WO2023094364A1 - Process for preparing a gas stream comprising chlorine - Google Patents
Process for preparing a gas stream comprising chlorine Download PDFInfo
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- WO2023094364A1 WO2023094364A1 PCT/EP2022/082760 EP2022082760W WO2023094364A1 WO 2023094364 A1 WO2023094364 A1 WO 2023094364A1 EP 2022082760 W EP2022082760 W EP 2022082760W WO 2023094364 A1 WO2023094364 A1 WO 2023094364A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gas stream
- hcl
- reaction zone
- catalyst
- range
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 82
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000000460 chlorine Substances 0.000 title claims abstract description 32
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 32
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 251
- 238000000034 method Methods 0.000 claims abstract description 81
- 230000008569 process Effects 0.000 claims abstract description 80
- 239000007789 gas Substances 0.000 claims description 269
- 239000003054 catalyst Substances 0.000 claims description 208
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 158
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 156
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 156
- 238000006243 chemical reaction Methods 0.000 claims description 131
- 239000007788 liquid Substances 0.000 claims description 73
- 239000007921 spray Substances 0.000 claims description 27
- 238000011144 upstream manufacturing Methods 0.000 claims description 22
- 238000005859 coupling reaction Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000010924 continuous production Methods 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 3
- 230000006854 communication Effects 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 28
- 239000002245 particle Substances 0.000 description 22
- 230000003068 static effect Effects 0.000 description 18
- 239000000463 material Substances 0.000 description 15
- 229910052759 nickel Inorganic materials 0.000 description 14
- 239000000543 intermediate Substances 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 5
- 229910010271 silicon carbide Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000007138 Deacon process reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000004514 thermodynamic simulation Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 229940000425 combination drug Drugs 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/04—Preparation of chlorine from hydrogen chloride
Definitions
- the present invention relates to a process for preparing a gas stream G(n) comprising Ch and a production unit for carrying out said process as well as a use of the production unit for continu- ously preparing chlorine.
- Electrochemical processes are expensive both in terms of investment and operating costs.
- the oxidation of HCI to chlorine the so-called Deacon process, is more economically attractive.
- the Ch produced can then be used to manufacture other commercially valuable products, and at the same time the emission of waste hydrochloric acid is curtailed.
- the Deacon process is based on the gas phase oxidation of hydrogen chloride.
- HCI is reacted with oxygen over a catalyst, for example copper chloride (CuCh), to form chlorine and water in the gas phase at temperatures of 200 to 500 °C. It is an equilibrium reaction with a slight exotherm. Cooled reactors are used to control the temperature development and avoid hot spots. Both tube-bundle reactors and fluidized beds are known.
- suitable materials are required that can withstand the aggressive substance system at high temperatures, including nickel and nickel-based alloys but also silicon carbide. These materials and their processing is comparatively expensive, which leads to corre- spondingly high costs for the reactor.
- a high-temperature cooling system is required, which causes additional costs.
- a nitrate I nitrite molten salt is used as the cooling sys- tem. In the event of a leak, this can react with the reaction gas and damage the reactor.
- W02007/134771 A discloses a method for producing chlorine by catalytic gas phase oxidation of hydrogen chloride using oxygen, wherein the reaction is carried on at least two catalyst beds under adiabatic conditions, wherein intermediate heat exchangers are required.
- the reaction is carried on at least two catalyst beds under adiabatic conditions, wherein intermediate heat exchangers are required.
- intermediate heat exchangers are required.
- the object of the present invention is to provide a new process for preparing chlorine which permits to improve the production of chlorine, avoid the problems of the prior art, such as deterioration of the production unit used for such processes, while reducing production costs.
- the process according to the present invention permits to obtain chlorine at good conversation rate starting from fresh starting materials or obtained from recycle streams and reduce the costs of production. Further, it has surprisingly been found that the pro- cess of the present invention permits to avoid the deterioration of the production unit and thus ensure high quality production of chlorine while reducing functioning costs.
- n is in the range of from 2 to 10, more preferably in the range of from 3 to 8, more preferably in the range of from 4 to 7.
- the process is a continuous process.
- reaction of HCI with O2 in at least one stage S(i), more preferably in all n stages S(i), is carried out under adiabatic conditions.
- G(0) consist of O2 and HCI.
- the gas stream G(0) can preferably be provided from the mixture of 02 gas stream and HCI gas stream, wherein said streams can preferably be recycled streams.
- the mole ratio of the amount of oxygen, in mol, to the amount of hydrogen chloride, in mol, in G(0) is in the range of from 0.1 :1 to 5:1 , more preferably in the range of from 0.2:1 to 2:1 , more preferably in the range of from 0.22:1 to 1 :1.
- the gas stream G(0) has a temperature in the range of from 150 to 350 °C, more preferably in the range of from 200 to 300°C, more preferably in the range of from 250 to 280°C.
- the n heterogeneous catalysts C(i) are chemically and physically the same or differ- ent. More preferably the n heterogeneous catalysts C(i) are chemically and physically the same.
- the catalyst C(i) it is preferred that it is selected from the group consisting of a Ru- containing catalyst, a Ce-containing catalyst, a Cu-containing catalyst and a mixture of two or more thereof, more preferably is selected from the group consisting of a Ru-containing catalyst, a Ce-containing catalyst and a Cu-containing catalyst. More preferably the catalyst C(i) is a Ru- containing catalyst. More preferably the catalyst C(i) comprises, more preferably consists of, particles having an average particle size in the range of from 1 to 10 mm, preferably in the range of from 1 to 4 mm, the average particle size being determined as described in the exam- ple section.
- each of the n serially coupled reaction zones Z(i) comprises, more preferably is, a catalyst bed B(i), wherein V(B(i+1 )) > V(B(i)), more preferably V(B(i+1 )) > V(B(i)), V(B(i+1 )) be- ing the volume of the catalyst bed B(i+1 ) and V(B(i)) being the volume of the catalyst bed B(i).
- the catalyst bed B(i) is an adiabatic catalyst bed.
- n serially coupled reaction zones Z(i) are located in a single reactor.
- the n serially coupled reaction zones Z(i) are preferably each located in a reactor R(i), wherein the reactor R(i) is in fluid communication with the reactor R(i+1 ), more preferably via a pipe.
- Gp(i) consist of Ch, O2 and one or more of H2O and HCI.
- Gp(i) may also comprise inert components such as N2, Ar and/or CO2.
- the gas stream G(i) has a temperature, T(G(i)), in the range of from 150 to 350 °C, more preferably in the range of from 200 to 300°C, more preferably in the range of from 250 to 280°C.
- T(Gp(i)) T(G(i))
- T(Gp(i)) being the temperature of the gas stream Gp(i)
- T(G(i)) being the temperature of G(i).
- neither Gp(i) exiting Z(i) or G(i) is cooled via a heat exchanger.
- the cooling is performed via the introduction and the mixing of the liquid stream L(i).
- the gas stream Gp(i) has a temperature, T(Gp(i)), of at most 450 °C, more preferably of at most 430 °C.
- the gas stream G(n) has a temperature T(G(n)) of at most 400 °C, more preferably of at most 395 °C.
- the liquid stream L(i) has temperature T(L(i)) in the range of from 10 to 60 °C, more preferably in the range of from 15 to 30 °C. More preferably the liquid stream L(i) consists of HCl and water.
- the liquid stream L(i) consists of HCl.
- the liquid stream L(i) consists of water and HCl.
- the liquid stream L(i) consists essentially of, more preferably consists of, water and HCl.
- G P (i) is admixed with the liquid stream L(i) and additionally a gas stream H(i), which comprises HCl.
- f H(i) (HCl) ⁇ f H(i+1) (HCl)
- f H(i) (HCl) being the HCl mass flow in H(i)
- f H(i+1) being the HCl mass flow in H(i+1).
- 98 to 100 weight-% more preferably from 99 to 100 weight-%, more preferably from 99.5 to 100 weight-%
- the gas stream H(i) consists of HCl.
- the gas stream H(i) consists essentially of, more preferably consists of, HCl.
- the gas stream H(i) has a temperature, T(H(i)), in the range of from - 50 to 250°C, more preferably in the range of from 0 to 100 °C.
- the liquid stream L(i), and more preferably a gas stream H(i) defined in the foregoing are introduced and admixed with G P (i) downstream of the reaction zone Z(i) via a nozzle, more preferably a spray nozzle or a venturi nozzle, more preferably via a spray nozzle, more prefera- bly the liquid stream L(i), and the gas stream H(i) are introduced and mixed with G P (i) via a dual- flow spray nozzle.
- the liquid stream L(i), and more preferably a gas stream H(i) defined in the foregoing, mixed with GP(i) are further mixed in one or more mixing devices, the mixing device being preferably one or more of a static mixer, a dynamic mixer, an ejector, a venturi nozzle and a spray nozzle, more preferably the mixing device is a static mixer. More preferably the liquid stream L(i), and more preferably a gas stream H(i) defined in the foregoing, are introduced and admixed with GP(i) downstream of the reaction zone Z(i) via a spray nozzle and the mixed streams are subsequently mixed in one or more static mixers, more preferably two static mixers.
- the gas stream G(n) consists of chlorine.
- the gas stream G(0) is provided continuously.
- n 5.
- the process preferably comprises (a) providing a gas stream G(0) which comprises O2 and HCl, more preferably continu- ously; (b) five successive process stages S(1), S(2), S(3), S(4) and S(5), wherein in S(1), - a gas stream G(0) is fed into a reaction zone Z(1) and brought in contact with C(1) in Z(1), obtaining a gas stream GP(1) which comprises Cl2, O2, H2O and HCl; - removing GP(1) from Z(1); - admixing G P (1) with a liquid stream L(1), which comprises H 2 O and HCl, and a gas stream H(1) comprising HCl, obtaining a gas stream G(1) which compris- es Cl2, O2, H2O and HCl; wherein c G(1) (Cl 2 ) > c G(0) (Cl 2 ), c G(1) (Cl 2 ) being the Cl 2 concentration in G(1) and c G(0) (Cl 2 ) being the Cl2 concentration in G(0); wherein in in
- reaction zones Z(1), Z(2), Z(3), Z(4) and Z(5) are located in a single reactor.
- reaction zones Z(1), Z(2), Z(3), Z(4) and Z(5) are located in reactors R(1), R(2), R(3), R(4) and R(5), respectively.
- Preferably from 20 to 70 weight-%, more preferably 40 to 60 weight-%, of the gas stream G(5) consist of chlorine. Alternatively, preferably n 6.
- the process preferably comprises (a) providing a gas stream G(0) which comprises O2 and HCl, more preferably continu- ously; (b) five successive process stages S(1), S(2), S(3), S(4), S(5) and S(6), wherein in S(1), - a gas stream G(0) is fed into a reaction zone Z(1) and brought in contact with C(1) in Z(1), obtaining a gas stream G P (1) which comprises Cl 2 , O 2 , H 2 O and HCl; - removing G P (1) from Z(1); - admixing G P (1) with a liquid stream L(1) which comprises H 2 O and HCl, and a gas stream H(1) comprising HCl, obtaining a gas stream G(1) which compris- es Cl2, O2, H2O and HCl; wherein c G(1) (Cl 2 ) > c G(0) (Cl 2 ), c G(1) (Cl 2 ) being the Cl 2 concentration in G(1) and c G(0) (Cl 2 ) being the Cl 2 concentration in
- reaction zones Z(1), Z(2), Z(3), Z(4), Z(5) and Z(6) are located in a single reactor.
- the reaction zones Z(1), Z(2), Z(3), Z(4), Z(5) and Z(6) are located in reactors R(1), R(2), R(3), R(4), R(5) and R(6), respectively.
- the process of the present invention consists of (a) and (b).
- reaction zone Z(i) comprises, more preferably is, a catalyst bed B(i) which com- prises the catalyst C(i).
- reaction zone Z(i) is an adiabatic reaction zone, more preferably the catalyst bed B(i) is an adiabatic catalyst bed.
- reaction zone Z(i), more preferably the catalyst bed B(i) operates adiabatically.
- the catalyst bed B(i) is isolated with ceramic walls.
- the total volume of the catalyst beds depend on different factors, such as the type of catalyst, the particle size of the catalyst, the space velocity. The skilled person knows how to adapt this parameter.
- the total volume of the catalyst beds B(i) to B(n) is in the range of from 10 to 100 m 3 .
- the total volume of the cata- lyst beds B(i) to B(n) can more preferably be in the range of from 20 to 40 m 3 , more preferably in the range of from 25 to 35 m 3 .
- the catalyst C(i) is selected from the group consisting of a Ru-containing catalyst, a Ce- containing catalyst, a Cu- containing catalyst and a mixture of two or more thereof, more preferably selected from the group consisting of a Ru- containing catalyst, a Ce- containing cat- alyst and a Cu- containing catalyst. More preferably the catalyst C(i) is a Ru-containing catalyst.
- the catalyst C(i) comprises, more preferably consists of, particles having an average particle size in the range of from 1 to 10 mm, preferably in the range of from 1 to 4 mm, the average particle size being determined as described in the example section.
- the apparatus further comprises a reactor Rs, said reactor Rs comprising the n seri- ally coupled reaction zones Z(i).
- the reactor Rs comprises an inlet end and an oulet end, wherein the inlet means for passing the gas stream G(0) into the reaction zone Z(i) is located at the inlet end of Rs and the outlet means for removing the gas stream G(n) from the reaction zone Z(n) is located at the outlet end of Rs.
- each of the n serially coupled reaction zones Z(i) is separated from each other by a space T(i) in the reactor Rs, wherein the means M(i) for introducing and admixing the liquid stream L(i), and preferably the gas stream H(i), with the gas stream Gp(i) is located in T(i).
- the means M(i) is a nozzle, more preferably a spray nozzle or a venturi nozzle, more preferably a spray nozzle.
- the means M(i) for introducing and admixing the liquid stream L(i), and the gas stream H(i), with the gas stream Gp(i) is a dual-flow spray nozzle.
- the production unit further comprises, in the space T(i) and downstream of the means M(i), one or more mixing devices, the mixing device being more preferably one or more of a static mixer, a dynamic mixer, an ejector, a venturi nozzle and a spray nozzle, more prefer- ably the mixing device being a static mixer.
- the mixing device being more preferably one or more of a static mixer, a dynamic mixer, an ejector, a venturi nozzle and a spray nozzle, more prefer- ably the mixing device being a static mixer.
- the inner diameter of the reactor Rs depends on different factors, such as the type of catalyst, the particle size of the catalyst, the space velocity. The skilled person knows how to adapt such parameter.
- the reactor Rs has an inner di- ameter in the range of from 0.5 m to 8.0 m.
- the reactor Rs may more preferably have an inner diameter which is in the range of from 1.0 m to 5.0 m, more preferably in the range of from 1.5 m to 2.5 m.
- the height of the reactor Rs depends on different factors, such as the type of catalyst, the particle size of the catalyst, the space velocity. The skilled per- son knows how to adapt such parameter.
- the reactor Rs has a height in the range of from 7 to 25 m.
- the reactor may more preferably have a height which is in the range of from 10 to 20 m.
- the reactor Rs is made of corrosion-resistant material, more preferably of iron-based alloys, nickel-based alloys, nickel or nickel-cladded material, more preferably of nickel or nickel- cladded material.
- the means M(i) for introducing and admixing the liquid stream L(i), and preferably a gas stream H(i) as defined in the foregoing, with the gas stream Gp(i) is made of silicon carbide.
- the reaction zone Z(i) comprises, more preferably is, a catalyst bed B(i), wherein the catalyst bed B(i) more preferably is an adiabatic catalyst bed.
- the catalyst bed (reaction zone) operates adiabatically.
- the catalyst bed B(i) has walls which are made of ceramic and metallic materials.
- the at least 50 weight-%, more preferably at least 60 weight-%, of the catalyst bed B(i) is made of ce- ramic material.
- the ceramic material is used for isolation.
- the height of the catalyst bed B(1) depends on different factors, such as the type of catalyst, the particle size of the catalyst, the space velocity. The skilled person knows how to adapt such parameter.
- h(B(1)) is in the range of from 0.05 to 0.5 m, h(B(1)) being the height of the most upstream catalyst bed B(1) of the production unit.
- h(B(1)) can more preferably be in the range of from 0.1 to 0.4 m.
- h(B(1)) being the height of the catalyst bed B(1)
- h(B(2)) being the height of the catalyst bed B(2)
- h(B(3)) being the height of the catalyst bed B(3)
- h(B(4)) being the height of the catalyst bed B(4)
- h(B(5)) being the height of the catalyst bed B(5).
- each of the n serially coupled reaction zones Z(i) is comprised in a respective reactor R(i), wherein the reactor R(i) is connected to the reactor R(i+1) via a pipe.
- the most upstream reactor R(1) comprises an inlet end and an outlet end and the most downstream reactor R(n) comprises an inlet end and an outlet end, wherein the inlet means for passing the gas stream G(0) into the reaction zone Z(i) is located at the inlet end of the reactor R(1) and the outlet means for removing the gas stream Gp(n) from the reaction zone Z(n) is located at the outlet end of the reactor R(n).
- the inner diameter of the reactors R(i) depends on differ- ent factors, such as the type of catalyst, the particle size of the catalyst, the space velocity. The skilled person knows how to adapt such parameter.
- the reactor R(i) has an inner di- ameter in the range of from 0.5 m to 8.0 m.
- the reactor R(i) may more preferably have an inner diameter which is in the range of from 1.0 m to 5.0 m, more preferably in the range of from 1.25 m to 2.75 m.
- the height of the reactors R(i) depends on different fac- tors, such as the type of catalyst, the particle size of the catalyst, the space velocity. The skilled person knows how to adapt such parameter.
- the reactor R(i) has a height in the range of from 0.4 to 10 m.
- the reactor R(i) may more preferably have a height which is in the range of from 0.5 to 8 m.
- the reactor R(i) is made of corrosion-resistant material, more preferably of iron-based alloys, nickel-based alloys, nickel or nickel-cladded material, more preferably of nickel or nickel- cladded material.
- the means M(i) for introducing and admixing the liquid stream L(i), and preferably the gas stream H(i), with the gas stream Gp(i) is located in the reactor R(i).
- the means M(i) is located in the pipes between the reactors R(i).
- the means M(i) is a nozzle, more preferably a spray nozzle or a venturi nozzle, more preferably a spray nozzle. More preferably the means M(i) for introducing and admixing the liquid stream L(i) and the gas stream H(i) with the gas stream Gp(i) is a dual-flow spray nozzle.
- the production unit further comprises, downstream of the means M(i) and upstream of the reactor R(i+1 ), one or more mixing devices, the mixing device being more preferably one or more of a static mixer, a dynamic mixer, an ejector, a venturi nozzle and a spray nozzle, more preferably the mixing device is a static mixer.
- the means M(i) for introducing and admixing the liquid stream L(i), and optionally a gas stream H(i) as defined in the foregoing, with the gas stream Gp(i) is made of silicon carbide.
- the reaction zone Z(i) comprises, more preferably is, a catalyst bed B(i), wherein the catalyst bed B(i) more preferably is an adiabatic catalyst bed. More preferably the catalyst bed B(i) has walls which are made of ceramic and metallic materials. In this context, it is noted that the at least 50 weight-%, more preferably at least 60 weight-%, of the catalyst bed B(i) is made of ceramic material.
- the height of the catalyst bed B(1 ) depends on different factors, such as the type of catalyst, the particle size of the catalyst, the space velocity. The skilled person knows how to adapt such parameter.
- h(B(1)) is in the range of from 0.05 to 0.5 m, h(B(1 )) being the height of the most upstream catalyst bed B(1) of the production unit.
- h(B(1 )) can more preferably be in the range of from 0.1 to 0.4 m.
- h(B(1)) being the height of the catalyst bed B(1 )
- h(B(2)) being the height of the catalyst bed B(2)
- h(B(3)) being the height of the catalyst bed B(3)
- h(B(4)) being the height of the catalyst bed B(4)
- h(B(5)) being the height of the catalyst bed B(5).
- the total volume of the catalyst beds depend on different factors, such as the type of catalyst, the particle size of the catalyst, the space velocity. The skilled person knows how to adapt these parameters.
- the total volume of the catalyst beds B(i) to B(n) is in the range of from 10 to 100 m 3 .
- the total volume of the cata- lyst beds B(i) to B(n) can more preferably be in the range of from 20 to 40 m 3 , more preferably in the range of from 25 to 35 m 3 .
- the production unit is free of heat exchanger between the reaction zones. Indeed, it is preferred that no heat exchanger is present between reactors R(i) and R(i+1). Without wanted to be bound to any theory, it is believed that the liquid stream L(i) permits sufficient cooling of the gas streams comprising chlorine.
- the present invention further relates to a use of a production unit according to the present in- vention for the continuous production of chlorine.
- the present invention further relates to a process for preparing phosgene comprising preparing chlorine according to the process of the present invention; reacting the obtained chlorine with carbon monoxide in the presence of a catalyst, in gas phase, obtaining phosgene.
- the catalyst C(i) is selected from the group consisting of a Ru-containing catalyst, a Ce-containing catalyst, a Cu-containing catalyst and a mixture of two or more thereof, preferably is selected from the group con- sisting of a Ru-containing catalyst, a Ce-containing catalyst and a Cu-containing catalyst, more preferably is a Ru-containing catalyst; wherein the catalyst C(i) preferably comprises, more preferably consists of, particles hav- ing an average particle size in the range of from 1 to 10 mm, preferably in the range of from 1 to 4 mm.
- each of the n serially coupled reaction zones Z(i) comprises, preferably is, a catalyst bed B(i), wherein V(B(i+1 )) > V(B(i)), preferably V(B(i+1)) > V(B(i)), V(B(i+1 )) being the volume of the catalyst bed B(i+1) and V(B(i)) being the volume of the catalyst bed B(i).
- liquid stream L(i) has tem- perature T(L(i)) in the range of from 10 to 60 °C, preferably in the range of from 15 to 30 °C, wherein the liquid stream L(i) preferably consists of HCI and water.
- a production unit for carrying out the process for preparing a gas stream G(n) comprising Cl 2 according to any one of embodiments 1 to 38, the apparatus comprising - n serially coupled reaction zones Z(i), i 1...n, n ⁇ 2, wherein each reaction zone Z(i) com- prises -- a catalyst C(i); - an inlet means for passing the gas stream G(0) into the reaction zone Z(i); - an outlet means for removing the gas stream Gp(i) from Z(i);
- reaction zone Z(i) comprises, prefera- bly is, a catalyst bed B(i) which comprises the catalyst C(i).
- the catalyst C(i) is se- lected from the group consisting of a Ru-containing catalyst, a Ce- containing catalyst, a Cu- containing catalyst and a mixture of two or more thereof, preferably is selected from the group consisting of a Ru- containing catalyst, a Ce- containing catalyst and a Cu- con- taining catalyst, more preferably is a Ru-containing catalyst.
- each of the n serially coupled reac- tion zones Z(i) is separated from each other by a space T(i) in the reactor Rs, wherein the means M(i) for introducing and admixing the liquid stream L(i), and preferably a gas stream H(i) as defined in any one of embodiments 23 to 26, with the gas stream Gp(i) is located in T(i).
- the means M(i) is a nozzle, more prefera- bly a spray nozzle or a venturi nozzle, more preferably a spray nozzle; wherein more preferably the means M(i) for introducing and admixing the liquid stream L(i) and the gas stream H(i) with the gas stream Gp(i) is a dual-flow spray nozzle.
- the production unit of embodiment 49 or 50 further comprising in the space T(i), one or more mixing devices, the mixing device being preferably one or more of a static mixer, a dynamic mixer, an ejector, a venturi nozzle and a spray nozzle, more preferably the mix- ing device is a static mixer.
- reaction zone Z(i) comprises, preferably is, a catalyst bed B(i), wherein the catalyst bed B(i) preferably is an adiabatic catalyst bed, wherein the catalyst bed B(i) more preferably has walls which are made of ceramic and metallic materials.
- each of the n serially coupled reaction zones Z(i) is comprised in a respective reactor R(i), wherein the reactor R(i) is connected to the reactor R(i+1) via a pipe.
- reactor R(i) is made of corrosion-resistant material, more preferably of iron-based alloys, nickel-based alloys, nickel or nickel-cladded material, more preferably of nickel or nickel-cladded material.
- the production unit of embodiment 66 further comprising, downstream of the means M(i) and upstream of the reactor R(i+1 ), one or more mixing devices, the mixing device prefer- ably being one or more of a static mixer, a dynamic mixer, an ejector, a venturi nozzle and a spray nozzle, more preferably the mixing device being a static mixer.
- the mixing device prefer-ably being one or more of a static mixer, a dynamic mixer, an ejector, a venturi nozzle and a spray nozzle, more preferably the mixing device being a static mixer.
- a process for preparing phosgene comprising preparing chlorine according to the process of any one of embodiments 1 to 38; reacting the obtained chlorine with carbon monoxide in the presence of a catalyst, in gas phase, obtaining phosgene.
- X is a chemical element and A, B and C are concrete elements such as Li, Na, and K, or X is a temperature and A, B and C are concrete temperatures such as 10 °C, 20 °C, and 30 °C.
- X is one or more of A and B” disclosing that X is either A, or B, or A and B, or to more specific realizations of said feature, e.g. “X is one or more of A, B, C and D”, disclosing that X is either A, or B, or C, or D, or A and B, or A and C, or A and D, or B and C, or B and D, or C and D, or A and B and C, or A and B and D, or B and C and D, or A and B and C and D, or A and B and C and D, or A and B and C and D, or A and B and C and D, or A and B and C and D.
- the particle size can be defined as the diameter of a sphere with equal volume. Particles are normally uniform and average dimensions can be derived from microscopic pictures of the par- ticles.
- Reference Example 1 Process for preparing chlorine not according to the present inven- tion
- Figure 1 shows a system according to Reference Example 1. The system was described using thermodynamic simulations coupled with the known equilibrium of Deacon reaction. Thereby it was assumed, that in each separate adiabatic catalyst bed the system runs into equilibrium.
- the pressure not given in the above mentioned example, was chosen at 1 bara.
- the feeds (amount) were the same like in example as well as the inlet temperatures of the single reactors. The results are shown in table below.
- Example 1 Process for preparing chlorine according to the present invention
- Example 2 Process for preparing chlorine according to the present invention
- a tray reactor contains 5 catalyst beds in series in a single reactor.
- Mixed HCI feeds as de- scribed in Table 3 are fed in between the catalyst beds.
- the system was described using ther- modynamic simulations coupled with the known equilibrium of Deacon reaction. Thereby it was assumed, that in each separate adiabatic catalyst bed the system runs into equilibrium.
- Mixed streams of gaseous HCI (25°C) and liquid, aqueous HCI (30 wt% HCI, 25°C) were introduced after catalyst beds 1 to 4.
- With mixing of the reaction mass of the upstream reactor with the mixed HCI stream the temperature is decreased due to evaporation of liquid HCI/water and heat-up of both HCI feed streams.
- the conversion of added HCI leads to adiabatic temperature rise as known.
- the reactor is illustrated in Figure 4 and a catalyst bed is illustrated in Figure 5.
- Figure 1 shows a set-up of 6 reactors in series according to the prior art.
- the production unit comprises reactors 1-6 arranged in series with intermediate heat exchangers a-f, positioned after each of the reactors 1-6 respectively.
- HCl (feed 1) and O 2 (feed 2) are introduced continuously at the inlet end of the reactor 1.
- Figure 2 shows a set-up of 5 reactors with no intermediate heat exchangers ( Figure 2(a)). This production unit is according to a preferred embodiment of the present invention.
- the production unit comprises five reactors R(1), R(2), R(3), R(4) and R(5), wherein the reactor R(1) is positioned upstream of the reactor R(2), the reactor R(2) is posi- tioned upstream of the reactor R(3), the reactor R(3) is positioned upstream of the reactor R(4) and the reactor R(4) is positioned upstream of the reactor R(5).
- the re- actor R(1) comprises an inlet end and an outlet end, wherein at the inlet end, the gas stream G(0), comprising HCl and O 2 , is introduced in the reaction zone Z(1) comprising, preferably consisting of a catalyst bed B(1).
- the catalyst bed B(1) com- prises the catalyst C(1).
- the gas stream G(0) reacts with the catalyst C(1) in the catalyst bed B(1) to obtain a gas stream GP(1) comprising Cl2, O2 and one or more of H 2 O and HCl, preferably Cl 2 , O 2 , H 2 O and HCl.
- Said gas stream is removed from the reaction zone Z(1) in a downstream portion of the reactor R(1) where it is mixed with a liquid stream L(1), comprising HCl and H2O, and a gas stream H(1) compris- ing HCl, the gas stream G(1) is obtained and removed from the reactor R(1) through a pipe.
- L(1) and H(1) are introduced into the downstream portion of the reactor R(1) via a means M(1), preferably a multi-component nozzle like the one described in Figure 2b (type of spray nozzle).
- the gas stream G(1) is optionally passed through one or two mixing devices, preferably static mixers, prior to entering the reactor R(2) at its inlet end.
- the gas stream G(1) comprising Cl 2 , O 2 , HCl and H 2 O, is introduced in the reaction zone Z(2) comprising, preferably consisting of a catalyst bed B(2).
- the catalyst bed B(2) comprises the catalyst C(2).
- the gas stream G(1) reacts with the catalyst C(2) in the catalyst bed B(2) to obtain a gas stream GP(2) comprising Cl2, O2 and one or more of H2O and HCl, preferably Cl2, O2, H2O and HCl.
- Said gas stream is removed from the reaction zone Z(2) in a downstream portion of the reac- tor R(2) where it is mixed with a liquid stream L(2), comprising HCl and H 2 O, and a gas stream H(2) comprising HCl, the gas stream G(2) is obtained and removed from the reactor R(2) through a pipe.
- L(2) and H(2) are introduced into the downstream portion of the reactor R(2) via a means M(2), preferably a multi-component nozzle like the one described in Figure 2b.
- the gas stream G(2) is optionally passed through one or two mixing devices, preferably static mixers, prior to entering the re- actor R(3) at its inlet end.
- the gas stream G(2) comprising Cl 2 , O 2 , HCl and H 2 O, is introduced in the reaction zone Z(3) comprising, preferably consisting of a catalyst bed B(3).
- the catalyst bed B(3) comprises the catalyst C(3).
- the gas stream G(2) reacts with the catalyst C(3) in the catalyst bed B(3) to obtain a gas stream GP(3) comprising Cl 2 , O 2 and one or more of H 2 O and HCl, preferably Cl 2 , O 2 , H 2 O and HCl.
- Said gas stream is removed from the reaction zone Z(3) in a downstream por- tion of the reactor R(3) where it is mixed with a liquid stream L(3), comprising HCl and H2O, and a gas stream H(3) comprising HCl, the gas stream G(3) is obtained and removed from the reactor R(3) through a pipe.
- L(3) and H(3) are introduced into the downstream portion of the reactor R(3) via a means M(3), preferably a multi- component nozzle like the one described in Figure 2b.
- the gas stream G(3) is op- tionally passed through one or two mixing devices, preferably static mixers, prior to entering the reactor R(4) at its inlet end.
- the gas stream G(3) comprising Cl 2 , O 2 , HCl and H 2 O, is introduced in the reaction zone Z(4) comprising, preferably consist- ing of a catalyst bed B(4).
- the catalyst bed B(4) comprises the catalyst C(4).
- the gas stream G(3) reacts with the catalyst C(4) in the catalyst bed B(4) to obtain a gas stream GP(4) comprising Cl 2 , O 2 and one or more of H 2 O and HCl, preferably Cl 2 , O 2 , H 2 O and HCl.
- Said gas stream is removed from the reaction zone Z(4) in a downstream portion of the reactor R(4) where it is mixed with a liquid stream L(4), comprising HCl and H 2 O, and a gas stream H(4) comprising HCl, the gas stream G(4) is obtained and removed from the reactor R(4) through a pipe.
- L(4) and H(4) are introduced into the downstream portion of the reactor R(4) via a means M(4), preferably a multi-component nozzle like the one described in Figure 2b.
- the gas stream G(4) is optionally passed through one or two mixing devices, preferably stat- ic mixers, prior to entering the reactor R(5) at its inlet end.
- the gas stream G(4) comprising Cl2, O2, HCl and H2O, is introduced in the reaction zone Z(5) comprising, preferably consisting of a catalyst bed B(5).
- the catalyst bed B(5) comprises the catalyst C(5).
- the gas stream G(4) reacts with the catalyst C(5) in the catalyst bed B(5) to obtain a final gas stream G(5) comprising Cl2, O2 and one or more of H2O and HCl, preferably Cl 2 , O 2 , H 2 O and HCl, which is removed from the reactor R(5) at its outlet end through a pipe, wherein c G(5) (Cl 2 ) > c G(4) (Cl 2 ) > c G(3) (Cl 2 ) > c G(2) (Cl 2 ) > c G(1) (Cl 2 ), c G(5) (Cl 2 ) being the Cl 2 concentration in G(5), c G(4) (Cl 2 ) being the Cl 2 con- centration in G(4), cG(3)(Cl2) being the Cl2 concentration in G(3), c
- FIG. 2 shows one of the means M(i), in particular M(4), wherein L(i) and H(i), in particular wherein L(4) and H(4), are introduced tangentially via a multicom- ponent nozzle to the reactor downstream of the catalyst bed to be mixed with GP(i), in particular GP(4), the means M(4) preferably being a multicomponent nozzle.
- Figure 3 shows one of the reactors of the set-up illustrated in Figure 2(a).
- Figure 3 shows a reactor R(2) comprising an inlet end and an outlet end, wherein at the inlet end of the reactor R(2) and upstream of the reaction zone Z(2) comprising the catalyst bed B(2), the reactor R(2) comprises a gas distributor D(2) for distributing the gas stream G(1) entering the reactor into the reaction zone Z(2).
- the reactor R(2) has walls sur- rounding (see d2 in Figure 3) the catalyst bed B(2) which can be made of an insulat- ing material, preferably ceramic material.
- a removable support grid c2 can preferably be placed.
- the gas stream G(1) then re- acts with the catalyst C(2) (not shown) to form the gas stream GP(2) which is re- moved from the catalyst bed to be mixed with the liquid stream L(2) and the gas stream H(2) which were introduced in the reactor R(2) via a means M(2), preferably one or more tubes with openings at the end directed tangentially related to sym- metry axis of R(2).
- the three streams are then mixed in the downstream part of the reactor R(2) obtaining the gas stream G(2).
- the gas stream G(2) is passed through a pipe and optionally two mixing devices, such as static mixers.
- Figure 4 shows a set-up of 5 catalyst beds in a single reactor. This production unit is accord- ing to a preferred embodiment of the present invention.
- the production unit com- prises five reaction zones Z(1), Z(2), Z(3), Z(4) and Z(5) disposed serially in a single reactor Rs, wherein the reaction zone Z(1) is positioned upstream of the reaction zone Z(2), the reaction zone Z(2) is positioned upstream of the reaction zone Z(3), the reaction zone Z(3) is positioned upstream of the reaction zone Z(4) and the re- action zone Z(4) is positioned upstream of the reaction zone Z(5).
- the reactor Rs comprises an inlet end and an outlet end, wherein at the inlet end, the gas stream G(0), comprising HCl and O 2 , is introduced in the reaction zone Z(1) comprising, preferably consisting of a catalyst bed B(1).
- the catalyst bed B(1) comprises the catalyst C(1).
- the gas stream G(0) reacts with the catalyst C(1) in the catalyst bed B(1) to obtain a gas stream GP(1) comprising Cl 2 , O 2 and one or more of H 2 O and HCl.
- Said gas stream is removed from the reaction zone Z(1) in a downstream por- tion of the reactor Rs, named T(1), where it is mixed with a liquid stream L(1), com- prising HCl and H 2 O, and a gas stream H(1) comprising HCl, the gas stream G(1) is obtained and removed from T(1) to enter the reaction zone Z(2) at its inlet end.
- the gas stream G(1), comprising Cl2, O2, HCl and H2O is introduced in the reaction zone Z(2) comprising, preferably consisting of a catalyst bed B(2).
- the catalyst bed B(2) comprises the catalyst C(2).
- the gas stream G(1) reacts with the catalyst C(2) in the catalyst bed B(2) to obtain a gas stream GP(2) comprising Cl 2 , O 2 and one or more of H2O and HCl.
- Said gas stream is removed from the reaction zone Z(2) in a downstream portion of the reactor R(2), named T(2), where it is mixed with a liquid stream L(2), comprising HCl and H 2 O, and a gas stream H(2) comprising HCl, the gas stream G(2) is obtained and removed from T(2) to enter the reaction zone Z(3) at its inlet end.
- the gas stream G(2) comprising Cl 2 , O 2 , HCl and H 2 O, is introduced in the reaction zone Z(3) comprising, preferably consisting of a catalyst bed B(3).
- the catalyst bed B(3) comprises the catalyst C(3).
- the gas stream G(2) reacts with the catalyst C(3) in the catalyst bed B(3) to obtain a gas stream GP(3) comprising Cl 2 , O 2 and one or more of H 2 O and HCl.
- Said gas stream is removed from the reac- tion zone Z(3) in a downstream portion of the reactor R(3), named T(3), where it is mixed with a liquid stream L(3), comprising HCl and H2O, and a gas stream H(3) comprising HCl, the gas stream G(3) is obtained and removed from T(3) to enter the reaction zone Z(4) at its inlet end.
- the gas stream G(3) comprising Cl 2 , O 2 , HCl and H2O, is introduced in the reaction zone Z(4) comprising, preferably consisting of a catalyst bed B(4).
- the catalyst bed B(4) comprises the catalyst C(4).
- the gas stream G(3) reacts with the catalyst C(4) in the catalyst bed B(4) to obtain a gas stream GP(4) comprising Cl 2 , O 2 and one or more of H 2 O and HCl.
- Said gas stream is removed from the reaction zone Z(4) in a downstream portion of the reactor R(4), named T(4), where it is mixed with a liquid stream L(4), comprising HCl and H2O, and a gas stream H(4) comprising HCl, the gas stream G(4) is obtained and re- moved from T(4) to enter the reaction zone Z(5) at its inlet end.
- the gas stream G(4), comprising Cl 2 , O 2 , HCl and H 2 O is introduced in the reaction zone Z(5) com- prising, preferably consisting of a catalyst bed B(5).
- the catalyst bed B(5) comprises the catalyst C(5).
- the gas stream G(4) reacts with the catalyst C(5) in the catalyst bed B(5) to obtain a final gas stream G(5) comprising Cl 2 , O 2 and one or more of H2O and HCl which is removed from the reactor Rs at its outlet end through a pipe, wherein cG(5)(Cl2) > cG(4)(Cl2) > cG(3)(Cl2) > cG(2)(Cl2) > cG(1)(Cl2), cG(5)(Cl2) being the Cl2 concentration in G(5), c G(4) (Cl 2 ) being the Cl 2 concentration in G(4), c G(3) (Cl 2 ) being the Cl 2 concentration in G(3), c G(2) (Cl 2 ) being the Cl 2 concentration in G(2) and cG(1)(Cl2) being the Cl2 concentration in G(1).
- FIG. 5 shows a possible design of T(2) of the single reactor Rs shown in Figure 4.
- Ax- isymmetric guiding plates are introduced to first drive GP(2) to the middle of the re- actor followed by another plate to direct the flow radially outwards.
- the streams L(2) and H(2) are introduced into GP(2) via several dual-flow nozzles. This mixture is redirected radially inwards by another plate and mixing elements in this section ensure complete mixing of GP(2), L(2) and H(2) to get G(2).
- G(2) is dis- tributed finally via distribution plates (Orifice plates) equally across the reactor cross area before entering Z(3) .
- Orifice plates f2 can be added for the distributing GP(2) equally into the following catalyst bed B(3) not shown here.
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CN202280077412.8A CN118284576A (en) | 2021-11-23 | 2022-11-22 | Method for producing a gas flow containing chlorine |
EP22821453.2A EP4436916A1 (en) | 2021-11-23 | 2022-11-22 | Process for preparing a gas stream comprising chlorine |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2542961A (en) * | 1948-11-08 | 1951-02-20 | Shell Dev | Chlorine production |
US20070274901A1 (en) * | 2006-05-23 | 2007-11-29 | Bayer Material Science Ag | Processes and apparatus for the production of chlorine by gas phase oxidation |
US20100260660A1 (en) * | 2007-07-13 | 2010-10-14 | Bayer Technology Services Gmbh | Method for producing chlorine by multi step adiabatic gas phase oxidation |
US20110182801A1 (en) * | 2008-10-09 | 2011-07-28 | Bayer Technology Services Gmbh | Multi-stage method for the production of chlorine |
US20120213693A1 (en) * | 2011-02-18 | 2012-08-23 | Basf Se | Use of liquid hydrogen chloride as refrigerant in processes for preparing chlorine |
-
2022
- 2022-11-22 WO PCT/EP2022/082760 patent/WO2023094364A1/en active Application Filing
- 2022-11-22 CN CN202280077412.8A patent/CN118284576A/en active Pending
- 2022-11-22 EP EP22821453.2A patent/EP4436916A1/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2542961A (en) * | 1948-11-08 | 1951-02-20 | Shell Dev | Chlorine production |
US20070274901A1 (en) * | 2006-05-23 | 2007-11-29 | Bayer Material Science Ag | Processes and apparatus for the production of chlorine by gas phase oxidation |
WO2007134771A1 (en) | 2006-05-23 | 2007-11-29 | Bayer Materialscience Ag | Method for producing chlorine by gas phase oxidation |
US20100260660A1 (en) * | 2007-07-13 | 2010-10-14 | Bayer Technology Services Gmbh | Method for producing chlorine by multi step adiabatic gas phase oxidation |
US20110182801A1 (en) * | 2008-10-09 | 2011-07-28 | Bayer Technology Services Gmbh | Multi-stage method for the production of chlorine |
US20120213693A1 (en) * | 2011-02-18 | 2012-08-23 | Basf Se | Use of liquid hydrogen chloride as refrigerant in processes for preparing chlorine |
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