CN112569953B - 一种脱硫催化剂及其制备方法 - Google Patents
一种脱硫催化剂及其制备方法 Download PDFInfo
- Publication number
- CN112569953B CN112569953B CN202011413217.7A CN202011413217A CN112569953B CN 112569953 B CN112569953 B CN 112569953B CN 202011413217 A CN202011413217 A CN 202011413217A CN 112569953 B CN112569953 B CN 112569953B
- Authority
- CN
- China
- Prior art keywords
- desulfurization catalyst
- desulfurization
- oxide
- element oxide
- catalyst
- 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.)
- Active
Links
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 62
- 230000023556 desulfurization Effects 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910000311 lanthanide oxide Inorganic materials 0.000 claims abstract description 8
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 22
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 11
- 239000001569 carbon dioxide Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 7
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 10
- 229930192474 thiophene Natural products 0.000 abstract description 8
- 239000002912 waste gas Substances 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000571 coke Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000001741 organic sulfur group Chemical group 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000010908 plant waste Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/83—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 rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/408—Alkaline earth metal or magnesium compounds of barium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Environmental & Geological Engineering (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biomedical Technology (AREA)
- Catalysts (AREA)
Abstract
本发明提供一种脱硫催化剂及其制备方法。所述脱硫催化剂包含：Al2O3载体；ⅡA元素氧化物，为Mg、Ca和Ba元素氧化物的至少一种；IVB元素氧化物，为Ti和Zr元素氧化物的至少一种；Ⅷ元素氧化物，为Fe、Co、Ni、Ru和Rh元素氧化物的至少一种；镧系元素氧化物，为La、Ce和Pr元素氧化物的至少一种。本发明脱硫催化剂的脱硫效率高，尤其是能高效脱除噻吩。本发明脱硫催化剂的制备方法实现了废物的再利用、减少废气排放，降低了成本，是一种绿色环保的工艺。
Description
技术领域
本发明涉及工业脱硫的技术领域，更具体地，涉及一种脱硫催化剂及其制备方法。
背景技术
焦炉煤气是炼焦用煤在炼焦炉中经过高温干馏后，在产出焦炭和焦油产品的同时而产生的一种可燃性气体，是炼焦工业的副产品。焦炉煤气的主要成分为氢气、甲烷、一氧化碳、二氧化碳和含硫杂质(H2S、CS2、硫醇、硫醚和噻吩等)，这些硫化物的脱除通常采用干法和湿法。干法脱硫工艺的核心技术之一是用于脱硫的催化剂，其也成为研究的热点。
目前，焦炉煤气加氢脱硫催化剂主要是以Fe、Mo等为活性组分、Al2O3为载体，虽然已经普遍使用，但在实际应用中仍然存在缺陷，如催化剂活性低、脱硫率低，尤其用于脱除噻吩时，催化活性有待提升。另外，现有的有机硫加氢转化催化剂大多在使用前需要进行预硫化处理，使用起来较为繁琐。
因此，亟需一种新型的、可以便捷使用的、适用性好的新型催化剂来实现高效脱硫。
发明内容
本发明的目的首先在于提供一种新型的脱硫催化剂。该脱硫催化剂的脱硫效率高，尤其是能高效脱除噻吩，工业应用前景好。
为达到上述效果，本发明采用的技术方案如下：
一种脱硫催化剂，其包含：
Al2O3载体；
IIA元素氧化物，为Mg、Ca和Ba元素氧化物的至少一种；
IVB元素氧化物，为Ti和Zr元素氧化物的至少一种；
VIII元素氧化物，为Fe、Co、Ni、Ru和Rh元素氧化物的至少一种；
镧系元素氧化物，为La、Ce和Pr元素氧化物的至少一种。
作为一种方式，所述脱硫催化剂至少包含Al2O3载体、CaO、TiO2、Fe2O3和La2O3。
作为一种方式，所述Al2O3载体为大孔氧化铝，大孔氧化铝的孔容0.7～1.0mL/g，比表面积200～500m2/g。
作为一种方式，所述大孔氧化铝的孔容为0.8～1.0mL/g，比表面积为300～500m2/g。
作为一种方式，以重量分数计，所述脱硫催化剂包含：Al2O3载体85～98％，II A元素氧化物0.1～10％，IVB元素氧化物0.01～2％，VIII元素氧化物0.1～5％，镧系元素氧化物0.01～0.5％。
本发明还涉及一种脱硫催化剂的制备方法，其包括如下步骤：
(1)将Al2O3载体、IVB元素氧化物、VIII元素氧化物和镧系元素氧化物的固体粉末混合均匀，得到混合粉体；
(2)将含IIA元素化合物配制成溶液A，将所述混合粉体分散于溶液A中搅拌均匀，调节pH≥9，然后通入可使II A元素沉淀的气态沉淀剂，过滤、洗涤反应后的固体，得到催化剂前体；
(3)将所述的催化剂前体进行成型、干燥和焙烧，即得。
作为一种方式，所述步骤(1)中：
IVB元素氧化物，为Ti和Zr元素氧化物的至少一种；
VIII元素氧化物，为Fe、Co、Ni、Ru和Rh元素氧化物的至少一种；
镧系元素氧化物，为La、Ce和Pr元素氧化物的至少一种；
所述步骤(2)中，所述的含II A元素化合物选自Mg、Ca和Ba元素的可溶性化合物的至少一种。
作为一种方式，所述步骤(3)中，干燥的温度为75-110℃，干燥的时间为2-4小时；焙烧的温度为550-700℃，焙烧的时间为2-6小时。
作为一种方式，所述的Al2O3载体为大孔氧化铝，大孔氧化铝的孔容0.7～1.0mL/g，优选为0.8～1.0mL/g；比表面积200～500m2/g，优选为300～500m2/g。
作为一种方式，所述步骤(2)中，所述气态沉淀剂为二氧化碳和二氧化硫的一种或两种，优选地，所述二氧化碳和二氧化硫来自工厂废气。
本发明和现有技术相比，具有如下优点：
(1)本发明的脱硫催化剂在使用前可以不进行预硫化，并且可高效脱除有机硫，尤其针对噻吩的脱除效果好；
(2)本发明使用的具有特定孔容和比表面积的大孔氧化铝载体进一步改善了脱硫效果；
(3)本发明脱硫催化剂的制备方法步骤简单，而且可以利用工厂产生的二氧化碳或二氧化硫废气得到脱硫催化剂的其中一种原料成分-IIA元素氧化物，实现了废弃物的再利用、减少废气排放，降低了成本，是一种绿色环保的工艺。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面对本发明实施例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的一部分实施例，而不是全部的实施例。基于所描述的本发明的实施例，本领域普通技术人员在无需创造性劳动的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。
下列实施例中使用的化学物质未特别说明的，均直接从市场采购使用的。未注明具体条件的实验方法，按照化学领域的常规方法和条件或按照商品说明书选择操作。
本发明实施例中，气体沉淀剂具体是用二氧化碳或二氧化硫，还是同时使用，可以根据II A元素的沉淀性能而定。具体实施例中的二氧化碳或二氧化硫可以是本化工厂区的废气/尾气处理系统出来的，如此，可以实现废物利用并减少尾气排放，利于环境保护。
实施例1
脱硫催化剂的制备方法，包括如下步骤：
(1)将下列各组分的固体粉末混合均匀，得到混合粉体；
Al2O3载体：孔容为0.7mL/g的大孔氧化铝，98g
IVB元素氧化物：TiO2，0.01g
VIII元素氧化物：Fe2O3，0.1g
镧系元素氧化物：La2O3，0.01g
(2)将1.94g CaCl2加水充分溶解配制成溶液A，将混合粉体分散于溶液A中搅拌均匀，调节pH≥9，然后通入足量二氧化碳气体使钙离子完全沉淀，过滤、洗涤反应后的固体，得到催化剂前体；该二氧化碳可以来自本厂区的二氧化碳废气处理装置；
(3)将所述的催化剂前体进行成型，在75℃下干燥4小时，然后在550℃下焙烧6小时，即得。
上述制备方法得到的脱硫催化剂包含：98g Al2O3载体、0.98g CaO、0.01g TiO2、0.1g Fe2O3和0.01g La2O3。
实施例2-8、对比例1-3
以下实施例或对比例与实施例1的区别在于：脱硫催化剂的组分不同，具体如下表所示。表格中未涉及的组分、参数以及制备方法均与实施例1保持一致。
表1
实施例9-16
以下实施例或对比例与实施例1的区别在于：脱硫催化剂中使用的大孔氧化铝有所不同，具体如下表所示，其他参数均与实施例1保持一致。
表2
实施例17-21
以下实施例或对比例与实施例1的区别在于：脱硫催化剂制备方法中的步骤(3)的工艺参数不同，具体如下表所示，其他参数均与实施例1保持一致。
表3
对比例4
本对比例与实施例1的区别在于，脱硫催化剂的制备方法不同，具体包括以下步骤：
(1)将下列各组分的固体粉末混合均匀，得到混合粉体；
Al2O3载体：孔容为0.7mL/g的大孔氧化铝，98g
II A元素氧化物，CaO，0.98g
IVB元素氧化物：TiO2，0.01g
VIII元素氧化物：Fe2O3，0.1g
镧系元素氧化物：La2O3，0.01g
(2)将所述的混合粉体进行成型，在75℃下干燥4小时，然后在550℃下焙烧6小时，即得。
实验例
针对本发明实施例1-21和对比例1-4制备得到的脱硫催化剂，采用如下方法测试其脱硫性能：
模拟焦炉煤气：有机硫总含量258mg/m3，噻吩含量为30.5mg/m3。
反应装置：微型固定床反应器、在线定硫仪。
评价条件：将脱硫催化剂在氢气气氛下进行还原，还原温度为300℃，还原时间为2小时，氢气的流动速度为200sccm。还原结束后，通入模拟焦炉煤气进行脱硫。
脱硫的反应条件为：常压、温度200℃，空速1000h-1，反应稳定4h后，用在线定硫仪测试出口处的气体样品的硫含量，分析计算总脱硫率和噻吩脱除率。
实施例1-6、对比例1-3的试验结果见表4。
表4
分析上表4的实验结果可知，本发明实施例1-8的脱硫催化剂具有较高的有机硫脱除效率，尤其还具备较优异的噻吩脱除效率。其中，实施例1-6由于采用了相对更优的组分配方，其脱硫效果总体比实施例7-8较好。对比例1-3未采用本发明的脱硫催化剂的组分构成，脱硫效果较差。
实施例9-16的试验结果见表5。
表5
从上表的实验结果可知，实施例9-16的Al2O3载体不同于实施例1，得到的脱硫催化剂的脱硫性能有所不同，其中，实施例13-16的Al2O3载体的孔容和比表面不是本发明较优选的范围，得到的脱硫催化剂的脱硫性能稍逊于实施例1。
实施例17-21、对比例4的试验结果见表6。
表6
从上表的实验结果可知，实施例17-21的干燥工艺和焙烧工艺不同于实施例1，得到的脱硫催化剂的脱硫性能有所不同。其中，实施例20-21的干燥工艺和焙烧工艺的参数取值不是本发明较优选的范围，得到的脱硫催化剂的脱硫性能稍逊于实施例1。对比例4的制备方法不同于实施例1，得到的脱硫催化剂的性能比实施例1稍差。
虽然本发明所揭露的实施方式如上，但所述的内容仅为便于理解本发明而采用的实施方式，并非用以限定本发明。任何本发明所属领域内的技术人员，在不脱离本发明所揭露的精神和范围的前提下，可以在实施的形式及细节上进行任何的修改与变化，但本发明的专利保护范围，仍须以所附的权利要求书所界定的范围为准。
Claims (7)
1.一种脱硫催化剂在脱硫中的应用，其特征在于，所述脱硫催化剂包含：
Al2O3载体；
ⅡA元素氧化物，为Mg、Ca和Ba元素氧化物的至少一种；
IVB元素氧化物，为Ti和Zr元素氧化物的至少一种；
Ⅷ元素氧化物，为Fe、Co、Ni、Ru和Rh元素氧化物的至少一种；
镧系元素氧化物，为La、Ce和Pr元素氧化物的至少一种；
所述Al2O3载体为大孔氧化铝，大孔氧化铝的孔容0.7~1.0mL/g，比表面积200~500m2/g；
以重量分数计，所述脱硫催化剂包含：Al2O3载体85~98%，ⅡA元素氧化物0.1~10%，IVB元素氧化物0.01~2%，Ⅷ元素氧化物0.1~5%，镧系元素氧化物0.01~0.5%；
所述脱硫催化剂的制备方法包括如下步骤：
（1）将Al2O3载体、IVB元素氧化物、Ⅷ元素氧化物和镧系元素氧化物的固体粉末混合均匀，得到混合粉体；
（2）将含ⅡA元素化合物配制成溶液A，将所述混合粉体分散于溶液A中搅拌均匀，调节pH≥9，然后通入可使ⅡA元素沉淀的气态沉淀剂，过滤、洗涤反应后的固体，得到催化剂前体；
（3）将所述的催化剂前体进行成型、干燥和焙烧，即得。
2.根据权利要求1所述的脱硫催化剂在脱硫中的应用，其特征在于，所述大孔氧化铝的孔容为0.8~1.0mL/g，比表面积为300~500m2/g。
3.根据权利要求1所述的脱硫催化剂在脱硫中的应用，其特征在于，所述步骤（2）中，所述的含ⅡA元素化合物选自Mg、Ca和Ba元素的可溶性化合物的至少一种。
4.根据权利要求1所述的脱硫催化剂在脱硫中的应用，其特征在于，所述步骤（3）中，干燥的温度为75-110℃，干燥的时间为2-4小时；焙烧的温度为550-700℃，焙烧的时间为2-6小时。
5.根据权利要求1所述的脱硫催化剂在脱硫中的应用，其特征在于，所述步骤（2）中，所述气态沉淀剂为二氧化碳和二氧化硫的一种或两种。
6.根据权利要求5所述的脱硫催化剂在脱硫中的应用，其特征在于，所述步骤（2）中，所述二氧化碳和二氧化硫来自工厂废气。
7.根据权利要求1所述的脱硫催化剂在脱硫中的应用，其特征在于，所述脱硫催化剂至少包含Al2O3载体、CaO、TiO2、Fe2O3和La2O3。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011413217.7A CN112569953B (zh) | 2020-12-02 | 2020-12-02 | 一种脱硫催化剂及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011413217.7A CN112569953B (zh) | 2020-12-02 | 2020-12-02 | 一种脱硫催化剂及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112569953A CN112569953A (zh) | 2021-03-30 |
| CN112569953B true CN112569953B (zh) | 2022-08-23 |
Family
ID=75127558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011413217.7A Active CN112569953B (zh) | 2020-12-02 | 2020-12-02 | 一种脱硫催化剂及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112569953B (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113546644B (zh) * | 2021-06-27 | 2022-05-27 | 昆明理工大学 | 焦炉煤气有机硫深度脱除催化剂的制备方法和应用 |
| CN114950424B (zh) * | 2022-06-15 | 2023-07-14 | 万华化学（宁波）有限公司 | 一种循环气两段式脱硫催化剂、制备方法及其应用 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101703934B (zh) * | 2009-12-03 | 2012-02-01 | 熊世平 | 煤制天然气催化剂及其制造方法 |
| CN102423713A (zh) * | 2011-09-30 | 2012-04-25 | 南京工业大学 | 一种加氢脱硫催化剂及其制备方法 |
| CN107175108A (zh) * | 2017-07-10 | 2017-09-19 | 中国科学院过程工程研究所 | 一种用于烟气中二氧化硫还原制硫的钴系催化剂及其制备方法和用途 |
-
2020
- 2020-12-02 CN CN202011413217.7A patent/CN112569953B/zh active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112569953A (zh) | 2021-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2556687C2 (ru) | Способ обработки серосодержащего газа и используемый для данных целей катализатор гидрирования | |
| CN112569953B (zh) | 一种脱硫催化剂及其制备方法 | |
| DK2438986T3 (en) | RENEWABLE AND RECYCLABLE SULFURING EQUIPMENT AND PROCEDURES FOR PRODUCING AND RECOVERING THEREOF | |
| CN101070491A (zh) | 一种常、低、中温脱硫剂活性组分制备方法 | |
| CN106693632A (zh) | 一种氧化锌基常温深度脱硫剂及其制备方法与应用 | |
| CN101322915A (zh) | 一种复合吸附脱硫剂及其制备方法 | |
| CN109847730B (zh) | 一种脱硫吸附剂的再生方法 | |
| CN112619648B (zh) | 一种用于有机硫水解脱除的铜钴基催化剂及其制备方法 | |
| WO2019010811A1 (zh) | 一种用于烟气中二氧化硫还原制硫的钴系催化剂及其制备方法和用途 | |
| CN109721027B (zh) | 甲烷硫化氢重整反应制氢的方法 | |
| CN114768859A (zh) | 适用于甲烷干重整的镍硅催化剂及其制备方法 | |
| CN109894118B (zh) | 一种镍基加氢催化剂及其应用 | |
| CN110711584A (zh) | 半焦负载型焦油水蒸气重整催化剂及其制备方法和应用 | |
| CN116020434B (zh) | 一种不积硫、抗失活的羰基硫水解催化剂及其应用 | |
| CN103769043B (zh) | 一种气体脱硫吸附剂、其制备方法及应用 | |
| WO2023072134A1 (zh) | 催化剂及应用与脱除天然气中羰基硫的方法 | |
| CN103028363A (zh) | 气体脱硫吸附剂及其制备方法和含硫气体的脱硫方法 | |
| CN111068746B (zh) | 一种多功能硫磺回收催化剂及其制备方法 | |
| CN107597183B (zh) | 一种脱硝催化剂的制备方法 | |
| CN115041218A (zh) | 一种分级沸石核壳催化剂及其制备方法和在净化高炉煤气有机硫中的应用 | |
| CN112604709A (zh) | 一种含硫废气处理用加氢催化剂及其应用 | |
| CN112221510A (zh) | 一种有机硫加氢催化剂及其制备方法和应用 | |
| CN103769038B (zh) | 一种气体脱硫吸附剂、其制备方法及应用 | |
| CN103028367B (zh) | 气体脱硫吸附剂及其制备方法和含硫气体的脱硫方法 | |
| CN112206743A (zh) | 一种改性凹凸棒土脱硫吸附剂的制备方法与应用 |
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 |