GB1574646A - Removal of co2 and/or h2s form gases - Google Patents

Removal of co2 and/or h2s form gases Download PDF

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Publication number
GB1574646A
GB1574646A GB11542/77A GB1154277A GB1574646A GB 1574646 A GB1574646 A GB 1574646A GB 11542/77 A GB11542/77 A GB 11542/77A GB 1154277 A GB1154277 A GB 1154277A GB 1574646 A GB1574646 A GB 1574646A
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solvent
gas
mixture
methyl isopropyl
polyethylene glycol
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BASF SE
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BASF SE
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/14Separation 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
    • B01D53/1493Selection of liquid materials for use as absorbents
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00Purification; Separation; Use of additives
    • C07C7/11Purification; Separation; Use of additives by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/40Capture or disposal of greenhouse gases of CO2
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/151Reduction of greenhouse gas [GHG] emissions, e.g. CO2

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)
  • Gas Separation By Absorption (AREA)
  • Industrial Gases (AREA)
  • Detergent Compositions (AREA)

Description

(54) REMOVAL OF CO2 AND/OR H2S FROM GASES (71) We, BASF AKTIENGESELL SCHAFT, A German Joint Stock Company of 6700 Ludwigshafen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following Statement:- The present invention relates to a process for removing H2S and/or CO2 from gases which contain these constituents, especially as impurities, by washing the gases with a solvent which contains as ether of a polyethylene glycol.
The use of organic solvents or aqueous solutions of organic solvents to remove undesired acid constituents, e.g. H2S and CO2, from natural gases and synthesis gases, has been disclosed. A review article in Hydrocarbon Processing, April 1975, pages 84-105, may be mentioned as representative of the extensive prior art.
The solvents for the selective removal of H2S in the presence of CO2 comprise two groups. Firstly, there are chemical solvents, e.g. aqueous solutions of methyldiethanolamine and solutions of salts of a-aminocarboxylic acids, e.g. glycine or alanine (Alkazide), the selectivity of which is due to the fact that they dissolve 112S many times more rapidly than they dissolve CO2.
Secondly, there are physical solvents, e.g.
N-methylpyrrolidone (Purisole) and the dimethyl ethers of polyethylene glycols (Selexolg), which thermodynamically dissolve more H2S than CO2.
In addition to the solubility of a gas in a solvent, from which the minimum amounts of circulating solvent are calculated, the rate of solution of the gas in the solvent is of great importance, since it determines the size of the absorber.
The present invention seeks to provide a solvent for removing H2S and/or CO2 from gases, which solvent not only exhibits a high rate of solution of H2S but in which H2S is also adequately soluble.
The use of dimethyl ethers of polyethylene glycols or their mixtures to remove CO2 and/or H2S from gases is disclosed in U.S. Patents 2,649,166, 3,362,133 and 3,533,732. German Laid Open Application DOS 2,263,980 discloses alkylpolyethylene glycol tert.-butyl ethers as solvents for acid gases.
It is true that as a rule the above solvents exhibit adequate absorption of H2S and/or Ò2 and also satisfactory viscosity chracteristics; according to the expèriments described in German Laid Open Application DOS 2,263,980 the unsymmetrical ethers have somewhat higher absorption capacities than the dimethyl ethers described in the above U.S.
Patents. However, the rate of absorption of H2S, both with dimethyl ethers and with methyl tert.-butyl ethers of polyethylene glycols, is not satisfactory in every case.
We have found, surprisingly, that good results may be achieved, in the washing of gases containing CO2 and/or H2S to remove these contaminants from them, by the use of the methyl isopropyl ether of a polyethylene glycol. Such an ether has in general a higher rate of solution of H2S than the conventional dimethyl ethers and alkyl tert.butyl ethers; it is therefore possible to choose a relatively smaller absorber.
Accordingly, the invention provides a process for removing CO2 and/or H2S from a gas which contains one or both or these constituents, by washing the gas under normal or superatmospheric pressure with a solvent comprising one or more polyethylene glycol methyl isopropyl ether containing from 2 to 8
units, followed by regeneration of the solvent.
Gases which may be purified in this way include coke oven gases, coal gasification gases, synthesis gases and, preferably, natural gases, from which H2S is to be removed selectively.
According to the invention, the methyl isopropyl ethers of polyethylene glycols of the following formula, which contain from 2 to 8 ethylene glycol groups (i.e. n=from 2 to 8) are used as the solvent:
The use of ethers with from 3 to 7 ethylene glycol units is preferred; from the point of view of the rate of solution of H2S, the compound with 3 ethylene glycol units, i.e., the methyl isopropyl ether of triethylene glycol, has proved best, whereas compounds with 6 to 8 ethylene glycol units are more suitable for removing CO2. However, in practice, mixtures obtained by synthesizing these compounds in the presence of strongly acid cation exchange resins are as a rule employed (cf. German Laid-open Application DOS 25 44 569). If mixtures of monomethyl ethers with 3 to 5 ethylene glycol units are reacted with propylene in accordance with German Laid-open Application DOS 25 44 569 and the low boiling constituents are removed, the residual mixture of monomethyl ethers and methyl isopropyl ethers may be employed as the solvent.
As a rule, the solvents are employed in a virtually anhydrous form. If steam stripping is carried out in the desorption column, the water content of the solvent should not exceed 8% by weight, based on the solvent.
From the point of view of the ability to dissolve CO2 and H2S, the methyl isopropyl ethers of polyethylene glycols behave like physical solvents, i.e. Henry's law applies as a good approximation, and thermo dynamically more H2S than CO2 is dissolved.
A process within the invention can be carried out at normal or preferably super atmospheric pressure, advantageously at H2S partial pressures greater than 0.05 bar and especially greater than 0.5 bar. When removing CO2 from gases not containing H2S, the CO2 partial pressure should advantageously be greater than 4 bars and especially greater than 10 bars. The washing process may be carried out in one stage or two stages. The choice of washing process as a rule depends on the partial pressures of the gases to be washed out and on the final purity required, or in the permissible heat consumption or stripper gas consumption.
A process within the invention may be carried out either with a packed column or with a column fitted with exchange trays.
The temperature of the solvent at the top of the absorber should preferably not exceed 50"C. since the higher temperatures, the lower is the gas loading of the solvent.
The absorption is as a rule carried out at from 20 to 400C. The top temperature of the absorber is fixed in accordance with the conventional criteria and as a rule depends on the desired degree of purity and on the temperature of the cooling water.
The rich solvent can be flashed in one or more stages, e.g. using a flash turbine, and it may then be substantially regenerated in a packed desorption column or a desorption column equipped with trays, using stripping gas or steam which can be injected directly or can be generated by adding from 2 to 80% by weight; especially from 3 to 50/, by weight, of water to the solvent and employing indirect heat exchange. The solvent can also be stripped with an inert gas.
If, after flashing, the stripping is carried out in a column, it is advantageous to choose a pressure of from 1.1 to 1.5 bars in the main flashing stage.
The solvent running into the desorption column can be heated by means of the solvent discharged, in a countercurrent heat exchanger. The temperature at the bottom 'of the absorber as a rule is from 110 to 140"C, especially 115 to 1300C. The solvent may be conveyed by means of a pump to the top of the absorber via a cooler which can be used to set up the desired top temperature of the absorber.
If the wash is carried out in two stages, only a part of the solvent, coming from the desorption column, need be fed to the top of the absorber, while the remainder can be fed, at a somewhat higher temperature, to another point of the absorber as it comes from the main flashing stage (cf. Figure 2).
Figures 1 and 2 of the accompanying drawings show two preferred process flow charts for carrying out a one-stage wash and a two-stage wash (rough wash and fine wash), respectively.
Figure 1 shows a one-stage wash. This type of wash is particularly suitable for gases with low partial pressures of the components to be washed out.
A rough wash using a flashing circuit may be carried out as follows (cf. Figure 1): The gas to be washed is supplied through line 11 to the absorption column 1 through which it flows from bottom to top countercurrent to the solvent which is charged at the top of the column. The washed (treated) gas leaves the absorption column 1 at the top via line 12. The solvent loaded with sour gas leaves column 1 at the bottom and is flashed through a flash turbine 4 into a flash column 2. It is then supplied via heat exchanger 7 to the desorption column 3. The degassed solvent leaves the desorption column at the bottom and is forced by pump 5 via solvent cooler 9 into the top of the absorption column. The flash gas from the flash stage leaves column 2 at the top through line 13. The off-gas from desorption column 3 leaves at the top and is then cooled in off-gas cooler 10. The heat balance of the wash is maintained by heat exchanger 8 at the bottom of column 3.
In the Figures, the numbers denote the following: 1. Absorption column 2. Flash column 3. Desorption column 4. Flash turbine 5. Solvent pump 6. Condensate pump 7. Solvent/solvent heat exchanger 8. Reboiler 9. Solvent cooler 10. Off-gas cooler 11. Crude gas 12. Treated gas 13. Flashing gas (inert gas+component washed out) 14. Off-gas (component washed out) Figure 2 shows a preferred flow diagram for two-stage washing (rough and fine washing) with one flashing stage and one desorption stage (stripper). The absorption column 1 comprises two sections 21 (rough wash) and 22 (fine wash). The solvent loaded with sour gas is flashed, as in Fig. 1, in turbine 4 and column 2. The solvent leaving flash column 2 at the bottom is divided into two streams. One portion of the stream goes to rough wash column 21 after passing through pump 25, while another portion of the flashed solvent passes through heat exchanger 7 to the top of desorption column 3. Reboiler 8 converts some of the solvent into vapor with which the solvent in column 3 is stripped from sour gas. The solvent stream thus regenerated is pumped by pump 5 through heat exchangers 7 and 9 for cooling, and then fed to fine wash column 22. The off-gas leaving at the top of desorption column 3 is cooled in offgas cooler 10.
In this Figure, the numbers denote the following: 21. Rough wash column 22. Fine wash column 25. Solvent pump 2.
In addition to their ability to dissolve H2S and CO2, the methyl isopropyl ethers of polyethylene glycols are able to absorb water. Hence, the solvents to be used according to the invention can also be used for conditioning natural gases. In that case, the water contained in the natural gas would be removed at the top of the stripper (compare position 3 in Figures 1 and 21. If the solvent of the invention is used for this purpose, the procedure followed would be as described in German Laid-Open Application DOS 2,437,576, which proposes a process for conditioning natural gases by means of solvents other than those now proposed.
The present invention is illustrated by Examples I and 2 which follow.
Comparative Example I compares the rate of absorption of H2S by methyl isopropyl ethers of polyethylene glycols with the rate of absorption by the ethers mentioned in U.S. Patent 3,362,133 (e) and German Laid Open Application DOS 2,263,980 (f), and Comparative Example 2 the stability of the methyl tert.-butyl ethers of DOS 2,263,980 with the methyl isopropyl ethers of the invention.
EXAMPLE 1 Selective H2S removal 200 m3 (S.T.P.)/h of a dry synthesis gas at 16 bars and 50"C are supplied to a packed column of 0.3 m diameter packed to a height of 7.5 m. The composition of the gas is as follows (in /a by vol.): CO2 4.0 CO 46.8 CH4 0.2 n2 0.2 Ar 0.4 H2 48.0 H2S 0.4 COS 24 vol. ppm The gas is washed countercurrently with 1.6 m3/h of a solvent comprising 90% w/w of asymmetrical methyl isopropyl ethers of polyethylene glycols [26 wt. /n tri, 36 tetra, 23 penta, 11 hexa and 4 hepta], 6% of similarly composed monomethyl ethers and 4% of water, the feed temperature being relatively unfavorable at 500 C. The treated gas leaving the top of the absorber contains 2.9 v/v CO2, 8 vol. ppm of COS and 0.8 vol. /a H2S. The wash liquid loaded with sour gas has a temperature of 51"C at the bottom of the absorber. It is regeberated by flashing to 1.25 bars and stripping with steam in a desorption column (bottoms temperature 130"C), allowed to cool to 500 and returned to the top of the absorber.
EXAMPLE 2 Joint removal of H2S and CO2 The method of Example 1 is followed, but 7 m3 (S.T.P.) wash liquid is used per hour.
At the top of the absorber the treated gas contains 1200 vol. ppm CO2, < 1 vol. ppm H2S and < 8 vol. ppm COS.
COMPARATIVE EXAMPLE 1 Table 1 which follows shows the transfer coefficients Kg for the solvents of the invention and for various solvents of the prior art. The Kg values were determined in a jet stream chamber, the Kg value of the methyl isopropyl ether of triethylene glycol being taken arbitrarily as 1.
TABLE I relative mass transfer (a) Methyl isopropyl ether of triethylene glycol 1 (b) Methyl isopropyl ether of tetraethylene glycol 0.86 (c) Methyl isopropyl ether of pentaethylene glycol 0.79 (d) Undistilled mixture of A, B and C 0.72 (e) Mixture of dimethyl ethers of polyethylene glycols with low boiling constituents 0.57 (f) Methyl tert.-butyl ether of triethylene glycol 0.79 (g) Methyl tert.-butyl ether of tetraethylene glycol 0.58 COMPARATIVE EXAMPLE 2 (a) Table 2 which follows shows the results of comparative experiments on the decomposition of the methyl tert.-butyl ether of tetraethylene glycol (A) and of the corresponding methyl isopropyl ether (B) with sulfuric acid. In each case, 30 g of the ether (A) or (B) were heated with 2 drops of concentrated sulfuric acid at 1400C (A) or 270"C (B only) for 1 hour. In the case of compound (B), a further 2 drops of concentrated sulfuric acid were afterward added at the higher temperature and the material was heated for a further 2 hours at 270"C. In each case, the isobutene or isopropylene eliminated was determined.
TABLE 2
Proportion decomposed A B in% Amount of concentrated H2SO4 2 2 4 l400C,afterlhour 100% 270"C after 1 hour 0 0 - after 3 hours ~ 2% Table 2 shows that the solvents to be used according to the invention are substantially more stable in an acid medium than the solvents of the prior art, as may be seen from the low degree of decomposition.
(b) In a further experiment, the rate of decomposition of the ethers (A) and (B) was determined. For this purpose, 100 g portions of the ethers were heated with 5% of the acid ion exchanger used for the manufacture of the ether (B) (a sulfonated crosslinked polystyrene resin in the H form) at 700 C, and the rate of elimination of olefins was measured. If the rate constant of the decomposition reaction for (B) is taken as = I, a value of 562 is found for the compounds (A) of the prior art.

Claims (13)

WHAT WE CLAIM IS:
1. A process for removing CO2 and/or H2S from a gas which contain one or both of these constituents, by washing the gas under normal or superatmospheric pressure with a solvent comprising one or more polyethylene glycol methyl isopropyl ethers containing from 2 to 8
units, with subsequent regeneration of the solvent.
2. A process as claimed in claim 1, wherein hydrogen sulfide is selectively removed from natural gas.
3. A process as claimed in claim 1 or 2, wherein a solvent comprising a mixture of polyethylene glycol methyl isopropyl ethers containing from 2 to 8
units is used.
4. A process as claimed in claim I or 2, wherein a solvent comprising one or more polyethylene glycol methyl isopropyl ethers containing from 3 to 7
units are used.
5. A process as claimed in claim 1 or 2, wherein a solvent comprising a mixture of polyethylene glycol methyl isopropyl ethers. containing from 3 to 7
units is used.
6. A process as claimed in claim 3, wherein the mixture of polyethylene glycol methyl isopropyl ethers has been obtained by reacting a mixture of polyethylene glycol monomethyl ethers containing from 2 to 8
units in the presence of strongly acid cation exchange resins with propylene.
7. A process as claimed in claim 5, wherein the mixture of polyethylene glycol methyl isopropyl ethers has been obtained by reacting a mixture of polyethylene glycol monomethyl ethers containing from 3 to 7
units in the presence of strongly acid cation exchange resins with propylene.
8. A process as claimed in claim 1 or 2, wherein the methyl isopropyl mixture obtained by reacting a mixture of monomethyl ethers of polyethylene glycols of 3 to 5 oxyethylene units with propylene followed by removal of low-boiling constituents is used as solvent.
9. A process as claimed in.any of claims 1 to 8, wherein the solvent is employed in a virtually anhydrous form.
10. A process as claimed in any of claims 1 to 9, wherein the gas has an H2S partial pressure of greater than 0.05 bar or a CO2 partial pressure greater than 4 bars.
I I. A process as claimed in any of claims 1 to 10, carried out at from 20 to 400 C.
12. A process as claimed in claim I, carried out substantially as hereinbefore described with reference to Figure 1 or Figure 2 of the accompanying drawings.
13. A process for removing H2S or CO2 and H2S from a gas containing it or them, carried out substantially as described in either of the foregoing Examples 1 and 2.
GB11542/77A 1976-03-19 1977-03-18 Removal of co2 and/or h2s form gases Expired GB1574646A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2611613A DE2611613B2 (en) 1976-03-19 1976-03-19 Process for the separation of CO2 and / or H25 from gases containing these components

Publications (1)

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GB1574646A true GB1574646A (en) 1980-09-10

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JP (1) JPS5945034B2 (en)
BE (1) BE852612A (en)
CA (1) CA1091897A (en)
DE (1) DE2611613B2 (en)
FR (1) FR2344322A1 (en)
GB (1) GB1574646A (en)
NL (1) NL7702916A (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2909335A1 (en) * 1979-03-09 1980-09-18 Linde Ag METHOD AND DEVICE FOR DISASSEMBLING NATURAL GAS
DE2923012A1 (en) * 1979-06-07 1980-12-18 Basf Ag METHOD FOR THE SIMULTANEOUS REMOVAL OF WATER AND SULFURIUM FROM GASES
US4741745A (en) * 1986-05-07 1988-05-03 Norton Company Process for separation of carbon dioxide from other gases
JPH0698262B2 (en) * 1987-11-06 1994-12-07 株式会社日本触媒 Acid gas absorbent composition
US8435325B2 (en) 2008-10-23 2013-05-07 Hitachi, Ltd. Method and device for removing CO2 and H2S

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2139375A (en) * 1937-06-14 1938-12-06 Shell Dev Removal of so from gases
US3591641A (en) * 1968-10-28 1971-07-06 Allied Chem Production of dialkyl ethers of polyalkylene glycols
US3737392A (en) * 1969-06-11 1973-06-05 Allied Chem Solvent composition useful in acid gas removal from gas mixtures
DE2544569C3 (en) * 1975-10-04 1984-06-07 Basf Ag, 6700 Ludwigshafen Methyl isopropyl ether of tri-, tetra- and / or pentaethylene glycol

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Publication number Publication date
DE2611613A1 (en) 1977-10-20
CA1091897A (en) 1980-12-23
JPS52125502A (en) 1977-10-21
BE852612A (en) 1977-09-19
FR2344322A1 (en) 1977-10-14
JPS5945034B2 (en) 1984-11-02
NL7702916A (en) 1977-09-21
FR2344322B1 (en) 1982-07-16
DE2611613B2 (en) 1979-04-26

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Legal Events

Date Code Title Description
PS Patent sealed [section 19, patents act 1949]
746 Register noted 'licences of right' (sect. 46/1977)
PCNP Patent ceased through non-payment of renewal fee