the HF/ organism | ||
| Embodiment 4 | 260 | 220 | 10∶1 | 9∶1 | 98.5 |
| Embodiment 5 | 265 | 230 | 10∶1 | 10∶1 | 99.1 |
| Embodiment 6 | 270 | 235 | 10∶1 | 8∶1 | 98.8 |
| Embodiment 7 | 265 | 235 | 10∶1 | 9∶1 | 98.3 |
Claims (9)
1.1,1,1,3, the production method of 3-pentafluoropropane, be in the presence of chromium-based catalysts, with 1,1,1,3,3-pentachloropropane and anhydrous hydrogen fluoride are produced HFC-245fa by the gas phase catalytic fluorination reaction of two steps, and it is characterized in that: the first step resultant of reaction HCFC-1233zd, HFC-1234ze, a small amount of purpose product HFC-245fa, by product HCl and unreacted raw material are after " HCl knockout tower " removes HCl, tell HCC-240fa through the raw material knockout tower again and return the first step reaction, all the other organic materialss enter the reaction of second step.
2. described 1,1,1,3 according to claim 1, the production method of 3-pentafluoropropane, the molar ratio of HF and HCC-240fa is 4～20: 1 in the described the first step reaction, 180～280 ℃ of temperature of reaction.
3. described 1,1,1,3 according to claim 2, the production method of 3-pentafluoropropane, the molar ratio of HF and HCC-240fa is for being 6～15 in the described the first step reaction: 1, temperature of reaction is 200～250 ℃.
4. described 1,1,1,3 according to claim 1, the production method of 3-pentafluoropropane, the molar ratio of HF and organic materials is 4～20: 1 in described second step reaction, temperature of reaction is 160～250 ℃.
5. described 1,1,1,3 according to claim 1, the production method of 3-pentafluoropropane, the molar ratio of HF and organic materials is 6～15: 1 in described second step reaction, temperature of reaction is 180～240 ℃.
6. described 1,1,1,3 according to claim 1, the production method of 3-pentafluoropropane, described chromium-based catalysts is through being heated to 250 ℃～430 ℃ in N2 or other inert gas, and pre-activated is handled in the HF air-flow of N2 dilution then.
7. described 1,1,1,3 according to claim 1, the production method of 3-pentafluoropropane, the HF gas in the second step reaction product absorbs by extraction agent, and all the other products obtain product HFC-245fa after washing, alkali cleaning, rectifying.
8. described 1,1,1,3 according to claim 7, the production method of 3-pentafluoropropane, described extraction agent is that concentration is hydrofluoric acid, the vitriol oil or the high boiling point fluorochlorohydrocarbon of 37%-47%.
9. described 1,1,1,3 according to claim 7, the production method of 3-pentafluoropropane, the HF of described extraction agent and absorption thereof recycle after resolving.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2234685A2 (en) * | 2008-01-10 | 2010-10-06 | Honeywell International Inc. | Compositions and methods containing fluorine substituted olefins |
| CN102149659A (en) * | 2008-09-11 | 2011-08-10 | 中央硝子株式会社 | Process for producing fluorinated propene |
| CN102596402A (en) * | 2009-09-04 | 2012-07-18 | 霍尼韦尔国际公司 | Catalysts for fluoroolefins hydrogenation |
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