CN102936185A - Method for preparing 1,1-difluoroethylene by cracking of 1,1,1-difluoro-1-chloroethane - Google Patents
Method for preparing 1,1-difluoroethylene by cracking of 1,1,1-difluoro-1-chloroethane Download PDFInfo
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- CN102936185A CN102936185A CN2012104740684A CN201210474068A CN102936185A CN 102936185 A CN102936185 A CN 102936185A CN 2012104740684 A CN2012104740684 A CN 2012104740684A CN 201210474068 A CN201210474068 A CN 201210474068A CN 102936185 A CN102936185 A CN 102936185A
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Abstract
The invention discloses a method for preparing 1,1-difluoroethylene by cracking of 1,1,1-difluoro-1-chloroethane. The method includes steps of uniformly mounting inner metal components with catalysis effect in a cracking tube made of an inert material according to the filling quantity that the surface area of the inner metal components in each cubic meter of cracking tube is 100-500 square meters; placing the cracking tube into an electric heating furnace, controlling the temperature of the cracking tube within the range of 500-580 DEG C, leading 1,1,1-difluoro-1-chloroethane and retaining the same in a reaction section of the cracking tube for 20-400 seconds; quenching reaction products at an outlet of the cracking tube to below 100 DEG C through a water cooler, absorbing acid gas such as hydrogen chloride therein through a secondary washing absorption tower and a primary alkali cleaning absorption tower, freezing and drying to obtain cracked products. The method has the advantages that crack reaction temperature is low, conversion rate of raw materials is high, reaction selectivity is good, the service life of the cracking tube is long, and the method is applicable to industrial production.
Description
Technical field
The present invention relates to a kind ofly 1,1, the method for the standby vinylidene fluoride of 1-difluoromono-chloroethane cracking is specifically related to adopt inner member as catalytic material catalyzes cracking 1,1, the standby vinylidene fluoride of 1-difluoromono-chloroethane cracking.
Technical background
Vinylidene fluoride claims that also vinylidene (Vinylidene Fluoride, VDF) is a kind of important fluorochemical monomer, can prepare polyvinylidene difluoride (PVDF) by the homopolymerization mode, can prepare fluoro-resin and viton with R 1216, tetrafluoroethylene copolymerization.Polyvinylidene difluoride (PVDF) has preferably erosion resistance, weathering resistance and hot workability, is widely used in the industries such as coating, lithium cell, water treatment.
1, the 1-difluoroethylene is mainly prepared by 1,1,1-difluoromono-chloroethane (R142b) thermo-cracking, cracking process can carry out in blank pipe, also can improve reaction conversion ratio, selectivity and technology stability by adding the methods such as rare gas element, promotor, catalyzer.
1, blank pipe cracking technology
In United States Patent (USP) (US 2627529), adopting quartz glass pipe cracking 1,1,1-difluoromono-chloroethane, 870 ℃ of cracking temperatures, 1,1,1-difluoromono-chloroethane transformation efficiency can reach 74.2%, the vinylidene fluoride selectivity is 90.3%, but has occurred a small amount of many carbon compounds in the product.Can improve blank pipe cracking transformation efficiency by prolonging the residence time, but in the time of 800 ~ 1000 ℃, prolong the residence time very easily to tie the carbon coking phenomenon, silica glass is realized in industrial being difficult to as cracking tubing simultaneously.
In United States Patent (USP) (US 2551573), then adopt platinum to carry out the cracking of 1,1,1-difluoromono-chloroethane as the nickel pipe of inner lining material, cracking temperature is 715 ℃, and the transformation efficiency of 1,1,1-difluoromono-chloroethane is 50%, and the vinylidene fluoride selectivity is near 100%.This method per pass conversion is not high, and cracking temperature is higher, the same knot carbon phenomenon that occurs easily.
2, dilution cracking technology
In Chinese patent (CN 1428320), use superheated vapour and 1,1,1-difluoromono-chloroethane mixed pyrolysis method prepares vinylidene fluoride, steam and 1, the ratio of 1,1-difluoromono-chloroethane is 12 ~ 20:1, and cracking temperature is 600-850 ℃, the transformation efficiency of this cleavage method can reach 95%, and selectivity can reach 99%.But a large amount of steam makes cracking process produce large volume low-concentration waste hydrochloric acid, and is difficult to process because containing the F ion in this waste hydrochloric acid.
3, add the promotor cracking technology
In United States Patent (USP) (US3246041), employing is 1, the method that adds 0.5 ~ 4%(wt) chlorine in 1, the 1-difluoromono-chloroethane cracking process is so that reaction can be carried out under 525 ~ 575 ℃, when the chlorine add-on is 2.5%, when range of reaction temperature was 500 ~ 550 ℃, reaction conversion ratio can reach 60 ~ 78%, 1,1-difluoroethylene selectivity reaches about 96%, and 1 ~ 2% CF is arranged in the reaction process
2=CHCl generates.Add chlorine and can obviously reduce the scission reaction temperature, but the adding of chlorine makes and contain polychloride in the split product, and the transformation efficiency of reaction in 500-600 ℃ of scope is not high.
United States Patent (USP) (US 2628989) proposes 1,1, add the tetracol phenixin of 2.0% ~ 25% (wt) during 1-difluoromono-chloroethane thermo-cracking as promotor, temperature of reaction can be reduced to 550 ℃, 1,1,1-difluoromono-chloroethane per pass conversion is 69% ~ 80%, the vinylidene fluoride selectivity is 45% ~ 80%.Can reduce cracking temperature although add tetracol phenixin, reaction conversion ratio is not high, and the vinylidene fluoride selectivity is also low.
4, Deep Catalytic Cracking process
United States Patent (USP) (US 2774799) is to load on MgF
2On CuCl
2As catalyzer, in being housed, the copper pipe of this copper salt catalyst carries out 1,1,1-difluoromono-chloroethane scission reaction.When scission reaction was carried out in 450 ~ 610 ℃ of scopes, reaction conversion ratio was not higher than 50%, and the vinylidene fluoride selectivity is about 80%.The application mantoquita carries out catalytic pyrolysis and can reduce temperature of reaction, but transformation efficiency and selectivity are not high.
European patent (EP 0407711) discloses a kind of with NiF
2As catalyst cracking 1,1, the 1-difluoromono-chloroethane prepares the method for vinylidene fluoride.Needing to add 2 ~ 21%(wt) oxygen in this reaction process and be used for improving reaction conversion ratio, is 500 ~ 600 ℃ than optimal temperature.Because the adding of oxygen contains a large amount of CH in this method split product
2=CFCl, the later separation difficulty.
In view of early application AlF
3, the more shortcoming of side reaction when gac and the fluorine-containing alkane cracking of other metal catalyst catalysis, United States Patent (USP) (US 3444251) proposes with surface-area less than 50m
2α-Al of/g
2O
3As catalyzer, the distinguishing feature of this catalyzer is that the cracking by-product should be less.1,1,1-difluoromono-chloroethane produces vinylidene fluoride and CH 370 ℃ of cracking
2=CFCl, wherein the vinylidene fluoride selectivity is 50%, CH
2=CFCl selectivity is 40%, and reaction conversion ratio only has 6%.This patent proposes to add the auxiliary agents such as Ni, Zn, Rh, Co, Mo, and reaction conversion ratio can bring up to 80% in the time of 370 ℃, and the selectivity of vinylidene fluoride also can bring up to 80%.Application α-the Al of this patent disclosure
2O
3The method low conversion rate, selectivity is not high yet, though can improve transformation efficiency and selectivity after adding promotor, has the comparatively serious catalyst stream deactivation phenomenom of becoming estranged.
In sum, 1,1 of bibliographical information, there is following problem in the method for the standby vinylidene fluoride of 1-difluoromono-chloroethane cracking:
(1) the blank pipe cracking technology needs high temperature could obtain higher reaction conversion ratio, and under the hot conditions 1,1, the carbon coking phenomenon is very easily tied in the cracking of 1-difluoromono-chloroethane.
(2) the dilution cracking technology can improve the knot carbon coking phenomenon in the cracking process, but the adding of Macrodilution agent descends throughput, and energy consumption increases, and the subsequent separation process load is larger.
(3) promotor can be reduced cracking temperature, but it is limited to improve effect, simultaneously side reaction aggravation.
(4) catalyzer can reduce cracking temperature, and volatile appearing vividly resembles but the catalyzer ubiquity catalyst stream that is used for the cracking of 1,1,1-difluoromono-chloroethane is become estranged.
Summary of the invention
For the deficiencies in the prior art, the purpose of this invention is to provide a kind of 1,1, the method for the standby vinylidene fluoride of 1-difluoromono-chloroethane cracking.
The method that 1,1,1-difluoromono-chloroethane catalytic pyrolysis prepares vinylidene fluoride may further comprise the steps:
(1) the metal inner member with katalysis evenly is installed in the cracking tube of inert material manufacturing, the surface-area that its loadings provides for inner member in every cubic metre of cracking tube volume is 100 ~ 500m
2
(2) cracking tube is put in the electrical heater, the temperature of control cracking tube is 500 ~ 580 ℃, passes into 1,1,1-difluoromono-chloroethane, and making its residence time in the cracking tube conversion zone is 20 ~ 400 seconds;
(3) reaction product gas of cracking tube outlet is quickly cooled to below 100 ℃ through watercooler, then through secondary water absorption tower and one-level alkali cleaning absorption tower absorption hydrogenchloride, hydrogen fluoride sour gas wherein, again through lyophilize, obtains split product.
Described inert material refers to quartz or platinum.Described have the metal inner member of katalysis by the metallic substance manufacturing of iron content, chromium, nickel, can select single metallic substance, also can select the alloy of any two metal formation or the alloy that is formed by three kinds of metals.
The present invention adopts the inner member of selected metal manufacturing as catalyzer, can obviously reduce temperature of reaction, improves reaction conversion ratio and vinylidene fluoride selectivity.Simultaneously, the adding of inner member has improved gas flow and heat distribution situation in the cracking tube, and the gas less turbulence is high, has eliminated the local superheating phenomenon, reduces the generation that finishes carbon, coking phenomenon, thus the life cycle that can significantly prolong cracking reactor.
Below in conjunction with embodiment the present invention is described in detail.
Description of drawings
Fig. 1 (a) is the vertical view of inner member a of the present invention;
Fig. 1 (b) is the left view of inner member a of the present invention;
Fig. 2 (a) is the vertical view of inner member b of the present invention;
Fig. 2 (b) is the left view of inner member b of the present invention;
Fig. 3 (a) is the vertical view of inner member c of the present invention;
Fig. 3 (b) is the left view of inner member c of the present invention;
Fig. 4 (a) is the vertical view of inner member d of the present invention;
Fig. 4 (b) is the left view of inner member d of the present invention.
Specific implementation method
The method that 1,1,1-difluoromono-chloroethane catalytic pyrolysis prepares vinylidene fluoride may further comprise the steps:
(1) the metal inner member with katalysis evenly is installed in the cracking tube of inert material manufacturing, the surface-area that its loadings provides for inner member in every cubic metre of cracking tube volume is 100 ~ 500m
2
(2) cracking tube is put in the electrical heater, the temperature of control cracking tube is 500 ~ 580 ℃, passes into 1,1,1-difluoromono-chloroethane, and making its residence time in the cracking tube conversion zone is 20 ~ 400 seconds;
(3) reaction product gas of cracking tube outlet is quickly cooled to below 100 ℃ through watercooler, then through secondary water absorption tower and one-level alkali cleaning absorption tower absorption hydrogenchloride, hydrogen fluoride sour gas wherein, again through lyophilize, obtains split product.
Described inert material refers to quartz or platinum.
Described have the metal inner member of katalysis by the metallic substance manufacturing of iron content, chromium, nickel, can select single metallic substance, also can select the alloy of any two metal formation or the alloy that is formed by three kinds of metals.
The existence of iron can improve 1,1,1-difluoromono-chloroethane transformation efficiency in the inner member metallic substance, but too high iron level can affect the vinylidene fluoride selectivity.
The inner member configuration is without particular requirement, with can aggravate cracking tube inner fluid less turbulence be configured as suitable.Inner member in the accompanying drawing shown in the structure is adoptable configuration, but never only limits to this.
Inner member material of the present invention can produce the metal halide surface with katalysis under cracking condition, the active ingredient of catalyzer can constantly be produced by the inner member surface, thereby can activity not descend with the prolongation in reaction times.
Embodiment 1
Evenly load inner member in Ф 32 * 1200mm crystalline silica cracking tube, loadings is inner member outer surface area 500m in every cubic metre of reaction tubes volume
2(inner member forms: nickel content 100%); Cracking tube is put in the electrical heater, and the energising heating is preheated to 500 ℃ with cracking tube.Keeping the cracking tube temperature is 500 ℃, control raw material 1,1, and the flow of 1-difluoromono-chloroethane, making its residence time of (length 570mm) in the effective thermostatically heating section of cracking tube is 200s; Reacted mixed gas is chilled to below 100 ℃ through watercooler, and the sour gas that produces by secondary water wash column and the cracking of one-level soda-wash tower flush away is again removed wherein moisture by lyophilize again, and gas forms by gas chromatographic detection after collecting.
The mole of each component consists of in the product: vinylidene fluoride accounts for 83.7%, CH
3CF
3Account for 4.3%, CH
2=CFCl accounts for 4.2%, 1,1,1-difluoromono-chloroethane and accounts for 7.2%, calculates raw material 1,1 with this, and the transformation efficiency of 1-difluoromono-chloroethane is 92.8%, and the selectivity of vinylidene fluoride is 90.2%.
Sampling analysis when reaction unit moves 200,400,600,800,1000 hours continuously, reaction product forms without considerable change.Observe in the cracking tube without knot carbon, coking phenomenon.
Embodiment 2
Evenly load inner member in Ф 32 * 1200mm crystalline silica cracking tube, loadings is inner member outer surface area 100m in every cubic metre of reaction tubes volume
2(inner member forms: nickel content 100%); Cracking tube is put in the electrical heater, and the energising heating is preheated to 580 ℃ with cracking tube.Keeping the cracking tube temperature is 580 ℃, control raw material 1,1, and the flow of 1-difluoromono-chloroethane, making its residence time of (length 570mm) in the effective thermostatically heating section of cracking tube is 100s; Reacted mixed gas is chilled to below 100 ℃ through watercooler, and the sour gas that produces by secondary water wash column and the cracking of one-level soda-wash tower flush away is again removed wherein moisture by lyophilize again, and gas forms by gas chromatographic detection after collecting.
The mole of each component consists of in the product: vinylidene fluoride accounts for 89.6%, CH
3CF
3Account for 2.8%, CH
2=CFCl accounts for 3.1%, 1,1,1-difluoromono-chloroethane and accounts for 4.2%, calculates raw material 1,1 with this, and the transformation efficiency of 1-difluoromono-chloroethane is 95.8%, and the selectivity of vinylidene fluoride is 93.5%.
Sampling analysis when reaction unit moves 200,400,600,800,1000 hours continuously, reaction product forms without considerable change.After 800 hours, observe slight knot carbon phenomenon is arranged in the cracking tube.
Embodiment 3
Evenly load inner member in Ф 32 * 1200mm crystalline silica cracking tube, loadings is inner member outer surface area 300m in every cubic metre of reaction tubes volume
2(inner member forms: nickel 90%, iron 10%); Cracking tube is put in the electrical heater, and the energising heating is preheated to 560 ℃ with cracking tube.Keeping the cracking tube temperature is 560 ℃, control raw material 1,1, and the flow of 1-difluoromono-chloroethane, making its residence time of (length 570mm) in the effective thermostatically heating section of cracking tube is 80s; Reacted mixed gas is chilled to below 100 ℃ through watercooler, and the sour gas that produces by secondary water wash column and the cracking of one-level soda-wash tower flush away is again removed wherein moisture by lyophilize again, and gas forms by gas chromatographic detection after collecting.
The mole of each component consists of in the product: vinylidene fluoride accounts for 86.9%, CH
3CF
3Account for 3.7%, CH
2=CFCl accounts for 4.2%, 1,1,1-difluoromono-chloroethane and accounts for 5.4%, calculates raw material 1,1 with this, and the transformation efficiency of 1-difluoromono-chloroethane is 94.6%, and the selectivity of vinylidene fluoride is 91.9%.
Sampling analysis when reaction unit moves 200,400,600,800,1000 hours continuously, reaction product forms without considerable change.Observe in the cracking tube without knot carbon, coking phenomenon.
Embodiment 4
Evenly load inner member in Ф 32 * 1200mm crystalline silica cracking tube, loadings is inner member outer surface area 200m in every cubic metre of reaction tubes volume
2(inner member forms: nickel 80%, iron 16%, chromium 4%); Cracking tube is put in the electrical heater, and the energising heating is preheated to 530 ℃ with cracking tube.Keeping the cracking tube temperature is 530 ℃, control raw material 1,1, and the flow of 1-difluoromono-chloroethane, making its residence time of (length 570mm) in the effective thermostatically heating section of cracking tube is 400s; Reacted mixed gas is chilled to below 100 ℃ through watercooler, and the sour gas that produces by secondary water wash column and the cracking of one-level soda-wash tower flush away is again removed wherein moisture by lyophilize again, and gas forms by gas chromatographic detection after collecting.
The mole of each component consists of in the product: vinylidene fluoride accounts for 87.7%, CH
3CF
3Account for 4.1%, CH
2=CFCl accounts for 3.9%, 1,1,1-difluoromono-chloroethane and accounts for 3.8%, calculates raw material 1,1 with this, and the transformation efficiency of 1-difluoromono-chloroethane is 96.2%, and the selectivity of vinylidene fluoride is 91.2%.
Sampling analysis when reaction unit moves 200,400,600,800,1000 hours continuously, reaction product forms without considerable change.Observe in the cracking tube without knot carbon, coking phenomenon.
Embodiment 5
Evenly load inner member in Ф 32 * 1200mm crystalline silica cracking tube, loadings is inner member outer surface area 500m in every cubic metre of reaction tubes volume
2(inner member forms: nickel 90%, chromium 10%); Cracking tube is put in the electrical heater, and the energising heating is preheated to 550 ℃ with cracking tube.Keeping the cracking tube temperature is 550 ℃, control raw material 1,1, and the flow of 1-difluoromono-chloroethane, making its residence time of (length 570mm) in the effective thermostatically heating section of cracking tube is 140s; Reacted mixed gas is chilled to below 100 ℃ through watercooler, and the sour gas that produces by secondary water wash column and the cracking of one-level soda-wash tower flush away is again removed wherein moisture by lyophilize again, and gas forms by gas chromatographic detection after collecting.
The mole of each component consists of in the product: vinylidene fluoride accounts for 87.6%, CH
3CF
3Account for 3.3%, CH
2=CFCl accounts for 3.7%, 1,1,1-difluoromono-chloroethane and accounts for 5.1%, calculates raw material 1,1 with this, and the transformation efficiency of 1-difluoromono-chloroethane is 94.9%, and the selectivity of vinylidene fluoride is 92.3%.
Sampling analysis when reaction unit moves 200,400,600,800,1000 hours continuously, reaction product forms without considerable change.Observe in the cracking tube without knot carbon, coking phenomenon.
Embodiment 6
Evenly load inner member in Ф 32 * 1200mm crystalline silica cracking tube, loadings is inner member outer surface area 500m in every cubic metre of reaction tubes volume
2(inner member forms: iron 20%, chromium 80%); Cracking tube is put in the electrical heater, and the energising heating is preheated to 570 ℃ with cracking tube.Keeping the cracking tube temperature is 570 ℃, control raw material 1,1, and the flow of 1-difluoromono-chloroethane, making its residence time of (length 570mm) in the effective thermostatically heating section of cracking tube is 20s; Reacted mixed gas is chilled to below 100 ℃ through watercooler, and the sour gas that produces by secondary water wash column and the cracking of one-level soda-wash tower flush away is again removed wherein moisture by lyophilize again, and gas forms by gas chromatographic detection after collecting.
The mole of each component consists of in the product: vinylidene fluoride accounts for 84.5%, CH
3CF
3Account for 4.1%, CH
2=CFCl accounts for 4.5%, 1,1,1-difluoromono-chloroethane and accounts for 6.4%, calculates raw material 1,1 with this, and the transformation efficiency of 1-difluoromono-chloroethane is 93.6%, and the selectivity of vinylidene fluoride is 90.3%.
Sampling analysis when reaction unit moves 200,400,600,800,1000 hours continuously, reaction product forms without considerable change.Observe in the cracking tube without knot carbon, coking phenomenon.
Embodiment 7
Evenly load inner member in the nickel cracking tube processed of Ф 32 * 1200mm liner platinum, loadings is inner member outer surface area 500m in every cubic metre of reaction tubes volume
2(inner member forms: nickel 70%, iron 30%); Cracking tube is put in the electrical heater, and the energising heating is preheated to 560 ℃ with cracking tube.Keeping the cracking tube temperature is 560 ℃, control raw material 1,1, and the flow of 1-difluoromono-chloroethane, making its residence time of (length 570mm) in the effective thermostatically heating section of cracking tube is 30s; Reacted mixed gas is chilled to below 100 ℃ through watercooler, and the sour gas that produces by secondary water wash column and the cracking of one-level soda-wash tower flush away is again removed wherein moisture by lyophilize again, and gas forms by gas chromatographic detection after collecting.
The mole of each component consists of in the product: vinylidene fluoride accounts for 86.3%, CH
3CF
3Account for 5.5%, CH
2=CFCl accounts for 3.2%, 1,1,1-difluoromono-chloroethane and accounts for 4.5%, calculates raw material 1,1 with this, and the transformation efficiency of 1-difluoromono-chloroethane is 95.5%, and the selectivity of vinylidene fluoride is 90.4%.
Sampling analysis when reaction unit moves 200,400,600,800,1000 hours continuously, reaction product forms without considerable change.1000 hours finish, and stopped reaction is observed in the cracking tube without knot carbon, coking phenomenon.
Claims (3)
1. one kind 1,1,1-difluoromono-chloroethane catalytic pyrolysis prepares the method for vinylidene fluoride, it is characterized in that may further comprise the steps:
(1) the metal inner member with katalysis evenly is installed in the cracking tube of inert material manufacturing, the surface-area that its loadings provides for inner member in every cubic metre of cracking tube volume is 100 ~ 500m
2
(2) cracking tube is put in the electrical heater, the temperature of control cracking tube is 500 ~ 580 ℃, passes into 1,1,1-difluoromono-chloroethane, and making its residence time in the cracking tube conversion zone is 20 ~ 400 seconds;
(3) reaction product gas of cracking tube outlet is quickly cooled to below 100 ℃ through watercooler, then through secondary water absorption tower and one-level alkali cleaning absorption tower absorption hydrogenchloride, hydrogen fluoride sour gas wherein, again through lyophilize, obtains split product.
2. one kind 1,1,1-difluoromono-chloroethane catalytic pyrolysis prepares the method for vinylidene fluoride, it is characterized in that described inert material refers to quartz or platinum.
3. one kind 1,1,1-difluoromono-chloroethane catalytic pyrolysis prepares 1, the method of 1-difluoroethylene, it is characterized in that describedly having the metal inner member of katalysis by the metallic substance manufacturing of iron content, chromium, nickel, single metallic substance be can select, the alloy of any two metal formation or the alloy that is formed by three kinds of metals also can be selected.
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|---|---|---|---|
| CN201210474068.4A CN102936185B (en) | 2012-11-21 | 2012-11-21 | Method for preparing 1,1-difluoroethylene by cracking of 1,1,1-difluoro-1-chloroethane |
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|---|---|---|---|
| CN201210474068.4A CN102936185B (en) | 2012-11-21 | 2012-11-21 | Method for preparing 1,1-difluoroethylene by cracking of 1,1,1-difluoro-1-chloroethane |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103708993A (en) * | 2013-12-30 | 2014-04-09 | 江苏梅兰化工有限公司 | Alkali washing and dehydrating process for crude cracked gas in vinylidene fluoride production |
| CN108440238A (en) * | 2018-04-28 | 2018-08-24 | 山东海益化工科技有限公司 | The method that 1,2- dichloropropane catalysis oxidations prepare chlorallylene |
| CN110026212A (en) * | 2019-05-23 | 2019-07-19 | 临海市利民化工有限公司 | A kind of catalyst for cracking and the method using the catalyst preparation sitafloxacin intermediate |
| CN114478183A (en) * | 2022-02-21 | 2022-05-13 | 浙江三美化工股份有限公司 | 143a and 142b processes for preparing VDF |
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|---|---|---|---|---|
| US2551573A (en) * | 1945-11-30 | 1951-05-08 | Du Pont | Pyrolysis of chloro-fluoro alkanes |
| US2627529A (en) * | 1947-10-23 | 1953-02-03 | Socony Vacuum Oil Co Inc | Pyrolysis of difluoromonochloroethane |
| US3830856A (en) * | 1970-09-08 | 1974-08-20 | Bayer Ag | Preparation of vinylidene fluoride |
-
2012
- 2012-11-21 CN CN201210474068.4A patent/CN102936185B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2551573A (en) * | 1945-11-30 | 1951-05-08 | Du Pont | Pyrolysis of chloro-fluoro alkanes |
| US2627529A (en) * | 1947-10-23 | 1953-02-03 | Socony Vacuum Oil Co Inc | Pyrolysis of difluoromonochloroethane |
| US3830856A (en) * | 1970-09-08 | 1974-08-20 | Bayer Ag | Preparation of vinylidene fluoride |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103708993A (en) * | 2013-12-30 | 2014-04-09 | 江苏梅兰化工有限公司 | Alkali washing and dehydrating process for crude cracked gas in vinylidene fluoride production |
| CN103708993B (en) * | 2013-12-30 | 2016-06-29 | 江苏梅兰化工有限公司 | A kind of vinylidene is thick cracking gas alkali cleaning and dehydrating process in producing |
| CN108440238A (en) * | 2018-04-28 | 2018-08-24 | 山东海益化工科技有限公司 | The method that 1,2- dichloropropane catalysis oxidations prepare chlorallylene |
| CN110026212A (en) * | 2019-05-23 | 2019-07-19 | 临海市利民化工有限公司 | A kind of catalyst for cracking and the method using the catalyst preparation sitafloxacin intermediate |
| CN114478183A (en) * | 2022-02-21 | 2022-05-13 | 浙江三美化工股份有限公司 | 143a and 142b processes for preparing VDF |
| CN114478183B (en) * | 2022-02-21 | 2023-10-10 | 浙江三美化工股份有限公司 | 143a and 142b method for preparing VDF |
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| CN102936185B (en) | 2015-01-28 |
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