CN108097237A - 改性锰砂、其作为载体的变换甲烷化催化剂及制备方法 - Google Patents
改性锰砂、其作为载体的变换甲烷化催化剂及制备方法 Download PDFInfo
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- 239000004576 sand Substances 0.000 title claims abstract description 71
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 150000002696 manganese Chemical class 0.000 title claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 25
- 239000011572 manganese Substances 0.000 claims abstract description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- 239000011259 mixed solution Substances 0.000 claims description 16
- 229910052702 rhenium Inorganic materials 0.000 claims description 15
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical group [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 10
- 238000007598 dipping method Methods 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
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- 239000002253 acid Substances 0.000 claims 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 8
- 229910001868 water Inorganic materials 0.000 abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 45
- 235000019580 granularity Nutrition 0.000 description 21
- 239000000843 powder Substances 0.000 description 8
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- 229910052739 hydrogen Inorganic materials 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
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- 239000003795 chemical substances by application Substances 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- 239000012298 atmosphere Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 modified manganese sand (Modified Manganese Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- HIGRAKVNKLCVCA-UHFFFAOYSA-N alumine Chemical compound C1=CC=[Al]C=C1 HIGRAKVNKLCVCA-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 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
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 235000019587 texture Nutrition 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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Abstract
本发明公开了一种改性锰砂及利用改性锰砂作为载体的变换甲烷化催化剂及其制备方法。本发明所述改性锰砂,由锰砂与改性溶液混合加热而成;所述改性溶液为硝酸、氨水或双氧水;利用改性锰砂制备的催化剂具有变换和甲烷化双功能,可同时催化水气变换反应和甲烷化反应,简化了工艺流程,降低了系统能耗,具有广阔的应用前景。
Description
技术领域
本发明涉及一种催化剂载体及其制备方法,特别涉及锰砂载体及其制备方法。
背景技术
生物质资源分布广泛,来源丰富,如若采用气化技术代替传统的直接燃烧方式,不仅可以减少环境污染,而且产生的气化燃气可应用于城镇供气以解决城镇化快速发展过程中的能源支撑问题,然而生物质气化燃气由于原料来源、气化介质和操作条件的不同,其H2/CO变化范围较大。对于低H2/CO生物质气化燃气而言,由于其有毒气体CO含量较高而热值较小,往往需要进行技术预处理以符合国家城镇燃气标准中针对CO含量和热值的要求。水气变换反应和甲烷化反应由于可将CO转变为H2和高热值的CH4,因此常被应用于解决上述问题。
现有及工业上使用的催化剂以具有甲烷化和变换反应单一功能的催化剂居多,而同时拥有变换甲烷化双重功能的催化剂公开报导较少。如若开发一种变换甲烷化双功能催化剂,不仅可以节约催化剂制造成本,而且在工艺流程上可将甲烷化和变换反应两个单元整合为一,在简化工艺流程节省设备投资的同时又能提高系统操作性。
适用于作为催化剂载体的物质很多,如Al2O3、SiO2、CeO2等氧化物,碳纤维、石墨烯、碳纳米管等碳材料,海泡石、高岭土、高铝矾土等矿石。锰砂由优质天然锰矿石加工而成,在我国储量丰富,常被用于地下水处理以去除水中铁、锰、砷等有害物质,具有机械强度大、不易破碎等特点。
发明内容
发明目的:本发明旨在提供一种改性锰砂及其作为载体的变换甲烷化催化剂及其制备方法,该催化剂特别适用于低H2/CO生物质气化燃气制取城镇燃气,在保持较高变换和甲烷化活性的前提下,具有成本低廉,制备工艺简单的特点。
技术方案:本发明所述一种改性锰砂,由锰砂与改性溶液混合加热而成;所述改性溶液为硝酸、氨水或双氧水。由于锰砂(Raw Manganese Sand,RMS)质地硬密,表面积很小,负载能力有限,故本发明对锰砂改性得到改性锰砂(Modified Manganese Sand,MMS),改性后锰砂的比表面积大大增加,孔道结构变得发达,负载能力增加。
所述锰砂粒径为2-4mm;所述锰砂中MnO2质量百分含量为20-35%。
所述改性溶液的浓度为0.05-0.15mol/L。
所述加热温度为60-100℃;所述加热时间为1-3h。
所述锰砂与改性溶液的体积比为1:1-2。
由上述改性锰砂为载体的变换甲烷化催化剂,包括活性成分、助剂和载体;所述活性成分为镍,以金属质量计,占催化剂质量百分比的5-30%;所述助剂为铼,以金属质量计,占催化剂质量百分比为0.1-1.5%;所述载体为改性锰砂。镍具有催化甲烷化反应的作用,锰砂载体中的锰具有催化水气变换反应的作用,因此可以实现变换甲烷化反应,铼作为助剂能够提高催化剂的催化性能。
上述改性锰砂为载体的变换甲烷化催化剂的制备方法,包括以下步骤:
(1)将改性锰砂研磨,浸渍于镍的可溶性盐和铼的可溶性盐混合溶液、烘干得催化剂前驱体;
(2)将催化剂前驱体焙烧,研磨,压片,破碎,筛分得成品。
步骤(1)中,所述改性锰砂研磨后的粒度为60-100目。
步骤(1)中,所述镍的可溶性盐为镍的硝酸盐或镍的硫酸盐;所述铼的可溶性盐为过铼酸铵。
步骤(1)中,所述浸渍温度为40-80℃,浸渍时间为8-12h。
步骤(1)中,所述烘干温度为80-120℃,干燥时间为10-24h。
步骤(2)中,所述焙烧温度为400-500℃;所述焙烧时间为4-6h。
步骤(2)中,所述筛分得到的颗粒状催化剂粒度为8-10目。
本发明的催化剂经过还原后用于催化变换甲烷化反应,催化剂还原步骤具体为:在氮气氛围下以3-5℃/min的升温速率将催化剂床层温度缓慢升至250℃,切换气体为氮气和氢气混合的还原性气氛,氢气占气体总体积浓度为15-25%,同时维持升温速率2-4℃/min,进一步将催化剂床层温度提升至450℃,恒温还原2-4h。
本发明的催化剂运行条件为:压力0.1-1.0MPa,温度350-450℃,气体体积空速1000-5000h-1,H2/CO比值0.6-1.0,特别适用于低H2/CO生物质气化燃气制取城镇燃气过程,其中H2/CO表示H2与CO的体积比。
有益效果:本发明采用廉价锰砂作为催化剂载体,拓宽了催化剂载体来源,降低了催化剂制造成本,且制备过程简单,易实现催化剂载体批量生产;本发明利用改性锰砂作为载体的变换甲烷化催化剂,与传统的单一功能催化剂相比,具有变换和甲烷化双功能,可同时催化水气变换反应和甲烷化反应,对于需要串联以上两个反应的工艺流程而言,可以整合在一个反应单元进行,因此简化了工艺流程,降低了系统能耗;本发明催化剂特别适用于低H2/CO生物质燃气制取城镇燃气过程,无需在工艺流程中对原料气预先进行变换以增大H2/CO。
具体实施方式
一、原料来源
1、本发明所用锰砂粒径为2-4mm,锰砂中MnO2质量百分含量为20-35%;
2、本发明其余所用的材料均市购所得。
二、改性锰砂的制备
2.1双氧水改性锰砂的制备
将锰砂与0.05mol/L双氧水的按体积比为1:1混合后加热,加热温度为60℃,加热时间为1h,将加热后的双氧水改性锰砂干燥,用破碎机破碎研细,分别得到粒度为80目和100目双氧水改性锰砂(MMS-H2O2)备用。
2.2氨水改性锰砂的制备
将锰砂与0.1mol/L氨水按体积比为1:2混合后加热,加热温度为80℃,加热时间为2h,将加热后的改性锰砂干燥,用破碎机破碎研细,得到粒度为100目的氨水改性锰砂(MMS-NH3·H2O)备用。
2.3硝酸改性锰砂的制备
将锰砂与0.15mol/L硝酸按体积比为1:1.5混合后加热,加热温度为100℃,加热时间为3h,将加热后的改性锰砂干燥,破碎机破碎研细,得到粒度为80目的硝酸改性锰砂(MMS-HNO3)备用。
二、样品制备
实施例1:取74.32g Ni(NO3)2·6H2O和1.44g NH4ReO4配制成混合溶液,另称取78.31g粒度为80目的双氧水改性锰砂将其浸渍于混合溶液中,60℃恒温浸渍12h,浸渍完成后放入烘箱中于110℃下干燥12h,再转移入马弗炉中于400℃下焙烧5h,粉末压片后破碎得到粒度为10目的含镍15.0wt.%和含铼1.0wt.%的Ni-Re/MMS-H2O2变换甲烷化催化剂。
实施例2:取74.32g Ni(NO3)2·6H2O和1.44g NH4ReO4配制成混合溶液,另称取78.31g粒度为100目的氨水改性锰砂将其浸渍于混合溶液中,80℃恒温浸渍10h,浸渍完成后放入烘箱中于100℃下干燥14h,再转移入马弗炉中于450℃下焙烧4h,粉末压片后破碎得到粒度为8目的含镍15.0wt.%和含铼1.0wt.%的Ni-Re/MMS-NH3·H2O变换甲烷化催化剂。
实施例3:取74.32g Ni(NO3)2·6H2O和1.44g NH4ReO4配制成混合溶液,另称取78.31g粒度为80目的硝酸改性锰砂将其浸渍于混合溶液中,70℃恒温浸渍10h,浸渍完成后放入烘箱中于100℃下干燥14h,再转移入马弗炉中于400℃下焙烧5h,粉末压片后破碎得到粒度为10目的含镍15.0wt.%和含铼1.0wt.%的Ni-Re/MMS-HNO3变换甲烷化催化剂。
实施例4:取99.07g Ni(NO3)2·6H2O和2.16g NH4ReO4配制成混合溶液,另称取70.65g粒度为100目的双氧水改性锰砂将其浸渍于混合溶液中,60℃恒温浸渍12h,浸渍完成后放入烘箱中于110℃下干燥12h,再转移入马弗炉中于400℃下焙烧5h,粉末压片后破碎得到粒度为8目的含镍20.0wt.%和含铼1.5wt.%的Ni-Re/MMS-H2O2变换甲烷化催化剂。
实施例5:取24.77g Ni(NO3)2·6H2O和0.15g NH4ReO4配制成混合溶液,另称取93.38g粒度为100目的双氧水改性锰砂将其浸渍于混合溶液中,60℃恒温浸渍12h,浸渍完成后放入烘箱中于110℃下干燥12h,再转移入马弗炉中于400℃下焙烧5h,粉末压片后破碎得到粒度为8目的含镍5.0wt.%和含铼0.1wt.%的Ni-Re/MMS-H2O2变换甲烷化催化剂。
实施例6:取148.61g Ni(NO3)2·6H2O和2.16g NH4ReO4配制成混合溶液,另称取57.92g粒度为100目的双氧水改性锰砂将其浸渍于混合溶液中,60℃恒温浸渍12h,浸渍完成后放入烘箱中于110℃下干燥12h,再转移入马弗炉中于400℃下焙烧5h,粉末压片后破碎得到粒度为8目的含镍30.0wt.%和含铼1.5wt.%的Ni-Re/MMS-H2O2变换甲烷化催化剂。
对比例1:取74.32g Ni(NO3)2·6H2O和1.44g NH4ReO4配制成混合溶液,另称取78.31g粒度为80目的未经任何改性的粗锰砂将其浸渍于混合溶液中,60℃恒温浸渍12h,浸渍完成后放入烘箱中于110℃下干燥12h,再转移入马弗炉中于400℃下焙烧5h,粉末压片后破碎得到粒度为10目的含镍15.0wt.%和含铼1.0wt.%的Ni-Re/RMS变换甲烷化催化剂。
对比例2:取74.32g Ni(NO3)2·6H2O配制成溶液,另称取80.91g粒度为80目的双氧水改性锰砂将其浸渍于溶液中,60℃恒温浸渍12h,浸渍完成后放入烘箱中于110℃下干燥12h,再转移入马弗炉中于400℃下焙烧5h,粉末压片后破碎得到粒度为10目的含镍15.0wt.%的Ni/MMS-H2O2变换甲烷化催化剂。
三、结果评价
实施例5和实施例6均为双氧水改性的催化剂,其催化效果与实施例1相似,故选择实施例1-4制备的样品和对比例1和对比例2制备的催化剂置于固定床装置中,在氮气氛围下以3-5℃/min的升温速率将催化剂床层温度缓慢升至250℃,切换气体为氮气和氢气混合的还原性气氛,氢气占气体总体积浓度为15-25%,同时维持升温速率2-4℃/min,进一步将催化剂床层温度提升至450℃,恒温还原2-4h,将经过还原后的催化剂用于生物质燃气变换甲烷化反应,催化剂装填体积为50mL,反应条件为压力0.1MPa,温度400℃,空速2000h-1,进料干气组成为CO2占总体积的12%,N2占总体积的8%,剩余体积为H2与CO,占总体积的80%,附加水蒸气中H2O与CO体积比为1:1,结果见表1。
表1不同催化剂热值转化表
从对比例1可以看出,对锰砂载体改性可以提高催化剂的催化效果,改性锰砂作为催化剂载体具有更好的催化效率,从对比例2又可以看出铼可以显著地提高甲烷选择性与燃气的热值。由实施例1-4的催化结果可以看出,选用不同的改性溶液制备的催化剂催化效果不同,实施例1出口气的低位热值更高。
Claims (12)
1.一种改性锰砂,其特征在于,由锰砂与改性溶液混合加热而成;所述改性溶液为硝酸、氨水或双氧水。
2.根据权利要求1所述的改性锰砂,其特征在于所述锰砂粒径为2-4mm;所述锰砂中MnO2质量百分含量为20-35%。
3.根据权利要求1所述的改性锰砂,其特征在于所述改性溶液的浓度为0.05-0.15mol/L。
4.根据权利要求1所述的改性锰砂,其特征在于所述加热温度为60-100℃;所述加热时间为1-3h。
5.根据权利要求1所述的改性锰砂,其特征在于所述锰砂与改性溶液的体积比为1:1-2。
6.根据权利要求1-5所述的任一改性锰砂为载体的变换甲烷化催化剂,其特征在于,包括活性成分、助剂和载体;所述活性成分为镍,以金属质量计,占催化剂质量百分比的5-30%;所述助剂为铼,以金属质量计,占催化剂质量百分比为0.1-1.5%;所述载体为改性锰砂。
7.根据权利要求6所述的改性锰砂为载体的变换甲烷化催化剂的制备方法,其特征在于包括以下步骤:
(1)将改性锰砂研磨,浸渍于镍的可溶性盐和铼的可溶性盐混合溶液,烘干得催化剂前驱体;
(2)将催化剂前驱体焙烧,研磨,压片,破碎,筛分得成品。
8.根据权利要求7所述的改性锰砂为载体的变换甲烷化催化剂的制备方法,其特征在于步骤(1)中,所述改性锰砂研磨后的粒度为60-100目。
9.根据权利要求7所述的改性锰砂为载体的变换甲烷化催化剂的制备方法,其特征在于步骤(1)中,所述镍的可溶性盐为镍的硝酸盐或镍的硫酸盐;所述铼的可溶性盐为过铼酸铵。
10.根据权利要求7所述的改性锰砂为载体的变换甲烷化催化剂的制备方法,其特征在于步骤(1)中,所述浸渍温度为40-80℃;所述浸渍时间为8-12h。
11.根据权利要求7所述的改性锰砂为载体的变换甲烷化催化剂的制备方法,其特征在于步骤(2)中,所述焙烧温度为400-500℃;所述焙烧时间为4-6h。
12.根据权利要求7所述的改性锰砂为载体的变换甲烷化催化剂的制备方法,其特征在于步骤(2)中,所述筛分得到的颗粒状催化剂粒度为8-10目。
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