CN115569649A - 用于硫化氢选择氧化制硫磺的催化剂及其制备和使用方法 - Google Patents
用于硫化氢选择氧化制硫磺的催化剂及其制备和使用方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 31
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000011593 sulfur Substances 0.000 title claims abstract description 25
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000003647 oxidation Effects 0.000 title claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000011148 porous material Substances 0.000 claims abstract description 34
- 239000007789 gas Substances 0.000 claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 16
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 4
- 229920000053 polysorbate 80 Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000011863 silicon-based powder Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 239000004480 active ingredient Substances 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 238000011084 recovery Methods 0.000 abstract description 11
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract description 2
- 230000019635 sulfation Effects 0.000 abstract description 2
- 238000005670 sulfation reaction Methods 0.000 abstract description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 10
- 101150116295 CAT2 gene Proteins 0.000 description 7
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 7
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 7
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 7
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 7
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 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 description 4
- 230000008569 process Effects 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
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- 238000004898 kneading Methods 0.000 description 2
- 238000002803 maceration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- 239000003208 petroleum Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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- 150000004763 sulfides Chemical class 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- 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
- C01B17/0426—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 characterised by the catalytic conversion
- C01B17/0434—Catalyst compositions
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Abstract
本发明提供了一种硫化氢选择氧化制硫磺的催化剂,及其制备和使用方法。所述的催化剂以二氧化硅为载体,氧化铁为活性组分。入口段温度低,气体分子扩散速率小,选用比表面积低、孔容孔径小的二氧化硅,能有效保证硫化氢的转化率;出口高温段选用比表面积高、孔容孔径大的二氧化硅,缩短气体在孔道内的停留时间,可显著提高硫磺的回收率。制备时选用了稳定性高的二氧化硅作为载体,使得催化剂抗硫酸盐化能力强,可延长催化剂的使用寿命;入口低温段和出口高温段选用不同方法生产的原料,保证了硫磺的高回收率,拓宽了催化剂的使用温区。
Description
技术领域
本发明属于催化剂制备及使用领域,涉及的是一种硫化氢选择氧化制硫磺的催化剂及其制备和使用方法,更具体的说涉及一种硫化氢转化率和硫回收率更高的硫化氢选择氧化制硫磺催化剂及其制备和使用方法。
背景技术
石油工业、天然气的提炼、钢铁生产中金属的熔化、煤的液化等过程中常常伴有相当量的硫化物生成,其中主要是H2S。它是硫化物类污染物的一种形式,也是酸雨形成的污染源之一。
对于高浓度的H2S尾气处理,工业上普遍采用克劳斯尾气回收法。对于低浓度的H2S(小于15%)尾气处理,由于克劳斯法受热力学限制,经济上不合算,而且,克劳斯法处理后仍有3%~5%的H2S没有转化。
直接氧化法硫磺回收工艺的基本反应原理是:H2S+O2→S+H2O+Q,该反应不是平衡反应,理论上转化率可以达到100%,对酸气中H2S浓度没有下限要求,而且具有装置简单、操作弹性大,投资较少、脱除率高、消耗低、易于控制和操作等优点,特别适用于处理贫酸气。
随着环境保护法律法规的完善,以及国家对环保排放标准要求的提高,直接氧化发硫磺回收工艺引起了业内的高度重视。该法的关键是反应器设计、工艺优化和催化剂的开发,而催化剂的开发在其中起着关键的作用。
目前选择氧化硫磺回收催化剂使用时存在的主要问题是:(1)催化剂的选择性较低,主要是二氧化硫的选择性较高,导致硫磺的回收率较低;(2)催化剂的稳定性较差,主要是使用了易硫酸盐化的原料,虽然初始活性及低温活性较高,但使用寿命较短;(3)H2S+O2→S+H2O+Q是强放热反应,随着温度的升高,催化剂的活性、选择性下降较快,导致催化剂的适用温区较窄。
CN201110255125.5公开了一种以二氧化硅为原料,加入碱金属氧化物和碱土金属氧化物进行改性,挤条成型的载体孔容大于0.5ml/g,平均孔径大于30nm,以氧化铁为活性组分,浸渍法制备硫化氢选择氧化制硫催化剂的方法。该催化剂在低温时活性和选择性较高,使用温度高于220℃时,选择性和收率下降明显。
CN201310256676.2公开了一种以二氧化硅、β-碳化硅、改性剂等为载体,以氧化铁为活性组分的硫化氢选择氧化制硫催化剂的制备方法。通过加入β-碳化硅,使载体的比表面积不大于100m2/g,平均孔径大于20nm。使用温度升高时,该催化剂的硫磺收率也会明显下降。
CN201710652988.3公开了一种以偏钛酸、二氧化硅粉和硅酸钙为原料制备载体,以氧化铁和氧化钙为活性组分制备硫化氢选择氧化制硫催化剂的方法。虽然可以降低克劳斯反应逆反应的发生,但是因为加入的偏钛酸对克劳斯逆反应有活性,导致硫化氢的转化率在97%左右。
硫化氢选择氧化生成硫磺的反应是强放热反应,王治红等人(《石油化工应用》,2016,35(3),10-14)介绍,每反应1%的H2S,会导致60℃的温升,催化剂在绝热反应器中使用时,整个床层上的反应环境差别较大。
CN201780058737.0公开了一种催化剂的使用方法,即第一床层装填活性组分含量较高的催化剂,第二床层装填活性组分含量较低的催化剂,这可以提高硫磺的产率,但是该方法适用的温区较窄。
发明内容
为了克服现有技术中的上述缺陷,本发明提供一种硫化氢选择氧化制硫磺的催化剂及其制备和使用方法。制备时选用了稳定性高的二氧化硅作为载体,使得催化剂抗硫酸盐化能力强,可延长催化剂的使用寿命;入口低温段和出口高温段选用不同方法生产的载体原料,保证了硫磺的高回收率,拓宽了催化剂的使用温区。本发明能够积极推动硫磺回收新工艺的开发及推广,具有良好的经济效益和环境效益。
本发明的关键在于:所述的催化剂以二氧化硅为载体,氧化铁为活性组分,并添加一定量的活性助剂、造孔剂、粘结剂、分散剂等制成。入口段温度低,气体分子扩散速率小,选用气相法生产的比表面积低、孔容孔径小的二氧化硅,能有效保证硫化氢的转化率;出口高温段选用硅粉沉淀法生产的比表面积高、孔容孔径大的二氧化硅,缩短气体在孔道内的停留时间。
解决本发明中技术关键的具体技术方案为:
(1)一种选择氧化硫磺回收催化剂,由载体、助剂、活性组分组成。用二氧化硅粉末、活性助剂、造孔剂、粘结剂通过挤条成型制备载体,然后等体积浸渍铁、助剂的可溶性盐。催化剂中二氧化硅占90wt%以上;氧化铁占催化剂的2-8wt%,活性助剂,以氧化物计其含量占催化剂的0.5-5wt%。
(2)催化剂按照分层装填的方法使用。入口低温段装填的催化剂其比表面积20-60m2/g,孔容0.15-0.40ml/g,平均孔径10-25nm,最好是比表面积30-50m2/g,孔容0.20-0.35ml/g,平均孔径15-20nm;出口高温段装填的催化剂其比表面积61-120m2/g,孔容0.41-1.20ml/g,平均孔径26-60nm,最好是比表面积80-100m2/g,孔容0.50-0.80ml/g,平均孔径30-50nm。上层入口低温段装填量占催化剂总体积的20-70%,下层出口高温段装填量占催化剂总体积的30-80%。
(3)制备载体所用的二氧化硅,低温段选用气相法生产的二氧化硅粉末,该产品比表面积低,孔容孔径小,可延长气体分子在孔道内的停留时间,有利于提高硫化氢的转化率。高温段选用硅粉沉淀法生产的二氧化硅粉末,该产品孔容孔径大,有利于气体分子快速通过,可降低二氧化硫的选择性,从而提高硫磺的产率。
(4)活性组分所用原料为含铁的硝酸盐、硫酸盐、亚硫酸盐、氯化物等,最好是硝酸盐;加入量按照氧化物计,占催化剂总质量的2-8wt%,最好是3-7wt%。
(5)活性助剂所用原料为钙、铜、钠、锌、镁、铝、钾、镧、铈元素等的氧化物、氢氧化物、硝酸盐、硫酸盐、氯化物、碳酸盐或磷酸盐等,最好是碱金属或/和碱土金属的硝酸盐;加入量按照氧化物计,占催化剂总质量的0.5-5wt%,最好是1-3%。
(6)造孔剂选用田菁粉、面粉、羧甲基纤维素等,在载体制备时加入。在载体制备过程的干粉混合步骤中,占所有干粉总质量的2-8wt%,最好是3-6wt%。
(7)分散剂选用吐温-80、甘油、聚乙二醇-400等,在载体浸渍时使用,占浸渍液总体积的0.2-5%,最好是0.5-3%。
(8)粘结剂选用硝酸、聚乙烯醇、硅溶胶中的任一种,加入量占催化剂总质量的2-10wt%,最好是4-7%。
(9)催化剂制备方法如下:
载体的制备:二氧化硅粉与造孔剂干粉混合5-20min,加入粘结剂、活性助剂配成的溶液进行湿混15-40min,最好是20-30min,然后用2.5-4.5mm的模板挤条成型,陈化8-24h,最好是12-18h,40-100℃干燥5-24h,再经400-600℃焙烧2-6h。
催化剂的制备:将活性组分、助剂、分散剂按照等体积浸渍的量配成浸渍液,常温浸渍3-12h,或者40-80℃浸渍1-5h,然后80-120℃干燥2-8h,再经350-500℃焙烧2-6h。
具体实施方式
本部分将结合详细实施例进一步说明本发明的技术方案。在此公开的实施例是本发明的示例,其可以以不同的形式体现。因此,包括具体结构和功能细节的公开的详细内容无意限制本发明,而仅仅是作为权利要求的基础。
实施例1:
气相法生产的二氧化硅224.6g,田菁粉9.2g,氧化钙5.6g,混合10min,记为物料A。50.0g聚乙烯醇加入1000mL水中配成溶液,记为B。将适量的B溶液加入粉体A中,捏合30min,3.5mm模板挤条。陈化12h后50℃烘12h,550℃焙烧4h,得到载体C。
32.4g硝酸铁、3.2g硝酸钠溶解在46mL的水中,加5mL吐温-80混合均匀,配成浸渍液D。取100g载体C加入到浸渍液D中,进行等体积浸渍。浸渍8h后,100℃烘干5h,500℃分解4h,得催化剂编号为Cat-1。
经测试,Cat-1的指标:比表面积45.6m2/g,孔容0.28cm3/g,平均孔径17.8nm。
催化剂在常压微反评价装置上进行评价。反应炉由内径20mm的不锈钢管制成,催化剂装填量为10mL。反应入口、出口的气体组成由北分瑞利的3420A气相色谱仪在线分析。
催化剂评价条件:入口气体H2S 1%,O20.7%,H2O 30%,余为N2,气体空速1000h-1。
计算方法为:
转化率:αH2S=(YH2S 0-YH2S)/YH2S 0
选择性:ηSn=(YH2S 0-YH2S-YSO2)/(YH2S 0-YH2S)
收率:XSn=(YH2S 0-YH2S-YSO2)/YH2S0
αH2S——H2S转化率
ηSn——选择性
XSn——收率
YH2S 0——反应入口H2S的含量
YH2S——反应后尾气中H2S的含量
YSO2——反应后尾气中SO2的含量
表1全部装填Cat-1催化剂时的性能
从表1可以看出,当催化剂全床层均装填Cat-1时,入口低温段即180-220℃,催化剂的转化率、选择性和收率均比较高,但随着温度的升高,催化剂的各项性能下降明显。
实施例2:
硅粉沉淀法生产的二氧化硅232.7g,田菁粉9.6g,氧化钙6.2g,混合均匀,记为物料A。50.0g聚乙烯醇加入1000mL水中配成溶液,记为B。将适量的B溶液加入粉体A中,捏合30min,3.5mm模板挤条。陈化12h后50℃烘8h,550℃焙烧4h,得到载体C。
32.8g硝酸铁、3.6g硝酸钠溶解在49mL的水中,加5mL吐温-80混合均匀,配成浸渍液D。取100g载体C加入到浸渍液D中,进行等体积浸渍。浸渍8h后,100℃烘干5h,500℃分解4h,得催化剂编号为Cat-2。
经测试,Cat-2的指标:比表面积89.5m2/g,孔容0.61cm3/g,平均孔径35.2nm。
催化剂评价条件:入口气体H2S 1%,O20.7%,H2O 30%,余为N2,气体空速1000h-1。
表2全部装填Cat-2催化剂时的性能
从表2可以看出,当催化剂全床层均装填Cat-2时,入口低温段即180-220℃,催化剂的性能不及使用Cat-1时,但是随着温度的升高,至240℃及更高温度时,使用Cat-2的优越性比较明显。
实施例3
实施例1中的Cat-1占总装填体积的40%,装在反应炉上层入口低温段,实施例2中的Cat-2占总装填体积的60%,装在反应炉下层出口高温段。
催化剂评价条件:入口气体H2S 1%,O20.7%,H2O 30%,余为N2,气体空速1000h-1。
表3催化剂分层装填时的性能
从表3可以看出,将Cat-1和Cat-2分层装填时,催化剂在各个温度点的转化率、选择性和产率均比单独装填时性能优越。
按照表3的装填方法进行稳定性实验,并与工业样品进行对比,结果如表4所示。与工业样品相比,经过1000h后,催化剂的转化率和收率基本没有变化,这是因为使用了稳定性更高的二氧化硅做原料。
表4催化剂稳定性实验对比
评价条件:入口气体H2S 1%,O20.7%,H2O 30%,余为N2,气体空速1000h-1,温度220℃。
应当理解,本实施例的优选实施方式的工艺不是将本发明限制为所公开的特定形式,本发明涵盖了落入说明书描述的以及所附的权利要求限定的范围内的所有的修改、等价物和替换物。
Claims (8)
1.一种硫化氢选择氧化制硫磺的催化剂,该催化剂包含二氧化硅载体、活性助剂、活性组分氧化铁,通过浸渍法制备;二氧化硅占催化剂的90wt%以上;氧化铁占催化剂的2-8wt%;活性助剂,以氧化物计其含量占催化剂的0.5-5wt%;其特征在于:所述催化剂分层装填,上层入口低温段装填的催化剂,比表面积20-60m2/g,孔容0.15-0.40ml/g,平均孔径10-25nm;下层出口高温段装填的催化剂,比表面积61-120m2/g,孔容0.41-1.20ml/g,平均孔径26-60nm;上层入口低温段装填量占催化剂总体积的20-70%,下层出口高温段装填量占催化剂总体积的30-80%。
2.根据权利要求1所述的催化剂,其特征在于:制备载体所用的二氧化硅,低温段选用气相法生产的低比表面积的二氧化硅粉末,高温段选用硅粉沉淀法生产的大孔二氧化硅粉末。
3.根据权利要求1所述的催化剂,其特征在于:活性组分所用原料为含铁的硝酸盐、硫酸盐、亚硫酸盐、氯化物中的任一种,加入量按照氧化物计,占催化剂总质量的2-8wt%。
4.根据权利要求1所述的催化剂,其特征在于:活性助剂所用原料为钙、铜、钠、锌、镁、铝、钾、镧、铈元素任一种的氧化物、氢氧化物、硝酸盐、硫酸盐、氯化物、碳酸盐或磷酸盐,加入量按照氧化物计,占催化剂总质量的0.5-5wt%。
5.根据权利要求1所述的催化剂,其特征在于:载体中加入造孔剂,所述造孔剂选用田菁粉、面粉、羧甲基纤维素中的任一种;在载体制备过程的干粉混合步骤中,占所有干粉总质量的2-8wt%。
6.根据权利要求1所述的催化剂,其特征在于:在载体浸渍时使用分散剂,所述分散剂选用吐温-80、甘油、聚乙二醇-400中的任一种,占浸渍液总体积的0.2-5%。
7.根据权利要求1所述的催化剂,其特征在于:粘结剂选用硝酸、聚乙烯醇、硅溶胶中的任一种,加入量占催化剂总质量的2-10wt%。
8.根据权利要求1-7任一项所述的催化剂的制备方法,步骤如下:
(1)载体的制备:二氧化硅粉与造孔剂的干粉混合均匀,加入粘结剂、活性助剂的溶液进行湿混,然后挤条成型,陈化8-24h,40-100℃干燥5-24h,再经400-600℃焙烧2-6h;
(2)催化剂的制备:将活性组分、助剂、分散剂按照等体积浸渍的量配成浸渍液,常温浸渍3-12h,或者40-80℃浸渍1-5h,80-120℃干燥2-8h,再经350-500℃焙烧2-6h。
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