Method and a Device for Synthesizing 1.2-Dichloroethane

Abstract

The invention relates to a method for synthesizing 1.2-dichloroethane from ethylene and chlorine via low temperature direct chlorination of ethylene in the presence of a catalyst under conditions in which the synthesized 1.2-dichloroethane is condensed out, however, the ethylene and the chlorine are gaseous, in a reactor (3), wherein the stoichiometric ratio of ethylene to chlorine is adjusted in the reactor (3) such that there is an excess of ethylene. The invention further relates to a device for synthesizing 1.2-dichloroethane from ethylene and chlorine via low temperature direct chlorination of ethylene in the presence of a catalyst under conditions in which the synthesized 1.2-dichloroethane is condensed out, however, the ethylene and the chlorine are gaseous, in a reactor (3), wherein the stoichiometric ratio of ethylene to chlorine is adjustable in the reactor (3) such that there is an excess of ethylene.

Claims

1. A method for synthesizing 1,2-dichloroethane from ethylene and chlorine by low temperature direct chlorination of ethylene in the presence of a catalyst in a reactor (3) under conditions where the synthesized 1,2-dichloroethane condenses out while the ethylene and the chlorine are gaseous, which method comprises the step of adjusting the stoichiometric ratio of ethylene to chlorine in the reactor (3) such that ethylene is present in excess.

2. The method as claimed in claim 1, characterized in that the stoichiometric ratio of ethylene to chlorine is not less than 1.01:1.

3. The method as claimed in claim 1, characterized in that the stoichiometric ratio of ethylene to chlorine in the reactor (3) is monitored and the feed of ethylene and chlorine to the reactor (3) is closed loop controlled such that ethylene is present in excess.

4. The method as claimed in claim 1, characterized in that the reactor has withdrawn from it a 1,2-dichloroethane liquid stream (5) which is partly vaporized in a specifically single-stage vaporizing device (110).

5. The method as claimed in claim 4, characterized in that less than 50% of the 1,2-dichloroethane stream (5) removed from the reactor (3) is vaporized in the vaporizing device (110).

6. The method as claimed in claim 4, characterized in that the proportion to which the 1,2-dichloroethane stream (5) removed from the reactor (3) is vaporized in the vaporizing device (110) corresponds to the 1,2-dichloroethane quantity produced in said reactor (3).

7. The method as claimed in claim 4, characterized in that the vaporizing device (110) is configured as a falling stream evaporator.

8. The method as claimed in claim 4, characterized in that the nonvaporized proportion of the 1,2-dichloroethane stream (5) withdrawn from the reactor is returned into the reactor (3).

9. The method as claimed in claim 4, characterized in that the vaporizing device (110) is heated using the reaction heat from a plant for high temperature direct chlorination (214) of ethylene.

10. The method as claimed in claim 4, characterized in that the vaporous 1,2-dichloroethane stream (121) emerging from the vaporizing device (110) is fed into a distillation column (114).

11. The method as claimed in claim 4, characterized in that the vaporizing device (110) is heated using the condensation heat from the vapor of a distillation column (114).

12. The method as claimed in claim 10, characterized in that the distillation column (114) is used to separate off compounds having a higher boiling point than 1,2-dichloroethane.

13. The method as claimed in claim 11, characterized in that the distillation column (114) is operated at an overhead temperature in the range from 120° C. to 150° C., preferably at an overhead temperature in the range from 127° C. to 135° C.

14. The method as claimed in claim 4, characterized in that before being fed to the vaporizing device (110), the 1,2-dichloroethane stream (5) removed from the reactor (3) is preheated using a 1,2-dichloroethane stream (104, 120) withdrawn from the vaporizing device (110) and/or using a specifically liquid 1,2-dichloroethane stream (220) from a plant for high temperature direct chlorination of ethylene.

15. The method as claimed in claim 1, characterized in that the catalyst comprises FeCl3 and/or NaCl.

16. The method as claimed in claim 1, characterized in that an ethylene-containing off-gas (217) from a high temperature direct chlorination reactor (214) is fed to the reactor (3).

17. A device for synthesizing 1,2-dichloroethane from ethylene and chlorine by low temperature direct chlorination of ethylene in the presence of a catalyst in a reactor (3) under conditions where the synthesized 1,2-dichloroethane condenses out while the ethylene and the chlorine are gaseous, wherein the stoichiometric ratio of ethylene to chlorine in the reactor (3) is adjustable such that ethylene is present in excess.

Description

SHORT DESCRIPTION OF FIGURES

[0027] FIG. 1 shows in a schematic depiction a device for synthesizing 1,2-dichloroethane from ethylene and chlorine by low temperature direct chlorination of ethylene as per the prior art.

[0028] FIG. 2 shows in a schematic depiction a first exemplary embodiment of a device as provided by the invention for synthesizing 1,2-dichloroethane from ethylene and chlorine.

[0029] FIG. 3 shows in a schematic depiction a second exemplary embodiment of a device as provided by the invention for synthesizing 1,2-dichloroethane from ethylene and chlorine.

EMBODIMENTS OF THE INVENTION

[0030] In the various figures, like reference signs are provided for like parts and these are therefore each generally only identified/mentioned once.

[0031] FIG. 1 depicts a prior art device for synthesizing 1,2-dichloroethane from ethylene and chlorine by low temperature direction chlorination of ethylene (an LTDC plant).

[0032] Ethylene 1 and chlorine 2 are fed under the conditions of excess chlorine into an LTDC reactor 3, where they are dissolved in EDC and react with each other to form EDC. The reactor off-gas 4 is withdrawable at the top of the reactor. The reaction proceeds at a temperature below the boiling point of EDC. The produced, catalyst-containing EDC 5 is withdrawn from the reactor in liquid form and subjected to a wash with water 7 and aqueous sodium hydroxide solution 8, in the course of which the catalyst transfers into the aqueous phase and any chlorine still present is converted by reaction with aqueous sodium hydroxide solution into sodium hypochlorite, which likewise dissolves in the aqueous phase. The wastewater stream 10 has to be sent to a further treatment.

[0033] The now moist EDC 11 is fed into a dewatering column 12, where, in an integrated system with a plant for production of VCM, likewise still moist EDC 18 from an oxychlorination plant may be worked up and at the top of which water and low boilers 16 are separated off.

[0034] The dried EDC 9 is fed into a high boilers column 13, at the top of which the purified product EDC 17 is withdrawn. At the bottom end of the high boilers column, a concentrated solution of high boilers in EDC 20 is withdrawn and fed into a vacuum column 15. In this column, high boilers 22 are separated off at the bottom end while the EDC 21 generated at the top is returned to the high boilers column 13. Where there is a complete plant complex for production of VCM, a backstream 19 of EDC from a plant for thermal cracking of EDC is additionally worked up in the high boilers column.

[0035] The depiction of the three-stage distillative workup of EDC via columns 12, 13 and 15 is exemplary—this manner of working up is known to a person skilled in the art and does not form part of the invention. To clarify the incorporation in a plant complex for production of vinyl chloride, reference is made to EDC streams from an oxychlorination plant 18 and from a plant for thermal cracking of EDC 19. These interrelationships are also known to a person skilled in the art.

[0036] FIG. 2 depicts a first exemplary embodiment of a device for synthesizing 1,2-dichloroethane according to the invention. In this exemplary embodiment, the vaporizing device is heated with the vapor of a distillation column.

[0037] FIG. 2 shows an LTDC plant whose reaction product is vaporized in a single-stage vaporizing step wherein the heat required for vaporization is supplied as the latent heat of the vapor stream of a high boilers column. No additional steam is consumed in the process. Ethylene 1 and chlorine 2 are fed into an LTDC reactor 3, where they react to form EDC. The reactor off-gas stream 4 is withdrawable at the top of the reactor. The LTDC reactor has withdrawn from it a liquid, catalyst-containing EDC stream 5, which is passed into a receiver 111. In a preferred embodiment, the EDC stream 5 is greater than the EDC quantity produced in the reactor. A pump 106 passes the EDC stream through one or more heat exchangers 107, 108, which are used for preheating, and it is preheated with the bottoms stream 104 from the vaporizing apparatus 110 and/or with the vaporous product EDC 120 from the vaporizing apparatus 110. After preheating, the EDC stream enters the vaporizing apparatus 110, where an EDC quantity corresponding to the EDC quantity produced in the LTDC reactor 3 is vaporized. The vaporized EDC stream 120 is cooled down in the preheater 108 and in a further heat exchanger 109, collected in the product receiver 112 and pumped to the plant limits or to a downstream part of the integrated plant for VCM production. The nonvaporized, catalyst-containing EDC fraction 104 from the vaporizing apparatus 110 is pumped back into the receiver 111, after being cooled down by heat exchange in the preheater 107. From the receiver 111, an EDC stream corresponding to the nonvaporized EDC fraction is pumped back into the LTDC reactor.

[0038] The vaporizing apparatus 110 serves as overhead condenser to the distillation column, which is configured as a high boilers column 114 and which may also be used to work up further streams from the integrated plant for VCM production such as back EDC from the thermal EDC cracker 116 or EDC from an oxychlorination 117 and dried in a dewatering column. The condensed EDC 121 is collected in the return stream container 113 of the high boilers column 114 and pumped as return stream to the column 114 and/or as product to the plant limits.

[0039] The method described in the first exemplary embodiment is particularly useful for upgrading existing LTDC plants where the capacity is not to be simultaneously increased as part of the upgrade.

[0040] FIG. 3 depicts a second exemplary embodiment of a device for synthesizing 1,2-dichloroethane according to the invention. In this exemplary embodiment, the vaporizing step is heated with reaction heat coupled out of an HTDC plant.

[0041] The HTDC plant depicted by way of example in FIG. 3 was already described in EP 1 161 406. However, other HTDC processes are also suitable for heating the vaporizing step of the present invention.

[0042] Ethylene 1 and chlorine 2 are fed into an LTDC reactor 3, where they react to form EDC. The reactor off-gas stream 4 is withdrawable at the top of the reactor 3. The LTDC reactor 3 has withdrawn from it a liquid, catalyst-containing EDC stream 5, which is passed into a receiver 111. In a preferred embodiment, the EDC stream 5 is greater than the EDC quantity produced in the LTDC reactor 3. The receiver 111 has withdrawn from it, by means of a pump 106, an EDC stream 122 which, in a preferred embodiment of the invention, is greater than the EDC quantity produced in the LTDC reactor 3. The EDC stream 122 is passed through one or more heat exchangers 107, 108 which serve to preheat the stream and are heated with the EDC stream 104 from the bottom end of the vaporizing apparatus 110 and/or with a liquid, hot EDC stream 220 from the HTDC plant. After preheating, the EDC stream 122 enters the vaporizing apparatus 110, where an EDC quantity corresponding to the EDC quantity produced in the LTDC reactor 3 is vaporized. The vaporized LTDC product stream 215 may for example be fed in vapor form into a distillation column or, in a further preferred (non-depicted) embodiment of the invention, used to preheat, by condensation, the liquid EDC from the LTDC reactor 3.

[0043] The nonvaporized fraction of the EDC from the vaporizing apparatus 110 is cooled down by heat exchange with the stream 122 from the receiver 111 and conveyed back into the receiver 111. The EDC partly condensed in the vaporizing apparatus 110 is collected in the HTDC product receiver 212 and pumped as product 213 to the plant limits and/or as backstream 223 back to the HTDC reactor 214. Downstream of the product receiver 212 is an off-gas condensation sector 221, which also may contain a freezer (not depicted). The off-gas from the HTDC reactor 214, which contains ethylene in addition to other noncondensable constituents, is compressed in a gas jet gas compressor 216 by means of the ethylene feed stream 1 to the LTDC reactor 3 and fed into the LTDC reactor 3.

[0044] The method described in the second exemplary embodiment is particularly useful for upgrading existing LTDC plants when the capacity is to be increased at the same time as the LTDC plant upgrade by installing an additional HTDC plant.

[0045] In the above-described devices and methods for synthesizing 1,2-dichloroethane from ethylene and chlorine by low temperature direct chlorination of ethylene in the presence of a catalyst in a reactor 3 under conditions where the synthesized 1,2-dichloroethane condenses out, while the ethylene and the chlorine are gaseous, the stoichiometric ratio of ethylene to chlorine in the reactor 3 is adjusted such that ethylene is present in excess. This reduces the purification requirements of the synthesized 1,2-dichloroethane and substantially extends the useful life of reactor 3.

LIST OF REFERENCE SIGNS

[0046] 1 ethylene
2 chlorine
3 LTDC reactor
4 LTDC reactor off-gas
5 product EDC from reactor
6 EDC wash
7 wash water
8 aqueous sodium hydroxide solution

9 EDC, dry

[0047] 10 wastewater stream
11 product EDC, water-containing
12 dewatering column
13 high boilers column
14 EDC product stream, purified
15 vacuum column
16 water and low boilers
17 product EDC, purified
18 EDC, moist, from oxychlorination
19 back EDC from EDC cracking
20 EDC+high boilers
21 back EDC from vacuum column
22 high boilers
23 column off-gas
104 EDC backstream to circuit receiver
106 circuit pump
107 preheater
108 preheater
109 product condenser
110 falling stream evaporator
111 circuit receiver
112 product receiver
113 return stream container
114 high boilers column
115 vapor stream
116 back EDC from EDC cracking
117 dried EDC from oxychlorination
118 EDC backstream to LTDC reactor
119 LTDC reactor off-gas
120 EDC from evaporator
121 condensed EDC from evaporator
122 EDC to evaporator
212 HTDC product receiver
213 HTDC product
214 HTDC reactor
215 LTDC product stream
216 gas jet gas compressor
217 HTDC reactor off-gas
220 EDC circulation stream, HTDC
221 HTDC postcondenser
223 EDC to HTDC reactor