CN1247499C - Process for preparing vinylidene chloride from rectifying residual liquid of dichloroethane - Google Patents
Process for preparing vinylidene chloride from rectifying residual liquid of dichloroethane Download PDFInfo
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- CN1247499C CN1247499C CN 200310122646 CN200310122646A CN1247499C CN 1247499 C CN1247499 C CN 1247499C CN 200310122646 CN200310122646 CN 200310122646 CN 200310122646 A CN200310122646 A CN 200310122646A CN 1247499 C CN1247499 C CN 1247499C
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- sodium hydroxide
- reaction
- vinylidene chloride
- residual liquid
- reactor
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- 239000007788 liquid Substances 0.000 title claims abstract description 28
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 title claims abstract description 22
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 title abstract 2
- 238000004519 manufacturing process Methods 0.000 title description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 81
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 19
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012808 vapor phase Substances 0.000 claims abstract description 6
- 238000007796 conventional method Methods 0.000 claims abstract description 4
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 22
- 238000004821 distillation Methods 0.000 claims description 17
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 8
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 8
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical compound ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- 238000007086 side reaction Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000007033 dehydrochlorination reaction Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- DIWKDXFZXXCDLF-UHFFFAOYSA-N chloroethyne Chemical group ClC#C DIWKDXFZXXCDLF-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a method for preparing vinylidene chloride from residual rectified liquid of dichloroethane. Residual rectified liquid enters a first reaction vessel and then flows into a plurality of reaction vessels behind the first reaction vessel, and simultaneously, sodium hydroxide solution flows into the reaction vessels. Trichloroethane are excessive in the first reaction vessel and the second reaction vessel, and sodium hydroxide is kept excessive in the last reaction vessel. The reaction temperature is from 70 to 90 DEG C, the stay time is from 10 to 45 minutes, and a conventional method is adopted to collect vinylidene chloride from vapor phase products of the reaction vessels. The method of the present invention can be used for preparing vinylidene chloride by utilizing residual rectified liquid with low trichloroethane concentration, and the conversion rate can reach more than 90%. The method of the present invention can comprehensively utilize waste liquid for producing VDC, so that not only can the discharge of three wastes be reduced greatly, but also valuable VDC products can be obtained, and favorable social benefits and economic benefits are obtained.
Description
Technical field
The present invention relates to the preparation method of vinylidene chloride.
Background technology
Vinylidene chloride (being called for short VDC, down together), its chemical name is a vinylidene chloride, structural formula CH
2=CCl
2, be a kind of monomer, normal temperature is down for having the colourless liquid of special odor, volatile gasification.Fusing point-122.5 ℃, 31.7 ℃ of boiling points, relative density 1.212 (20 ℃), specific refractory power 1.425 (20 ℃), flash-point-17.8 ℃, 570 ℃ of spontaneous ignition temperatures, water-soluble hardly, dissolve in multiple organic solvent.Be mainly used in polymkeric substance, particularly multipolymer is synthetic.Polyvinylidene dichloride also waits Application and Development at present, and the potential of demand of this product of this respect is very big.
VDC has multiple production method, and conventional VDC is that (1,1,2-TCE) method of hydrogenchloride is prepared for raw material alkalescence removes, as the ammonium hydroxide method of rising sun road company proposition with vinyl trichloride; Or with 1, the 2-ethylene dichloride is a raw material, or is raw material thermo-cracking dehydrochlorination method with the 1.
In course of production of chloroethylene, usually need be to containing 1,1, ethylene dichloride (EDC) material of high boiling material such as 2-trichloroethane carries out rectifying, to reclaim ethylene dichloride (EDC), and tower still heavy constituent waste liquid also contains very most of 1,1, the 2-trichloroethane contains 1 in the waste liquid, 1,2-trichloroethane 5～50% (wt).If this distillation residual liquid is entered three wastes processing unit, both contaminate environment caused the waste of raw material again.The present invention utilizes the vinyl trichloride in this distillation residual liquid to prepare vinylidene chloride.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of method by ethylene dichloride distillation residual liquid preparing vinylidene chloride, to overcome the above-mentioned defective that prior art exists, to satisfy the production development demand of relevant department.
Technical conceive of the present invention is such:
The present invention adopts 1,1,2-trichloroethane dehydrochlorination preparing vinylidene chloride is according to test-results, with the raising of NaOH concentration, yield descends, illustrate that the series connection side reaction is more responsive to the change in concentration of NaOH than main reaction, illustrate that back-mixing is little to the yield influence, therefore, the present invention proposes following preparation method, comprises the steps:
With the aqueous solution of distillation residual liquid and sodium hydroxide at 65～90 ℃, reaction 10～60min;
Add acid then, it is 6.9～7.2 that the neutralization reaction raffinate reaches pH, with stopped reaction, adopts conventional method to collect vinylidene chloride then from reaction product, and transformation efficiency reaches more than 90%.
The component and the weight percent content of the distillation residual liquid of being addressed mainly comprise:
Vinyl trichloride 5～50% (wt)
1,2-ethylene dichloride 40～80% (wt)
Sym.-tetrachloroethane 5～10% (wt)
Pentaline 1～7% (wt)
Polychloride 0.1～2.5% (wt)
The weight concentration of aqueous sodium hydroxide solution is preferably 5～45% (wt);
The mol ratio of vinyl trichloride and sodium hydroxide is: 1: 1.0～1.4;
Said acid comprises a kind of in hydrochloric acid, sulfuric acid or other mineral acids.
The present invention preferably adopts many still series connection continuous production, to satisfy the needs of response characteristic.From the analysis of trichloroethane dehydrochlorination preparing vinylidene chloride response characteristic as can be known, the reaction selection rate be improved, series connection side reaction and parallel side reaction must be suppressed, suppress the series connection side reaction, can adopt many still series connection, make first and second still trichloroethane excessive, alkali concn is reduced as far as possible.Simultaneously, strengthen to stir making the product vinylidene chloride leave reactor as much as possible, thereby play the effect that suppresses the series connection side reaction.In the end in the still, keep sodium hydroxide excessive, improve the transformation efficiency of trichloroethane, can play the effect that suppresses parallel side reaction simultaneously.
Many still series connection quantity-produced methods comprise the steps:
Distillation residual liquid enters first reactor, order flows into a plurality of reactors thereafter, simultaneously weight concentration is that 5～45% sodium hydroxide solution flows into a plurality of reactors, and first and second still trichloroethane is excessive, in last still, keep sodium hydroxide excessive, temperature of reaction is 65～90 ℃, and the residence time is 10min～60min, neutralizes wherein unreacted sodium hydroxide with stopped reaction with acid, adopt conventional method to collect vinylidene chloride from the vapor phase product of a plurality of reactors, transformation efficiency reaches 90%.
The component and the weight percent content of the distillation residual liquid of being addressed mainly comprise:
Vinyl trichloride 5～50% (wt)
1,2-ethylene dichloride 40～80% (wt)
Sym.-tetrachloroethane 5～10% (wt)
Pentaline 1～7% (wt)
Polychloride 0.1～2.5% (wt)
Said acid comprises a kind of in hydrochloric acid, sulfuric acid or other mineral acid acid.
A plurality of placed in-line continuous tank reactors are adopted in reaction, and the mol ratio of vinyl trichloride and sodium hydroxide is 1: 0.2～0.9 in first and second still, and the mol ratio of vinyl trichloride and sodium hydroxide is 1: 1.0～1.4 in last reactor;
According to the present invention, preferably adopt three reactors, the mol ratio of vinyl trichloride and sodium hydroxide is 1: 0.2～0.9 in first and second still;
The mol ratio of vinyl trichloride and sodium hydroxide is 1: 1.0～1.4 in the 3rd reactor.
Adopt method of the present invention, at first and second still, because the existence and the trichloroethane proportioning of back-mixing are excessive, in the reactor basically eliminate sodium hydroxide, the residual a small amount of vinylidene chloride of trichloroethane and evaporation back that has only low concentration, thereby avoided in first and second still generating chloroacetylene may, the relation of temperature of reaction, proportioning raw materials and transformation efficiency:
Method of the present invention, reaction pair temperature are quite responsive, when temperature of reaction during less than 65 ℃, speed of reaction is very little, and the vapor phase product amount is quite few, when temperature of reaction during greater than 70 ℃, speed of reaction increases obviously, and when temperature of reaction during greater than 80 ℃, speed of reaction is bigger.
Residence time of material is not highstrung factor, when feed stock conversion greater than 90% the time, residence time of material can change between 10min～60min.
Be used to realize that the device of method of the present invention comprises the placed in-line reactor that is provided with whipping appts more than two or two at least.
Method of the present invention, can utilize the distillation residual liquid that contains the trichloroethane component to prepare vinylidene chloride, transformation efficiency can reach more than 90%, method of the present invention can fully utilize waste liquid and produce VDC, can significantly reduce the discharging of the three wastes, extremely valuable VDC product be can obtain again, good social benefit and economic benefit received.
Description of drawings
Fig. 1 is the process flow diagram of three continuous tank reactors of series connection.
Embodiment
Referring to Fig. 1, the present invention comprises placed in-line first reactor 1, second reactor 2 and the 3rd reactor 3 that is provided with whipping appts at least by the device of ethylene dichloride distillation residual liquid preparing vinylidene chloride method, distillation residual liquid enters first reactor 1, order flows into second reactor 2 and the 3rd reactor 3 thereafter, simultaneously weight concentration is that 5～45% sodium hydroxide solution flows into first reactor 1, second reactor 2 and the 3rd reactor 3, the vapor phase product of each reactor enters the condenser liquid trap 4 that is connected with each reactor, collects vapour phase compositions such as vinylidene chloride.
Embodiment 1
Distillation residual liquid enters first reactor, order flows into a plurality of reactors thereafter, simultaneously weight concentration is that 15% sodium hydroxide solution flows into second reactor 2 and the 3rd reactor 3, temperature of reaction is 80 ℃, the residence time is 40min, the vapor phase product of a plurality of reactors enters coupled logical condenser liquid trap 4, collects vapour phase compositions such as vinylidene chloride.
The component and the weight percent content of the distillation residual liquid of being addressed comprise:
Vinyl trichloride 5% (wt), 1,2-ethylene dichloride 80% (wt), sym.-tetrachloroethane 6% (wt), pentaline 7% (wt), polychloride 2% (wt);
The mol ratio of vinyl trichloride and sodium hydroxide is 1: 0.2 in first and second still;
The mol ratio of vinyl trichloride and sodium hydroxide is 1: 1.1 in the 3rd reactor.
Transformation efficiency reaches 95%.
Adopt processing condition and the device of embodiment 1, wherein, the residence time is 30min, and the component and the weight percent content of the distillation residual liquid of being addressed comprise:
Vinyl trichloride 50% (wt), 1,2-ethylene dichloride 40% (wt), sym.-tetrachloroethane 6% (wt), pentaline 2% (wt), polychloride 2% (wt)
Vinyl trichloride 5% (wt), 1,2-ethylene dichloride 80% (wt), sym.-tetrachloroethane 6% (wt), pentaline 7% (wt), polychloride 2% (wt);
The mol ratio of vinyl trichloride and sodium hydroxide is 1: 0.9 in first and second still;
The mol ratio of vinyl trichloride and sodium hydroxide is 1: 1.4 in the 3rd reactor.
Transformation efficiency reaches 94.5%.
Claims (3)
1. the method by ethylene dichloride distillation residual liquid preparing vinylidene chloride is characterized in that, comprises the steps:
A plurality of placed in-line continuous tank reactors are adopted in reaction;
Distillation residual liquid enters first reactor, order flows into a plurality of reactors thereafter, sodium hydroxide solution flows into a plurality of reactors simultaneously, first and second still trichloroethane is excessive, in last still, keeps sodium hydroxide excessive, temperature of reaction is 65～90 ℃, the residence time is 10min～60min, with stopped reaction, adopts conventional method to collect vinylidene chloride with the wherein unreacted sodium hydroxide of acid neutralization from the vapor phase product of a plurality of reactors;
The component and the weight percent content of the distillation residual liquid of being addressed mainly comprise:
Vinyl trichloride 5～50% (wt)
1,2-ethylene dichloride 40～80% (wt)
Sym.-tetrachloroethane 5～10% (wt)
Pentaline 1～7% (wt)
Polychloride 0.1～2.5% (wt).
2. method according to claim 1 is characterized in that, the mol ratio of vinyl trichloride and sodium hydroxide is 1: 0.2～0.9 in first and second still.
3. method according to claim 2 is characterized in that the mol ratio of vinyl trichloride and sodium hydroxide is 1: 1.0～1.4 in last reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310122646 CN1247499C (en) | 2003-12-22 | 2003-12-22 | Process for preparing vinylidene chloride from rectifying residual liquid of dichloroethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310122646 CN1247499C (en) | 2003-12-22 | 2003-12-22 | Process for preparing vinylidene chloride from rectifying residual liquid of dichloroethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1554627A CN1554627A (en) | 2004-12-15 |
| CN1247499C true CN1247499C (en) | 2006-03-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200310122646 Expired - Lifetime CN1247499C (en) | 2003-12-22 | 2003-12-22 | Process for preparing vinylidene chloride from rectifying residual liquid of dichloroethane |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI683803B (en) * | 2014-11-11 | 2020-02-01 | 美商陶氏全球科技責任有限公司 | Process for the production of ethylene, vinylidene, and hydrogen chloride from ethane |
| CN112774591B (en) * | 2020-12-25 | 2022-09-23 | 北京化工大学 | Continuous preparation system and method of vinylidene chloride |
| CN114569929B (en) * | 2022-02-18 | 2023-01-31 | 宁夏英力特化工股份有限公司 | Decomposition device and decomposition method for chloroethylene rectification residual liquid |
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2003
- 2003-12-22 CN CN 200310122646 patent/CN1247499C/en not_active Expired - Lifetime
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