NZ214165A - Selectively removing hydrogen sulphide from gaseous mixtures containing carbon dioxide, by absorption - Google Patents
Selectively removing hydrogen sulphide from gaseous mixtures containing carbon dioxide, by absorptionInfo
- Publication number
- NZ214165A NZ214165A NZ214165A NZ21416585A NZ214165A NZ 214165 A NZ214165 A NZ 214165A NZ 214165 A NZ214165 A NZ 214165A NZ 21416585 A NZ21416585 A NZ 21416585A NZ 214165 A NZ214165 A NZ 214165A
- Authority
- NZ
- New Zealand
- Prior art keywords
- process according
- pressure
- regeneration
- column
- absorption
- Prior art date
Links
- 238000010521 absorption reaction Methods 0.000 title claims description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 10
- 239000008246 gaseous mixture Substances 0.000 title claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims description 5
- 239000001569 carbon dioxide Substances 0.000 title claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 5
- 230000008929 regeneration Effects 0.000 claims description 56
- 238000011069 regeneration method Methods 0.000 claims description 56
- 239000007789 gas Substances 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 38
- 230000008569 process Effects 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 7
- 150000003512 tertiary amines Chemical class 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- FGQBGDBLZZPFCM-UHFFFAOYSA-N 4-methylmorpholin-3-one Chemical compound CN1CCOCC1=O FGQBGDBLZZPFCM-UHFFFAOYSA-N 0.000 claims description 2
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 claims 2
- SWKPGMVENNYLFK-UHFFFAOYSA-N 2-(dipropylamino)ethanol Chemical compound CCCN(CCC)CCO SWKPGMVENNYLFK-UHFFFAOYSA-N 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229960002887 deanol Drugs 0.000 claims 1
- 239000012972 dimethylethanolamine Substances 0.000 claims 1
- 210000000056 organ Anatomy 0.000 claims 1
- 238000011144 upstream manufacturing Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 26
- 239000006096 absorbing agent Substances 0.000 description 17
- 230000009102 absorption Effects 0.000 description 16
- 230000002378 acidificating effect Effects 0.000 description 9
- 239000000543 intermediate Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 208000036366 Sensation of pressure Diseases 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- -1 N-methyIpyrroIidone Chemical compound 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 1
- ZYWUVGFIXPNBDL-UHFFFAOYSA-N n,n-diisopropylaminoethanol Chemical compound CC(C)N(C(C)C)CCO ZYWUVGFIXPNBDL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229950004864 olamine Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000009103 reabsorption Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- B01D53/14—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 absorption
- B01D53/1425—Regeneration of liquid absorbents
-
- 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
- B01D53/14—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 absorption
- B01D53/1456—Removing acid components
- B01D53/1462—Removing mixtures of hydrogen sulfide and carbon dioxide
-
- 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
- B01D53/14—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 absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Gas Separation By Absorption (AREA)
- Treating Waste Gases (AREA)
- Industrial Gases (AREA)
Description
2 141
PriorttY Date(s):
I1 - II - "i>:
Complete Specification Filed:
Class:
ZZc^Z^mmZ
1 ^ o 6
P.O. Journal, Mo: • ••;
\2WNf&'
NEW ZEALAND PATENTS ACT. 1953
No.:
Date:
COMPLETE SPECIFICATION
PROCESS FOR SELECTIVELY REMOVING HYDROGEN SULPHIDE FROM GASEOUS MIXTURES CONTAINING ALSO CARBON DIOXIDE
<*XWe, SNAMPROGETTI S.p.A., a company organised under the laws of the Italian Republic, of Corso Venezia 16, Milan, Italy, ;hereby declare the invention for whichPt / we pray that a patent may be granted to rfiWus, and the method by which it is to be performed, to be particularly described in and by the following statement: - ;- 1 - ;(followed by page la) ;■eASS 2 1 Oj- ;1 C4. ;The present invention relates to a process for the selective separation of hydrogen sulphide from gaseous mix tures containing.a I so carbon dioxide, by means of a mixture of a tertiary amine and an organic solvent in aqueous 5 solution. ;It is known from the Patent, in Xev." Zealand :,TO197.203 ^rantrd ;O Or. to be r 17,19 ?■ C ;on /in the same applicant's name the use as the absorption means a mixture of a tertiary amine and of an organic solvent with a water content not higher than 10% by weight. 10 We illustrate the process being the object of said ;Patent Specification by means of the scheme of attached Fig. ;1 . ;By means of the pipe 1, the gas to be processed is delivered to the absorber 2, to which the absorbent solu-15 tion is supplied via the pipe 3. ;From the top of the absorber 2 the processed gas is drawn via the pipe 4. ;The exhausted absorbent solution is discharged from the absorber 2 by means of the pipe 5, is expanded in the 20 valve 6, heated in the heat exchanger 7, and sent to the regeneration column 8 equipped with the reboiler 9. ;From the bottom of the column 8 the regenerated solu-O tion 10 is sent to the column 2 by the pump 11, after having been colled first in 7 by the exhausted stream 5, j t i ;25 and then in 12 by a fan. j ;From the head of the column 8 the acidic gases 13 con-^ tain^ng the H^S absorbed by the solution outcome, and are cooled in 14 and separated in 15 into a liquid stream 16, ;which is recycled by the pump 17 to the regenerati ;/?' ^ ^ ;30 umn 8, and a gas 18 containing H S. ;L -<••• ;2 ;2 14165 ;© ;By the said process the obtainment is possible of a treated gas substantially free from H^S, and of a gaseous stream mainly consisting of H^S and CO^, enriched in H^S relatively to the relative H^S and CO^ amounts in the raw 5 gas. ;Whilst for most applications the enrichment in H^S of the acidic gas stream is more than enough, some cases exist in whigh a higher selectivity may be desirable. Obtaining a higher selectivity is particularly advantageous 10 when the acidic gases must be fed to a Claus plant for s u I ;phur production, to the purpose of reducing the gas volumes fed to the Claus plant. The selectivity is also important when C0^ is to be used (as chemical product, or for alimentary use, or for the raws' assisted recovery), 15 and has hence a value by its own, so that after the selec tive plant a conventional plant for CO^ recovery is instal led; in this case, minimizing the C0^ amount lost together with H^S is obviously advantageous. ;The increase in selectivity is usually obtained in 20 the plants operating with aqueous tertiary amines, with a second selective treatment, i.e. by using the so-called "con centrator" plant. In such a plant, the stream of acidic gases is processed again, producing a still more concentrated H S stream. This of course requires considerable 2 ;25 additional investment expenses and involves greater con sumptions of related utilities. ;One of the reasons why the concentrator plant is par ticularly burdensome is the fact that the acidic gas stream is produced at a pressure slightly higher than the 30 atmospheric pressure, so that also the reabsorption of H^S ;in the concentrator plant occurres at a slightly super-at ;21416 5 ;o o ;mo spheric pressure, and hence under particularly disadvantageous conditions. On the other hand, recompressing the whole acidic gas stream would result too expensive. ;We have found a process allowing the selectivity in 5 H^S removal from the gas mixtures containing also CO^ to be increased. ;The process being the object of the present invention, comprising essentially an absorption in a column by means of a tertiary amine and of an organic solvent with a water 10 content not greater than 25% by weight and a regeneration in a distillation column of the exhausted abs.orbent mixture, is characterized in that said exhausted absorbent mixture is submitted, before being regenerated in the distillation column, to a partial regeneration in one or more 15 steps, the separation being obtained of a gas having a ;CO^/H^S ratio greater than that of the exhausted mixture leaving the absorption column. ;The gas as obtained from the partial regeneration can be recycled to the main absorption column, or to an-20 other absorption column. ;The partial regeneration can be carried out by expansion or by heating or by stripping, or by means of one or more exhausting columns, or by means of a suitable combination of these treatments, and can be repeated a suita-25 ble number of times. The regeneration steps may be equal to or different from each other. ;The partial regeneration by expansion consists in ex panding the exhausted solution to an intermediate pressure between the absorption pressure and the regeneration pres 30 sure, and separating the gases formed. ;This process may be repeated more than once, greater ;o o ;A. ;214165 ;selectivities being obtained with a greater number of intermediate expansions. ;It has been found however that the selectivity increase decreases when passing from the second to the third expan 5 sion, so that in practice providing more than three inter mediate expansions in series between the absorber and the regeneration column is not suitable. ;The partial regeneration by heating consists in a heating of the exhausted mixture, e.g., by using the heat of the 10 mixture regenerated in the regeneration coluan, and in the separation of used gases. ;The heating occurs under the pressure of the absorption column, or at an intermediate pressure between the absorption pressure and the regeneration pressure. 15 The partial regeneration by means of one or aore ex hausting columns,is carried out by operating under the same pressure as of the absorption column, or under a pres sure intermediate between the absorption pressure and the regeneration pressure. ;20 Another possible embodiment of the invention consists in allowing a slight heating between the expansion and the separation, thus a further selectivity increase being obtained. This heating is of the order of 5 - 25°C, according to the selectivity increase desired, and to the number 25 of expansion stages used. If more than one stages are used, ;it is generally convenient a higher heating degree before the first stage, the subsequent heatings being lower and lower.- ;The partial regeneration by stripping consists in 30 stripping the exhausted mixture with a H^S-free gaseous mixture, operating under the same pressure as of the ab- ;W. ;2)4165 ;sorption pressure, or under an intermediate pressure between the absorption and the regeneration pressures. ;As examples of gas streams which can be used to that purpose, we can mention fuel gas or the nitrogen available from the air fractionation unit in the plants for synthesis gas production by partial oxidation. ;These gas streams may be used as well in the strig pers and in the exhausting column, in addition to the heat action, in the nearby of the reboiler, or immediately a-bove, or some trays under the saae reboiler, in an additional adiabatic stripping column. ;The partial regeneration may comprise also an intermediate heating inside the exhausting column and/or the stripping column. ;All these systems, besides improving the selectivity of H^S relatively to ^ave a*-so another advantage: the heavy hydrocarbons are noticeably reduced,by being co-ab sorbed with H^S in the exhausted solution, if they are present in the raw gas. It is known that these heavy hydro carbons, when present in the supply to the Claus plant, can impair the quality of sulphur, in particular the colour thereof.
According to another embodiment of the present invention, the gases obtained from the partial regeneration in the expansion stages, are compressed to the pressure of the highest partial regeneration stage and H^S is reabsorb ed with a portion of the regenerated mixture. A CO^ stream substantially free from H^S becomes hence available for possible uses.
The tertiary amines which can be used either individually or as mixtures with each other are dimethylethan
2 14165
olamine, ethyldiethanoLamine, propyIdietha no I amine, diprog y I etha no I amine, isopropyIdiethanolamine, diisopropy lethan olamine, methyIdiisopropano I amine, ethyldiisopropanola-mine, propyLdiisopropanoLamine, isopropy ldiisopropanola-5 mine, N-methylmorpholine.
The solvents which may be used either individually or as mixtures with each other as components of the solution are sulpholane, N-methyIpyrroIidone, N-methy l-3-morpholone, dialkylethermonoethyleneglycols, dialkyletherpolyethylene-10 glycols (wherein each one of the alkyl groups contains from 1 to 4 carbon atoms), N,N-dunethyIformamide, N-form-yImorpho Iine, N,N-dimethy I imidazoIin-2-one and N-methyl-imidazole.
Tfie invention shall be now better disclosed with the 15 aid of the flow charts of Figs. 2, 3, 4, 5, 6, 7 and 8
hereto attached, representing embodiments preferred, but which are not to be considered as limitative of the inven tion itself.
The flow chart of fig. 2 represents a process provided 20 with three partial regeneration steps, constituted by an expansion in valve, under a pressure intermediate between the absorber pressure and the regeneration column pres-sure, and subsequent separation of developed gases, which are recycled to the absorber.
By means of the pipe 1 the gas to be treated is sent to the absorption column 2, to which the absorption solution too is fed via the pipe 3. Within the column 2, which can be equipped with trays / or with a packing of conventional type, the gas to be processed and the absorption 30 solution flow in countercurrent to selectively remove H^S.
From the top of the colunn 2 the treated gas (hydro-
G
2 14165
carbons + CO^) is drawn by the pipe 4.
The exhausted absorption solution is discharged from the column 2 through the pipe 5 and is partly regenerated in three steps, by expansion in the valves 19, 20 and 21 5 and separation in the separators 22, 23 and 24.
From the top of the separators 22, 23 and 24 three ^ gas streams 2 5, 26 and 27 come out, with CO^/H^S ratios ?
greater than the stream 5, and decreasing relatively to J
J
each other. :
The stream 27 is compressed in 28 to the same pres- f j
sure as of the stream 26, and is combined with the same; '
the formed mixture 29 is compressed in 30 to the pressure as of the stream 25, and is combined with it; the nexfmix-ture formed 31 is compressed in 32 to the pressure as of 15 the absorber 2 and is recycled by 33 to the same absorb-
e r.
The liquid streams 34 and 35 leaving from the separators 22 and 23 are respectively sent into the separators 23 and 24, whilst the Liquid stream 36 leaving from the 20 separator 24 is first expanded in the valve 37, then pre-
tillation column 8 provided with the reboiler 9 to complete the regeneration.
From the bottom of the column 8 the regenerated solu-25 tion 10 is sent to the column 2 by means of the pump 11,
after having been first cooled in 7 with the partly regenerated stream 36 and then air-cooled by means of the fan 12.
From the head of the column 8 there come out the ac-30 idic gases 13 containing the H^S absorbed by the solution,
which gases are cooled by means of the fan 14, and are
I
j heated in the heat exchanger 7, and finally fed to the dis j
2 14 165
sent into the separator 15 from whose botton a liquid stream 16 is drawn and recycled to the regeneration column by means of the pump 17. From the head of the separator 15 a H^S-containing gas 18 comes out.
The flow chart of fig. 3 represents a process having three partial regeneration steps constituted each by a heating, by an expansion in valve and by a separation of the developed gases, which are recycled to the absorber.
Relatively to the flow chart of fig. 1, the addition al exchangers 38, 39 and 40 are provided, which respective ly heat the streams 5, 34 and 35 after having been expand ed in valve.
The heat is supplied by the regenerated solution 10 before being recycled to the absorber 2.
In fig. 4 a partial regeneration step is shown, which uses an exhausting column.
The exhausted solution 5 enters the exhausting column 41 from whose bottom a stream 42 is drawn, a portion 43 of which is heated in 44 by themal exchange, e.g.,
with the regenerated solution 10, whilst the remaining por tion 45 is sent to a second partial regeneration stage or to the regeneration column.
From the head of the column 41 a gas stream 46 enrich ed in CO^ comes out.
In fig. 5 the partial regeneration step using a strig ping column is used.
The exhausted solution 5 enters the stripping column 47 into the bottom of which a gas stream in fed by means of the pipe 48. From the head of the stripper a gas 49 enriched in CO^ comes out, whilst from the bottom a stream 50 is drawn and is sent to a second partial regeneration
214165
step or to the regeneration column.
The flow chart of fig. 6 represents a process provided with two regeneration stages wherein the first stage is an exhausting column, and the second one is constitut-5 ed by an expansion, a heating and a separation.
The exhausted solution 5 coming out of the absorber 2 is fed, after having been expanded in 6, to the exhausting column 41, from whose bottom a solution 42 comes out, which is partly C43) recycled to the same column, after 10 having been heated in 44 by means of the regenerated solu tion 10, and partly (45) is expanded in the valve 21, heated in 40 and separated in 24. From the bottom of the Separa tor 24 a liquid stream 36 in drawn and is sent, as in pre ceding schemes, to the regeneration column 8; from the 15 head of the separator a gas 27 leaves which is compressed in 28 to the pressure of the exhausting column 41 and recycled to the same column.
H^S in the column 41 is reabsorbed by a portion of the regenerated solution 10, i.e., the stream 51, so that 20 from the head a stream 46 containing CO^ and substantial ly free from H^S comes out.
The flow chart of fig. 7 represents a process simpU fied relatively to the preceding process, having two regeneration stages, wherein the first stage is an exhaust-25 ing column operating under the same pressure as of the ab sorption column, and the second is constituted by an expansion, a heating and a separation.
The exhausted solution 5 coming out of the absorber 2 is partly (43) recycled to the absorber 2, after having 30 been heated in 44 by means of the regenerated solution 10,
partly (45) expanded in the valve 21, heated in 40 and se-
2 14 16 5
parated in 24. From the bottom of the separator 24 a liquid stream 36 is drawn arid is sent to the regeneration column 8 similarly to the preceding schemes, whilst from the head a gas 27 comes out, which is conpressed in 28 to the pressure of the column 2 and is then recycled to the same column.
The flow chart of fig. 8 represents a process with two absorption columns and with a partial regeneration stage constituted by an expansion, a heating and a separa tion.
The solution 5 leaving the absorber 2 after having been expanded in 6 and heated in 52 with the regenerated solution 10 is fed to a second absorber 53, from whose bot torn comes out a solution 54, which is expanded in 23, heat ed in 40 and separated 24.
From the bottom of the separator 24 a liquid stream 36 is drawn which is sent, similarly to the preceding schemes, to the regeneration column 8; from the head of the separator 24 a gas 27 comes out, which is conpressed in 28 to the pressure of the absorber 53, and recycled to the same absorber.
The H^S in the absorber 53 is reabsorbed by the stream 51, which is a portion of the regenerated solution 10., so that from the head a stream 55 of CO^ substantially free from H^S comes out.
As Example is now supplied to the purpose of better illustrating the invention, which example should not be considered as a limitation to the same invention. Said Example shall be followed by a Comparison Example.
Ex amg j. e_1
A natural gas, available under 56 kg/cm^, with 4.5%
214165
by volume of H^S and 64% by volume of CO^ is treated with a dimethyIethano I amine solution at 40% by weight, of N-methyIpyrrolidone at 50% by weight and water (10% by weight), according to the process as schematically shown in fig. 8.
There are obtained a purified gas with less than 1 ppm of H^S/ a stream of acidic gases containing 71.93% by volume of H^S, a stream of CO^ with less than 1 ppm of
3
H^S under a pressure of 15 kg/cm , representing 11.6% of the C0^ contained in the raw gas.
(Comparison) Examgle_2 The same natural gas is treated according to the proc ess as schematically shown in fig. 1 (known art), with the same type of solution, a purified gas being obtained with less than 1 ppm of ^S, and a stream of acidic gases being obtained, containing about 32.652 by volume of It can be noticed hence that, besides yielding a stream of C(>2 substantially free from the process claimed ac cording to the present Patent Application yields a strean of acidic gases containing 71.93X by volume of H^S, with a decrease of the volume of gases fed to the Claus process of 2.2 times relatively to the known art.
Claims (20)
1. Process for selectively removing hydrogen sulph ide from gaseous mixtures also containing carbon dioxide, essentially comprising an absorption in a column by means of a mixture of a tertiary amine and of an organic solvent 5 with a water content not greater than 25Z by weight and a regeneration in a distillation column of the exhausted absorbing mixture, characterized in that it uses a tertiary amine selected among dimethy lethanolamine, ethyLdiethanol-amine, propyLdiethanoI amine , dipropylethanolamine, iso- * 10 propy Ldi ethanolami ne, di i sopropy lethanolamine, methyldii- sopropanoI amine, ethyldiisopropanolamine, propy ldiisoprop-anolamine, isopropyldiisopropanoI amine, N-methy ImorphoIine either alone or as mixtures with each other, and an organ ic solvent selected from the group forced by sulpholane, ? i 15 N-methylpyrrolidone, N-methyl-3-morpholone, dialkylether- ? monoethyleneglycols, diaLkyletherpoLyethyleneglycols, N,N- j i t dimethylformamide, N-formylmorpholine, N,N-dimethylimidazoJ. \ in-2-one, N-me t hy I i m i da zo I e, alone or mixed with each oth jj er, and in that the exhausted mixture is submitted, before ? 20 being regenerated in the distillation column, to a partial j regeneration in one or more stages, the separation being \ obtained of a gas having a greater CO^/H^S ratio than the j exhausted mixture coming out from the absorption column. |
2. Process according to claim 1, wherein the gas ob- f 25 tained from the partial regeneration is recycled to the absorption column.
3. Process according to claim 1, wherein the partial regeneration occurs by expansion.
A. Process according to claim 1, wherein the partial 30 regeneration occurs by heating. ^ 2 14165
5. Process according to claim 1, wherein the partial regeneration occurs by stripping.
6. Process according to claim 1, wherein the partial regeneration occurs by means of one or lore exhausting col umns .
7. Process according to claim 1, wherein the partial regeneration occurs by expansion and/or by heating and/or by stripping and/or by means of one or lore exhausting co lumns.
8. Process according to claim 7, wherein the stages of partial regeneration are from 1 to 3.
9. Process according to claim 3, wherein the partial regeneration by expansion consists in expanding in valve the exhausted mixture to a pressure ■intermediate between the absorption pressure and the regeneration pressure, and separating the gas formed.
10. Process according to claim wherein the partial regeneration by heating consists in a heating of the exhausted mixture and in the separation of the developed gases.
11. Process according to claim 10, wherein the heating is carried out by using the heat of the regenerated mixture.
12. Process according to claim 10, wherein the heating occurs under the pressure of the absorption column, or under a pressure intermediate between the absorption pressure and the regeneration pressure.
13. Process according to claim 12, wherein the exhaust i ng column operates under the same pressure as of the absorption column, or under a pressure intermediate between the absorption pressure and the regeneration pressure. J 1 * i - i4lbL
14. Process according to claim 5, wherein the partial regeneration by stripping consists in stripping the exhaust
15. Process according to claim 14, wherein the strifi ping occurs under the same pressure of the absorption co] umn or under a pressure intermediate between the absorption pressure and the regeneration pressure.
16. Process according to claims 12 and 13, wherein to the exhausting column stripping gas in fed in the nearby of the reboiler, or immediately above, or some plates under the same reboiler.
17. Process according to claim 1, wherein the partial regeneration steps are equal or different to each other.
18. Process according to claims 12 and/or 14, wherein the partial regeneration comprises also a heating upstream of the exhausting columns and/or of the stripping operation.
19. Process according to claim 3, wherein the gases obtained from the partial regeneration in the expansion stages are compressed to the pressure as of the highest partial regeneration stage, the H^S contained therein being then reabsorbed with a portion of the regenerated mix ture.
20. A process for selectively removing hydrogen sulphide from gaseous mixtures also containing carbon dioxide substantially as herein described with reference to any one of Figures 2 to 8 of the accompanying drawings. ed mixture with a H^S-free gas stream. I.... By J^te/their authorised Agent*., A. J. PARK & SON.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT23739/84A IT1177324B (en) | 1984-11-26 | 1984-11-26 | PROCEDURE FOR SELECTIVELY REMOVING HYDROGEN SULFUR FROM GASEOUS MIXTURES CONTAINING ALSO CARBON DIOXIDE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NZ214165A true NZ214165A (en) | 1988-03-30 |
Family
ID=11209577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NZ214165A NZ214165A (en) | 1984-11-26 | 1985-11-12 | Selectively removing hydrogen sulphide from gaseous mixtures containing carbon dioxide, by absorption |
Country Status (16)
| Country | Link |
|---|---|
| JP (1) | JPS61136421A (en) |
| AU (1) | AU5005185A (en) |
| BR (1) | BR8506058A (en) |
| DD (1) | DD241015A5 (en) |
| DE (1) | DE3541775C2 (en) |
| DK (1) | DK544185A (en) |
| ES (1) | ES8607181A1 (en) |
| FR (1) | FR2573671A1 (en) |
| GB (1) | GB2167397B (en) |
| HU (1) | HUT41994A (en) |
| IT (1) | IT1177324B (en) |
| NL (1) | NL8503265A (en) |
| NO (1) | NO162218C (en) |
| NZ (1) | NZ214165A (en) |
| PL (1) | PL256454A1 (en) |
| SE (1) | SE8505463L (en) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1989011327A1 (en) * | 1988-05-24 | 1989-11-30 | Societe Nationale Elf Aquitaine (Production) | Liquid absorbing acid gases |
| FR2631853B1 (en) * | 1988-05-24 | 1992-01-24 | Elf Aquitaine | ACID GAS ABSORBING LIQUID CONTAINING A TERTIARY ALKANOLAMINE COMPONENT AND A CO2 ABSORPTION ACTIVATOR AND ITS APPLICATION TO THE DEACIDIFICATION OF CO2-CONTAINING GASES AND POSSIBLY OTHER ACID GASES |
| IT1244687B (en) * | 1991-01-24 | 1994-08-08 | Snam Progetti | PROCESS FOR THE REMOVAL OF ACID GASES FROM GASEOUS MIXTURES |
| JP2931153B2 (en) * | 1991-11-28 | 1999-08-09 | 株式会社日立製作所 | Method for removing acid gas from combustion exhaust gas |
| DE19753903C2 (en) * | 1997-12-05 | 2002-04-25 | Krupp Uhde Gmbh | Process for the removal of CO¶2¶ and sulfur compounds from technical gases, in particular from natural gas and raw synthesis gas |
| JP3771708B2 (en) * | 1998-03-23 | 2006-04-26 | 三菱重工業株式会社 | Method for removing carbon dioxide in gas |
| EP1022046A1 (en) * | 1999-01-22 | 2000-07-26 | Krupp Uhde GmbH | Process for removing carbon dioxide, sulphur compounds, water and aromatic and higher aliphatic hydrocarbons from technical gases |
| US6203599B1 (en) | 1999-07-28 | 2001-03-20 | Union Carbide Chemicals & Plastics Technology Corporation | Process for the removal of gas contaminants from a product gas using polyethylene glycols |
| RU2176266C1 (en) * | 2000-03-27 | 2001-11-27 | Дочернее открытое акционерное общество "Гипрогазцентр" | Method of treatment and dehydration of natural and associated petroleum gas with high content of hydrogen sulfide |
| NZ514666A (en) * | 2001-10-08 | 2003-01-31 | Canterprise Ltd | Apparatus for continuous carbon dioxide absorption comprising a reactor containing a carbon dioxide absorbent liquid recycled via a regenerator |
| EP1663452B1 (en) * | 2003-09-09 | 2009-04-15 | Fluor Corporation | Improved solvent use and regeneration |
| RU2270233C1 (en) * | 2004-08-06 | 2006-02-20 | Открытое акционерное общество криогенного машиностроения (ОАО "Криогенмаш") | Method of combined purification of a natural gas and the device for its realization |
| FR2877858B1 (en) * | 2004-11-12 | 2007-01-12 | Inst Francais Du Petrole | METHOD FOR DEACIDIFYING A GAS WITH A FRACTIONED REGENERATION ABSORBENT SOLUTION |
| JP5023512B2 (en) * | 2006-02-27 | 2012-09-12 | 三菱マテリアル株式会社 | Gas separation and recovery method and apparatus |
| FR2911516B1 (en) | 2007-01-19 | 2009-11-13 | Total Sa | PROCESS FOR PURIFYING A GASEOUS MIXTURE CONTAINING ACIDIC GASES |
| JP2011025100A (en) * | 2007-11-22 | 2011-02-10 | Research Institute Of Innovative Technology For The Earth | Process for recovering carbon dioxide from high-pressure gas and aqueous composition |
| CA2707106A1 (en) * | 2007-11-27 | 2009-06-04 | Linde Aktiengesellschaft | Process and apparatus for the regeneration of the laden scrubbing medium in a physical gas scrubbing |
| NL2001111C2 (en) | 2007-12-21 | 2009-06-29 | Airpack Holding B V | Process for separating acid gas. |
| US8993488B2 (en) * | 2011-02-24 | 2015-03-31 | United Laboratories International, Llc | Process for removal of hydrogen sulfide in downhole oilfield applications |
| AU2012236725B2 (en) * | 2011-03-28 | 2017-05-18 | The Board Of Trustees Of The University Of Alabama | N-functionalized imidazole-containing systems and methods of use |
| US9352270B2 (en) | 2011-04-11 | 2016-05-31 | ADA-ES, Inc. | Fluidized bed and method and system for gas component capture |
| WO2014047354A1 (en) * | 2012-09-20 | 2014-03-27 | ADA-ES, Inc. | Method and system to reclaim functional sites on a sorbent contaminated by heat stable salts |
| FR2996464B1 (en) * | 2012-10-05 | 2015-10-16 | IFP Energies Nouvelles | METHOD FOR THE SELECTIVE ABSORPTION OF HYDROGEN SULFIDE FROM A GASEOUS EFFLUENT COMPRISING CARBON DIOXIDE BY AN AMINOUS ABSORBENT SOLUTION COMPRISING A VISCOSIFYING AGENT |
| JP2014097498A (en) * | 2013-12-26 | 2014-05-29 | Toshiba Corp | Acid gas absorbent, acid gas removal device and acid gas removal method |
| US10350544B2 (en) | 2015-02-04 | 2019-07-16 | The Board Of Trustees Of The University Of Alabama | Gas treating solutions containing imidazole-amine compounds |
| JP6841676B2 (en) | 2017-01-31 | 2021-03-10 | 三菱重工エンジニアリング株式会社 | Complex amine absorber, CO2 and / or H2S removal device and method |
| JP7185421B2 (en) * | 2018-05-25 | 2022-12-07 | 株式会社東芝 | Acid gas absorbent, method for removing acid gas, and apparatus for removing acid gas |
| RU2708853C1 (en) * | 2019-07-02 | 2019-12-11 | Юрий Михайлович Михайлов | Plant for purification of associated petroleum and natural gas from sulfur-containing compounds |
| IT202000002353A1 (en) * | 2020-02-06 | 2021-08-06 | Eni Spa | PROCESS AND PLANT FOR THE TREATMENT OF GAS MIXTURES CONTAINING ACID GASES |
| JP7702205B2 (en) * | 2021-09-15 | 2025-07-03 | 株式会社東芝 | Novel amine compound, acidic gas absorbent, method for removing acidic gas, and method for removing acidic gas |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE935144C (en) * | 1949-09-16 | 1955-11-10 | Linde Eismasch Ag | Process for the purification of gases, in particular those for synthesis and heating purposes |
| DE1222198B (en) * | 1949-09-16 | 1966-08-04 | Linde Ag | Process for the regeneration of the loaded organic polar absorbents from cryogenic gas scrubbing processes |
| US3837143A (en) * | 1973-08-06 | 1974-09-24 | Allied Chem | Simultaneous drying and sweetening of wellhead natural gas |
| DE2928858A1 (en) * | 1979-07-17 | 1981-02-05 | Linde Ag | Gas purificn. by one-stage physical absorption - for simultaneous removal of sulphur cpds., heavy hydrocarbon(s) and water |
| IT1132170B (en) * | 1980-07-04 | 1986-06-25 | Snam Progetti | SELECTIVE SEPARATION PROCESS OF HYDROGEN SULFURATED FROM GASEOUS MIXTURES CONTAINING ALSO CARBON DIOXIDE |
| CA1205276A (en) * | 1981-06-15 | 1986-06-03 | Malcolm W. Mcewan | Process for the removal of co.sub.2 and, if present h.sub.2s from a gas mixture |
-
1984
- 1984-11-26 IT IT23739/84A patent/IT1177324B/en active
-
1985
- 1985-11-12 NZ NZ214165A patent/NZ214165A/en unknown
- 1985-11-19 AU AU50051/85A patent/AU5005185A/en not_active Abandoned
- 1985-11-19 SE SE8505463A patent/SE8505463L/en not_active Application Discontinuation
- 1985-11-19 GB GB08528409A patent/GB2167397B/en not_active Expired
- 1985-11-22 ES ES549798A patent/ES8607181A1/en not_active Expired
- 1985-11-22 NO NO854680A patent/NO162218C/en unknown
- 1985-11-25 DD DD85283215A patent/DD241015A5/en unknown
- 1985-11-25 HU HU854488A patent/HUT41994A/en unknown
- 1985-11-25 DK DK544185A patent/DK544185A/en not_active Application Discontinuation
- 1985-11-25 BR BR8506058A patent/BR8506058A/en unknown
- 1985-11-25 FR FR8517402A patent/FR2573671A1/en not_active Withdrawn
- 1985-11-26 PL PL25645485A patent/PL256454A1/en unknown
- 1985-11-26 JP JP60263923A patent/JPS61136421A/en active Pending
- 1985-11-26 DE DE3541775A patent/DE3541775C2/en not_active Expired
- 1985-11-26 NL NL8503265A patent/NL8503265A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| NO162218B (en) | 1989-08-21 |
| GB2167397A (en) | 1986-05-29 |
| PL256454A1 (en) | 1986-09-23 |
| DK544185D0 (en) | 1985-11-25 |
| DK544185A (en) | 1986-05-27 |
| GB2167397B (en) | 1988-03-30 |
| SE8505463D0 (en) | 1985-11-19 |
| IT8423739A0 (en) | 1984-11-26 |
| HUT41994A (en) | 1987-06-29 |
| BR8506058A (en) | 1986-08-19 |
| DE3541775A1 (en) | 1986-05-28 |
| FR2573671A1 (en) | 1986-05-30 |
| JPS61136421A (en) | 1986-06-24 |
| NO162218C (en) | 1989-11-29 |
| SE8505463L (en) | 1986-05-27 |
| ES549798A0 (en) | 1986-05-16 |
| GB8528409D0 (en) | 1985-12-24 |
| NL8503265A (en) | 1986-06-16 |
| NO854680L (en) | 1986-05-27 |
| DD241015A5 (en) | 1986-11-26 |
| AU5005185A (en) | 1986-06-05 |
| IT1177324B (en) | 1987-08-26 |
| ES8607181A1 (en) | 1986-05-16 |
| DE3541775C2 (en) | 1987-03-05 |
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