CN114433112A - 一种焦炉煤气加氢脱硫催化剂及其制备方法 - Google Patents
一种焦炉煤气加氢脱硫催化剂及其制备方法 Download PDFInfo
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- 239000000571 coke Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 27
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 16
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
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- 229910052681 coesite Inorganic materials 0.000 claims abstract description 10
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- 239000002904 solvent Substances 0.000 claims abstract description 10
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 5
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- 239000010703 silicon Substances 0.000 claims description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910010298 TiOSO4 Inorganic materials 0.000 claims description 3
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 3
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- KADRTWZQWGIUGO-UHFFFAOYSA-L oxotitanium(2+);sulfate Chemical group [Ti+2]=O.[O-]S([O-])(=O)=O KADRTWZQWGIUGO-UHFFFAOYSA-L 0.000 claims description 3
- 229910001868 water Inorganic materials 0.000 claims description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 22
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- 238000001816 cooling Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
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- 241000282414 Homo sapiens Species 0.000 description 1
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- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 125000005619 boric acid group Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- DSMZRNNAYQIMOM-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe].[Mo] DSMZRNNAYQIMOM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
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Abstract
本发明公开了一种焦炉煤气加氢脱硫催化剂及其制备方法。以质量百分比计,该催化剂包括下述原料:TiO2载体:75.0‑95.0%,MoO3:3.0‑15.0%,NiO:0.1‑10.0%,SiO2:0.5‑5.0%;TiO2载体采用下述方法制得:将含Ti原料混悬于溶剂中得混悬液,将混悬液经保温、过滤得固体,将固体煅烧,即可;其中:溶剂为甘油、乙醇和乙醚的混合溶剂,甘油、乙醇和乙醚的体积比为(0.5‑2):2:1;保温的温度为140‑160℃,保温的时间为12‑48小时。本发明中的焦炉煤气加氢脱硫催化剂在200℃能够实现≥90%的噻吩转化率,在300℃能够实现≥95%的噻吩转化率。
Description
技术领域
本发明涉及一种焦炉煤气加氢脱硫催化剂及其制备方法。
背景技术
焦炉煤气是炼焦过程中产生的一种重要产品,它可以用来作为燃气,也可以用来生产甲醇,合成液化天然气(LNG)等。焦炉煤气中的主要成分为氢气和甲烷,同时含有少量的H2S。焦炉煤气最终作为燃料时,H2S以及它的燃烧产物二氧化硫都是有毒气体,会严重破坏大气环境,危害人类的健康。作为原料气时不脱除其中的H2S会腐蚀反应器设备,会使催化剂中毒,影响产品质量。
焦炉煤气中的有机硫包括有硫醇、硫醚、噻吩以及COS和CS2等,由于有机硫加氢反应的平衡常数相当大,甚至温度提高到500℃时仍为正值,所有有机硫中,噻吩最难脱除。
目前,常用的加氢脱硫催化剂包括钴钼催化剂、镍钼催化剂、铁钼催化剂等等,但是该些催化剂用于脱除噻吩时,难以达到令人满意的催化活性。
因此,如何进一步提升焦炉煤气中噻吩的转化率,脱除焦炉煤气中的有机硫,是本领域亟待解决的技术问题。
发明内容
本发明所要解决的技术问题在于克服现有技术中用于焦炉煤气的加氢脱硫催化剂噻吩转化率低的缺陷,而提供了一种焦炉煤气加氢脱硫催化剂及其制备方法。
本发明提供了一种焦炉煤气加氢脱硫催化剂,以质量百分比计,所述催化剂包括下述原料:
TiO2载体:75.0-95.0%,MoO3:3.0-15.0%,NiO:0.1-10.0%,SiO2:0.5-5.0%;所述TiO2载体采用下述方法制得:将含Ti原料混悬于溶剂中得混悬液,将所述混悬液经保温、过滤得固体,将所述固体煅烧,即可;其中:
所述溶剂为甘油、乙醇和乙醚的混合溶剂;所述溶剂中,所述甘油、所述乙醇和所述乙醚的体积比为(0.5-2)∶2∶1;
所述保温的温度为140-160℃,所述保温的时间为12-48小时。
本发明中,优选地,所述TiO2载体的含量为80.0-95.0%,例如80%、85%、 86.9%或95%,百分是指在所述催化剂中的质量百分比。
本发明中,优选地,所述MoO3的含量为8.0-15.0%,例如8.0%、12.0%或15.0%,百分是指在所述催化剂中的质量百分比。
本发明中,优选地,所述NiO的含量为1.5-10.0%,例如1.5%、5.0%或 10.0%,百分是指在所述催化剂中的质量百分比。
本发明中,优选地,所述SiO2的含量为1.0-5.0%,例如1.0%、2.0%或5.0%,百分是指在所述催化剂中的质量百分比。
本发明中,优选地,所述催化剂包括下述原料:TiO2载体:80.0-95.0%, MoO3:8.0-15.0%,NiO:1.5-10.0%,SiO2:1.0-5.0%,百分是指在所述催化剂中的质量百分比。
本发明中,优选地,所述催化剂原料组成如下表所示:
本发明中,所述TiO2载体的制备方法中,所述含Ti原料可为本领域常规的原料,例如TiOSO4·2H2O。
本发明中,所述TiO2载体的制备方法中,所述含Ti原料的用量可为本领域常规的用量,例如所述含Ti原料的质量g和所述溶剂的体积mL之比为1∶40。
本发明中,优选地,所述甘油、所述乙醇和所述乙醚的体积比为(1-2)∶2∶1,例如1∶2∶1、1.5∶2∶1或2∶2∶1。
本发明中,所述混悬液可通过搅拌获得。所述搅拌的时间可为36小时。
本发明中,所述混悬液可在高压釜中进行保温。
本发明中,所述保温的温度优选为150-160℃,例如150℃或160℃。
本发明中,所述保温的时间优选为24-48小时,例如24小时或48小时。
本发明中,所述煅烧之前可采用无水乙醇进行洗涤。所述洗涤后可在40℃条件下进行干燥。
本发明中,所述煅烧的温度可为500-700℃,例如600℃。
本发明中,所述煅烧的时间可为2-5小时,例如3小时。
本发明还提供了一种如前所述的焦炉煤气加氢脱硫催化剂的制备方法,其包括下述步骤:
(1)将所述MoO3的前体原料和所述NiO的前体原料溶于水或氨水中得混合液 A;
(2)将所述混合液A和含硅前体混合后,调节pH为3-5,得到浸渍液;
(3)将所述浸渍液和所述TiO2载体混合浸渍后,烘干、煅烧,即可。
步骤(1)中,所述MoO3的前体原料可为本领域常规的能够转化为MoO3的前体原料,例如七钼酸铵。
步骤(1)中,所述NiO的前体原料可为本领域常规的能够转化为NiO 的前体原料,例如六水合硝酸镍。
步骤(2)中,所述含硅前体可为本领域常规的含硅前体,例如四甲氧基硅烷、三甲氧基硅烷和四乙氧基硅烷中的一种或多种,再例如四甲氧基硅烷。
步骤(2)中,可通过pH调节剂调节pH,例如加入酸。所述的酸可为无机酸,例如硫酸、硝酸、磷酸、盐酸、草酸、柠檬酸和硼酸中的一种或多种,例如柠檬酸。
步骤(3)中,所述浸渍的温度可为30-50℃,例如40℃。
步骤(3)中,所述浸渍的时间可为1-3小时,例如2小时。
步骤(3)中,所述烘干的温度可为80-120℃,例如100℃。
步骤(3)中,所述烘干的时间可为5-8小时,例如6小时。
步骤(3)中,所述煅烧的温度可为350-500℃,例如350℃、400℃、420℃、 450℃或500℃。
步骤(3)中,所述煅烧的时间可为2-5小时,例如2小时、3小时、4 小时、4.5小时或5小时。
本发明的积极进步效果在于:
(1)本发明中的焦炉煤气加氢脱硫催化剂在200℃能够实现≥92%的噻吩转化率,在300℃能够实现≥95%的噻吩转化率。
(2)本发明中的焦炉煤气加氢脱硫催化剂从200℃至300℃噻吩转化率提升≥2.20%。
具体实施方式
下面通过实施例的方式进一步说明本发明,但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法,按照常规方法和条件,或按照商品说明书选择。
实施例1
(1)介孔TiO2纳米片层结构基础层次管(MTNHTS,简称MTN)的制备 20mL甘油,40mL乙醇,20mL乙醚按照体积比1∶2∶1混合,将2g TiOSO4·2H2O 加入上述溶液中,形成的白色悬浊液搅拌36小时。将悬浊液转移到100mL高压釜中,160℃下保持24小时。室温下冷却,将固体过滤,用无水乙醇洗净,40 ℃下干燥并在600℃煅烧3小时。
(2)取步骤(1)中的MTN、MoO3、NiO、SiO2按照质量百分比为85.0%、 8.0%、5.0%、2.0%的比例混合制得焦炉煤气加氢脱硫催化剂。具体制备工艺如下:
按比例称取七钼酸铵溶于氨水中,溶解后按比例加入六水合硝酸镍,溶解后按比例加入四甲氧基硅烷,在搅拌条件下加入柠檬酸(C6H8O7·H2O)调节溶液pH=4,继续搅拌得到浸渍液。在40℃下,将步骤(1)中的MTN载体放入浸渍液中浸渍2小时,完成浸渍后,在100℃条件下干燥6小时,将干燥好的样品放入马弗炉中420℃煅烧4小时,得到催化剂成品。
实施例2-9、对比例1-8
除下表1所示工艺外,其他条件均同实施例1。
表1
对比例9
将SiO2替换为P2O5,其余同实施例1。
对比例10
将SiO2替换为B2O3,其余同实施例1。
效果实施例1
催化剂活性检测条件:在模拟焦炉煤气气氛下(瓶装压力10MPa,购自北京氦普气体公司),在固定床反应器上进行催化剂评价,将催化剂破碎至60-80目,量取0.2mL,置于反应器床层,使热电偶接近床层的位置。先在气路中通N2,确定无泄漏后方可进行实验。400℃下用CS2对催化剂预硫化3小时。然后切换 N2吹扫床层的同时降温,温度降至200℃后,切换原料气,为了使原料气接近工业焦炉煤气含有一定量水蒸汽这一情况,原料气先通过去离子水再进入反应器,待反应稳定2小时后,用注射器取样,用氮气稀释后注入微量硫分析仪中进行分析。催化反应条件:常压、反应温度200-300℃、空速2000h-1、噻吩进口浓度 450mg/m3。
催化剂的相关性能测试结果如表2所示。
表2
Claims (10)
1.一种焦炉煤气加氢脱硫催化剂,其特征在于,以质量百分比计,所述催化剂包括下述原料:
TiO2载体:75.0-95.0%,MoO3:3.0-15.0%,NiO:0.1-10.0%,SiO2:0.5-5.0%;所述TiO2载体采用下述方法制得:将含Ti原料混悬于溶剂中得混悬液,将所述混悬液经保温、过滤得固体,将所述固体煅烧,即可;其中:
所述溶剂为甘油、乙醇和乙醚的混合溶剂;所述溶剂中,所述甘油、所述乙醇和所述乙醚的体积比为(0.5-2)∶2∶1;
所述保温的温度为140-160℃,所述保温的时间为12-48小时。
2.如权利要求1所述的焦炉煤气加氢脱硫催化剂,其特征在于,所述TiO2载体的含量为80.0-95.0%,例如80%、85%、86.9%或95%,百分是指在所述催化剂中的质量百分比;
和/或,所述MoO3的含量为8.0-15.0%,例如8.0%、12.0%或15.0%,百分是指在所述催化剂中的质量百分比;
和/或,所述NiO的含量为1.5-10.0%,例如1.5%、5.0%或10.0%,百分是指在所述催化剂中的质量百分比;
和/或,所述SiO2的含量为1.0-5.0%,例如1.0%、2.0%或5.0%,百分是指在所述催化剂中的质量百分比。
3.如权利要求2所述的焦炉煤气加氢脱硫催化剂,其特征在于,所述催化剂包括下述原料:TiO2载体:80.0-95.0%,MoO3:8.0-15.0%,NiO:1.5-10.0%,SiO2:1.0-5.0%,百分是指在所述催化剂中的质量百分比。
5.如权利要求1-4中任一项所述的焦炉煤气加氢脱硫催化剂,其特征在于,所述含Ti原料为TiOSO4·2H2O;
和/或,所述含Ti原料的质量g和所述溶剂的体积mL之比为1∶40;
和/或,所述混悬液通过搅拌获得,所述搅拌的时间可为36小时;
和/或,所述混悬液在高压釜中进行保温;
和/或,所述煅烧的温度为500-700℃,例如600℃;
和/或,所述煅烧的时间为2-5小时,例如3小时。
6.如权利要求1-4中任一项所述的焦炉煤气加氢脱硫催化剂,其特征在于,所述甘油、所述乙醇和所述乙醚的体积比为(1-2)∶2∶1,例如1∶2∶1、1.5∶2∶1或2∶2∶1;
和/或,所述保温的温度为150-160℃,例如150℃或160℃;
和/或,所述保温的时间为24-48小时,例如24小时或48小时。
7.一种如权利要求1-6中任一项所述的焦炉煤气加氢脱硫催化剂的制备方法,其特征在于,其包括下述步骤:
(1)将所述MoO3的前体原料和所述NiO的前体原料溶于水或氨水中得混合液A;
(2)将所述混合液A和含硅前体混合后,调节pH为3-5,得到浸渍液;
(3)将所述浸渍液和所述TiO2载体混合浸渍后,烘干、煅烧,即可。
8.如权利要求7所述的焦炉煤气加氢脱硫催化剂的制备方法,其特征在于,步骤(1)中,所述MoO3的前体原料为七钼酸铵;
和/或,步骤(1)中,所述NiO的前体原料为六水合硝酸镍。
9.如权利要求7或8所述的焦炉煤气加氢脱硫催化剂的制备方法,其特征在于,步骤(2)中,所述含硅前体为四甲氧基硅烷、三甲氧基硅烷和四乙氧基硅烷中的一种或多种,例如四甲氧基硅烷;
和/或,步骤(2)中,通过加入酸调节pH,所述的酸可为无机酸,例如硫酸、硝酸、磷酸、盐酸、草酸、柠檬酸和硼酸中的一种或多种。
10.如权利要求7或8所述的焦炉煤气加氢脱硫催化剂的制备方法,其特征在于,步骤(3)中,所述浸渍的温度为30-50℃,例如40℃;
和/或,步骤(3)中,所述浸渍的时间为1-3小时,例如2小时;
和/或,步骤(3)中,所述烘干的温度为80-120℃,例如100℃;
和/或,步骤(3)中,所述烘干的时间为5-8小时,例如6小时;
和/或,步骤(3)中,所述煅烧的温度为350-500℃,例如350℃、400℃、420℃、450℃或500℃;
和/或,步骤(3)中,所述煅烧的时间为2-5小时,例如2小时、3小时、4小时、4.5小时或5小时。
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