CN101429460B - 通过负载的金属氧化物从流体中除汞 - Google Patents
通过负载的金属氧化物从流体中除汞 Download PDFInfo
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- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 17
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 8
- 239000012530 fluid Substances 0.000 title abstract description 11
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003463 adsorbent Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 229960004643 cupric oxide Drugs 0.000 claims abstract description 12
- 239000005864 Sulphur Substances 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 45
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 11
- 239000003345 natural gas Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- -1 halide anion Chemical class 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 8
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 7
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000002594 sorbent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 241000907663 Siproeta stelenes Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910001502 inorganic halide Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MMKDSKOQWHBXCT-UHFFFAOYSA-N [Cu].[Hg] Chemical compound [Cu].[Hg] MMKDSKOQWHBXCT-UHFFFAOYSA-N 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- PGZIKUPSQINGKT-UHFFFAOYSA-N dialuminum;dioxido(oxo)silane Chemical compound [Al+3].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O PGZIKUPSQINGKT-UHFFFAOYSA-N 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910001682 nordstrandite Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1025—Natural gas
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treating Waste Gases (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明涉及通过负载的金属氧化物从流体中除汞，即，使用氧化铜吸附剂从进料流中除汞的用途。当进料流的硫含量低时，应该在进料流中加入硫化剂，例如硫化氢。
Description
技术背景
本发明涉及从烃液体和气体中除去污染物。更特别地，本发明涉及使用氧化铜吸附剂从天然气流中除去硫和汞。
流体流，如烃液体和气体，如天然气，常常被硫化合物和其它污染物(例如单质汞)污染。负载的金属硫化物，例如硫化铜CuS，是用于从流体中除汞的已知清除剂。例如，US 4,094,777描述了作为气体或液体中的汞的吸收剂的含有载体和硫化铜的固体。Axens，JMC等提供了用在天然气和烃工业中的CuS基除汞材料。但是，需要更有效的汞吸收剂，尤其是在无硫流体和在进料中存在还原剂(例如氢)的情况下。
发明概要
本发明提供了一种净化天然气进料流的方法，所述天然气进料流含有至少一种硫污染物和至少一种汞污染物，该方法通过使进料流通过包含负载在载体上的金属氧化物吸附剂的吸附剂床实现净化。氧化铜是优选吸附剂。
本发明使用负载在具有高BET表面积的氧化铝载体上的金属氧化物，例如氧化铜，而硫化合物(优选硫化氢)始终以超过进料中Hg浓度的浓、度(为Hg浓度的至少3倍，或至少4倍)混入要净化的进料中。这通过原位制造结合汞所需的硫化铜中间体同时抑制与进料组分的竞争性反应(该反应导致生成不适合除汞的铜相)来提高该方法的驱动力，从而大大地改进了除汞。
发明详述
实施本发明的优选方式是确保在含Hg的进料流穿过除汞吸附剂的同时在该进料流中存在容易与CuO反应的硫化合物。该吸附剂含有在高表面积载体上的氧化铜CuO。
制备该吸附剂的优选方法以碱性碳酸铜例如CuCO3 Cu(OH)2为原料，其可以通过铜盐例如Cu(NO)3、CuSO4和CuCl2与碳酸钠的沉淀产生。根据所用条件，尤其根据对所得沉淀物的洗涤，最终材料可能含有来自该沉淀法的一些残留产物。在用CuCl2作原材料时，氯化钠是沉淀法的副产物。已经确定，具有残留氯和钠的市售碱性碳酸铜表现出比几乎无氯化物的另一商业BCC低的受热稳定性和改进的抗还原性。
在本发明的一些实施方案中，形成了包含载体材料(如氧化铝)、氧化铜和卤化物盐的附聚物。氧化铝通常以过渡氧化铝的形式存在，其包含结晶较差的氧化铝相(例如“ρ(rho)”、“χ(chi)”和“假γ”氧化铝)的混合物，这些氧化铝能够迅速再水合，并可以留住相当大量的反应性形式的水。氢氧化铝Al(OH)3，例如三水铝石，是用于制备过渡氧化物的来源。用于制造过渡氧化铝的典型工业方法包括如专利文献(例如US2,915,365)中所述将三水铝石研磨至1-20微米粒度，然后快速煅烧短接触时间。也可以使用非晶态氢氧化铝和其它天然存在的矿物结晶氢氧化物，例如三羟铝石和新三水氧化铝，或氢氧化一氧化物(AlOOH)，例如勃姆石和水铝石，作为过渡氧化铝源。在为实施本发明而简化进行的实验中，过渡氧化铝由位于Baton Rouge，Louisiana的UOP LLC工厂供应。该过渡氧化铝材料的BET表面积为300平方米/克，且通过氮吸附测定的平均孔径为30埃。
通常，使用过渡金属的固体含氧盐作为复合材料的组分。“含氧盐”在定义上是指含氧酸的任何盐。该定义有时扩宽至“含氧以及给定阴离子的盐”。例如，FeOCl被视为符合此定义的含氧盐。对于本发明的所列实例，我们使用碱性碳酸铜(BCC)CuCO3Cu(OH)2，其是Phibro Tech，Ridgefield Park，New Jersey制造的合成形式的矿物孔雀石。BCC粒子的粒度大致在过渡氧化物的粒度范围内，即1至20微米。另一可用的含氧盐是蓝铜矿Cu3(CO3)2(OH)2。通常，可以成功地使用铜、镍、铁、锰、钴、锌或元素组合的含氧盐。
如下制造氧化铜吸附剂：将无机卤化物添加剂与碱性碳酸铜结合以制造混合物，然后将该混合物煅烧足以分解碱性碳酸铜的时间。优选的无机卤化物是氯化钠、氯化钾或其混合物。溴化物盐也是有效的。氧化铜吸附剂中的氯化物含量可以为0.05至2.5质量％，且优选为0.3至1.2质量％。可以使用多种形式的碱性碳酸铜，优选形式是合成孔雀石CuCO3Cu(OH)2。
含有卤化物盐的氧化铜吸附剂表现出比不用卤化物盐制成的类似吸附剂高的抗还原性。优选的卤化物是氯化物。制备含金属氧化物的吸附剂的其它方法可以如本领域技术人员已知的那样制备。
所用载体材料可以选自由碳、活性炭、焦炭、二氧化硅、氧化铝、二氧化硅-氧化铝、硅酸盐、铝酸盐和硅铝酸盐(例如沸石)组成的组。优选地，该载体选自由二氧化硅、氧化铝、二氧化硅-氧化铝、硅酸盐、氧化铝和硅铝酸盐组成的组，优选使用氧化铝。
据计算，当除汞反应与CuO硫化反应结合以产生最终产物HgS时，除汞的驱动力极大提高。下表列出了去除过程中所涉及的平衡常数的对数。
可以看出，反应2CuO+Hg(g)+2H2S(g)＝HgS+Cu2S+2H2O(g)是最优选的选项。这种反应也确保了与吸附剂材料平衡的液相中最低的Hg浓度。
该吸附剂含有5至65％CuO，优选10至40％。其可以通过例如常见的浸渍或共球化方式制造。氧化铝是优选载体，而复合材料的BET表面积优选超过200平方米/克。
该吸附剂材料的使用减缓了竞争性反应，其中2CuS+H2＝Cu2S+H2S。该氢化反应通常在热力学方面是高度有利的。有利地，吸附剂组分减缓了铜还原反应。
本发明可以在常见固定床反应器中用含Hg的进料实施。H2S优选作为该流体中的硫化组分。以摩尔表示的其浓度应该超过该流体中总Hg的浓度，为总Hg浓度的至少2.5倍，优选至少3.5倍。硫化剂可以为进料的一部分。如果S在进料中不可得，进入床入口的小的侧流应该提供发生总CuO-Hg-H2S反应所必需的S量。
Claims (8)
1.净化天然气进料流的方法，所述天然气进料流含有至少一种硫污染物和至少一种汞污染物，所述方法包括使所述进料流穿过包含吸附剂的吸附剂床，所述吸附剂包含负载在载体上的金属氧化物，其中所述金属氧化物是氧化铜，其中在所述进料流中加入硫化组分。
2.权利要求1的方法，其中所述吸附剂包含5至65％的氧化铜。
3.权利要求1的方法，其中所述吸附剂包含10至40％的氧化铜。
4.权利要求1的方法，其中所述载体选自由二氧化硅、氧化铝、二氧化硅-氧化铝、硅酸盐、氧化铝和硅铝酸盐组成的组。
5.权利要求1的方法，其中所述吸附剂具有大于200平方米/克的BET表面积。
6.权利要求1的方法，其中所述硫化组分是硫化氢。
7.权利要求1的方法，其中所述吸附剂含有阻碍铜还原成较低价态的添加剂。
8.权利要求7的方法，其中所述添加剂含有卤素阴离子。
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| US11/955,470 US7645306B2 (en) | 2007-12-13 | 2007-12-13 | Removal of mercury from fluids by supported metal oxides |
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| FR2980722B1 (fr) * | 2011-10-04 | 2015-03-20 | IFP Energies Nouvelles | Masse de captation a performances ameliorees et son utilisation dans la captation de metaux lourds |
| FR2980721B1 (fr) | 2011-10-04 | 2015-03-13 | IFP Energies Nouvelles | Mise en forme de masses de captation pour la purification d'une charge gaz ou liquide contenant du mercure |
| US9006508B2 (en) * | 2012-02-06 | 2015-04-14 | Uop Llc | Protected adsorbents for mercury removal and method of making and using same |
| US8876952B2 (en) * | 2012-02-06 | 2014-11-04 | Uop Llc | Method of removing mercury from a fluid stream using high capacity copper adsorbents |
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| CN104107631B (zh) * | 2014-07-30 | 2016-09-07 | 沈阳三聚凯特催化剂有限公司 | 一种脱硫脱汞剂及其制备方法 |
| US10286373B2 (en) | 2014-10-16 | 2019-05-14 | Chem32, Llc | Methods of sulfurizing metal containing particles |
| GB201509822D0 (en) * | 2015-06-05 | 2015-07-22 | Johnson Matthey Plc | Method for preparing a sorbent |
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| GB201509823D0 (en) * | 2015-06-05 | 2015-07-22 | Johnson Matthey Plc | Method for preparing a sorbent |
| CN108348833B (zh) | 2015-11-10 | 2020-12-18 | 环球油品公司 | 用于气体纯化的铜吸附剂 |
| MY187291A (en) | 2017-08-01 | 2021-09-19 | Petroliam Nasional Berhad Petronas | Process for the production of copper sulfide |
| MY197566A (en) | 2017-08-01 | 2023-06-23 | Petroliam Nasional Berhad Petronas | New form of copper sulphide |
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| CN108499340A (zh) * | 2018-04-28 | 2018-09-07 | 盐城东博环保科技有限公司 | 一种基于clp过程的燃煤烟气中汞脱除回收及吸附剂再生方法 |
| FR3130635A1 (fr) | 2021-12-20 | 2023-06-23 | IFP Energies Nouvelles | Procede de captation de metaux lourds par co-alimentation d’un flux sulfurant |
| FR3130636A1 (fr) | 2021-12-20 | 2023-06-23 | IFP Energies Nouvelles | Procede de rejuvenation de masses de captation de metaux lourds |
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| BRPI0805258A2 (pt) | 2010-04-06 |
| MY144111A (en) | 2011-08-15 |
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| CN101429460A (zh) | 2009-05-13 |
| NL1036208C2 (en) | 2009-12-01 |
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