CN1050527C - Process and apparatus for absorbing hydrogen sulphide - Google Patents
Process and apparatus for absorbing hydrogen sulphide Download PDFInfo
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- CN1050527C CN1050527C CN94191218A CN94191218A CN1050527C CN 1050527 C CN1050527 C CN 1050527C CN 94191218 A CN94191218 A CN 94191218A CN 94191218 A CN94191218 A CN 94191218A CN 1050527 C CN1050527 C CN 1050527C
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- hydrogen sulfide
- hydrogen
- carbon dioxide
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000008569 process Effects 0.000 title abstract description 7
- 239000000243 solution Substances 0.000 claims abstract description 106
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000007789 gas Substances 0.000 claims abstract description 67
- 238000010521 absorption reaction Methods 0.000 claims abstract description 45
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 36
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 36
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000012670 alkaline solution Substances 0.000 claims abstract description 14
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000007599 discharging Methods 0.000 claims abstract description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 64
- 230000008016 vaporization Effects 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000005864 Sulphur Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- -1 sulfur ion Chemical class 0.000 claims description 8
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 19
- 238000001704 evaporation Methods 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 abstract description 2
- 238000012856 packing Methods 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 53
- 230000009102 absorption Effects 0.000 description 41
- 239000002250 absorbent Substances 0.000 description 19
- 235000017550 sodium carbonate Nutrition 0.000 description 16
- 230000002745 absorbent Effects 0.000 description 14
- 125000005587 carbonate group Chemical group 0.000 description 13
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- 241000024287 Areas Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
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
- B01D53/34—Chemical or biological purification of waste gases
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/06—Treatment of pulp gases; Recovery of the heat content of the gases; Treatment of gases arising from various sources in pulp and paper mills; Regeneration of gaseous SO2, e.g. arising from liquors containing sulfur compounds
- D21C11/08—Deodorisation ; Elimination of malodorous compounds, e.g. sulfur compounds such as hydrogen sulfide or mercaptans, from gas streams
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working
Abstract
A process and an apparatus in black-liquor evaporation for the selective removal, by liquid absorption, of hydrogen sulphide from the generated gas (3) containing hydrogen sulphide as well as carbon dioxide, are disclosed. In the process, the gas is countercurrently brought into multistage contact, with circulating carbonate-containing alkaline solutions, preferably sodium carbonate solutions (25), the pH of which is adjusted during the absorption to about 9-12 by the addition of a hydroxide. It is preferred that the gas flow is turbulent and the liquid flow is laminar when contacted with one another. The apparatus comprises a container (1) and a packing (9) arranged in several successive stages (6, 7, 8). The apparatus has means (25) for supplying a carbonate-containing solution to the last stage and through this stage countercurrently to the gas, and for recycling the solution across this stage; conduits (29, 30) arranged between the stages for supplying a partial flow of the solution from one stage to a preceding stage; means (26, 27, 28) for supplying a hydroxide to the carbonate-containing solution in at least one of the stages ; and an outlet conduit (31) from the first stage, as seen in the feed direction of the gas, for discharging a sulphide-containing liquid.
Description
The present invention relates to the method and apparatus of absorbing hydrogen sulphide, more particularly, is the method and apparatus of optionally removing hydrogen sulfide with liquid-absorbent in black liquor vaporizing from the gas of sulfide hydrogen and carbon dioxide.
Hydrogen sulfide mainly is with sulphur hydrogen ion (HS
-) form absorbed, but also with sulphion (S
2-) form is absorbed.Total content collection with these ions is called " total sulfur ion concentration " or abbreviates " sulphion content " as below.
Use alkaline aqueous solution (as sodium hydrate aqueous solution) or monoethanolamine (as monoethanolamine or diethanol amine) to absorb, it is well-known removing hydrogen sulfide from hydrogen sulfide containing gas.This absorption process can for example be used for producing pure hydrogen sulfide, and can further be processed into sulphur with Claus method (Claus process).Except hydrogen sulfide, as containing carbon dioxide in the gas, then carbon dioxide is also absorbed by alkaline solution.Solubility and the hydrogen sulfide of carbon dioxide in water is roughly the same, so the absorption of carbon dioxide in solution will contend with hydrogen sulfide.The absorption in alkaline aqueous solution (for example NaOH) of hydrogen sulfide and carbon dioxide is carried out in the following manner:
Above-mentioned from the gas of sulfide hydrogen and carbon dioxide, in the effort of the rough sledding of absorbing hydrogen sulphide, opened up the method for selecting absorbing hydrogen sulphide correcting.For example, carried out in for example effort of selectivity absorbing hydrogen sulphide in potassium permanganate, sodium dichromate or the iron salt solutions of strong oxidizer.In other method of selecting to absorb, be to use the alkaline solution such as sodium carbonate or potash, the careful operating condition of regulating when absorbing.The more detailed data of this prior art is asked for an interview C.Oloman, F.E.Murray and J.B.Risk article " TheSelective Absorption of Hydrogen Sulphite from.Stack Gas ", be reported in " Pulp and Paper Magazine of Canada " (1969.12.5.) P.69 ff. and E.Bendall, R.C.Aiken and F.Mandas article " Selective Absorp-tion of H2S from Larger Qantities of CO2 by Absorption and Reactionin Fine Sprays ", be reported in AICHE Journal (Vol.29, No.1), 1983.1, ff. p.66
One of prior art example is described in US3, and in 554,859, it relates to the method that reclaims sulphur from the furnace gas that the burning of for example black liquor produces.The burning gases of sulfide hydrogen and carbon dioxide reach with the gas of molecule-containing keto and contact with the alkaline aqueous solution that contains sodium ion (for example with the form of NaOH with sodium carbonate or sodium carbonate and sodium bicarbonate).Therefore, hydrogen sulfide is absorbed and is oxidized to thiosulfate from gas.Add iron oxide (Fe
2O
3), absorb even more effective, sulphion concentration thereby remain on a very low level in the solution, promptly sulphion content should be low as far as possible.
Use carbonate solution such as sodium carbonate liquor to replace hydroxide solution such as sodium hydroxide solution, the absorption selectivity of hydrogen sulfide can increase to 30-50%.It is generally as follows that this absorbs the reaction that takes place:
If absorbent solution is carbonate solution, the absorption of hydrogen sulfide almost is instantaneous, and carbon dioxide only can form bicarbonate ion with the carbanion slow reaction.When using carbonate solution as absorbing medium, because the content height of the bicarbonate ion that produces, its " back-pressure " (equalizing pressure) for the absorption of carbon dioxide is another advantage, as above-mentioned equilibrium equation (6) finding.
Using carbonate solution is the sulphion content that can only reach low relatively in solution as the problem of absorbing medium, and reason is the reduction that the formation of bicarbonate ion causes absorptive capacity.Therefore, the sulphion content that obtain above about 0.3 mol is extremely difficult.As a result, the carbonate of prior art is that the whole bag of tricks that the hydrogen sulfide of absorbing medium is selected to absorb is not very successful, although there is strong requirement in the many fields of sulfide hydrogen and carbon dioxide that produce to this method.The black-liquor combustion that the example of these Application Areass has petroleum refining, Gas Production and particularly carries out in sulfate pulp industry.
When Tomlinson method routinely (Tomlinson process) reclaimed chemical agent in sulfate industry, black liquor burnt in a soda ash retracting device, consequently produced steam and formed the molten mass of mainly being made up of sodium carbonate and vulcanized sodium.This molten mass dissolves in water and causticization then, so sodium carbonate has been transformed into NaOH, and obtains a kind of white liquid, and white liquid can be used further to digest wood material.Because many reasons, comprise that pipe in the soda ash retracting device has the danger of unexpected blast, Recent study the new method of black-liquor combustion, black liquor is carried out pyrolysis under reducing condition, and does not form molten mass.This method collection is called " black liquor vaporizing ", and one of them is that (E.Horntvedt and J.Gomy, Paper Trade Journal 158 (1974): 16, pp32-34) for so-called SCA-Billerud method.In the method, black liquor carries out pyrolysis under the temperature conditions of the fuel gas that forms sode ash and the particularly sulfur-containing compound mainly be made of sodium carbonate and carbon in a reactor, another example of black liquor vaporizing sees US4,872,950, the method that it relates to is greater than the pressure of 10 crust with do not form under the temperature of molten mass to be lower than the oxygen amount that Chemical Calculation requires and to flow the result that oxygen supply makes black liquor carry out the thermal decomposition evaporation, forms mainly the solid phase is made up of sodium carbonate and the main gas of being made up of hydrogen sulfide, carbon monoxide, carbon dioxide, hydrogen, aqueous vapor and methane mutually.
EP459,962 relate to the purification of processing gas in the black liquor vaporizing, and in this purification method, gas contacts to remove sulphur compound and sodium compound wherein with the alkaline solution of sulfur-bearing hydrogen ion and hydroxyl ion.Purification method comprises two stages.In the phase I, by a venturi (Venturi) ozzle, thereby the black liquor melt aerosol drops in the gas is by solution absorption with alkaline solution for gas, then with gas with contain hydroxyl ion and contact with sulphur hydrogen ion (mol ratio was greater than 4: 1) solution.The hydrionic high molar ratio energy of hydroxyl ion and sulphur and obtain the absorbent solution of protosulphide concentration.The alkaline solution that is used to absorb as white liquid or cleaning solution, has the high pH value that is about 13-14, and its result makes the absorption selectivity of hydrogen sulfide very poor.Moreover the absorbent solution that is adopted has low carbanion content, and has pointed out that particularly the high green liquor of carbanion content can not be used as wash solution.
In order to reclaim the chemical reagent that is used for black liquor vaporizing, the black liquor vaporizing that promptly in reducing atmosphere, burns, and be used to make the white liquid of paper pulp from these chemical reagent productions, must from the gas that produces, remove hydrogen sulfide.Because also carbonated in the gas, in liquid-absorbent, carbon dioxide will be competed with hydrogen sulfide, also owing to hydrogen sulfide content low (about 0.5-2%) in the gas, and carbon dioxide content high approximately 20 times (approximately 10-20%), conventional liquid-absorbent method can not make the people satisfied to the recovery of hydrogen sulfide.
Therefore, need that from black liquor vaporizing, produce and gas sulfide hydrogen and carbon dioxide in liquid, make the method that the high-sulfur ion concentration is wherein arranged with high separation and Selective Separation hydrogen sulfide and with hydrogen sulfide absorption.
According to the present invention, have been found that and use carbonato alkaline solution the multistage absorption of adverse current that pH value of solution transfers to about 9-12 to be had high hydrogen sulfide separating degree and high hydrogen sulfide selectivity as absorbing medium and with hydro-oxidation thing rather than the method that adds new carbonate.Therefore, the present invention's separating degree of making the absorption selectivity of hydrogen sulfide reach 60-70%, hydrogen sulfide is about 90-99%.According to the present invention, the total sulfur ion concentration in the absorption liquid that flows out is high, promptly greater than 0.30 mol, be preferably greater than about 0.47 mol, normally in the scope of about 0.30-1.30 mol, preferably about 0.47-1.1 mol, particularly about 0.65-1.0 mol.This solution can be used to produce white liquid in the sulfate pulp manufacturing.
More particularly, the present invention provides the method for institute's narrating type in a kind of foreword, this method is that gas and carbonato circulation alkaline solution are carried out MULTI CONTACT, in absorption process, the pH of solution is transferred to about 9-12, make the absorbed total sulfur ion concentration of hydrogen sulfide in the outflow solution that contacts with air inlet, surpass about 0.30 mol with the method for hydro-oxidation thing.
The present invention further provides the equipment of the described type of foreword, it is characterized in that this equipment includes the container of gas feed and outlet, the filler that places a plurality of continuous levels is arranged in the container, equipment has the device (seeing the gas feed explanation) that carbonate containing solution is provided to afterbody, each grade has provides carbonato solution to counter to gas by this grade and with the device of solution through this grade circulation, equipment has the pipeline (seeing the gas feed explanation) that the solution shunting is provided from one-level to previous stage at inter-stage, equipment has at least a level provides hydroxide to transfer to the device of 9-12 with the pH with solution to carbonato solution, and from the outlet conduit (seeing the gas feed explanation) of the first order so that discharging total sulfur ion concentration surpasses the liquid of 0.30 mol.
Further distinctive feature of the present invention will be narrated below and in claims.
" carbonato alkaline solution " used herein meaning promptly contains carbanion (CO
3 2-) the aqueous solution.This solution is alkali metal carbonate solution preferably, as sodium carbonate, potash or lithium carbonate solution.Sodium carbonate is particularly preferred, because it is easy to get and is very cheap.The concentration of carbonate is not crucial in the solution, and what be fit to is about 0.1-3M carbonate, preferably about 1-2.5M, particularly about 2M.
According to the present invention, it is very important that the pH of carbonato alkaline solution is at least about 9.The pH value is lower than at about 9 o'clock, and the absorption of hydrogen sulfide can not be satisfactory, and the danger that discharges from solution of the hydrogen sulfide that will absorb in addition.But the pH value of solution can not be too high because with the absorption of carbon dioxide contrast, the absorption of hydrogen sulfide will have bad effect.Therefore, the pH of solution can not surpass about 12, so that the absorption of carbon dioxide is not too remarkable, the pH of solution is preferably in about 10.0-11.5 scope, particularly about 10.0-11.0, most preferably about 10.2-10.8.In the end in the close limit, can obtain the optimal separation of hydrogen sulfide as the pH regulator of solution.
By balanced reaction formula (5) and (6) as can be known, in the absorption of hydrogen sulfide and carbon dioxide, formed bicarbonate ion (HCO
3 -).This is the pH that has reduced absorbent solution of the absorption of explanation hydrogen sulfide and carbon dioxide.When the pH of solution was brought down below 9 left and right sides, the absorption of hydrogen sulfide becomes can not be satisfactory, as if precedingly point out, and the danger that has the hydrogen sulfide that absorbed from solution, to discharge on the contrary.If avoid this situation, solution must be regenerated, and is about to pH and increases to more than the lower limit of allowing to reach gaseous state H under temperature of discussing and pH value
2Poised state between the sulphion content in S and the solution, but the pH value can not be higher than 12, and carbon dioxide absorption is in the case taken the lead.Add the result of hydroxide such as alkali metal hydroxide (for example NaOH) with the increase of realization pH by the present invention, formed bicarbonate ion is pressed column balancing reaction being transformed into carbanion again:
So the carbonate solution of regeneration can absorb more hydrogen sulfide by above-mentioned reaction equation (5).Because the pH of solution regulates and maintains the given range of about 9-12 with hydroxide, preferably about 10.0-11.5, particularly about 10.0-11.0,10.2-10.8 most preferably from about, the absorption of carbon dioxide promptly is maintained at one can be uncared-for low-level.
On address, carbonato alkaline solution can be regenerated with adding hydroxide.Basically available hydrogen sulfide absorption is not played ill-effect and the pH of solution can be about the 9 any hydroxide that increase to the value of requirement from given lower bound, it is about 12.0 that this required value is no more than, and preferably is no more than approximately 11.5, particularly is no more than about 10.8.According to the present invention, preferably use alkali metal or alkaline earth metal hydroxide, such as NaOH (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH), calcium hydroxide (Ca (OH)
2) and magnesium hydroxide (Mg (OH)
2).NaOH is inexpensive owing to being easy to get, and is that override is selected.
The temperature of used liquid is not a key issue in the absorption of the present invention, and it can change in a wide scope, but preferably should be lower than about 80 ℃, because be about more than 80 ℃ or 80 ℃ the time in temperature, the danger that reduces hydrogen sulfide absorption is arranged just.Best temperature range is extremely about 80 ℃ of room temperatures (promptly 20 ℃), preferably about 40-70 ℃, and particularly about 50-70 ℃, most preferably from about 60-70 ℃.
The present invention finds that the hydrogen sulfide selectivity can be carried out optimization in the following manner in the liquid-absorbent: gas stream and absorption liquid stream are carried out counter current contacting, and make turbulence, liquid laminar flow.And, if with from the gas volume of absorbing hydrogen sulphide wherein relatively, the volume that absorbs liquid is bigger, then can promote the separation of hydrogen sulfide.This liquid/gas at high proportion is that the absorption liquid recirculation that will contact with hydrogen sulfide containing gas obtains.
Moreover, hydrogen sulfide containing gas with absorb contacting between liquid (carbonato solution) and comprise several levels, two or three levels preferably, but three levels most preferably.The advantage of this MULTI CONTACT is, the length of single level has been shortened, thereby the pH of carbonato solution is not free in single level reduces to approximately below 9, and the sulphion content of simultaneously upper level can remain on low-level.Degree at different levels or length preferably can make the pH of solution reduce to about 10.0-10.2 at this grade end, are recycled to this level in the liquid outflow and after with hydroxide regeneration then.
For clarity sake, the present invention will be narrated with reference to the accompanying drawings, is a preferred specific embodiments of present device shown in the accompanying drawing.
Equipment of the present invention comprises a tower or container 1, and it has the import 2 of gas 3, and gas 3 is also sulfide hydrogen and the carbon dioxide that produced by black liquor vaporizing.The opposite end of equipment has the outlet 4 of gas 5, and gas 5 is the gas of having been removed hydrogen sulfide by liquid-absorbent.Contacting between hydrogen sulfide containing gas and the carbonato solution comprises 3 levels 6,7,8.Each level contains filler 9 (as scheming shown in the middle rank 6).Be the selectivity of optimization hydrogen sulfide in absorption, the shape of filler 9 should make fluid produce laminar flow by level 6,7 and 8.The present invention finds that the tabular filler of corrugation is suitable especially this purpose.Filler can for example be made with plastics and metal.
Contacting with the adverse current form between the carbonate containing solution of absorbing hydrogen sulphide and the H 2 S-containing gas carried out.For this reason, each level all has provides carbonato solution to counter to gas by the device of this grade and with the device of solution in this grade circulation, as shown in the figure, these devices are made of pump 10,11,12, they feed carbonato alkaline solution through pipeline 13,14,15 at different levels 6,7,8, and by pipeline 16,17,18 with solution from importing collection containers 19,20,21 at different levels.Solution is recycled at different levels again from the pipeline 22,23,24 of collection container through linking to each other with pump 10,11,12 respectively, fresh carbonate solution, and preferably sodium carbonate liquor feeds last level 6 by sodium carbonate liquor storage (not shown) through pipeline 25.
Except providing the fresh carbonate solution to last level, can provide sodium hydroxide solution to produce carbonate solution and to allow hydroxide solution absorbing carbon dioxide from gas to this level, so just obtained carbonato solution by reaction equation (3)-(4).
In order to regulate the pH value of (increase) absorbent solution, can provide hydroxide solution by pipeline 26,27,28 to collection container 19,20,21 respectively, preferably sodium hydroxide solution imports alkali from the storage (not shown).Storage preferably each pipeline is common.It is to be the (not shown) that carry out on the basis with the pH value of solution value measured in the collection container 19,20,21 with the pH that regulates absorbent solution that sodium hydroxide solution is provided.
As shown in the figure, different levels can be further couple together from a level shunting of absorption liquid is fed previous stage with pipeline 20 and 30, promptly from level 6 to level 7 and from level 7 to level 8.
At last, disposed outlet 31 with liquid from container 21 and level 8 discharging sulfur compounds.
The present invention is existing to be further elaborated with limiting examples.
Example 1
This example has been carried out the test that selection removes hydrogen sulfide from the gas that black liquor vaporizing produces.Employed equipment is the equipment and as shown in drawings of the above-mentioned type.
Absorb and under atmospheric pressure carry out, about 60 ℃ of intake air temperature contains 1.13 (mole) % hydrogen sulfide and 16.9 (mole) % carbon dioxide.This gas is saturated with aqueous vapor under described temperature, is equivalent to the water of about 18.7 (mole) %.Air inlet body stream is 38,280Nm
3/ h makes that gas flow rate is about 3.1m/s in the absorption tower.Absorb tower height 6.25m, each high 1.5m of a secondary, the high 1m of afterbody is shown in the gas feed explanation.Each level has Mellapack 500 type fillers, is provided by Sulzer.Absorption tower diameter 2.3m.
Temperature be about 60 ℃ by 8.8m
3The fresh absorbent solution that the 2M sodium carbonate of/h is formed is supplied with the afterbody on absorption tower with circulating absorption solution, makes total absorbent solution of tower afterbody be about 50m
3/ h.The pH of absorption liquid is about 11.0, and owing to absorbing hydrogen sulphide, the pH of absorbent solution reduces to about 10.2 to flow of solution through this level.Solution by this level after enter 1.5m
3Collection container, add temperature at this and be about 60 ℃ 2.5M sodium hydroxide solution and regenerate, after this pH value of solution rises to 11.0 again.Actified solution is circulated to the afterbody on absorption tower to reuptake hydrogen sulfide with pump then.
About 11m
3The absorbent solution of/h flows into intergrade collection container, about thus 50m from last level collection container
3/ h pH is about 11.0 absorbent solution and is gone into intergrade by pump (as previous stage), needs the absorbent solution of the pH about 10.2 that regenerates to flow into collection container thus.In collection container, solution is about 60 ℃ 2.5M sodium hydroxide solution regeneration as previous stage through adding temperature.
By the collection container of intergrade, about 13.5m
3The absorbent solution of/h flows into the first order (lowermost level), the 50m of pH about 11.0 thus
3/ h absorbent solution is pumped to the first order (shown in the gas feed explanation).Absorbed hydrogen sulfide through behind this grade, solution (this moment, pH was about 10.2) flows into collection container.Solution is about 60 ℃ 2.5M sodium hydroxide solution regeneration adding temperature in the collection container as previous stage, makes the pH of actified solution be about 11.0.Amount to nearly 8.6m
3The 2.5M sodium hydroxide solution of/h is supplied with the collection container of three levels.
About 17.4m
3The sulphion concentration of/h is that the solution of 1 mol is emitted from the collection container of first (minimum) level.Leave gas sulfide hydrogen 0.113 (mole) % and carbon dioxide 16.4 (mole) % on absorption tower, the hydrogen sulfide separating degree of this test is about 90%, and the hydrogen sulfide selectivity is about 67% in the separation.
Have high sulfur content, have the high-load alkali carbonate simultaneously, sodium carbonate preferably, the solution that has been undertaken absorbing by the inventive method is particularly suitable for being used to produce white liquid in the manufacturing of sulfate pulp.According to the present invention, leave the solution on absorption tower behind the absorbing hydrogen sulphide, as pointed before the literary composition, the sulphion content that has surpasses about 0.30 mol, preferably surpasses 0.47 mol.Common sulphion content is in about 0.30-1.30 mol scope, preferably about 0.47-1.1 mol scope, most preferably from about 0.65-1.0 mol scope.As mentioned above, the carbonate concentration of Shi Heing is about 0.1-3M, preferably about 1-2.5M, most preferably from about 2M.
Claims (10)
1. the method for optionally removing hydrogen sulfide in the gas (3) of sulfide hydrogen that from black liquor vaporizing, produces with liquid absorption method and carbon dioxide, it is characterized in that gas (3) and the alkaline solution that contains carbanion (13,14,15) that circulates are carried out multistage (6,7,8) counter current contacting, the pH of solution transferred to 9-12 by adding hydroxide (26,27,28) when each grade absorbed, make hydrogen sulfide be absorbed as sulphur hydrogen ion and sulphion, with solution after air inlet contacts in the total sulfur ion concentration surpass 0.30 mol.
2. the described method of claim 1 is characterized in that having added alkali metal hydroxide.
3. claim 1 or 2 described methods is characterized in that the pH of solution is adjusted to 10-11.5.
4. the method for claim 1 is characterized in that the sulphion content that hydrogen sulfide is absorbed in the solution is the 0.47-1.1 mol.
5. the method for claim 1, the carbanion content that it is characterized in that containing the alkaline solution of carbanion is about 0.1-3M.
6. the method for claim 1 is characterized in that gas contacts with sodium carbonate liquor.
7. the method for claim 1 is characterized in that gas contacts with solution in three levels (6,7,8).
8. the method for claim 1 is characterized in that it is to carry out that gas contacts with solution under the condition of laminar flow and turbulent gas.
9. optionally remove the equipment of hydrogen sulfide the gas (3) that one kind is used for the sulfide hydrogen that produces from black liquor vaporizing with liquid absorption method and carbon dioxide, it is characterized in that this equipment includes the container (1) of gas feed (2) and gas vent (4), container (1) contains and is configured in a plurality of continuous levels (6,7,8) filler in (9), the afterbody of the oriented gas outlet of this equipment provides the device of the solution that contains carbanion, each grade has provides the solution that contains carbanion and back flow of gas by this grade and device that solution is circulated through this grade, this equipment is promising to be provided solution shunting and is placed in pipeline (29 between the level along be directed downwards one-level away from gas vent from one-level, 30), this equipment has the device (26 that hydroxide is provided to the solution that contains carbanion, 27,28) outlet (31) that transfers to 9-12 with the pH with each grade solution and come from the first order at gas access place contains with discharging and is absorbed into the liquid that surpasses 0.30 mol into the total sulfur ion concentration of the hydrogen sulfide of sulphur hydrogen ion and sulphion.
10. the said equipment of claim 9 is characterized in that it comprises three levels, and filler wherein (9) is the corrugated sheet shape.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE93005338 | 1993-02-18 | ||
| SE9300533A SE9300533L (en) | 1993-02-18 | 1993-02-18 | Methods and apparatus for the absorption of hydrogen sulphide |
| SE9300533-8 | 1993-02-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1118146A CN1118146A (en) | 1996-03-06 |
| CN1050527C true CN1050527C (en) | 2000-03-22 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94191218A Expired - Fee Related CN1050527C (en) | 1993-02-18 | 1994-01-18 | Process and apparatus for absorbing hydrogen sulphide |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPH08506993A (en) |
| KR (1) | KR100286384B1 (en) |
| CN (1) | CN1050527C (en) |
| AU (1) | AU6158694A (en) |
| BR (1) | BR9406271A (en) |
| CA (1) | CA2156411C (en) |
| FI (1) | FI114084B (en) |
| PL (1) | PL180733B1 (en) |
| RU (1) | RU2103050C1 (en) |
| SE (1) | SE9300533L (en) |
| WO (1) | WO1994019091A1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE501782C2 (en) * | 1993-09-17 | 1995-05-15 | Flaekt Ab | Method and apparatus for selectively removing hydrogen sulfide from a gas |
| JPH09183618A (en) * | 1995-12-28 | 1997-07-15 | Kansai Electric Power Co Inc:The | Production of gypsum |
| KR100347970B1 (en) * | 1999-08-11 | 2002-08-07 | 대경기계기술주식회사 | System for eliminating malodorous substance from malodorous gas |
| KR100415917B1 (en) * | 2001-11-14 | 2004-01-24 | 주식회사 포스코 | Method for cleaning expanded metal packing in hydrogen sulfide collecting tank |
| WO2006016979A1 (en) | 2004-07-12 | 2006-02-16 | Exxonmobil Upstream Research Company | Methods for removing sulfur-containing compounds |
| US7727374B2 (en) * | 2004-09-23 | 2010-06-01 | Skyonic Corporation | Removing carbon dioxide from waste streams through co-generation of carbonate and/or bicarbonate minerals |
| EP2030670A1 (en) * | 2007-08-31 | 2009-03-04 | Intega GmbH | Method and apparatus for removing at least one hydrogen chalcogen compound from an exhaust gas stream |
| KR100943537B1 (en) | 2008-05-27 | 2010-02-22 | 주식회사 애니텍 | An Air Cleaner with Function Capable of CO2 Removal |
| DE102009009476A1 (en) * | 2009-02-19 | 2010-08-26 | Linde-Kca-Dresden Gmbh | Process and apparatus for purifying a carbon dioxide-containing gas stream |
| US8617494B2 (en) * | 2012-03-30 | 2013-12-31 | Alstom Technology Ltd | Condenser and method for cleaning flue gases |
| CN105056709A (en) * | 2015-07-30 | 2015-11-18 | 江苏金曼科技有限责任公司 | Tail gas processing method |
| CN105854549A (en) * | 2016-05-06 | 2016-08-17 | 铜仁学院 | Mercury-containing waste gas treatment method |
| KR102325084B1 (en) * | 2019-10-04 | 2021-11-10 | 서정봉 | Composition for neutralizing acidic waste water or harmful gas having low freezing point |
| CN111330413A (en) * | 2020-02-13 | 2020-06-26 | 东营联合石化有限责任公司 | Petroleum cracking gasification substance desulfurization device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057306A (en) * | 1990-05-31 | 1991-12-25 | 剑列克公司 | The purification process of the process gas that partial combustion of black liquor produces |
| WO1993025751A1 (en) * | 1992-06-18 | 1993-12-23 | Combustion Engineering, Inc. | Circulating fluidized bed black liquor gasification process and apparatus |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE319078B (en) * | 1968-06-07 | 1969-12-22 | British Columbia Res Council | |
| SE448173B (en) * | 1985-06-03 | 1987-01-26 | Croon Inventor Ab | PROCEDURE FOR THE RECOVERY OF CELLULOSA DISPOSAL CHEMICALS BY PYROLYSIS |
-
1993
- 1993-02-18 SE SE9300533A patent/SE9300533L/en not_active Application Discontinuation
-
1994
- 1994-01-18 RU RU95118712A patent/RU2103050C1/en not_active IP Right Cessation
- 1994-01-18 BR BR9406271A patent/BR9406271A/en not_active IP Right Cessation
- 1994-01-18 WO PCT/SE1994/000030 patent/WO1994019091A1/en active IP Right Grant
- 1994-01-18 KR KR1019950703518A patent/KR100286384B1/en not_active IP Right Cessation
- 1994-01-18 AU AU61586/94A patent/AU6158694A/en not_active Abandoned
- 1994-01-18 JP JP6518871A patent/JPH08506993A/en active Pending
- 1994-01-18 PL PL94310320A patent/PL180733B1/en not_active IP Right Cessation
- 1994-01-18 CN CN94191218A patent/CN1050527C/en not_active Expired - Fee Related
- 1994-01-18 CA CA002156411A patent/CA2156411C/en not_active Expired - Fee Related
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057306A (en) * | 1990-05-31 | 1991-12-25 | 剑列克公司 | The purification process of the process gas that partial combustion of black liquor produces |
| WO1993025751A1 (en) * | 1992-06-18 | 1993-12-23 | Combustion Engineering, Inc. | Circulating fluidized bed black liquor gasification process and apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1118146A (en) | 1996-03-06 |
| JPH08506993A (en) | 1996-07-30 |
| FI114084B (en) | 2004-08-13 |
| AU6158694A (en) | 1994-09-14 |
| FI953882A0 (en) | 1995-08-17 |
| WO1994019091A1 (en) | 1994-09-01 |
| BR9406271A (en) | 1996-01-02 |
| FI953882A (en) | 1995-08-17 |
| RU2103050C1 (en) | 1998-01-27 |
| KR100286384B1 (en) | 2001-04-16 |
| SE9300533D0 (en) | 1993-02-18 |
| CA2156411A1 (en) | 1994-09-01 |
| KR960700799A (en) | 1996-02-24 |
| CA2156411C (en) | 2004-05-11 |
| SE9300533L (en) | 1994-08-19 |
| PL310320A1 (en) | 1995-12-11 |
| PL180733B1 (en) | 2001-03-30 |
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