EP1682616A2 - Method for converting hydrogenous gaseous flows arising from chemical reactor units using hydrogen - Google Patents
Method for converting hydrogenous gaseous flows arising from chemical reactor units using hydrogenInfo
- Publication number
- EP1682616A2 EP1682616A2 EP04805754A EP04805754A EP1682616A2 EP 1682616 A2 EP1682616 A2 EP 1682616A2 EP 04805754 A EP04805754 A EP 04805754A EP 04805754 A EP04805754 A EP 04805754A EP 1682616 A2 EP1682616 A2 EP 1682616A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrogen
- unit
- pressure
- effluent
- rich
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 178
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 178
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000000126 substance Substances 0.000 title description 2
- 239000007789 gas Substances 0.000 claims abstract description 80
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 238000010926 purge Methods 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 28
- 150000002431 hydrogen Chemical class 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 20
- 238000001179 sorption measurement Methods 0.000 claims description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 14
- 230000006837 decompression Effects 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 150000003738 xylenes Chemical class 0.000 claims description 5
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 3
- 238000009434 installation Methods 0.000 abstract description 2
- 239000003463 adsorbent Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000004064 recycling Methods 0.000 description 8
- 239000002912 waste gas Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- RJMZIUFNDNYWDU-UHFFFAOYSA-N 3-chloro-2-hydroxy-5-phenylbenzoic acid Chemical compound ClC1=C(O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1 RJMZIUFNDNYWDU-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000003348 petrochemical agent Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite 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
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
- C07C4/12—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene
- C07C4/14—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene splitting taking place at an aromatic-aliphatic bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/006—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenation of aromatic hydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
- C07C6/123—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of only one hydrocarbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/16—Hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
- B01D2259/4002—Production
- B01D2259/40022—Production with two sub-steps
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
- C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/048—Composition of the impurity the impurity being an organic compound
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- the present invention relates to a process for recovering hydrogen-based effluents from chemical reaction units using hydrogen.
- Many petrochemical processes use a hydrogenation step in which hydrogen-rich gases are used. This is the case for the synthesis of large intermediaries bringing together products with high chemical reactivity directly derived from petroleum hydrocarbons.
- the main intermediaries involving important hydrogen-rich gases are:
- the make-up hydrogen must be of high purity in order to limit the losses of hydrogen by purging. Therefore, during these different processes, it is necessary to have recourse not only to high-purity make-up hydrogen but also to the elimination of a gas still rich in hydrogen by purging the recycling loop. In many industrial cases, the The performance of petrochemical units, and in particular the grades of the products obtained, are limited by the purity of the hydrogen supplied. Furthermore, under the effect of recycling gas purges, hydrogen consumption increases with the decrease in purity of the make-up gas; this results in additional operating costs for the unit.
- a first solution consists in purging a fraction of the recycling gas in order to limit its inert concentrations (light hydrocarbons, traces of reagents or hydrogenated product, ).
- this high pressure purge has several drawbacks:
- a third solution as described in US Patent 6,179,996 involves Jraiter effluent rich in hydrogen by a reverse selectivity membrane.
- the advantage of this type of membrane compared to hydrogen selective membranes is to keep the hydrogen under pressure.
- a compromise must be found between the desired hydrogen purity and the yield.
- the gaseous effluent for the hydrogenation of benzene to cyclohexane may be treated to pass from a purity of 75% by volume of hydrogen to 90% provided that approximately 30% of the hydrogen treated is lost.
- the transition from a hydrogen purity of 83% by volume to hydrogen to 95% results in a loss of almost 40% of the hydrogen treated.
- the purity of the hydrogen in the make-up gas required by each petrochemical process is most often greater than 99% by volume. However, there is not always a source of hydrogen available near the process (catalytic reforming, steam cracking, ...) and the hydrogen must be supplied at the purity required by dedicated producers. If there is a source of hydrogen available nearby, the hydrogen produced is purified to meet the make-up gas specifications. Make-up gas purification techniques are then similar to those previously mentioned for recycling gas. The two main ways of purifying a hydrogen-rich gas remain adsorption (PSA) or cryogenic separation followed by a methanation step since the compounds CO and C0 2 are poisons of the majority of the hydrogenation catalysts used. in petrochemicals.
- PSA adsorption
- cryogenic separation followed by a methanation step since the compounds CO and C0 2 are poisons of the majority of the hydrogenation catalysts used. in petrochemicals.
- An object of the present invention is to solve the above problems and more particularly to reduce the overall hydrogen consumption of petrochemical processes using a hydrogenation step. Another object is to drain or even increase the processing capacity of certain petrochemical processes using a hydrogenation step, by purifying the main make-up gas and / or by recovering the hydrogen molecules lost in the purges.
- the invention relates to a process for the recovery of gaseous effluents based on hydrogen from at least two reaction units RI and R2 consuming hydrogen, the unit R2 producing a gaseous effluent rich in hydrogen at a pressure P and possibly a gaseous effluent poor in hydrogen, the unit R1 producing at least one gaseous effluent poor in hydrogen, in which the following steps are implemented:
- step a all of the hydrogen-poor gaseous effluents from R1 and optionally from R2 are mixed so that the mixture obtained has a pressure P,
- the mixture of all the hydrogen-poor gaseous effluents from R1 and possibly R2 adjusted to the pressure P is treated during step a) in a gas separation unit U fed by the hydrogen-rich gaseous effluent from unit R2 so as to provide, at a first outlet, an enriched stream having a hydrogen concentration greater than that of the hydrogen-rich gaseous effluent from unit R2 and, in a second outlet, a residual stream, - during step c), the enriched stream from the first outlet of unit U is reinjected into a reaction unit R3 consuming hydrogen.
- the invention consists in installing a gas separation unit U between the hydrogen gas networks of several reaction units using hydrogen such as units at a petrochemical site.
- the gas separation unit U treats the hydrogenated gases of hydrogen purities different from the units R1 and R2 in order to supply the reaction unit R3 with high purity hydrogen or in order to purify the recycle hydrogen from this reaction unit R3 without loss of yield.
- the invention makes it possible to achieve the objectives set by using hydrogenated effluents from several reaction units consuming hydrogen, and in particular at least two reaction units R1 and R2.
- reaction unit is meant a production site implementing a reaction, the reaction unit can be both the reactor and a set of tanks collecting the different effluents from a production. These units must be chosen so that their effluents have certain characteristics, it being understood that according to the method of the invention, it is possible to treat only part of each of these effluents.
- the two units R1 and R2 must each produce at least one effluent comprising hydrogen at different concentrations.
- the R2 unit produces a hydrogenated effluent having a higher hydrogen concentration than all the other hydrogenated effluents from the R1 and R2 units. Therefore, by "hydrogen-rich effluent", is meant the effluent from the reaction units which has the highest hydrogen purity. Generally, this hydrogen-rich effluent has a hydrogen concentration of between 50 and 99% by volume.
- This hydrogen-rich effluent from unit R2 can have a pressure P of at least 5 bars, preferably at least 15 bars.
- the other gaseous effluents from units R1 and R2 are said to be "poor in hydrogen" which means that, for each one, the value of their hydrogen concentration is at least 10% lower than the value of the hydrogen concentration of l effluent rich in hydrogen, preferably lower by at least 15% and even more preferably lower by 15 to 50%.
- R2 produces at least one gaseous effluent poor in hydrogen, preferably this gaseous effluent poor in hydrogen has a pressure close to the pressure P.
- other gaseous effluents poor in additional hydrogen can be produced either by R1 or by R2.
- the pressure of the effluent poor in hydrogen or of the mixture of effluents poor in hydrogen is adjusted so that it is close to P. If only R1 produces an effluent poor in hydrogen, the pressure can be adjusted by compression or pressure drop. If R1 and / or R2 produce several effluents poor in hydrogen, they are all mixed so that their mixture has a pressure equal to P. To obtain such a pressure, it may be necessary to compress some of the effluents poor in hydrogen and a pressure lower than the pressure P. However, this compression can be optional if at least one of the effluents poor in hydrogen presents a pressure higher than P.
- the invention covers the process where the hydrogen-poor effluent from R2 or the mixture of hydrogen-poor effluents from R1 and possibly R2 already have a pressure close to P; in these cases, no pressure adjustment is necessary.
- the invention makes it possible to enrich the hydrogen-rich effluent from R2 so that it can be used in a reaction unit consuming hydrogen. This enrichment is obtained by depletion of effluents poor in hydrogen.
- the unit thus produces the enriched flow generally having a hydrogen purity greater than 99% by volume, and the unit also produces a residual flow of low hydrogen purity and low pressure which can be sent into a fuel gas network.
- the pressure and the concentration of hydrogen in the waste stream are respectively lower than the pressure and hydrogen concentration values of all the effluents entering the unit U.
- the reaction unit R3 consuming l hydrogen can be the reaction unit R2.
- the invention makes it possible both to recover the gaseous effluent rich in hydrogen coming from the reaction unit R2 and to enrich it in hydrogen using the gaseous effluent poor in hydrogen coming from R1 of so as to be able to recycle this enriched effluent in the R2 unit.
- the gas separation unit (U) is preferably of the adsorption type.
- the gas separation unit (U) is a pressure modulated adsorption unit (PSA) associated with an integrated compressor, in which a modulation cycle is implemented for each adsorber of the unit.
- PSA pressure modulated adsorption unit
- pressure comprising a succession of phases which define phases of adsorption, decompression, purging and pressure rise, such as: - during the adsorption phase:.
- the gaseous effluent rich in hydrogen and having a pressure P coming from the unit R2 is brought into contact with the bed of the adsorber, and. during a second step, the pressure mixture P consisting of: is introduced into contact with the bed of the adsorber.
- the mixture of all the gaseous effluents poor in hydrogen coming from R1 and possibly from R2 adjusted to the pressure P during step a) is introduced into contact with the bed of the adsorber.
- PSA recycle gas so as to adsorb different compounds from hydrogen and produce at the head of the adsorber bed the enriched stream having a hydrogen concentration higher than that of the gaseous effluent rich in hydrogen from the R2 unit, - during the decompression phase, the residual PSA flow is produced,
- the PSA recycle gas is composed of the waste stream compressed at pressure P, and / or the purge gas compressed at pressure P.
- the gaseous effluent rich in hydrogen from R2 is brought into contact with a first bed of PSA adsorbent and in a second phase, it is the mixture of the other hydrogen-poor effluent (s) of units R1 and R2 and of PSA recycle gas which are brought into contact with this first set of adsorbent.
- the recycle gas can consist of two gases, alone or as a mixture: the waste gas from the PSA which has been compressed, and the purge gas from the PSA which has been compressed.
- the purge gas is the purge gas and not the waste gas.
- the waste gas comes from the final stage of the PSA decompression phase and is partly compressed by the compressor integrated in the PSA of the CPSA treatment device while the purge gas comes from the PSA purge phase and is partly compressed by the same compressor integrated in the PSA before being used as recycle gas.
- These two gases both include hydrogen and essentially impurities.
- the hydrogen-poor effluent (s) having very low pressures can be mixed with the residual gas or the purge gas, then this mixture can be compressed by the compressor integrated in the PSA up to the pressure P. If an effluent poor in hydrogen present a pressure higher than P, the compression of other effluents poor in hydrogen can be avoided; in this case, only the waste gas or the purge gas is compressed to form the recycle gas.
- the introduction into the bed of the adsorbent of all these gases mixed at the pressure P allows their reprocessing. During the adsorption phase, the gaseous effluents are introduced into the lower part of the bed in the so-called co-current direction.
- the most adsorbable compounds, different from H 2 , adsorb on the adsorbent and a gas essentially comprising hydrogen is produced at the pressure P reduced by about one bar of loss. dump.
- the hydrogen produced is generally of a purity greater than at least 99% by mole, preferably greater than at least 99.5%. This hydrogen can therefore be used in another hydrogenation reaction unit such as R3.
- the adsorbent of the PSA beds must in particular allow the adsorption and the desorption of the impurities.
- the adsorbent bed is generally composed of a mixture of several adsorbents, said mixture comprising for example at least two adsorbents chosen from: active charcoals, silica gels, aluminas or molecular sieves.
- the silica gels must have a pore volume of between 0.4 and 0.8 cm 3 / g and a mass area greater than 600 m 2 / g.
- the aluminas have a pore volume greater than 0.2 cnrrVg and a mass area greater than 220 m 2 / g.
- each bed of PSA adsorbent is composed of at least three layers of adsorbents of different natures.
- Each PSA adsorbent bed can comprise: in the lower part a protective layer composed of alumina and / or silica gel surmounted by a layer of activated carbon and / or carbon molecular sieve and optionally in the upper part of a layer of molecular sieve.
- the proportions vary according to the nature of the gas mixture to be treated (in particular according to its percentages of CH 4 and of C 3+ hydrocarbons).
- a gaseous mixture devoid of water comprising 75% by mole of H 2 , 5% of C 3 + and 20% of light hydrocarbons (C ⁇ -C 2 ), of CO and of N 2 can be treated with an adsorption unit whose beds comprise at least 10% by volume of alumina and 15% by volume of silica gel in a low bed, the complement being obtained by activated carbon.
- waste gas is produced. This production of the waste gas can be obtained by counter-current decompression initiated at a pressure below P.
- This waste gas includes the impurities and has a hydrogen concentration lower than all the effluents from R1 and R2.
- This waste gas can be removed from the process and burned or reused as recycle gas in the CPSA as indicated above.
- the low cycle pressure having been reached, a purge phase is carried out to finalize the regeneration of the adsorber.
- a gas is introduced against the current in the adsorber and a purge gas is produced.
- the gas introduced against the current into the adsorber during the purge phase is a gas flow originating from one of the stages of the decompression phase.
- Purge gas is generally used as recycle gas after recompression.
- the pressure of the adsorber is increased by introducing, against the current, a gas stream comprising hydrogen such as the gas produced during different stages of the decompression phase.
- CPSA pressure-modulated adsorption unit associated with an integrated compressor
- the invention can be implemented by combining the different units R1, R2 and R3 which can be found on the same site.
- the invention particularly relates to the case where the unit R1 is the hydrogenation unit of benzene for the synthesis of cyclohexane, the unit R2 is the hydrogenation unit of phenol for the synthesis of ⁇ -caprolactam and R3 is the unit of synthesis of a hydroxylamine, the hydrogenation of phenol and the synthesis of hydroxylamine being two stages in the synthesis of caprolactam.
- the invention can be implemented with several R1 units and one R2 unit.
- the invention thus relates to the case where there are two reaction units R1, one being a unit for hydrodealkylation of toluene and the other a unit for producing cyclohexane, and unit R2 is a unit, for hydrodisproportionation of xylenes or toluene.
- FIG. 1 illustrates a particular implementation of the method according to the invention.
- two reaction units using hydrogen R1 and R2 exist on the illustrated petrochemical site. They are supplied with hydrogen 2, 3 by a general and pure source of hydrogen 1.
- - R2 produces two effluents comprising hydrogen: effluent 6, which is rich in hydrogen and has a pressure P, and the effluent 7, which is poor in hydrogen and has a pressure less than P
- - R1 produces two effluents comprising hydrogen: effluent 5, which is poor in hydrogen and has a pressure P
- the effluent 4 which is poor in hydrogen and has a pressure lower than P.
- These four hydrogenated effluents are treated by the separation unit U, which is the combination of a PSA and a compressor .
- the hydrogen-rich effluent 6 is introduced at the top of the PSA, the impurities which it contains are eliminated.
- PSA purge gas 10 is mixed with effluents 7 and 4, which are poor in hydrogen and have a pressure lower than P.
- the mixture of these three effluents 10, 4 and 7 is optionally compressed by the compressor of unit U to the pressure P and the compressed mixture is mixed with effluent 5 from unit R1 so that the mixture of effluents 4, 5 and 7 and purge gas 10 has a pressure P and is treated with PSA during one of the stages of the adsorption phase.
- PSA produces stream 9 which has a higher hydrogen concentration than effluent 6 and a pressure close to P.
- This stream 9 is used in a reaction unit R3 with or without supplementing the source of hydrogen of high purity 1.
- the PSA also produces a residual stream 8 containing the impurities of the various hydrogenated effluents of the reaction units R1 and R2 and of low pressure.
- FIG. 2 illustrates a particular implementation of the variant of the method according to the invention.
- R11 and R12 are equivalent: they are supplied by a source rich in hydrogen and produce hydrogenated effluents, which supply the unit U.
- R11 is supplied with hydrogen 21 by a general and pure source of hydrogen 1.
- R12 is supplied with hydrogen 22 by source 1 also.
- the general source 1 can also supply the reaction unit R2.
- - R2 produces an effluent comprising hydrogen: it is effluent 6, which is rich in hydrogen and has an initial pressure P
- - R11 produces two effluents comprising hydrogen: effluent 51, which is poor in hydrogen and has a pressure greater than or equal to P
- effluent 41 which i is poor in hydrogen and has a pressure less than P
- - R12 produces two effluents comprising hydrogen: effluent 52, which is poor in hydrogen and has a pressure greater than or equal to P
- effluent 42 which is poor in hydrogen and has a pressure less than P.
- At least one of the effluents 51 and / or 52 may have a pressure greater than P; in this case, the use of the compressor may not be essential if the simple mixing of effluents 41, 42, 51, 52 and purge 10 allows a direct mixture to be obtained at pressure P.
- This mixture of effluents 41, 42, 51, 52 and purge gas 10 at pressure P is treated with PSA during its adsorption phase.
- the PSA produces the stream 9 which has a higher hydrogen concentration than the effluent 6 and a pressure close to P.
- This stream 9 is recycled to the reaction unit R2 with or without supplementing the source of hydrogen of high purity 1
- the PSA also produces a residual stream 8 containing the impurities of the various hydrogenated effluents from the reaction units R11, R12 and R2 and of low pressure.
- the presence of two R1 units is not compulsory.
- a single R1 unit, or more than two R1 units, can be used in the process according to the invention.
- the operator of the petrochemical site on which the reaction units R1, R2 and R3 take place, can improve the quality of the hydrogenated gas used by the different units and reduce its consumption in make-up hydrogen since it is no longer necessary to purge (purge 11 in FIG. 2) by recovering the hydrogen molecules from this purge.
- the process according to the invention can also allow the operator to unload some of these reaction units if he maintains the introduction of a make-up hydrogenated gas into his site simultaneously with the implementation of the process according to the invention .
- the invention has several advantages over existing solutions. Firstly, it makes it possible to recover several gases containing hydrogen at the outlet of hydrogenation reaction units while these gases are generally used as fuels.
- the hydrogen yield obtained during this purification of the recycle gas may exceed 100% (this hydrogen yield corresponding to the ratio of the hydrogen flow rate of the stream (9) from the first outlet of the unit U on the hydrogen flow rate of the hydrogen-rich gaseous effluent (6)), - the purge (11) can be omitted, - the unit can be stripped down or the properties of its products can be improved .
- the supply of “fresh” hydrogen is also significantly reduced.
- the invention makes it possible to treat a mixture of gases of high purity in hydrogen, a mixture of gases at high pressure of moderate purity in hydrogen as well as a mixture of low pressure gases of low purity in hydrogen within a same pressure-modulated adsorption cycle.
- the method according to the invention produces a residual flow at the pressure of the complex gas network and which can therefore be discharged into this network.
- the diagram illustrated in FIG. 1 is applied to different stages of the process for preparing ⁇ -caprolactam by hydrogenation of phenol, the unit R1 being a unit for hydrogenation of benzene from the synthesis of cyclohexane, the unit R2 being a phenol hydrogenation unit for the synthesis of ⁇ -caprolactam and the R3 unit being a synthesis unit for "hydroxylamine".
- the unit R1 being a unit for hydrogenation of benzene from the synthesis of cyclohexane
- the unit R2 being a phenol hydrogenation unit for the synthesis of ⁇ -caprolactam
- the R3 unit being a synthesis unit for "hydroxylamine".
- Table 2 summarizes the characteristics of the different effluents introduced and coming from the purification unit U comprising the PSA and the compressor.
- the method according to the invention makes it possible to reduce the losses of hydrogen to the fuel network of the site. Without the invention, the operation of the three units results in a loss of 6200 Nm 3 / h by means of purges.
- the installation of a traditional PSA for treating the hydrogen-rich effluent 6 makes it possible to reduce this loss to approximately 1850 Nm 3 / h. Thanks to the invention, it is possible to reduce this hydrogen loss to 600 Nm 3 / h. Therefore the consumption of high purity make-up hydrogen (1) necessary for the operation of the R3 unit is reduced by 45% from 12,500 to 6,900 Nm 3 / h
- the diagram illustrated in FIG. 2 is implemented with two reaction units R1, called R11 and R12, one being a hydrodealkylation unit of toluene and the other a unit for producing cyclohexane, and the unit R2 is a hydrodisproportionation unit for xylenes or toluene.
- R1 and R12 reaction units
- R11 and R12 hydrodealkylation units of toluene and the other a unit for producing cyclohexane
- the unit R2 is a hydrodisproportionation unit for xylenes or toluene.
- Table 4 summarizes the characteristics of the various effluents introduced and coming from the purification unit U comprising the PSA and the compressor. Table 4
- the process according to the invention makes it possible to increase the partial pressure of hydrogen by 15 to 20% in the hydrodisproportionation reaction unit R2.
- This unit can therefore be drained (increase in the processing capacity for isomerized hydrocarbons). It is also possible to reduce the cracking reactions and improve the selectivity in isomerized products at iso-charge rate.
- the entire gas purge can be eliminated and the supply of make-up hydrogen is greatly limited.
- the elimination of the purge makes it possible to make a gain of 1300 Nm 3 / h and the reduction of the make-up makes it possible to make a gain of 1500 Nm 3 / h.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation Of Gases By Adsorption (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0312819A FR2861717B1 (en) | 2003-10-31 | 2003-10-31 | PROCESS FOR THE VALORISATION OF HYDROGEN GAS FLOWS FROM CHEMICAL REACTION UNITS USING HYDROGEN |
PCT/FR2004/050511 WO2005042640A2 (en) | 2003-10-31 | 2004-10-19 | Method for converting hydrogenous gaseous flows arising from chemical reactor units using hydrogen |
Publications (1)
Publication Number | Publication Date |
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EP1682616A2 true EP1682616A2 (en) | 2006-07-26 |
Family
ID=34429813
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP04805754A Withdrawn EP1682616A2 (en) | 2003-10-31 | 2004-10-19 | Method for converting hydrogenous gaseous flows arising from chemical reactor units using hydrogen |
Country Status (8)
Country | Link |
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US (1) | US20080244972A1 (en) |
EP (1) | EP1682616A2 (en) |
JP (1) | JP2007516151A (en) |
CN (1) | CN100439447C (en) |
BR (1) | BRPI0415987A (en) |
CA (1) | CA2543653A1 (en) |
FR (1) | FR2861717B1 (en) |
WO (1) | WO2005042640A2 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2891538B1 (en) * | 2005-09-30 | 2007-11-16 | Air Liquide | PROCESS FOR PRODUCING HYDROGEN-ENRICHED GAS STREAM FROM HYDROGENATED GASEOUS FLOWS COMPRISING HYDROCARBONS |
WO2008047828A1 (en) * | 2006-10-20 | 2008-04-24 | Sumitomo Seika Chemicals Co., Ltd. | Method and apparatus for separating hydrogen gas |
WO2008056579A1 (en) * | 2006-11-08 | 2008-05-15 | Sumitomo Seika Chemicals Co., Ltd. | Hydrogen gas separation method and separation apparatus |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2300235A (en) * | 1940-10-12 | 1942-10-27 | Universal Oil Prod Co | Isomerization of paraffins |
US4115247A (en) * | 1976-07-16 | 1978-09-19 | Hydrocarbon Research, Inc. | Benzene production by solvent extraction and hydrodealkylation |
US5100447A (en) * | 1990-08-30 | 1992-03-31 | The Boc Group, Inc. | Argon recovery from partial oxidation based ammonia plant purge gases |
US5278344A (en) * | 1992-12-14 | 1994-01-11 | Uop | Integrated catalytic reforming and hydrodealkylation process for maximum recovery of benzene |
US5753010A (en) * | 1996-10-28 | 1998-05-19 | Air Products And Chemicals, Inc. | Hydrogen recovery by pressure swing adsorption integrated with adsorbent membranes |
US6179996B1 (en) * | 1998-05-22 | 2001-01-30 | Membrane Technology And Research, Inc. | Selective purge for hydrogenation reactor recycle loop |
US6011192A (en) * | 1998-05-22 | 2000-01-04 | Membrane Technology And Research, Inc. | Membrane-based conditioning for adsorption system feed gases |
US6183628B1 (en) * | 1999-03-19 | 2001-02-06 | Membrane Technology And Research, Inc. | Process, including PSA and membrane separation, for separating hydrogen from hydrocarbons |
US6589303B1 (en) * | 1999-12-23 | 2003-07-08 | Membrane Technology And Research, Inc. | Hydrogen production by process including membrane gas separation |
FR2836061B1 (en) * | 2002-02-15 | 2004-11-19 | Air Liquide | PROCESS FOR TREATING A GASEOUS MIXTURE COMPRISING HYDROGEN AND HYDROGEN SULFIDE |
FR2836057B1 (en) * | 2002-02-15 | 2004-04-02 | Air Liquide | METHOD AND INSTALLATION FOR ENRICHING A COMBUSTIBLE GAS MIXTURE WITH AT LEAST ONE OF ITS COMPONENTS |
US7300642B1 (en) * | 2003-12-03 | 2007-11-27 | Rentech, Inc. | Process for the production of ammonia and Fischer-Tropsch liquids |
US7790018B2 (en) * | 2005-05-11 | 2010-09-07 | Saudia Arabian Oil Company | Methods for making higher value products from sulfur containing crude oil |
-
2003
- 2003-10-31 FR FR0312819A patent/FR2861717B1/en not_active Expired - Fee Related
-
2004
- 2004-10-19 CN CNB2004800320911A patent/CN100439447C/en not_active Expired - Fee Related
- 2004-10-19 BR BRPI0415987-0A patent/BRPI0415987A/en not_active IP Right Cessation
- 2004-10-19 US US10/576,829 patent/US20080244972A1/en not_active Abandoned
- 2004-10-19 JP JP2006537377A patent/JP2007516151A/en not_active Withdrawn
- 2004-10-19 EP EP04805754A patent/EP1682616A2/en not_active Withdrawn
- 2004-10-19 CA CA002543653A patent/CA2543653A1/en not_active Abandoned
- 2004-10-19 WO PCT/FR2004/050511 patent/WO2005042640A2/en active Application Filing
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Title |
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See references of WO2005042640A2 * |
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Publication number | Publication date |
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WO2005042640A2 (en) | 2005-05-12 |
JP2007516151A (en) | 2007-06-21 |
FR2861717B1 (en) | 2006-01-20 |
CN100439447C (en) | 2008-12-03 |
US20080244972A1 (en) | 2008-10-09 |
WO2005042640A3 (en) | 2006-05-11 |
CA2543653A1 (en) | 2005-05-12 |
BRPI0415987A (en) | 2007-01-23 |
CN1875070A (en) | 2006-12-06 |
FR2861717A1 (en) | 2005-05-06 |
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