CN1092994C - Gas decarbonization, desulfuration and decyanation technology by Fe-alkalisolution catalyst method - Google Patents
Gas decarbonization, desulfuration and decyanation technology by Fe-alkalisolution catalyst method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 77
- 238000007255 decyanation reaction Methods 0.000 title claims abstract description 21
- 238000005262 decarbonization Methods 0.000 title claims abstract description 19
- 238000006477 desulfuration reaction Methods 0.000 title claims description 20
- 239000003054 catalyst Substances 0.000 title claims description 19
- 238000005516 engineering process Methods 0.000 title abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 99
- 230000008929 regeneration Effects 0.000 claims abstract description 95
- 238000011069 regeneration method Methods 0.000 claims abstract description 95
- 239000007789 gas Substances 0.000 claims abstract description 77
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000003513 alkali Substances 0.000 claims abstract description 66
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 50
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000011593 sulfur Substances 0.000 claims abstract description 38
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 37
- 230000008569 process Effects 0.000 claims abstract description 36
- 230000006837 decompression Effects 0.000 claims abstract description 29
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 238
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 140
- 229910052742 iron Inorganic materials 0.000 claims description 78
- 238000010521 absorption reaction Methods 0.000 claims description 34
- 239000005864 Sulphur Substances 0.000 claims description 31
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 claims description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 18
- -1 iron ion Chemical class 0.000 claims description 17
- 239000006228 supernatant Substances 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 15
- 150000002506 iron compounds Chemical class 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 10
- 238000010926 purge Methods 0.000 claims description 9
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 235000018553 tannin Nutrition 0.000 claims description 7
- 229920001864 tannin Polymers 0.000 claims description 7
- 239000001648 tannin Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 229910001415 sodium ion Inorganic materials 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000001741 organic sulfur group Chemical group 0.000 claims description 5
- 230000001172 regenerating effect Effects 0.000 claims description 5
- 238000005352 clarification Methods 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229940072033 potash Drugs 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- GVPLVOGUVQAPNJ-UHFFFAOYSA-M potassium;hydron;trioxido(oxo)-$l^{5}-arsane Chemical compound [K+].O[As](O)([O-])=O GVPLVOGUVQAPNJ-UHFFFAOYSA-M 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 24
- 229910001447 ferric ion Inorganic materials 0.000 abstract description 24
- 239000002912 waste gas Substances 0.000 abstract description 4
- 150000001447 alkali salts Chemical class 0.000 abstract description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract 2
- 239000012770 industrial material Substances 0.000 abstract 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract 1
- 229960004424 carbon dioxide Drugs 0.000 description 33
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 19
- 229910001448 ferrous ion Inorganic materials 0.000 description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005261 decarburization Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 201000011510 cancer Diseases 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- AZSYUHSAQICHNK-UHFFFAOYSA-N [C]=O.[S] Chemical compound [C]=O.[S] AZSYUHSAQICHNK-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 208000030303 breathing problems Diseases 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009719 regenerative response Effects 0.000 description 1
- 208000017520 skin disease Diseases 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
The present invention relates to a gas decarbonization, desulphurization and decyanation technology by an iron-alkali catalytic process, which is used for eliminating sulfur, hydrogen cyanide and carbon dioxide in gas by basic salt water solutions containing ferric ions. High purified carbon dioxide is generated during the decompression and regeneration of solutions under the joint catalysis of hydroquinone and ferric ions; sulfur is generated during the oxidation and regeneration by air; sodium cyanide is generated during further treatment by sodium hydroxide; the solutions can be used circularly. The content of sulfur and carbon dioxide in gas can be reduced to less than 1.0*10<-6> and 0.2%(according to volume ratio) respectively by using the technology. The removal rate of hydrogen cyanide is larger than 99%; besides, industrial material gas and waste gas can be purified effectively and economically.
Description
The present invention relates to waste gas and industrial gas purifying technology, the raw material of industry gas of especially a kind of sulfur-bearing, hydrogen cyanide or carbon dioxide and the purification method of waste gas.
Because the fast development of industry, sulfur-bearing, the consumption and the discharge capacity that contain hydrogen cyanide and carbonated raw material of industry gas and waste gas are increasing.Sulfur-bearing contains hydrogen cyanide and carbonated exhaust gas discharging has caused the serious environmental pollution, for example, the formation of acid rain, the acidizing corrosion of building, and synergy causes cancer, breathing problem and skin disease etc., direct harm humans health.
Sulfur-bearing, contain hydrogen cyanide and carbonated raw material of industry gas is very harmful to industrial production, for example, cause the equipment heavy corrosion, poisoning casualty accident etc., especially even more serious to the harm of ammonia synthesizing industry, for example, cause that transformation catalyst, synthetic ammonia catalyst poisoning lose activity, copper loss increases, [referring to the Jiang Shengjie work, " synthetic ammonia engineering " (second volume), Beijing, Chemical Industry Press of CNPC publishes, and 1976], product quality descends, phenomenons such as product blackout, wherein hydrogen sulfide have the title of ammonia synthesizing industry " cancer cell ".Therefore, development and research decarbonization, desulfuration and decyanation technology seem urgent and important day by day.
Up to now, all kinds of gases seldom passed through desulfurization, decyanation or carbonization treatment before entering atmosphere, even through handling, its content is still than higher.Existing hydramine method, A.D.A. method, G-V method, aqueous slkali method, weak aqua ammonia method, tannin extract method, and doctor treatment such as sulfolane process mainly are as elementary doctor treatment, and the hydrogen sulfide that removes in the raw material of industry gas [is seen F.C.Riesenfeld, A.L.Kohl, Shen Yusheng translates, " gas purification ", Beijing, Chinese architecture publishing house, 1982], and generally not being used for removing the hydrogen sulfide of general gas, mainly is because these sulfur method cost height, seriously corroded, effect is undesirable.The acetic acid of present ferrous hydroxide, the cushioning liquid method of sodium acetate and ammonia [see 1998 " chemical industry journals ", 49 (1), P48-58] have the ability that removes multiple sulphur, and desulfurized effect is good.But, more than these methods do not have the decyanation ability.
The purpose of this invention is to provide a kind of aqueous solution decarbonization, desulfuration and decyanation method of basic salt of ion of iron content, make it have the triple tasks of decarbonization, desulfuration and decyanation, and this solution is reduced the corrosion rate of equipment gas.
The present invention is with the aqueous solution (being designated hereinafter simply as " iron alkali solution ") of the basic salt of the ion (comprising ferrous ion and ferric ion) of iron content, remove organic sulfur, inorganic sulfur, hydrogen cyanide and carbon dioxide in the gas, iron alkali solution is under the common catalysis of the ion of hydroquinones and iron, when regenerating with air oxidation, by-product sulphur, and discharge carbon dioxide, when iron alkali solution is further used naoh treatment, the by-product Cymag, the remelted pig iron aqueous slkali recycles.
The compositing range of volume concentration of gas phase is: 20%≤carbon dioxide＜100%, and total sulfur≤0.07%, hydrogen cyanide≤0.004%, other gas＜80% o'clock adopts pressurizing absorption, decompression and thermal regeneration flow process; Absorption pressure is 1.0～5.0MPa (gauge pressure), and absorbing temperature is 30～90 ℃; Regeneration pressure is 0.05～0.3MPa (absolute pressure), and regeneration temperature is 90～130 ℃; Consisting of of the iron alkali solution of use iron compound, sodium carbonate, hydroquinones and water preparation: total Na ion concentration≤6.0mol/L, total iron concentration≤0.5mol/L, hydroquinones concentration≤0.15mol/L, 3≤pH≤11.5.When sulfur content hour, also can not add hydroquinones in the pairing iron alkali solution of this flow process, in this case, except that having sulphur produces, also have a small amount of ferrous sulfide to produce during regeneration.
The compositing range of volume concentration of gas phase is: 10%≤carbon dioxide≤20%, and total sulfur≤0.1%, hydrogen cyanide≤0.04%, 79.86%≤other gas＜90% o'clock adopts pressurizing absorption, decompression regeneration flow process; Absorption pressure is 0.3～2.0MPa (gauge pressure), and absorbing temperature is 30～60 ℃; During regeneration regeneration pressure is reduced to normal pressure, regeneration temperature is 35～120 ℃; Consisting of of the iron alkali solution of use iron compound, sodium carbonate, hydroquinones and water preparation: total Na ion concentration≤2.5mol/L, total iron concentration≤1.0mol/L, hydroquinones concentration≤0.25mol/L, 3≤pH≤12.
The compositing range of volume concentration of gas phase is: carbon dioxide≤10%, 0.1%≤total sulfur＜90%, 0.04%≤hydrogen cyanide＜90%, and other gas≤99.86% o'clock adopts normal pressure to absorb, normal pressure and temperature regeneration flow process; Absorbing temperature is 30～60 ℃, and regeneration temperature is 35～80 ℃; Consisting of of the iron alkali solution of use iron compound, sodium carbonate, hydroquinones and water preparation: total Na ion concentration≤1.5mol/L, total iron concentration≤2.1mol/L, hydroquinones concentration≤0.25mol/L, 4≤pH≤12.
During the preparation of iron alkali solution of the present invention, wherein said sodium carbonate can be used replacements such as potash, sodium phosphate, potassium phosphate, Boratex, potassium borate, natrium arsenicum, Macquer's salt, alcamines; Hydroquinones can replace with tannin (being tannin extract); Iron compound can be the inorganic iron compound, also can be organoiron compound.
Catalyst of the present invention is iron compound, hydroquinones or tannin.
Basic principle of the present invention is as follows:
When gas contacted with iron alkali solution, following absorption reaction took place:
CS in more than reacting
2, COS, R-SH,
Be respectively carbon disulfide, the sulphur carbonoxide, mercaptan and thiophenol, they belong to volatility organic sulfur compounds.
Absorbed the aqueous solution (being iron alkali solution) of sodium carbonate of ion of the iron content of sulphur, hydrogen cyanide and carbon dioxide, be designated hereinafter simply as " rich solution "." rich solution " under the common catalysis of the ion of hydroquinones and iron, with air oxidation regeneration, regenerative response is as follows:
" rich solution " after air oxidation regeneration is transformed into " lean solution ", and " lean solution " recycles; CN in " lean solution "
-Or SO
4 2-The concentration of ion is during greater than 0.001mol/L, extract part " lean solution " and use naoh treatment, can produce canescence sol layer and supernatant layer, canescence sol layer retrieval system reclaims to be used, Cymag in the extraction supernatant layer and sodium sulphate are as byproduct, and remaining liquid also can return " lean solution " system; Following reaction can take place in processing procedure:
In order to realize above-mentioned basic principle, designed three kinds of production procedures by the compositing range of gas with various: first kind is pressurizing absorption, decompression and thermal regeneration flow process; Second kind is pressurizing absorption decompression regeneration flow process; The third is that normal pressure absorbs, normal pressure and temperature regeneration flow process.
Carbanion in first kind of flow process iron alkali solution, bicarbonate ion, the concrete concentration of ferrous ion and ferric ion there is no need to stipulate exactly, because carbon dioxide a large amount of in absorption process change iron alkali solution over to, carbanion in the iron alkali solution almost all is transformed into bicarbonate ion, and contain a large amount of free carbon dioxides, at this moment the concentration of the carbanion in the iron alkali solution is almost nil, when decompression and thermal regeneration, discharge great amount of carbon dioxide in the iron alkali solution, bicarbonate ion wherein resolves into carbon dioxide and carbanion, and promptly the concentration of carbanion in the cyclic process of iron alkali solution and bicarbonate ion is marked change; Iron alkali solution is when air regenesis, ferrous ion is by the excellent one-tenth ferric ion of oxygen, when absorbing sulphur, ferric ion is reduced into elemental sulfur with sulphion, simultaneously, ferric ion is transformed into ferrous ion, and promptly the concentration of ferrous ion in the cyclic process of iron alkali solution and ferric ion is marked change, but the maximum value of ferrous ion and ferric ion concentration is 0.5mol/L in the iron alkali solution.Because iron alkali solution has adopted ferrous ion and the ferric ion main component as desulfuration and decyanation, generate the sulfur-bearing of corresponding iron ion or contained the complex compound and the sulphur of cyanogen, when decompression and thermal regeneration, these complex compounds can not decompose, so, not containing corresponding volatile organic sulfur and inorganic sulfur and hydrogen cyanide in the carbon dioxide of regeneration gained, these complex compounds and sulphur are when further using air regenesis, form the sulphur foam, separate together and remove.In the gas after this method is handled, carbon dioxide content is less than or equal to 0.2% (volume content), and total sulfur content is less than or equal to 1.0 * 10
-6(volume content), the hydrogen cyanide removal efficiency is greater than 90%; The carbon dioxide purity of regeneration gained reaches more than 99% (volume content), does not contain corresponding volatile organic sulfur and inorganic sulfur and hydrogen cyanide.
The concrete concentration of carbanion, bicarbonate ion, ferrous ion and ferric ion in second kind of flow process iron alkali solution there is no need to stipulate exactly, because carbon dioxide a large amount of in absorption process change iron alkali solution over to, carbanion major part in the iron alkali solution is transformed into bicarbonate ion, when regeneration, discharge carbon dioxide in the iron alkali solution, bicarbonate ion wherein resolves into carbon dioxide and carbanion, and promptly the concentration of carbanion in the cyclic process of iron alkali solution and bicarbonate ion changes; Iron alkali solution is when air regenesis, ferrous ion is oxidized to ferric ion, when absorbing sulphur, ferric ion is reduced into elemental sulfur with sulphion, simultaneously, ferric ion is transformed into ferrous ion, and promptly the concentration of ferrous ion in the cyclic process of iron alkali solution and ferric ion changes, but the maximum value of ferrous ion and ferric ion concentration is 1.0mol/L in the iron alkali solution.In the gas after this method is handled, the carbon dioxide eliminating rate is 3.0～20% (volume contents), and total sulfur content is less than or equal to 1.0 * 10
-6(volume content), the hydrogen cyanide removal efficiency is greater than 95%.And by-product sulphur and Cymag.
The concrete concentration of carbanion, bicarbonate ion, ferrous ion and ferric ion in the third flow process iron alkali solution there is no need to stipulate exactly, because carbon dioxide a large amount of in absorption process change iron alkali solution over to, carbanion in the iron alkali solution almost all is transformed into bicarbonate ion, when regeneration, discharge carbon dioxide in the iron alkali solution, bicarbonate ion wherein resolves into carbon dioxide and carbanion, and promptly the concentration of carbanion in the cyclic process of iron alkali solution and bicarbonate ion changes; Iron alkali solution is when air regenesis, ferrous ion is oxidized to ferric ion, when absorbing sulphur, ferric ion is reduced into elemental sulfur with sulphion, simultaneously, ferric ion is transformed into ferrous ion, and promptly the concentration of ferrous ion in the cyclic process of iron alkali solution and ferric ion changes, but the maximum value of ferrous ion and ferric ion concentration is 2.1mol/L in the iron alkali solution.In the gas after this method is handled, the carbon dioxide eliminating rate is about 3.0% (volume content), and the removal efficiency of sulphur is more than 99%, and the hydrogen cyanide removal efficiency is greater than 99.5%.And by-product sulphur and Cymag.
Owing to contain the ferrous ion and the ferric ion of higher concentration in the iron alkali solution of the present invention, from Chemical Kinetics and thermodynamics and chemical reaction equilibrium point of theory, can reduce the reaction speed that fe is oxidized to ferrous ion or ferric ion effectively, promptly alleviated the corrosivity of iron alkali solution, prolonged the service life of equipment equipment.
The present invention and traditional hydramine method, A.D.A. method, G-V method, aqueous slkali method, weak aqua ammonia method, tannin extract method, and decarburization such as sulfolane process compare with doctor treatment, has following advantage: 1. these traditional methods, in the pressurization decarburization, during decompression regeneration, contain some impurity such as sulphur in the carbon dioxide of regeneration gained, with the method for indication of the present invention, in the pressurization decarburization, during decompression regeneration, the purity height of the carbon dioxide of regeneration gained, the content of some impurity such as sulphur is seldom; 2. these traditional methods, do not have the effect that removes carbon dioxide and sulphur simultaneously, and do not have the ability of organic sulfide removal and hydrogen cyanide, the method for indication of the present invention, have the decarbonization, desulfuration and decyanation tricapability, and have the ability that removes multiple organic sulfur and multiple inorganic sulfur; 3. traditional method corrosivity is big, and this method corrosivity is little; When 4. this method is used for the decarbonization process of Ammonia Production line, can make decarbonizing liquid have the ability of decarbonization, desulfuration and decyanation simultaneously, so, the dry desulfurization operation in the original production flow process can be discarded.
Below in conjunction with specific embodiment embodiment of the present invention are described.
Fig. 1 is a pressurizing absorption, the enforcement schematic diagram of decompression and thermal regeneration flow process.
(1) purifying column, (2) semi-leanpump, (3) semi lean solution defecator, (4) lean pump, (5) lean solution defecator, (6) air regenesis groove, (7) air pump, (8) alkali regeneration tank, (9) catalyst adds groove, (10) semi lean solution heat exchanger, (11) lean solution heat exchanger, (12) decompression thermal regeneration tower, (13) steam flash vessel, (14) gas, (15) Purge gas, (16) steam under pressure, (17) regenerating carbon dioxide gas, (18) rich solution, (19) semi lean solution, (20) lean solution, (21) air, drop a hint (22), (23) sodium hydroxide solution, (24) sodium cyanide-containing supernatant layer, (25) contain the suspension layers of iron ion, the accessory substance of (26) sulfur-bearing.
Fig. 2 is a pressurizing absorption, the enforcement schematic diagram of decompression regeneration flow process.
(1) purifying column, (27) turbine type desulfur pump, (28) spray the absorption and regeneration groove, (8) alkali regeneration tank, (9) catalyst adds groove, (14) gas, (15) Purge gas, (18) rich solution, (20) lean solution, (25) contain the suspension layers of iron ion, (24) sodium cyanide-containing supernatant layer, (23) sodium hydroxide solution, (21) air, (22) drop a hint the accessory substance of (26) sulfur-bearing.
Fig. 3 is that normal pressure absorbs, the enforcement schematic diagram of normal pressure and temperature regeneration flow process.
(1) purifying column, (4) lean pump, (28) spray the absorption and regeneration groove, (8) alkali regeneration tank, (9) catalyst adds groove, (14) gas, (15) Purge gas, (18) rich solution, (20) lean solution, (25) contain the suspension layers of iron ion, (24) sodium cyanide-containing supernatant layer, (23) sodium hydroxide solution, (21) air, (22) drop a hint the accessory substance of (26) sulfur-bearing.
Embodiment one as shown in Figure 1, Fig. 1 is applicable to first kind of flow process, is pressurizing absorption, decompression and thermal regeneration flow process, gas (14) enters bottom the purifying column (1), successively and semi lean solution (19) and lean solution (20) counter current contacting; Sulphur, carbon dioxide and hydrogen cyanide in the gas (14) absorbed by semi lean solution (19) and lean solution (20), and gas (14) is transformed into Purge gas (15) and goes out from purifying column (1) top; The semi lean solution (19) and the lean solution (20) that have absorbed sulphur, carbon dioxide and hydrogen cyanide are mixed in purifying column (1) bottom, are transformed into rich solution (18); Rich solution (18) drives semi-leanpump (2) from the ejection of purifying column (1) end, and pressure can be passed to semi-leanpump (2); The rich solution (18) that has discharged energy enters semi lean solution heat exchanger (10), and semi lean solution (19) carries out heat exchange, and semi lean solution (19) temperature is reduced, and the temperature of rich solution (18) rises; The rich solution (18) that has absorbed heat enters lean solution heat exchanger (11) again and lean solution (20) is carried out heat exchange, reduces the temperature of lean solution (20), simultaneously, the temperature of rich solution (18) is further raise; The rich solution (18) that comes out from lean solution heat exchanger (11) enters decompression thermal regeneration tower (12) from the top, thermal regeneration reduces pressure in tower, discharge regenerating carbon dioxide gas (17), rich solution (18) becomes semi lean solution (19), part semi lean solution (19) is drawn from the middle part of decompression thermal regeneration tower (12), enter steam flash vessel (13) and carry out vacuum flashing regeneration, inject semi lean solution defecator (3) then and clarify separation, isolate the accessory substance (26) of sulfur-bearing, the accessory substance (26) that reclaims sulfur-bearing can prepare sulphur etc., be delivered to semi lean solution heat exchanger (10) by semi-leanpump (2) and rich solution (18) carries out heat exchange through the semi lean solution (19) of semi lean solution defecator (3) clarification, be lowered temperature, the semi lean solution (19) that has reduced temperature enters purifying column (1) from the middle part; Another part semi lean solution (19) continues to flow into the bottom of decompression thermal regeneration tower (12), carry out further thermal regeneration, become lean solution (20), flow out from the bottom of decompression thermal regeneration tower (12), enter lean solution heat exchanger (11), carry out heat exchange, temperature is lowered, the lean solution (20) that has reduced temperature enters air regenesis groove (6), air pump (7) blasts air (21) in the air regenesis groove (6), and lean solution (20) is mixed, in air regenesis groove (6), sulphion in the lean solution (20) etc. is changed into elemental sulfur by Catalytic Oxygen, and the accessory substance (26) that forms sulfur-bearing is removed; Air (21) becomes drop a hint (22) and is discharged into the external world; Lean solution (20) through air regenesis is clarified in lean solution defecator (5), isolate the accessory substance (26) of sulfur-bearing wherein, the lean solution (20) of clarification and catalyst add the catalyst or the fresh solution of coming in the groove (9) and join, and mixed, be transported to the purifying column (1) from the top by lean pump (4) together.When being higher than 0.001 mol through the cyanide ion content in the lean solution (20) of air regenesis, take out part lean solution (20), put into alkali regeneration tank (8), to wherein adding sodium hydroxide solution (23), be divided into sodium cyanide-containing supernatant layer (24) after the reaction and contain the suspension layers (25) of iron ion, the suspension layers (25) that contains iron ion is injected lean solution defecator (5) and lean solution (20) mixing, discharging sodium cyanide-containing supernatant layer (24) and recovery Cymag wherein.When the content of cyanide ion the lean solution (20) of coming out from lean solution heat exchanger (11) and sulphion all is lower than 0.001 mol, lean solution (20) there is no need to carry out air regenesis and NaOH regeneration, at this moment, lean solution (20) directly enters in the lean solution defecator (5), recycles.The part of steam under pressure (16) enters the injector head of steam flash vessel (13), pressure in the steam flash vessel (13) is reduced suddenly, semi lean solution wherein (19) discharges carbon dioxide, carbon dioxide that discharges and steam are mixed, enter decompression thermal regeneration tower (12) from the middle part, heating semi lean solution (19); Another part steam under pressure (16) enters the lean solution among the heating tower (20) from decompression thermal regeneration tower (12) bottom.
Embodiment two as shown in Figure 2, Fig. 2 is applicable to second kind of flow process, it is pressurizing absorption, decompression regeneration flow process, wherein: gas (14) enters purifying column (1) and lean solution (20) counter current contacting from the bottom, absorb sulphur, hydrogen cyanide and partial CO 2 in the gas (14), gas (14) becomes Purge gas (15), comes out from the top of purifying column (1); The lean solution (20) that has absorbed sulphur, hydrogen cyanide and partial CO 2 in the gas (14) is transformed into rich solution (18), come out from the bottom of purifying column (1), pressure can be transferred to turbine type desulfur pump (27), enter and spray absorption and regeneration groove (28), spray and absorb air (21); Rich solution (18) mixes in spraying absorption and regeneration groove (28) with air (21); Rich solution (18) discharges the accessory substance (26) of carbon dioxide and sulfur-bearing in the oxidation of air (21) and decompression regeneration down, and the carbon dioxide of release and air (21) mix formation drops a hint (22), the discharge system, and simultaneously, rich solution (18) is transformed into lean solution (20); Lean solution (20) and the catalyst that comes from catalyst interpolation groove (9) or fresh solution are mixed, and are transported to the purifying column (1) from the top by turbine type desulfur pump (27).When the content of the cyanide ion in the lean solution (20) after spraying absorption and regeneration groove (28) regeneration is higher than 0.001 mol, take out part lean solution (20), inject alkali regeneration tank (8), and adding sodium hydroxide solution (23), make it reaction, be divided into the suspension layers (25) and the sodium cyanide-containing supernatant layer (24) that contain iron ion after the reaction, the suspension (25) and the main flow lean solution (20) that contain iron ion are mixed, and recycle; Reclaim sodium cyanide-containing supernatant layer (24) taking-up Cymag wherein.
Embodiment three as shown in Figure 3, Fig. 3 is applicable to the third flow process, be that normal pressure absorbs, normal pressure and temperature regeneration flow process, wherein gas (14) enters purifying column (1) lean solution (20) counter current contacting next with the top from the bottom, and sulphur wherein, hydrogen cyanide and partial CO 2 change in the lean solution (20), at this moment, gas (14) becomes Purge gas (15), and lean solution (20) becomes rich solution (18); Rich solution (18) enters and sprays absorption and regeneration groove (28), and air self-suction (21), the air of self-priming (21) is mixed in spraying absorption and regeneration groove (28) with rich solution (18), rich solution (18) is become lean solution (20) by air (21) oxidation regeneration, and the sulphur in the rich solution (18) is oxidized to accessory substance (26) the discharge injection absorption and regeneration groove (28) that elemental sulfur forms sulfur-bearing; The carbon dioxide mix that air (21) that absorbs and rich solution (18) discharge forms drop a hint (22) and is discharged; Lean solution (20) and the catalyst mix of coming from catalyst interpolation groove (9) are sent into purifying column (1) by lean pump (4) from the top.When in the lean solution (20) of outflow from spray absorption and regeneration groove (28) the content of cyanide ion when being higher than 0.001 mol, take out part lean solution (20), inject alkali regeneration tank (8), and adding sodium hydroxide solution (23), make it reaction, be divided into the suspension layers (25) and the sodium cyanide-containing supernatant layer (24) that contain iron ion after the reaction, the suspension layers (25) and the main flow lean solution (20) that contain iron ion are mixed, and recycle; Reclaim sodium cyanide-containing supernatant layer (24) taking-up Cymag wherein.
Claims (10)
1. iron-alkali solution catalyzing gas decarbonization, desulfuration and decyanation method, it is characterized in that the iron alkali solution that is made into iron compound, sodium carbonate, hydroquinones and water, remove organic sulfur, inorganic sulfur, hydrogen cyanide and carbon dioxide in the gas, iron alkali solution under the common catalysis of hydroquinones and iron compound, when regenerating with air oxidation, by-product sulphur, and discharge carbon dioxide, when iron alkali solution is further used naoh treatment, the by-product Cymag, the iron alkali solution after the regeneration recycles.
2. iron as claimed in claim 1-alkali solution catalyzing gas decarbonization, desulfuration and decyanation method, the compositing range that it is characterized in that volume concentration of gas phase is: 20%≤carbon dioxide＜100%, total sulfur≤0.07%, hydrogen cyanide≤0.004%, other gas＜80% o'clock, adopt pressurizing absorption, decompression and thermal regeneration flow process; Absorption pressure is 1.0～5.0MPa gauge pressure, and absorbing temperature is 30～90 ℃; Regeneration pressure is 0.05～0.3MPa absolute pressure, regeneration temperature is 90～130 ℃: the iron alkali solution that uses iron compound, sodium carbonate, hydroquinones and water preparation, it consists of: total Na ion concentration≤6.0mol/L, total iron concentration≤0.5mol/L, hydroquinones concentration≤0.15mol/L, 3≤pH≤11.5.
3. iron as claimed in claim 2-alkali solution catalyzing gas decarbonization, desulfuration and decyanation method is characterized in that gas (14) enters from purifying column (1) bottom, successively and semi lean solution (19) and lean solution (20) counter current contacting; Sulphur, carbon dioxide and hydrogen cyanide in the gas (14) absorbed by semi lean solution (19) and lean solution (20), and gas (14) is transformed into Purge gas (15) and comes out from purifying column (1) top; The semi lean solution (19) and the lean solution (20) that have absorbed sulphur, carbon dioxide and hydrogen cyanide are mixed in purifying column (1) bottom, are transformed into rich solution (18); Rich solution (18) drives semi-leanpump (2) from the ejection of purifying column (1) bottom, and pressure can be passed to semi-leanpump (2); The rich solution (18) that has discharged energy enters semi lean solution heat exchanger (10), and semi lean solution (19) carries out heat exchange, and semi lean solution (19) temperature is reduced, and the temperature of rich solution (18) rises; The rich solution (18) that has absorbed heat enters lean solution heat exchanger (11) again and lean solution (20) is carried out heat exchange, reduces the temperature of lean solution (20), simultaneously, the temperature of rich solution (18) is further raise; The rich solution (18) that comes out from lean solution heat exchanger (11) enters decompression thermal regeneration tower (12) from the top, thermal regeneration reduces pressure in tower, discharge regenerating carbon dioxide gas (17), rich solution (18) becomes semi lean solution (19), a part is carried out vacuum flashing regeneration, inject semi lean solution defecator (3) then and clarify separation, isolate the accessory substance (26) of sulfur-bearing, the accessory substance (26) that reclaims sulfur-bearing can prepare sulphur etc., be delivered to semi lean solution heat exchanger (10) by semi-leanpump (2) and rich solution (18) carries out heat exchange through the semi lean solution (19) of semi lean solution defecator (3) clarification, be lowered temperature, the semi lean solution (19) that has reduced temperature enters purifying column (1) from the middle part; Another part semi lean solution (19) continues to flow into the bottom of decompression thermal regeneration tower (12), carry out further thermal regeneration, become lean solution (20), flow out from the bottom of decompression thermal regeneration tower (12), enter lean solution heat exchanger (11), carry out heat exchange, temperature is lowered, the lean solution (20) that has reduced temperature enters air regenesis groove (6), air pump (7) blasts air (21) in the air regenesis groove (6), and lean solution (20) is mixed, in air regenesis groove (6), sulphion in the lean solution (20) etc. is changed into elemental sulfur by Catalytic Oxygen, and the accessory substance (26) that forms sulfur-bearing is removed; Air (21) becomes drop a hint (22) and is discharged into the external world; Lean solution (20) through air regenesis is clarified in lean solution defecator (5), isolate the accessory substance (26) of sulfur-bearing wherein, catalyst that comes in the lean solution (20) of clarification and the catalyst interpolation groove (9) or fresh solution can merge mixed, are transported to the purifying column (1) from the top by lean pump (4) together; When being higher than 0.001 mol through the cyanide ion content in the lean solution (20) of air regenesis, take out part lean solution (20), put into alkali regeneration tank (8), to wherein adding sodium hydroxide solution (23), be divided into sodium cyanide-containing supernatant layer (24) after the reaction and contain the suspension layers (25) of iron ion, the suspension layers (25) that contains iron ion is injected lean solution defecator (5) and lean solution (20) mixing, discharges sodium cyanide-containing supernatant layer (24) and recovery Cymag wherein; When the content of cyanide ion the lean solution (20) of coming out from lean solution heat exchanger (11) and sulphion all is lower than 0.001 mol, lean solution (20) there is no need to carry out air regenesis and NaOH regeneration, at this moment, lean solution (20) directly enters in the lean solution defecator (5), recycles; The part of steam under pressure (16) enters the injector head of steam flash vessel (13), pressure in the steam flash vessel (13) is reduced suddenly, semi lean solution wherein (19) discharges carbon dioxide, carbon dioxide that discharges and steam are mixed, enter decompression thermal regeneration tower (12) from the middle part, heating semi lean solution (19); Another part steam under pressure (16) enters the lean solution (20) in the thermal regeneration tower (12) from decompression thermal regeneration tower (12) bottom.
4. iron as claimed in claim 1-alkali solution catalyzing gas decarbonization, desulfuration and decyanation method, the compositing range that it is characterized in that volume concentration of gas phase is: 10%≤carbon dioxide≤20%, total sulfur≤0.1%, hydrogen cyanide≤0.04%, 79.86%≤other gas＜90% o'clock, adopt pressurizing absorption, decompression regeneration flow process; Absorption pressure is 0.3～2.0MPa gauge pressure, and absorbing temperature is 30～60 ℃; During regeneration regeneration pressure is reduced to normal pressure, regeneration temperature is 35～120 ℃; Use the iron alkali solution of iron compound, sodium carbonate, hydroquinones and water preparation, it consists of: total Na ion concentration≤2.5mol/L, total iron concentration≤1.0mol/L, hydroquinones concentration≤0.25mol/L, 3≤pH≤12.
5. iron as claimed in claim 4-alkali solution catalyzing gas decarbonization, desulfuration and decyanation method, it is characterized in that gas (14) enters purifying column (1) and lean solution (20) counter current contacting from the bottom, absorb sulphur, hydrogen cyanide and partial CO 2 in the gas (14), gas (14) becomes Purge gas (15), comes out from the top of purifying column (1); The lean solution (20) that has absorbed sulphur, hydrogen cyanide and partial CO 2 in the gas (14) is transformed into rich solution (18), come out from the bottom of purifying column (1), pressure can be transferred to turbine type desulfur pump (27), enter and spray absorption and regeneration groove (28), spray and absorb air (21); Rich solution (18) mixes in spraying absorption and regeneration groove (28) with air (21); Rich solution (18) discharges the accessory substance (26) of carbon dioxide and sulfur-bearing in the oxidation of air (21) and decompression regeneration down, and the carbon dioxide of release and air (21) mix formation drops a hint (22), the discharge system, and simultaneously, rich solution (18) is transformed into lean solution (20); Lean solution (20) and the catalyst that comes from catalyst interpolation groove (9) or fresh solution are mixed, and are transported to the purifying column (1) from the top by turbine type desulfur pump (27); When the content of the cyanide ion in the lean solution (20) after spraying absorption and regeneration groove (28) regeneration is higher than 0.001 mol, take out part lean solution (20), inject alkali regeneration tank (8), and adding sodium hydroxide solution (23), make it reaction, be divided into the suspension layers (25) and the sodium cyanide-containing supernatant layer (24) that contain iron ion after the reaction, the suspension layers (25) and the main flow lean solution (20) that contain iron ion are mixed, and recycle; Reclaim sodium cyanide-containing supernatant layer (24), take out Cymag wherein.
6. iron as claimed in claim 1-alkali solution catalyzing gas decarbonization, desulfuration and decyanation method, the compositing range that it is characterized in that volume concentration of gas phase is: carbon dioxide≤10%, 0.1%≤total sulfur＜90%, 0.04%≤hydrogen cyanide＜90%, other gas≤99.86% o'clock, the employing normal pressure absorbs, normal pressure and temperature regeneration flow process; Absorbing temperature is 30～60 ℃, and regeneration temperature is 35～80 ℃; It consists of the iron alkali solution of use iron compound, sodium carbonate, hydroquinones and water preparation: total Na ion concentration≤1.5mol/L, total iron concentration≤2.1mol/L, hydroquinones concentration≤0.25mol/L, 4≤pH≤12.
7. iron as claimed in claim 6-alkali solution catalyzing gas decarbonization, desulfuration and decyanation method, it is characterized in that gas (14) enters purifying column (1) lean solution (20) counter current contacting next with the top from the bottom, sulphur wherein, hydrogen cyanide and partial CO 2 change in the lean solution (20), at this moment, gas (14) becomes Purge gas (15), and lean solution (20) becomes rich solution (18); Rich solution (18) enters and sprays absorption and regeneration groove (28), and air self-suction (21), the air of self-priming (21) is mixed in spraying absorption and regeneration groove (28) with rich solution (18), rich solution (18) is become lean solution (20) by air (21) oxidation regeneration, and the sulphur in the rich solution (18) is oxidized to accessory substance (26) the discharge injection absorption and regeneration groove (28) that elemental sulfur forms sulfur-bearing; The carbon dioxide mix that air (21) that absorbs and rich solution (18) discharge forms drop a hint (22) and is discharged; Lean solution (20) and the catalyst mix of coming from catalyst interpolation groove (9) are sent into purifying column (1) by lean pump (4) from the top; When the content of the cyanide ion in the lean solution (20) that flows out from spray absorption and regeneration groove (28) is higher than 0.001 mol, take out part lean solution (20), inject alkali regeneration tank (8), and adding sodium hydroxide solution (23), make it reaction, be divided into the suspension layers (25) and the sodium cyanide-containing supernatant layer (24) that contain iron ion after the reaction, the suspension layers (25) and the main flow lean solution (20) that contain iron ion are mixed, and recycle; Reclaim sodium cyanide-containing supernatant layer (24), take out Cymag wherein.
8. claim 2 or 4 or 6 described iron-alkali solution catalyzing gas decarbonization, desulfuration and decyanation method is characterized in that preparing used sodium carbonate and can use potash or sodium phosphate or potassium phosphate or Boratex or potassium borate or natrium arsenicum or Macquer's salt or alcamines replacement.
9. claim 2 or 4 or 6 described iron-alkali solution catalyzing gas decarbonization, desulfuration and decyanation method, it is characterized in that preparing used hydroquinones can be that tannin extract replaces with tannin.
10. claim 2 or 4 or 6 described iron-alkali solution catalyzing gas decarbonization, desulfuration and decyanation method, it is characterized in that preparing used iron compound can be the inorganic iron compound, also can be organoiron compound.
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| CN100438950C (en) * | 2003-12-26 | 2008-12-03 | 南化集团研究院 | Removing sulfide from CO2 enriched gas by complex iron method |
| CN101108337B (en) * | 2007-07-06 | 2010-09-22 | 萍乡庞泰实业有限公司 | Hydrogen cyanide decomposing catalyst |
| CN102604702A (en) * | 2012-04-01 | 2012-07-25 | 中国石油化工股份有限公司 | Purification method for low latent sulfur content natural gas |
| CN103432890B (en) | 2013-09-10 | 2015-12-09 | 北京博源恒升高科技有限公司 | Modified poly (ethylene glycol) removes the method for SOx in gas |
| CN103495340B (en) | 2013-10-15 | 2015-11-18 | 北京博源恒升高科技有限公司 | The method of SOx in compound alcamines solution removal gas |
| CN103611391B (en) | 2013-12-12 | 2016-01-20 | 北京博源恒升高科技有限公司 | Glycols composite solution removes the method for SOx in gas |
| CN103623689B (en) | 2013-12-12 | 2016-06-29 | 北京博源恒升高科技有限公司 | The method of SOx in polyhydric alcohol composite solution elimination gas |
| CN104069730B (en) * | 2014-07-15 | 2015-10-21 | 袁磊 | A kind of process contains the CO 2 aerated device and method of cyanogen |
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| JPS52111467A (en) * | 1976-03-16 | 1977-09-19 | Kureha Chem Ind Co Ltd | Improved double alkali desulfurization of exhaust gas |
| CN1133817A (en) * | 1996-02-17 | 1996-10-23 | 魏雄辉 | Pressurized decarburizing and desulfurizing in iron-alkali solution |
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Assignee: Zhangjiagang Huayuan Chemical Co., Ltd. Assignor: Beijing Boyuan Hengsheng High-Technology Co., Ltd. Contract fulfillment period: In August 19, 2003, 1 years Contract record no.: 200210135 Denomination of invention: Desulfurization and cyanide removal of gas by iron alkali solution catalysis Granted publication date: 20021023 License type: General Record date: 20020925 Assignee: Shaowu chemical fertilizer plant of Fujian Province Assignor: Beijing Boyuan Hengsheng High-Technology Co., Ltd. Contract fulfillment period: In September 5, 2004, 2 years Contract record no.: 200210134 Denomination of invention: Desulfurization and cyanide removal of gas by iron alkali solution catalysis Granted publication date: 20021023 License type: General Record date: 20020925 Assignee: Hunan Tianrun chemical development Limited by Share Ltd Assignor: Beijing Boyuan Hengsheng High-Technology Co., Ltd. Contract fulfillment period: In September 10, 2005, 3 years Contract record no.: 200210136 Denomination of invention: Desulfurization and cyanide removal of gas by iron alkali solution catalysis Granted publication date: 20021023 License type: General Record date: 20020925 Assignee: Fujian province clean ammonia chemical Co. Ltd. Sheng Assignor: Beijing Boyuan Hengsheng High-Technology Co., Ltd. Contract fulfillment period: In August 31, 2003, 1 years Contract record no.: 200210137 Denomination of invention: Desulfurization and cyanide removal of gas by iron alkali solution catalysis Granted publication date: 20021023 License type: General Record date: 20020925 Assignee: Shandong Luxi Chemical Limited by Share Ltd Luxi branch Assignor: Beijing Boyuan Hengsheng High-Technology Co., Ltd. Contract fulfillment period: In February 7, 2019, 17 years, the patent expires Contract record no.: 200210138 Denomination of invention: Desulfurization and cyanide removal of gas by iron alkali solution catalysis Granted publication date: 20021023 License type: General Record date: 20020925 |
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Free format text: LICENCE; TIME LIMIT OF IMPLEMENTING CONTACT: 2003.8.31, 1 YEAR Name of requester: QINGLIU ANSHENG CHEMICAL CO.,LTD.,FUJIAN PROVINCE Effective date: 20020925 Free format text: LICENCE; TIME LIMIT OF IMPLEMENTING CONTACT: 2005.9.10, 3 YEARS Name of requester: HUNAN TIANRUN CHEMICAL DEVELOPMENT STOCK CO., LTD Effective date: 20020925 Free format text: LICENCE; TIME LIMIT OF IMPLEMENTING CONTACT: 2003.8.19, 1 YEAR Name of requester: ZHANGJIAGANG HUAYUAN CHEMICAL CO., LTD. Effective date: 20020925 Free format text: LICENCE; TIME LIMIT OF IMPLEMENTING CONTACT: 2019.2.7, 17 YEARS, EXPIRATION OF PATENT RIGHT Name of requester: SHANDONG LUXI CHEMICAL ENGINEERING CO., LTD. LUXI Effective date: 20020925 Free format text: LICENCE; TIME LIMIT OF IMPLEMENTING CONTACT: 2004.9.5, 2 YEARS Name of requester: SHAOWU CHEMICAL FERTILIZER PLANT, FUJIAN PROVINCE Effective date: 20020925 |
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Assignee: Yongfeng Boyuan Industrial Co., Ltd. Assignor: Wei Xionghui Contract record no.: 2010360000027 Denomination of invention: Gas decarbonization, desulfuration and decyanation technology by Fe-alkalisolution catalyst method Granted publication date: 20021023 License type: Exclusive License Open date: 19990901 Record date: 20100625 |
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Assignee: Jiangxi Yongfeng Boyuan Industrial Co., Ltd. Assignor: Wei Xionghui Contract record no.: 2010360000027 Date of cancellation: 20140422 |
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Application publication date: 19990901 Assignee: Jiangxi Yongfeng Boyuan Industrial Co., Ltd. Assignor: Wei Xionghui Contract record no.: 2014990000307 Denomination of invention: Method for desulfurization and de cyanide of gas by iron alkali solution catalysis Granted publication date: 20021023 License type: Exclusive License Record date: 20140519 |
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Change date: 20160818 Contract record no.: 2014990000307 Assignee after: Jiangxi Yongfeng Boyuan Industrial Co. Ltd. Assignee before: Jiangxi Yongfeng Boyuan Industrial Co., Ltd. |
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Granted publication date: 20021023 |