CN109310946B - 气态烃原料脱除硫化氢和硫醇装置、方法和催化剂 - Google Patents
气态烃原料脱除硫化氢和硫醇装置、方法和催化剂 Download PDFInfo
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- CN109310946B CN109310946B CN201680084932.6A CN201680084932A CN109310946B CN 109310946 B CN109310946 B CN 109310946B CN 201680084932 A CN201680084932 A CN 201680084932A CN 109310946 B CN109310946 B CN 109310946B
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- catalyst
- amine
- amide
- reactor
- hydrogen sulfide
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 44
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 29
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 29
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 29
- 239000002994 raw material Substances 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims description 51
- 239000007789 gas Substances 0.000 claims abstract description 77
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 36
- 239000011593 sulfur Substances 0.000 claims abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 150000002019 disulfides Chemical class 0.000 claims abstract description 7
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 150000001408 amides Chemical class 0.000 claims description 26
- 150000001412 amines Chemical class 0.000 claims description 25
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000005864 Sulphur Substances 0.000 claims description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 10
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 5
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims 18
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 claims 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 5
- 150000003624 transition metals Chemical class 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000010926 purge Methods 0.000 abstract description 3
- 239000010891 toxic waste Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000002250 absorbent Substances 0.000 description 7
- 230000002745 absorbent Effects 0.000 description 7
- 239000006096 absorbing agent Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical class O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011356 non-aqueous organic solvent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000003918 potentiometric titration Methods 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- -1 copper halides Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000797 iron chelating agent Substances 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
本发明属于气态烃原料脱除硫化氢和硫醇技术这一领域,并可用于各种气态烃原料脱除硫化氢和硫醇。气态烃原料脱除硫化氢和硫醇装置包括充满催化剂溶液的催化反应器,基于有机溶剂催化剂溶液将氧化硫化氢和硫醇;硫磺溶液从反应器排出到硫磺分离模块的设备;硫磺分离模块;同时,该装置至少包括反应器供净化烃类气体和含氧气体设备,以及从反应器排出已净化气体设备。硫磺分离模块包括硫磺分选设备。反应器结构和催化剂成分将硫化氢和硫醇转化成硫磺和二硫化物的程度至少达到99.99%。催化剂本身是过渡金属混合络合物。运用已研制的技术方案,其技术结果是烃类气体一阶段脱除硫化氢和硫醇,剩余硫磺量‑SH达到0.001ppm,无有毒废物。
Description
技术领域
本发明属于气态烃原料(天然气、半生气、工艺气体等)脱除硫化氢和硫醇技术这一领域。可用于各种气态烃原料脱除硫化氢和硫醇。
背景技术
已有技术(RU专利号2394635,发布时间2010年7月20日)描述气体脱除硫化氢和硫醇的吸收法。在增加压力下用两种吸收剂将逐步进行净化气体的处理,先用氢硫酸和碳酸中性钠盐水溶液,后用氢氧化钠水溶液。
同一技术描述气体脱除硫化氢、硫醇以及脱除二氧化碳和其他酸性杂质的装备,其包括两个吸收器,每一个具有吸收剂罐和吸收剂泵,同时气体净化过程的第二个吸收器里循环氢氧化钠溶液,装备另外包括废吸收剂的收集器。串联连接的吸收器,在压力条件下而运行,第二个吸收器里装循环泵。第一吸收器的收集器连接到增压泵,增压泵用于泵入废吸收剂到有绝热装置的废料埋葬层。同时,第一个吸收器使用水和第二吸收器的废吸收剂作为吸收剂,装置另外包括用于产生净化气体定压的压缩机,以及连接到压缩机的分离器,分离器用于冷凝气体和水的分离。
对于已有技术缺点而言,必须指出如下缺点:净化质量低、碱耗量高、大量难处理有毒废物。
已有技术(US,专利号4622212,发布时间1986年11月11日)描述硫化氢液相氧化成硫磺的过程(Lo-Cat过程),使用螯合铁。Lo-Cat过程就使用催化反应器和催化剂溶液再生器,将硫化氢转化成硫磺。
上述过程脱除硫化氢程度不足,以及无法脱除硫醇必须被视为它的缺点。
已有技术(US专利号8735316,发布时间2014年5月27日)描述烃类溶液催化脱除硫醇过程,即通过硫醇转化成二硫化物而脱除硫醇。使用CuCl和单乙醇胺(MEA)、乙腈或一元醇的合成物作为催化剂。该过程在大气氧气下而进行的,温度为22-140℃。剩余硫醇硫量可降低至20ррm。
上述过程仅可净化液体,并且缺乏硫化氢脱除相关信息,必须被视为先前发明的缺点。
已有技术(RU,专利号2385180,发布时间27.03.2010)描述将硫化氢转化成硫磺的Claus-过程。
被净化气体初步氨基处理,多阶段,硫化氢转化成硫磺的程度不足,要再净化大气排放,工艺设备复杂,并且对处理硫醇不适应,必须被视为先前发明的缺点。
已有技术(US,专利号5286697,发布时间1994年2月15日)也描述Claus-升级过程。
先前发明对硫醇的处理一样不适应,而处理硫化氢的效率更低。
已有技术(RU,专利号2405738,发布时间2010年4月27日)描述工业气体制硫磺法,所使用催化剂制造法是脱羟基硅胶(97.65%)上涂2.35m%磷酸亚铁(III),其中硅胶提供烃类气体所含硫化氢制硫磺的条件。
上述技术硫化氢转化程度不足,催化剂制造有难度,必须被视为缺点。
已有技术(RU,专利号2398735,发表时间2010年9月10日)描述气流脱除硫化氢方法,即通过硫化氢液相催化氧化成元素硫,催化剂包含过渡金属化合物和有机络合物。为了氧化硫化氢,建议使用大气氧,并使用铜的卤化物作为过渡金属化合物,溶液含铜量为从0.015到0.1m%;同时,使用二甲基甲酰胺、吡咯烷酮、甲基吡咯烷酮、吡啶、喹啉等化合物作为有机络合物,反应基于溶剂特性而进行的,从以下系列溶剂可以做出选择:一元醇、多元醇、水或混合物,如煤油、异辛烷、凝析气,温度为20-40°С。
上述过程的缺点为中等效率。
发明内容
提出的发明所解决的技术问题在于其研制的技术方案,该技术方案将烃类气体同时脱除硫化氢和硫醇,转化程度99.999%以上。
运用提出的技术方案,其技术结果是烃类气体一阶段脱除硫化氢/硫醇,剩余硫磺量-SH达到0.001ppm,无有毒废物。
为了达成上述技术结果,建议使用烃类气体脱除硫化氢和硫醇装备(图1)和方法(图2),为了有效运用上述方法,还需要使用催化剂。提出的装置包括充满催化剂溶液脱硫反应器,里面有机溶剂氧化H2S和硫醇(RSH)分别成硫磺和二硫化物;硫磺排出设备,将硫磺从反应器排出到硫磺分离模块;还包括硫磺分离模块;该装置至少包括反应器供净化烃类气体和含氧气体设备,以及从反应器排出已净化气体设备;硫磺分离模块还包括硫磺分选设备;反应器结构和催化剂成分将硫化氢和硫醇转化成硫磺和二硫化物的程度至少达到99.99%,而催化剂本身是过渡金属混合络合物。
在气体经催化剂溶液过程中,根据以下反应公式硫化氢和硫醇将转成为硫磺和二硫化物:
Н2S+2RSH+O2=S+RSSR+2Н2O (1)
已净化气体从输出口到用户那里。根据反应(1)所产生的二硫化物将留在反应器里并不影响主要过程。根据反应(1)所产生的水,部分与净化气流一起从反应器排出,部分与微细硫磺溶液一起排出。
微细硫磺悬浮液将从反应器排出到硫磺分离模块。硫磺分离模块可装溶液分选硫磺设备,以便在反应器里循环利用溶液。
装置可另外包括净化气体和含氧气体混合气的均匀化设备。
反应器最好包括反应器供净化气流分配器或分配盘。
装置可另外包括催化剂定量进给设备。
装置最好使用铁和/或铜的卤化混合络合物作为催化剂。
为了达成所指出的技术结果,也可以运用已研制的烃类气体脱除硫化氢和硫醇过程。
按照已研制的过程,净化原料和含氧气体混合气将经充满有机催化剂溶液的反应器,催化剂将硫化氢和硫醇转化成硫磺和二硫化物的程度至少达到99.99%,而催化剂本身是过渡金属混合络合物。
装置温度最好保持在20-140℃范围内。
运用上述过程,氧气含量一般不低于硫化氢和硫醇总含量的50%。
混合气注入反应器时,最好在反应器里进行平匀分配。
运用上述过程,一般使用催化剂定量进给装置,同时从悬浮液中另外分离硫磺,而溶液再注入到反应器。
一般,使用铁和/或铜的卤化混合络合物作为催化剂。
另外,为了达成所指出的技术结果,建议使用烃类气体脱除硫化氢和硫醇一定成分的催化剂。上述催化剂是二氯化铁和/或铜、胺和酰胺混合物的0.0001-100%溶液,酒精中配比为1:20-1:0.1。
制造催化剂最好使用苄胺、环己胺、吡啶作为胺,以及二甲基甲酰胺作为酰胺。
附图说明
图1显示已研制装置最为合适应用方案的流程图,图例如下:1为供料管道,2为烃类气体和含氧气体混合器,3为供含氧气体管道,4为含氧气体流量增压器,5为烃类气体和含氧气体混合气输送管道,6为脱硫反应器,7为反应器6烃类气体和含氧气体混合气分配器,8为催化剂溶液罐,9为催化剂溶液从催化剂溶液罐8输送到反应器6增压器,10为催化剂溶液输送到反应器6管道,11为已净化气体排出管道,12为硫磺悬浮液排出到硫磺分离模块13管道,14为分离模块13硫磺排出管道,15为硫磺分选后催化剂溶液从分离模块13排出到反应器6管道,16为催化剂溶液从硫磺分离模块13输送到反应器6进行循环利用增压器。
图2显示运用方法的主要阶段,图例如下:17为到给反应器输入口供净化烃类气体原料和含氧气体混合气;18为净化原料经充满有机催化剂溶液的反应器;19为经反应器后获取已净化气体,同时硫化氢和硫醇转化成硫磺和二硫化物的程度达到99.99%;20为氧气含量不低于硫化氢和硫醇总含量的50%;21为反应器里混合气平匀分配;22为催化剂定量进给反应器;23为硫磺悬浮液中分离硫磺,而且将溶液再注入到反应器;24为装置温度保持在25-140℃范围内。
可以使用空气压缩机作为含氧气体流量增压器,可以使用定量泵作为催化剂溶液输送增压器,可以使用泵作为硫磺分离模块催化剂溶液循环利用增压器。
接下来,将通过应用案例显示已研制技术方案的本质和优势。
具体实施方式
案例1。C1催化剂制造法。在室温条件下烧瓶里注入乙醇10ml,辛烷100ml,CuCl2·2H2O 0.2-1g和胺(苄胺、环己胺、吡啶)0.5-3g。将烧瓶中的溶物搅拌成氯化铜的完全溶解。2405738号俄罗斯联邦专利描述上述成分的催化剂。
案例2。C2催化剂制造法。在室温条件下烧瓶里注入乙醇100ml,水20ml,二甲基甲酰胺(DMFA)20ml(0.25mol)和CuCl2·2H2O 15g(0.09mol)。将烧瓶中的溶物搅拌成氯化铜的完全溶解。2398735号俄罗斯联邦专利描述上述成分的催化剂,该科学研究为本发明打下了基础,但直到该研究结束,一直都没有关于该催化剂用于气体脱硫相关信息。
案例3。C3催化剂制造法.在室温条件下烧瓶里注入醇100ml,胺和二甲基甲酰胺(DMFA)混合物8-60g,CuCl2·2H2O 1.5-14g。将烧瓶中的溶物搅拌成氯化铜的完全溶解。
案例4。使用C1催化剂来净化气体。使用本发明提出的装置和过程来净化气体,但使用专利(RU专利号2405738发布时间2010年4月27日)中描述的C1催化剂。
反应器注入非水有机溶剂和C1催化剂,制造法见案例1。反应器输入口供气流,其成分含量为硫化氢0.1%,硫醇0.05%和氧气0.06%。溶液温度为25℃。根据电位滴定法数据,反应器输出口气体中硫化氢和硫醇含量分别为40和50ррm。硫化氢和硫醇转化程度分别为95.5%和91%。
可见,使用已知成分(根据RU专利号2405738发布时间2010年4月27日)催化剂,以及使用提出的装置和过程,使得硫化氢和硫醇转化成硫磺和二硫化物程度不超过95.5%。
案例5。按照本发明方法,使用C2催化剂来净化气体。反应器注入非水有机溶剂和C2催化剂。反应器输入口供含硫化氢、硫醇和氧气的气流,其比例分别为1.0%,0.05%和0.5025%。溶液温度为25℃。根据电位滴定法数据,反应器输出口气体中硫化氢和硫醇含量分别为60和60ррm。硫化氢和硫醇转化程度分别为99.4%和88%。
总之,案例4、5显示,使用成分不良催化剂,以及使用提出的装置和过程,使得硫化氢转化程度达到95.5-99.4%,而硫醇转化程度达到88-91%。
案例6-14。使用C3催化剂,使用提出的过程、催化剂和装置来净化气体。
反应器注入非水有机溶剂和C3催化剂,浓度为0.001-100%。反应器输入口供气流,其成分含量为硫化氢0.1-1.8%V,硫醇0.05-0.5%V和氧气0.075-1.15%V。溶液温度为20-40℃。根据电位滴定法数据,反应器输出口气体中硫化氢含量为10-0.001ррm,硫醇含量0.001-20ррm。硫化氢净化程度达到99.8-99.9999%,而硫醇净化程度达到98-99.9999%。使用C1-C3催化剂实验数据见表1。
表1.
本研究框架下,研究结果如下:
·使用催化剂C1以及本发明提出的装置和过程,使得硫化氢和硫醇转化程度不够高,分别达到95.5%和91%。
·使用催化剂C2以及本发明提出的装置和过程,使得不仅能脱除气体中的硫化氢,如2398735号发布时间2010年9月10日专利所述,而且脱除硫醇。转化程度为88%。
·发明的催化剂催化硫化氢和硫醇的氧化,转化程度高,见表2。
6-14案例硫化氢和硫醇转化见表2。
表2.
使用提出的过程和装置以及不同胺/酰胺/过渡金属成分比例的C3催化剂来净化气体,结果见表3。实验条件与6-14号实验条件相同。
表3.
使用提出的过程和装置以及胺/酰胺/过渡金属4:5:1成分比例的C3催化剂和不同溶剂来净化气体,结果见表4。实验条件与6-14号实验条件相同。
表4.
使用提出的过程和装置以及不同浓度的C3催化剂来净化气体,结果见表5。实验条件与6-14号实验条件相同。
表5.
使用提出的过程和装置以及C3催化剂,来净化不同成分的烃类气体,即甲烷、乙烷、С3+碳氢化合物含量不同,结果见表6。实验条件与6-14号实验条件相同。
表6.
上述案例证明技术结果的可达性,但没彻底发挥提出的技术方案的潜力。
应当着重指出,不偏离本发明的基本原理和特点,装置和方法可用于其他具体形式。因此,本发明应用案例和成果在各个方面均应被视为说明性而不是限制性的,而本发明的综合方法不限于本文件所提供的细节。
Claims (12)
1.基于充满催化剂有机溶剂溶液的催化反应器的气态烃原料脱除硫化氢和硫醇装置,将H2S和硫醇(RSH)分别氧化成硫磺和二硫化物;硫磺溶液从反应器排出到硫磺分离模块的设备;硫磺分离模块;该装置还至少包括反应器供净化烃类气体和含氧气体设备,以及从反应器排出已净化气体设备,硫磺分离模块还包括硫磺分选设备;反应器结构和催化剂成分将硫化氢和硫醇转化成硫磺和二硫化物的程度至少达到99.99%;
催化剂本身为二氯化铜、胺和酰胺混合物的0.0001-100%溶液;
所述催化剂中,二氯化铜、胺和酰胺的质量百分含量为如下任一种:
(1)二氯化铜1%、胺89%、酰胺10%;
(2)二氯化铜5%、胺45%、酰胺50%;
(3)二氯化铜10%、胺40%、酰胺50%;
(4)二氯化铜20%、胺10%、酰胺70%;
所述催化剂使用苄胺、环己胺、吡啶作为胺;
所述催化剂使用二甲基甲酰胺作为酰胺。
2.根据权利要求1所述的装置,其特征在于:所述装置中供烃类气体和含氧气体设备包括净化气体和含氧气体混合气的均匀化设备。
3.根据权利要求1所述的装置,其特征在于:所述装置中反应器包括反应器供净化气流分配器。
4.根据权利要求1所述的装置,其特征在于:所述装置另外包括催化剂定量进给设备。
5.根据权利要求1所述的装置,其特征在于:所述装置中硫磺分离模块包括溶液分选硫磺设备,以便在反应器里循环利用溶液。
6.气态烃原料硫化氢和硫醇的脱除工艺,净化气态烃原料和含氧气体混合气经充满催化剂有机溶液的反应器,使得硫化氢和硫醇转化成硫磺和二硫化物的程度至少达到99.99%;
催化剂本身为二氯化铜、胺和酰胺混合物的0.0001-100%溶液;
所述催化剂中,二氯化铜、胺和酰胺的质量百分含量为如下任一种:
(1)二氯化铜1%、胺89%、酰胺10%;
(2)二氯化铜5%、胺45%、酰胺50%;
(3)二氯化铜10%、胺40%、酰胺50%;
(4)二氯化铜20%、胺10%、酰胺70%;
所述催化剂使用苄胺、环己胺、吡啶作为胺;
所述催化剂使用二甲基甲酰胺作为酰胺。
7.根据权利要求6所述的脱除工艺,其特征在于:所述过程中氧气含量不低于硫化氢和硫醇总含量的50%。
8.根据权利要求6所述的脱除工艺,其特征在于:所述过程中混合气将在反应器里平匀分配。
9.根据权利要求6所述的脱除工艺,其特征在于:所述过程中催化剂定量进给装置。
10.根据权利要求6所述的脱除工艺,其特征在于:所述过程中从悬浮液中另外分离硫磺,并将溶液再注入到反应器。
11.根据权利要求6所述的脱除工艺,其特征在于:所述过程中装置温度保持在25-140℃范围内。
12.气态烃原料脱除硫化氢和/或硫醇催化剂,本身为二氯化铜、胺和酰胺混合物的0.0001-100%溶液;
所述催化剂中,二氯化铜、胺和酰胺的质量百分含量为如下任一种:
(1)二氯化铜1%、胺89%、酰胺10%;
(2)二氯化铜5%、胺45%、酰胺50%;
(3)二氯化铜10%、胺40%、酰胺50%;
(4)二氯化铜20%、胺10%、酰胺70%;
所述催化剂使用苄胺、环己胺、吡啶作为胺;
所述催化剂使用二甲基甲酰胺作为酰胺。
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PCT/RU2016/000415 WO2017188846A1 (en) | 2016-04-25 | 2016-07-04 | A device, process, and catalyst intended for desulfurization and demercaptanization of gaseous hydrocarbons |
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RU2764595C1 (ru) * | 2020-12-21 | 2022-01-18 | Акционерное общество "Зарубежнефть" | Установка и способ очистки газообразного углеводородного сырья от сероводорода и меркаптанов |
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RU2016116049A (ru) | 2017-10-30 |
US10427095B2 (en) | 2019-10-01 |
US20190151797A1 (en) | 2019-05-23 |
US10213740B2 (en) | 2019-02-26 |
EA038097B1 (ru) | 2021-07-06 |
US20180207579A1 (en) | 2018-07-26 |
WO2017188846A1 (en) | 2017-11-02 |
EP3448545A4 (en) | 2020-05-20 |
CN109310946A (zh) | 2019-02-05 |
US10478773B2 (en) | 2019-11-19 |
EP3448545A1 (en) | 2019-03-06 |
RU2649442C2 (ru) | 2018-04-03 |
EA201792667A1 (ru) | 2019-07-31 |
US20190118137A1 (en) | 2019-04-25 |
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