CN116477580A - A process and system for recyclable hydrogen sulfide adsorbent to decompose gas to sulfur - Google Patents
A process and system for recyclable hydrogen sulfide adsorbent to decompose gas to sulfur Download PDFInfo
- Publication number
- CN116477580A CN116477580A CN202310465095.3A CN202310465095A CN116477580A CN 116477580 A CN116477580 A CN 116477580A CN 202310465095 A CN202310465095 A CN 202310465095A CN 116477580 A CN116477580 A CN 116477580A
- Authority
- CN
- China
- Prior art keywords
- gas
- sulfur
- hydrogen sulfide
- tower
- adsorbent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007789 gas Substances 0.000 title claims abstract description 171
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000011593 sulfur Substances 0.000 title claims abstract description 78
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 78
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 68
- 239000003463 adsorbent Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 238000005338 heat storage Methods 0.000 claims abstract description 14
- 238000004458 analytical method Methods 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000006555 catalytic reaction Methods 0.000 claims abstract 3
- 239000003054 catalyst Substances 0.000 claims description 21
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000395 magnesium oxide Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910001570 bauxite Inorganic materials 0.000 claims description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052596 spinel Inorganic materials 0.000 claims description 4
- 239000011029 spinel Substances 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 3
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims 2
- 239000000377 silicon dioxide Substances 0.000 claims 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 abstract description 7
- 230000023556 desulfurization Effects 0.000 abstract description 7
- 238000003795 desorption Methods 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000003034 coal gas Substances 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910004349 Ti-Al Inorganic materials 0.000 description 1
- 229910004692 Ti—Al Inorganic materials 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0408—Pretreatment of the hydrogen sulfide containing gases
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Industrial Gases (AREA)
Abstract
Description
技术领域technical field
本发明涉及大气净化环境保护技术领域，具体涉及一种可循环使用的硫化氢吸附剂解析气制硫磺的工艺及系统。The invention relates to the technical field of air purification and environmental protection, in particular to a process and system for decomposing sulfur from gas with a recyclable hydrogen sulfide adsorbent.
背景技术Background technique
高炉煤气源头脱硫工艺已经在国内的多个钢铁厂成功使用，现有的脱硫工艺，一般做法是先将煤气中的COS转化成H2S，再将H2S进行吸附，或者将其直接部分氧化成硫磺进行回收。前者将吸附饱和的吸附剂进行解析，解析出来的含硫气体再进入烧结工艺进行后处理，这种做法并没有达到真正的脱硫效果。后者使用硫化氢部分氧化剂生成的硫磺，但是由于高炉煤气里的含硫量为200mgS/Nm3左右。一座1280m3的高炉每小时就可以产生40万方以上的高炉煤气，但是其硫的总量一般只有几十千克左右。如果直接采用这种部分氧化剂制备硫磺，就必须将所有的高炉煤气加热到部分氧化催化剂的工作温度，一般在200℃以上，可见为回收几十千克的硫磺而将几十万方的气体加热到200℃以上是多么地浪费能源。The blast furnace gas source desulfurization process has been successfully used in many domestic iron and steel plants. The existing desulfurization process is generally to convert COS in the gas into H 2 S, and then adsorb the H 2 S, or directly partially oxidize it into sulfur for recovery. The former decomposes the saturated adsorbent, and the decomposed sulfur-containing gas enters the sintering process for post-treatment. This method does not achieve the real desulfurization effect. The latter uses the sulfur generated by the hydrogen sulfide partial oxidant, but because the sulfur content in the blast furnace gas is about 200mgS/Nm 3 . A 1280m 3 blast furnace can produce more than 400,000 cubic meters of blast furnace gas per hour, but the total amount of sulfur is generally only about tens of kilograms. If this partial oxidant is directly used to prepare sulfur, all the blast furnace gas must be heated to the working temperature of the partial oxidation catalyst, which is generally above 200°C. It can be seen that it is a waste of energy to heat hundreds of thousands of cubic meters of gas to above 200°C in order to recover tens of kilograms of sulfur.
发明内容Contents of the invention
针对现有技术的缺陷，本发明提供了一种可循环使用的硫化氢吸附剂解析气制硫磺的工艺及系统，通过分析吸附剂的解吸气产生的特性，采用分段处理方法，大大提高高炉煤气的脱硫效率与硫磺产率。Aiming at the defects of the prior art, the present invention provides a process and system for recyclable hydrogen sulfide adsorbent desorption gas-to-sulfur production. By analyzing the characteristics of the desorbed gas produced by the adsorbent and adopting a staged treatment method, the desulfurization efficiency and sulfur yield of blast furnace gas are greatly improved.
本发明采用如下技术方案：The present invention adopts following technical scheme:
一方面，本发明提供了一种可循环使用的硫化氢吸附剂解析气制硫磺的工艺，将吸附饱和的硫化氢吸附剂经无硫净煤气进行加热解析，得到解析气；对解析气进行加热处理，并通过COS转化反应后生成硫化氢气体；将所得硫化氢气体中的一部分气体依次进行氧化和加热处理后，并与另一部分剩余气体进行催化反应；对反应后的气体进行降温处理，使硫磺蒸汽凝结成粉晶后并进行收集，制得硫磺。On the one hand, the present invention provides a recyclable hydrogen sulfide adsorbent desorption gas-to-sulfur process. The saturated hydrogen sulfide adsorbent is heated and decomposed through sulfur-free clean coal gas to obtain desorption gas; the desorption gas is subjected to heat treatment, and hydrogen sulfide gas is generated through COS conversion reaction; a part of the obtained hydrogen sulfide gas is sequentially oxidized and heat-treated, and catalyzed with another part of the remaining gas; the reacted gas is cooled to condense the sulfur vapor into powder crystals and collect them to obtain sulfur.
优选地，当解析气同时满足加热温度高于150℃、解析气中硫含量高于200ppm时，通过COS转化反应后生成硫化氢气体。Preferably, when the desorption gas satisfies that the heating temperature is higher than 150° C. and the sulfur content in the desorption gas is higher than 200 ppm, hydrogen sulfide gas is generated after the COS conversion reaction.
进一步地，对解析气进行加热处理时，使解析气温度达到180～220℃时，再通过COS转化反应后生成硫化氢气体。Further, when heat-treating the desorbed gas, when the temperature of the desorbed gas reaches 180-220° C., hydrogen sulfide gas is generated after the COS conversion reaction.
优选地，所述的经过氧化和加热处理的硫化氢中的一部分气体占所有生成硫化氢气体的80～95％，另一部分剩余气体占所有生成硫化氢气体的5～20％。Preferably, a part of the oxidized and heat-treated hydrogen sulfide accounts for 80-95% of all generated hydrogen sulfide gases, and another part of the remaining gas accounts for 5-20% of all generated hydrogen sulfide gases.
更进一步地，所得硫化氢气体中的一部分气体经氧化后，再经加热处理，其加热温度为250～280℃。Furthermore, after a part of the obtained hydrogen sulfide gas is oxidized, it is then subjected to heat treatment, and the heating temperature is 250-280°C.
优选地，所述的通过COS转化反应后生成硫化氢气体，所采用的催化剂载体为氮化碳、氧化铝、氧化硅、氧化镁、氧化钛、氧化锆、氧化铈中的一种或多种复合物，所采用的负载活性组分为氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、草酸钠、草酸钾、硫酸钠、硫酸钾中的一种或多种。Preferably, hydrogen sulfide gas is generated after the COS conversion reaction, the catalyst carrier used is one or more composites of carbon nitride, aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, zirconium oxide, and cerium oxide, and the loaded active component used is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium oxalate, potassium oxalate, sodium sulfate, and potassium sulfate.
优选地，所述的将所得硫化氢气体中的一部分气体依次进行氧化处理，所采用的催化剂载体为改性的铝土矿、氮化碳、氧化铝、氧化硅、氧化镁、氧化钛、氧化锆、氧化铈中的一种或多种复合物，所采用的负载活性组分为硝酸铁、硝酸钴、硝酸镍、硫酸铁、硫酸钴、硫酸镍、氯化铁、氯化钴、氯化镍、草酸铁、草酸钴、草酸镍、硝酸铜、醋酸铜、氯化铜、硫酸铜中的一种或多种。Preferably, a part of the obtained hydrogen sulfide gas is oxidized sequentially. The catalyst carrier used is one or more composites of modified bauxite, carbon nitride, aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, zirconium oxide, and cerium oxide. The active components used for loading are iron nitrate, cobalt nitrate, nickel nitrate, iron sulfate, cobalt sulfate, nickel sulfate, iron chloride, cobalt chloride, nickel chloride, iron oxalate, cobalt oxalate, nickel oxalate, copper nitrate, copper acetate, copper chloride, and sulfate. One or more of copper.
优选地，所述的将所得硫化氢气体中的一部分气体依次进行氧化和加热处理后，并与另一部分剩余气体进行催化反应，所采用的催化剂载体为改性的铝土矿、镁铝尖晶石、氧化铝、氧化硅、氧化镁、氧化钛、氧化锆、氧化铈中的一种或多种复合物。Preferably, a part of the obtained hydrogen sulfide gas is sequentially oxidized and heat-treated, and then catalyzed with another part of the remaining gas. The catalyst carrier used is one or more composites of modified bauxite, magnesium aluminum spinel, alumina, silicon oxide, magnesium oxide, titanium oxide, zirconium oxide, and cerium oxide.
另一方面，本发明还提供了一种可循环使用的硫化氢吸附剂解析气制硫磺的系统，其与硫化氢吸附塔连接，所述系统包括储热装置、COS转化塔、H2S氧化塔、加热装置、SO2转化塔和硫磺收集塔，所述储热装置与所述硫化氢吸附塔的出气口连接，用于对解析气进行加热处理；所述储热装置的出气口与所述COS转化塔的进气口连接，所述COS转化塔的出气口通过管路分别与所述的H2S氧化塔和SO2转化塔的进气口连接；所述加热装置的进气口与所述H2S氧化塔的出气口连接，所述加热装置的出气口与所述SO2转化塔的进气口连接；所述SO2转化塔的出气口与所述硫磺收集塔的进气端连接，所述的COS转化塔、H2S氧化塔和SO2转化塔中分别设有相应的催化剂载体。On the other hand, the present invention also provides a recyclable hydrogen sulfide adsorbent analysis gas-to-sulfur system, which is connected with a hydrogen sulfide adsorption tower, and the system includes a heat storage device, a COS conversion tower, a H2S oxidation tower, heating device, SO2conversion tower and sulfur collection tower, the heat storage device is connected with the gas outlet of the hydrogen sulfide adsorption tower, and is used for heat treatment of desorption gas; the gas outlet of the heat storage device is connected with the air inlet of the COS conversion tower, and the gas outlet of the COS conversion tower is respectively connected with the H2S oxidation tower and SO2The air inlet of conversion tower is connected; The air inlet of described heating device is connected with described H2The gas outlet of the S oxidation tower is connected, and the gas outlet of the heating device is connected with the SO2Inlet connection to reformer; the SO2The gas outlet of conversion tower is connected with the inlet end of described sulfur collecting tower, and described COS conversion tower, H2S oxidation tower and SO2Corresponding catalyst carriers are arranged in the conversion towers respectively.
进一步地，所述硫磺收集塔的侧面设有低硫出气口，所述储热装置的出气口和所述低硫出气口分别通过管路与煤气管网连接。Further, a low-sulfur gas outlet is provided on the side of the sulfur collection tower, and the gas outlet of the heat storage device and the low-sulfur gas outlet are respectively connected to the gas pipeline network through pipelines.
本发明技术方案，具有如下优点：The technical solution of the present invention has the following advantages:
A.本发明采用少量的无硫净化煤气对硫化氢吸附剂进行解析处理，并对所得解析气进行独立连续的分段集中处理，制得硫磺并收集，有效地降低高炉煤气源头脱硫处理的气量，提高了硫磺的产率。A. The present invention uses a small amount of sulfur-free purified coal gas to analyze the hydrogen sulfide adsorbent, and conducts independent and continuous segmental centralized treatment of the obtained analytical gas to obtain sulfur and collect it, effectively reducing the gas volume of blast furnace gas source desulfurization treatment and improving the yield of sulfur.
B.本发明在经过COS转化反应后，将生成的硫化氢气体分为两部分，其一部分经氧化、加热处理后与另一部分剩余的未参与氧化的硫化氢气体进行催化反应，制得硫磺蒸汽并凝结为硫磺粉晶，通过分段储热与热量再利用方式，有效降低工艺能耗。B. In the present invention, after the COS conversion reaction, the generated hydrogen sulfide gas is divided into two parts. After one part is oxidized and heat-treated, it is catalyzed with the other part of the remaining hydrogen sulfide gas that has not participated in the oxidation to obtain sulfur vapor and condense it into sulfur powder crystals. The energy consumption of the process is effectively reduced by means of segmental heat storage and heat reuse.
附图说明Description of drawings
为了更清楚地说明本发明具体实施方式，下面将对具体实施方式中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to illustrate the specific embodiments of the present invention more clearly, the following will briefly introduce the accompanying drawings used in the specific embodiments. Obviously, the accompanying drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained according to these drawings without creative work.
图1为本发明提供的用于可循环使用的硫化氢吸附剂解析气制硫磺的工艺框图；Fig. 1 is the technological block diagram that is used for recyclable hydrogen sulfide adsorbent analysis gas-produced sulfur provided by the present invention;
图2为本发明提供的用于可循环使用的硫化氢吸附剂解析气制硫磺的系统的结构组成示意图。Fig. 2 is a schematic diagram of the structure and composition of the system for decomposing sulfur from gas with a recyclable hydrogen sulfide adsorbent provided by the present invention.
具体实施方式Detailed ways
下面将结合附图对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions of the present invention will be clearly and completely described below in conjunction with the accompanying drawings. Apparently, the described embodiments are part of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
在本发明的描述中，需要说明的是，术语“中心”、“上”、“下”、“左”、“右”、“竖直”、“水平”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。此外，术语“第一”、“第二”、“第三”仅用于描述目的，而不能理解为指示或暗示相对重要性。In the description of the present invention, it should be noted that the orientations or positional relationships indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. are based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus cannot be construed as limiting the present invention. In addition, the terms "first", "second", and "third" are used for descriptive purposes only, and should not be construed as indicating or implying relative importance.
在本发明的描述中，需要说明的是，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域的普通技术人员而言，可以具体情况理解上述术语在本发明中的具体含义。In the description of the present invention, it should be noted that, unless otherwise specified and limited, the terms "installation", "connection" and "connection" should be understood in a broad sense, for example, it may be a fixed connection, a detachable connection, or an integral connection; it may be a mechanical connection or an electrical connection; it may be a direct connection or an indirect connection through an intermediate medium, or it may be an internal connection between two components. Those of ordinary skill in the art can understand the specific meanings of the above terms in the present invention in specific situations.
如图1所示，本发明提供了一种可循环使用的硫化氢吸附剂解析气制硫磺的工艺，其工艺包括如下步骤：As shown in Figure 1, the present invention provides a kind of technology that recyclable hydrogen sulfide adsorbent resolves gas-made sulfur, and its technology comprises the following steps:
【S01】将吸附饱和的硫化氢吸附剂经无硫净煤气进行加热解析，得到解析气。[S01] Heat and analyze the saturated hydrogen sulfide adsorbent through the sulfur-free clean coal gas to obtain the analysis gas.
对解析气进行加热处理时，使解析气温度达到180～220℃时。When heat-treating the analytic gas, the temperature of the analytic gas reaches 180-220°C.
【S02】对解析气进行加热处理，并通过COS转化反应后生成硫化氢气体。[S02] Heat the desorbed gas, and generate hydrogen sulfide gas after the COS conversion reaction.
在COS转化反应中所采用的催化剂载体为氮化碳、氧化铝、氧化硅、氧化镁、氧化钛、氧化锆、氧化铈中的一种或多种复合物，所采用的负载活性组分为氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、草酸钠、草酸钾、硫酸钠、硫酸钾中的一种或多种。The catalyst carrier used in the COS conversion reaction is one or more composites of carbon nitride, aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, zirconium oxide, and cerium oxide, and the loaded active component used is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium oxalate, potassium oxalate, sodium sulfate, and potassium sulfate.
当解析气同时满足加热温度高于150℃、解析气中硫含量高于200ppm时，通过COS转化反应后生成硫化氢气体。否者，若加热温度低于150℃，或者解析气中经检测，硫含量低于200ppm时，则不能进行COS转化反应，而是直接从旁路排出。When the desorption gas satisfies that the heating temperature is higher than 150°C and the sulfur content in the desorption gas is higher than 200ppm, hydrogen sulfide gas will be generated after the COS conversion reaction. Otherwise, if the heating temperature is lower than 150°C, or the sulfur content in the desorbed gas is detected to be lower than 200ppm, the COS conversion reaction cannot be carried out, but is directly discharged from the bypass.
【S03】将所得硫化氢气体中的一部分气体依次进行氧化和加热处理后，并与另一部分剩余气体进行催化反应。[S03] After a part of the obtained hydrogen sulfide gas is oxidized and heat-treated in sequence, it is catalyzed with another part of the remaining gas.
对一部分气体进行氧化处理，所采用的催化剂载体为改性的铝土矿、氮化碳、氧化铝、氧化硅、氧化镁、氧化钛、氧化锆、氧化铈中的一种或多种复合物，所采用的负载活性组分为硝酸铁、硝酸钴、硝酸镍、硫酸铁、硫酸钴、硫酸镍、氯化铁、氯化钴、氯化镍、草酸铁、草酸钴、草酸镍、硝酸铜、醋酸铜、氯化铜、硫酸铜中的一种或多种。A part of the gas is oxidized. The catalyst carrier used is one or more compounds of modified bauxite, carbon nitride, aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, zirconium oxide, and cerium oxide. The active component used is one or more of iron nitrate, cobalt nitrate, nickel nitrate, iron sulfate, cobalt sulfate, nickel sulfate, iron chloride, cobalt chloride, nickel chloride, iron oxalate, cobalt oxalate, nickel oxalate, copper nitrate, copper acetate, copper chloride, and copper sulfate.
而将两部分气体进行催化反应时，所采用的催化剂载体为改性的铝土矿、镁铝尖晶石、氧化铝、氧化硅、氧化镁、氧化钛、氧化锆、氧化铈中的一种或多种复合物。When the two parts of the gas are catalyzed, the catalyst carrier used is one or more composites of modified bauxite, magnesium aluminum spinel, alumina, silicon oxide, magnesium oxide, titanium oxide, zirconium oxide, and cerium oxide.
经过氧化和加热处理的硫化氢中的一部分气体占所有生成硫化氢气体的80～95％，另一部分剩余气体占所有生成硫化氢气体的5～20％。Part of the gas in the oxidized and heat-treated hydrogen sulfide accounts for 80-95% of all generated hydrogen sulfide gases, and another part of the remaining gas accounts for 5-20% of all generated hydrogen sulfide gases.
所得硫化氢气体中的一部分气体经氧化后，再经加热处理，其加热温度为250～280℃。A part of the obtained hydrogen sulfide gas is oxidized and then heated at a temperature of 250-280°C.
【S04】对反应后的气体进行降温处理，使硫磺蒸汽凝结成粉晶后并进行收集，制得硫磺。[S04] Lowering the temperature of the reacted gas to condense the sulfur vapor into powder crystals and collect them to obtain sulfur.
本发明通过分析吸附剂的解析气产生的特性，采用分段处理方法，能大大提高高炉煤气的脱硫效率与硫磺产率。其原理如下：吸附剂的解析过程可以分为三个阶段，第一阶段是从60～150℃之间，几乎没有硫化物脱付出来，这一阶段占总时间的1/5左右；第二阶段是从150～250℃之间，有大量的硫化物脱附出来，其浓度有时高达3.5％，这一阶段占总时间的1/3左右；第三阶段是当脱附出来的硫化物低于200ppm，这一阶段占总时间的1/3左右；最后的时间用于吸附剂的降温。解析气进入COS转化塔后的完成整个制硫过程的总时间约为10h～14h。The invention can greatly improve the desulfurization efficiency and sulfur yield of the blast furnace gas by analyzing the characteristics of the desorption gas generation of the adsorbent and adopting a segmented treatment method. The principle is as follows: The desorption process of the adsorbent can be divided into three stages. The first stage is from 60 to 150°C, almost no sulfide is desorbed, and this stage accounts for about 1/5 of the total time; the second stage is from 150 to 250°C, a large amount of sulfide is desorbed, and its concentration is sometimes as high as 3.5%, this stage accounts for about 1/3 of the total time; Cooling of the adsorbent. The total time to complete the entire sulfur production process after the analytical gas enters the COS conversion tower is about 10h to 14h.
如图2所示，本发明还提供了一种可循环使用的硫化氢吸附剂解析气制硫磺的系统，其与硫化氢吸附塔连接，系统包括储热装置、COS转化塔、H2S氧化塔、加热装置、SO2转化塔和硫磺收集塔。储热装置与硫化氢吸附塔的出气口连接，用于对解析气进行加热处理；储热装置的出气口与COS转化塔的进气口连接，COS转化塔的出气口通过管路分别与H2S氧化塔和SO2转化塔的进气口连接，可以通过管路上设置的流量调节阀分配进入H2S氧化塔和SO2转化塔中的气体量；加热装置的进气口与H2S氧化塔的出气口连接，加热装置的出气口与SO2转化塔的进气口连接；SO2转化塔的出气口与硫磺收集塔的进气端连接，COS转化塔、H2S氧化塔和SO2转化塔中分别设有相应的催化剂载体。As shown in Figure 2, the present invention also provides a recyclable hydrogen sulfide adsorbent analysis gas-to-sulfur system, which is connected to a hydrogen sulfide adsorption tower, and the system includes a heat storage device, a COS conversion tower, an H2S oxidation tower, a heating device, an SO2 conversion tower and a sulfur collection tower.储热装置与硫化氢吸附塔的出气口连接，用于对解析气进行加热处理；储热装置的出气口与COS转化塔的进气口连接，COS转化塔的出气口通过管路分别与H 2 S氧化塔和SO 2转化塔的进气口连接，可以通过管路上设置的流量调节阀分配进入H 2 S氧化塔和SO 2转化塔中的气体量；加热装置的进气口与H 2 S氧化塔的出气口连接，加热装置的出气口与SO 2转化塔的进气口连接；SO 2转化塔的出气口与硫磺收集塔的进气端连接，COS转化塔、H 2 S氧化塔和SO 2转化塔中分别设有相应的催化剂载体。
本发明在硫磺收集塔的侧面设有低硫出气口(图中未示出)，储热装置的出气口和低硫出气口分别通过管路与煤气管网连接，低硫的煤气回到煤气管网进一步作循环处理；对于由储热装置中出来的解析气，当其温度低于150℃时，或者当解析气中硫含量低于200ppm时，都不进入COS转化塔，而是直接从旁路出来后回到煤气管网。In the present invention, a low-sulfur gas outlet (not shown in the figure) is provided on the side of the sulfur collection tower. The gas outlet of the heat storage device and the low-sulfur gas outlet are respectively connected to the gas pipeline network through pipelines, and the low-sulfur gas returns to the gas pipeline network for further circulation treatment; for the desorption gas coming out of the heat storage device, when the temperature is lower than 150 ° C, or when the sulfur content in the desorption gas is lower than 200ppm, it does not enter the COS conversion tower, but directly returns to the gas pipeline network after coming out of the bypass.
上述中的储热装置、COS转化塔、H2S氧化塔、加热装置、SO2转化塔和硫磺收集塔均可以采用现有的设备，相关设备的结构及原理在此不再赘述。The above-mentioned heat storage device, COS conversion tower, H 2 S oxidation tower, heating device, SO 2 conversion tower and sulfur collection tower can all use existing equipment, and the structure and principle of related equipment will not be repeated here.
实施例1Example 1
将含有40吨的煤制活性炭对90000Nm3/h、80℃含有COS浓度为180mg/m3的高炉煤气进行脱硫处理。当吸附剂吸附饱和后，用4000Nm3/h的干净无硫的高炉煤气对吸附剂进行解析再生。当解析气温度达到150℃，开始通入装有Na2CO3/Ti-Al2O3催化剂的COS转化塔，将解析气中COS转化成硫化氢，经分流处理，其中90％的气体进入装有Fe/SiO2催化剂的H2S氧化塔进行氧化处理，处理的气体经加热至250℃后，再进入装有a-Al2O3催化剂的SO2转化塔；另外的10％的气体未经氧化处理直接进入SO2转化塔。这两组气体在SO2转化塔中，进一步反应生成硫磺。经SO2转化塔反应后的气体在硫磺收集器中降温至80℃，硫磺蒸气在收集器里冷却生成硫磺粉，沉积在底部。低硫的煤气回到煤气管网进一步作循环处理。当H2S测试口的硫含量低于200mg/m3时，解析气不再经过COS转化塔，直接从旁路经过回管网。这循环过程中，解析气进入COS转化塔的总时间约为10小时，总处理气量约为4万方，为收集硫磺量约为1215千克，计算硫磺的产率约为82％。The blast furnace gas containing 40 tons of coal-based activated carbon is desulfurized at 90000Nm 3 /h, 80°C and contains COS concentration of 180mg/m 3 . When the adsorbent is saturated, use 4000Nm 3 /h of clean sulfur-free blast furnace gas to desorb and regenerate the adsorbent. When the temperature of the analytic gas reaches 150°C, it starts to pass into the COS conversion tower equipped with Na 2 CO 3 /Ti-Al 2 O 3 catalyst, and converts COS in the analytic gas into hydrogen sulfide. After split flow treatment, 90% of the gas enters the H 2 S oxidation tower equipped with Fe/SiO 2 catalyst for oxidation treatment. After the treated gas is heated to 250°C, it enters the SO 2 conversion tower equipped with a-Al 2 O 3 catalyst; the other 10% of the gas is not oxidized Treatment goes directly to the SO2 conversion tower. These two groups of gases further react to produce sulfur in the SO2 conversion tower. The gas reacted by the SO2 conversion tower is cooled to 80°C in the sulfur collector, and the sulfur vapor is cooled in the collector to generate sulfur powder, which is deposited at the bottom. The low-sulfur gas returns to the gas pipeline network for further recycling. When the sulfur content at the H 2 S test port is lower than 200mg/m 3 , the analytical gas no longer passes through the COS conversion tower, and directly passes through the return pipe network through the bypass. During this cycle, the total time for the analytical gas to enter the COS conversion tower is about 10 hours, the total gas volume is about 40,000 cubic meters, the amount of sulfur collected is about 1215 kg, and the calculated sulfur yield is about 82%.
实施例2Example 2
将含有60吨的煤制活性炭对100000Nm3/h、70℃含有COS浓度为190mg/m3的高炉煤气进行脱硫处理。当吸附剂吸附饱和后，用5000Nm3/h的干净无硫的高炉煤气对吸附剂进行解析再生。当解析气温度达到150℃，开始通入装有K2CO3/Al2O3催化剂的COS转化塔，将解析气中COS转化成硫化氢，经分流处理，其中95％的气体进入装有Fe/Ce/SiO2催化剂的H2S氧化塔进行氧化处理，处理的气体经加热至260℃后，再进入装有镁铝尖晶石催化剂的SO2转化塔；另外的5％的气体未经氧化处理直接进入SO2转化塔。这两组气体在SO2转化塔中，进一步反应生成硫磺。经SO2转化塔反应后的气体在硫磺收集器中降温至70℃，硫磺蒸气在收集器里冷却生成硫磺粉，沉积在底部。低硫的煤气回到煤气管网进一步作循环处理。当H2S测试口的硫含量低于200mg/m3时，解析气不再经过COS转化塔，直接从旁路经过回管网。这循环过程中，解析气进入COS转化塔的总时间约为14小时，总处理气量约为7万方，为收集硫磺量约为1723千克，计算硫磺的产率约为85％。Desulfurize the blast furnace gas containing 60 tons of coal-based activated carbon at 100,000 Nm 3 /h, 70°C and COS concentration of 190 mg/m 3 . When the adsorbent is saturated, use 5000Nm 3 /h of clean sulfur-free blast furnace gas to analyze and regenerate the adsorbent. When the temperature of the analytic gas reaches 150°C, it starts to pass into the COS conversion tower equipped with K 2 CO 3 /Al 2 O 3 catalyst, and converts COS in the analytic gas into hydrogen sulfide. After split flow treatment, 95% of the gas enters the H 2 S oxidation tower equipped with Fe/Ce/SiO 2 catalyst for oxidation treatment. After the treated gas is heated to 260°C, it enters the SO 2 conversion tower equipped with magnesium aluminum spinel catalyst; SO 2 conversion tower. These two groups of gases further react to produce sulfur in the SO2 conversion tower. The gas reacted by the SO2 conversion tower is cooled to 70°C in the sulfur collector, and the sulfur vapor is cooled in the collector to generate sulfur powder, which is deposited at the bottom. The low-sulfur gas returns to the gas pipeline network for further recycling. When the sulfur content at the H 2 S test port is lower than 200mg/m 3 , the analytical gas no longer passes through the COS conversion tower, and directly passes through the return pipe network through the bypass. During this cycle, the total time for the analytical gas to enter the COS conversion tower is about 14 hours, the total gas treatment volume is about 70,000 cubic meters, and the amount of sulfur collected is about 1723 kg, and the calculated sulfur yield is about 85%.
实施例3Example 3
将含有30吨的煤制活性炭对60000Nm3/h、75℃含有COS浓度为200mg/m3的高炉煤气进行脱硫处理。当吸附剂吸附饱和后，用3000Nm3/h的干净无硫的高炉煤气对吸附剂进行解析再生。当解析气温度达到150℃，开始通入装有K2CO3/Ti/Al2O3催化剂的COS转化塔，将解析气中COS转化成硫化氢，经分流处理，其中80％的气体进入装有Fe/Co/SiO2催化剂的H2S氧化塔进行氧化处理，处理的气体经加热至280℃后，再进入装有氧化锆催化剂的SO2转化塔；另外的12％的气体未经氧化处理直接进入SO2转化塔。这两组气体在SO2转化塔中，进一步反应生成硫磺。经SO2转化塔反应后的气体在硫磺收集器中降温至80℃，硫磺蒸气在收集器里冷却生成硫磺粉，沉积在底部。低硫的煤气回到煤气管网进一步作循环处理。当H2S测试口的硫含量低于200mg/m3时，解析气不再经过COS转化塔，直接从旁路经过回管网。这循环过程中，解析气进入COS转化塔的总时间约为13小时，总处理气量约为4万方，为收集硫磺量约为1011千克，计算硫磺的产率约为86％。Desulfurize blast furnace gas containing 30 tons of coal-based activated carbon at 60,000 Nm 3 /h, 75°C and 200 mg/m 3 of COS. When the adsorbent is saturated, use 3000Nm 3 /h of clean sulfur-free blast furnace gas to analyze and regenerate the adsorbent. When the temperature of the analytic gas reaches 150°C, it starts to pass into the COS conversion tower equipped with K 2 CO 3 /Ti/Al 2 O 3 catalyst, and the COS in the analytic gas is converted into hydrogen sulfide. After split flow treatment, 80% of the gas enters the H 2 S oxidation tower equipped with Fe/Co/SiO 2 catalyst for oxidation treatment. After the treated gas is heated to 280°C, it enters the SO 2 conversion tower equipped with zirconia catalyst; the other 12% of the gas directly enters SO 2 conversion towers. These two groups of gases further react to produce sulfur in the SO2 conversion tower. The gas reacted by the SO2 conversion tower is cooled to 80°C in the sulfur collector, and the sulfur vapor is cooled in the collector to generate sulfur powder, which is deposited at the bottom. The low-sulfur gas returns to the gas pipeline network for further recycling. When the sulfur content at the H 2 S test port is lower than 200mg/m 3 , the analytical gas no longer passes through the COS conversion tower, and directly passes through the return pipe network through the bypass. During this cycle, the total time for the analytical gas to enter the COS conversion tower is about 13 hours, the total gas volume is about 40,000 cubic meters, the amount of sulfur collected is about 1011 kg, and the calculated sulfur yield is about 86%.
本发明未述及之处适用于现有技术。What is not mentioned in the present invention is applicable to the prior art.
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明的保护范围之中。Apparently, the above-mentioned embodiments are only examples for clear description, rather than limiting the implementation. For those of ordinary skill in the art, other changes or changes in different forms can be made on the basis of the above description. It is not necessary and impossible to exhaustively list all the implementation manners here. However, the obvious changes or changes derived therefrom still fall within the scope of protection of the present invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310465095.3A CN116477580B (en) | 2023-04-26 | 2023-04-26 | A process and system for producing sulfur from gas by using recyclable hydrogen sulfide adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310465095.3A CN116477580B (en) | 2023-04-26 | 2023-04-26 | A process and system for producing sulfur from gas by using recyclable hydrogen sulfide adsorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116477580A true CN116477580A (en) | 2023-07-25 |
| CN116477580B CN116477580B (en) | 2025-01-03 |
Family
ID=87211554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310465095.3A Active CN116477580B (en) | 2023-04-26 | 2023-04-26 | A process and system for producing sulfur from gas by using recyclable hydrogen sulfide adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116477580B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119461372A (en) * | 2024-11-18 | 2025-02-18 | 福州大学 | A process for preparing high-concentration carbonyl sulfide by desulfurization of blast furnace gas |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1356289A (en) * | 1970-07-17 | 1974-06-12 | Shell Int Research | Process for reducing the total sulphur content of claus off-gases |
| US4045371A (en) * | 1974-05-07 | 1977-08-30 | Exxon Research And Engineering Company | Process for preparing a gas desulfurization sorbent |
| CN102173379A (en) * | 2011-02-08 | 2011-09-07 | 何巨堂 | Method for producing sulfur, hydrogen and low-sulfur desorption gas from coal gas |
| CN104540577A (en) * | 2012-02-17 | 2015-04-22 | 亚康科技股份有限公司 | Process for the removal of sulfur compounds from gas streams |
| CN105858604A (en) * | 2016-03-31 | 2016-08-17 | 四川天采科技有限责任公司 | Full-temperature-range pressure-swing adsorption method for removing hydrogen sulfide from hydrogen rich gas source |
| CN106629727A (en) * | 2016-12-14 | 2017-05-10 | 山东迅达化工集团有限公司 | Process for preparing low-hydrogen CO gas |
| US20180119039A1 (en) * | 2015-07-03 | 2018-05-03 | Mitsubishi Heavy Industries, Ltd. | Source gas purification apparatus and purification method |
| CN108786441A (en) * | 2018-05-31 | 2018-11-13 | 武汉钢铁有限公司 | Coke oven flue gas electromigration desulfurization sulphur technique |
| CN108975281A (en) * | 2018-08-03 | 2018-12-11 | 山东大学 | The system and method for Recovered sulphur during a kind of Copper making |
| CN109160493A (en) * | 2018-11-07 | 2019-01-08 | 北京矿冶科技集团有限公司 | SO2The boiling reduction of flue gas during smelting two-part prepares the device and its technique of sulphur |
| CN109351126A (en) * | 2018-11-16 | 2019-02-19 | 中石化炼化工程（集团）股份有限公司 | Sulphur-containing exhaust gas processing method |
| CN112063422A (en) * | 2020-08-26 | 2020-12-11 | 中国科学院山西煤炭化学研究所 | A kind of blast furnace gas desulfurization and sulfur resource utilization method and device |
| CN113214879A (en) * | 2021-05-13 | 2021-08-06 | 安徽威达环保科技股份有限公司 | Dry type natural gas purification device and process |
| CN115285941A (en) * | 2022-06-24 | 2022-11-04 | 上海交通大学 | A kind of method for producing sulfur by low-temperature catalytic direct reduction of SO2 in flue gas |
-
2023
- 2023-04-26 CN CN202310465095.3A patent/CN116477580B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1356289A (en) * | 1970-07-17 | 1974-06-12 | Shell Int Research | Process for reducing the total sulphur content of claus off-gases |
| US4045371A (en) * | 1974-05-07 | 1977-08-30 | Exxon Research And Engineering Company | Process for preparing a gas desulfurization sorbent |
| CN102173379A (en) * | 2011-02-08 | 2011-09-07 | 何巨堂 | Method for producing sulfur, hydrogen and low-sulfur desorption gas from coal gas |
| CN104540577A (en) * | 2012-02-17 | 2015-04-22 | 亚康科技股份有限公司 | Process for the removal of sulfur compounds from gas streams |
| US20180119039A1 (en) * | 2015-07-03 | 2018-05-03 | Mitsubishi Heavy Industries, Ltd. | Source gas purification apparatus and purification method |
| CN105858604A (en) * | 2016-03-31 | 2016-08-17 | 四川天采科技有限责任公司 | Full-temperature-range pressure-swing adsorption method for removing hydrogen sulfide from hydrogen rich gas source |
| CN106629727A (en) * | 2016-12-14 | 2017-05-10 | 山东迅达化工集团有限公司 | Process for preparing low-hydrogen CO gas |
| CN108786441A (en) * | 2018-05-31 | 2018-11-13 | 武汉钢铁有限公司 | Coke oven flue gas electromigration desulfurization sulphur technique |
| CN108975281A (en) * | 2018-08-03 | 2018-12-11 | 山东大学 | The system and method for Recovered sulphur during a kind of Copper making |
| CN109160493A (en) * | 2018-11-07 | 2019-01-08 | 北京矿冶科技集团有限公司 | SO2The boiling reduction of flue gas during smelting two-part prepares the device and its technique of sulphur |
| CN109351126A (en) * | 2018-11-16 | 2019-02-19 | 中石化炼化工程（集团）股份有限公司 | Sulphur-containing exhaust gas processing method |
| CN112063422A (en) * | 2020-08-26 | 2020-12-11 | 中国科学院山西煤炭化学研究所 | A kind of blast furnace gas desulfurization and sulfur resource utilization method and device |
| CN113214879A (en) * | 2021-05-13 | 2021-08-06 | 安徽威达环保科技股份有限公司 | Dry type natural gas purification device and process |
| CN115285941A (en) * | 2022-06-24 | 2022-11-04 | 上海交通大学 | A kind of method for producing sulfur by low-temperature catalytic direct reduction of SO2 in flue gas |
Non-Patent Citations (1)
| Title |
|---|
| 陈赓良: "超克劳斯法硫黄回收工艺的技术进展", 天然气与石油, vol. 35, no. 6, 31 December 2017 (2017-12-31), pages 30 - 35 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119461372A (en) * | 2024-11-18 | 2025-02-18 | 福州大学 | A process for preparing high-concentration carbonyl sulfide by desulfurization of blast furnace gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116477580B (en) | 2025-01-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103898265B (en) | A kind of coke-oven gas upgrading direct-reduction iron ore system and device and method | |
| CN102895872B (en) | Method for removing sulfur oxides and nitrogen oxides in catalytic cracking regeneration flue gas | |
| CN104001403B (en) | The technique of a kind of activated coke/charcoal flue gas desulfurization and denitrification and recovery elemental sulfur and device | |
| JP5270903B2 (en) | Blast furnace gas calorie increase method | |
| CN102642810B (en) | Combined process for preparing Fischer-Tropsch synthetic oil raw material gas by utilizing coke-oven gas | |
| CN102895873A (en) | Method for simultaneously removing sulfur oxides, nitrogen oxides and carbon monoxide in flue gas | |
| EP3986596B1 (en) | Method and a direct reduction plant for producing direct reduced iron | |
| CN103805728B (en) | Method and device for producing reduced iron through synthetic gas prepared from high-nitrogen content retort gas | |
| CN111375273A (en) | Treatment method and device for sulfur dioxide-containing waste gas | |
| CN111748383B (en) | Blast furnace gas deoxidation and desulfurization method and system | |
| CN116477580A (en) | A process and system for recyclable hydrogen sulfide adsorbent to decompose gas to sulfur | |
| JP2017048087A (en) | Method and apparatus for producing hydrogen from fossil fuel | |
| CN111732976B (en) | A kind of blast furnace gas desulfurization method and system | |
| CN108011119A (en) | The method and system of hydrogeneous exhaust gas coupling fuel cells clean electric power generation recycling | |
| CN111498812A (en) | Method and system for near-zero emission sulfur recovery | |
| CN1675337A (en) | Apparatus for treating COS for gas produced by gasification and method for treating COS | |
| CN216427224U (en) | Treatment system for steel mill gas | |
| CN117861580A (en) | Reaction coupling device and method for sulfur dioxide reduction and methane reforming | |
| CN223722806U (en) | Hydrogen preparation purifying system | |
| CN103316578B (en) | Method for absorbing sulfur dioxide and co-producing sulphur | |
| CN114574647A (en) | System and method for preparing shaft furnace reducing gas by coupling coke oven gas with carbon dioxide | |
| CN1935646A (en) | Equipment and method for treating exhaust gas for carbon bisulfide preparing process | |
| CN113444545A (en) | Method for deeply removing impurities in coal gas | |
| CN217939688U (en) | Carbon dioxide and hydrogen sulfide separation device | |
| CN213772104U (en) | Shaft furnace reducing gas preparation and self-desorption system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |