CN108043415A - 一种煤制天然气高温甲烷化催化剂及生产工艺与应用 - Google Patents
一种煤制天然气高温甲烷化催化剂及生产工艺与应用 Download PDFInfo
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- 239000003345 natural gas Substances 0.000 title claims abstract description 33
- 239000003245 coal Substances 0.000 title claims abstract description 29
- 238000005516 engineering process Methods 0.000 title abstract description 8
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000004480 active ingredient Substances 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 9
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 9
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
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- 238000012423 maintenance Methods 0.000 claims description 12
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
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- 239000011265 semifinished product Substances 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 239000004568 cement Substances 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000008234 soft water Substances 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 4
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 229910002339 La(NO3)3 Inorganic materials 0.000 claims description 2
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- 239000002253 acid Substances 0.000 claims 1
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000007767 bonding agent Substances 0.000 description 3
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- HVMFKXBHFRRAAD-UHFFFAOYSA-N lanthanum(3+);trinitrate;hydrate Chemical compound O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HVMFKXBHFRRAAD-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- DWAHIRJDCNGEDV-UHFFFAOYSA-N nickel(2+);dinitrate;hydrate Chemical compound O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DWAHIRJDCNGEDV-UHFFFAOYSA-N 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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- 150000001336 alkenes Chemical group 0.000 description 1
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- 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
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Abstract
本发明公开了一种煤制天然气高温甲烷化催化剂,属于煤化工技术领域。包括载体和催化剂活性成分,催化剂活性成分包括催化剂主活性成分和催化剂助剂,催化剂主活性成分为NiO,催化剂助剂为La2O3,载体为Al2O3,其中,催化剂各组份质量百分含量为:NiO为25~45%,La2O3为0.75~1.5wt%,Al2O3为47~63wt%,石墨为1.5~2.5wt%。本发明还提供了上述催化剂的生产工艺与应用。本发明提供的催化剂含有较低含量的Ni和稀土元素La,降低了催化剂成本,且本发明制备该催化剂的方法相应的缩短了净化流程,同时通过方法制备的催化剂能在较高温度条件下反应,显著提高了甲烷化性能的稳定性。
Description
技术领域
本发明属于煤化工技术领域,具体涉及一种煤制天然气高温甲烷化催化剂及生产工艺与应用。
背景技术
国内天然气供应的缺口正逐年加大,对外依存度更是呈快速上升之势。据有关数据预测,到2020年,国内天然气缺口将达1000亿立方米。2011年,中国天然气对外依存度达24%,与2010年12.8%相比,呈成倍增长态势。这从客观上加大了对非常规天然气及替代天然气的需求力度,除页岩气开发力度加大外,煤制天然气也被寄予厚望。
随着煤化工行业的蓬勃发展和天然气消费量的大幅增长,我国煤制天然气行业取得长足发展,成为煤化工领域投资热点。2009年,神华集团鄂尔多斯20亿立方米煤制天然气项目奠基,大唐集团阜新40亿立方米/年煤制天然气项目通过了环保部的环评,中海油同煤集团40亿立方米/年煤制天然气项目正式启动,新汶矿业集团伊犁能源年产100亿立方米煤制天然气一期工程开工建设。一批投资数额巨大的煤制气项目陆续动工,我国煤制天然气领域呈现良好发展势头。
部分数据显示,未来我国天然气供不应求的局面将长期存在,利用我国煤炭资源相对丰富的特点发展煤制天然气产业,补充天然气资源的不足,是一条缓解我国天然气供求矛盾的有效途径,有着广阔的发展前景。随着我国工业化、城镇化的发展和人民生活水平的提高,对清洁能源天然气的需求量迅速增长,天然气供不应求的局面将会长期存在。煤制天然气作为液化石油气和天然气的替代和补充,既实现了清洁能源生产的新途径,优化了煤炭深加工产业结构,又具有能源利用率高的特点,符合国内外煤炭加工利用的发展方向,对于缓解国内天然气短缺,保障我国能源安全具有重要意义。
从长远来看,我国天然气价格逐步上涨的趋势是确定的,因此,煤制天然气的成本优势将逐渐显现,经济效益十分可观,中国煤制天然气行业发展前景广阔。在我国80年代就先后有一些科研院所开始从事过甲烷化技术的相关研究工作。其中中科院大连化学物理研究所在“65”至“95”科技攻关期间,开展了常压水煤气部分甲烷化生产中热值城市煤气的研究并进行了工业推广。同期,大连化物所在贵州省毕节市建设了耐硫甲烷化试验装置,而目前开展的耐高温甲烷化实验工作也取得了很好的成果。西北化工研究院从20世纪80年代开展了城市煤气甲烷化催化剂的研究,于1987年完成了耐硫甲烷化催化剂立升级试验运行,通过了城建部的技术鉴定。并于1988年完成了规模为50 m3/h的甲烷化催化剂及多段固定床甲烷化工艺中间试验。同时,采用该院的甲烷化技术,建设了北京顺义4100 m3/h煤气甲烷化项目。
然而,目前国内外甲烷化催化剂都具有高Ni含量和较高的稀土含量,增加了催化剂成本,且在甲烷化反应过程中,由于反应温度一般较高,对催化剂的热稳定性要求也比较高,因此制备一种具有高稳定性,能降低催化剂成本,控制企业项目投资成本的煤制天然气高温甲烷化催化剂就变得尤为重要。
发明内容
本发明旨在提供一种煤制天然气高温甲烷化催化剂及生产工艺与应用,以解决上述技术问题。
为了实现上述技术目的,本发明的一种煤制天然气高温甲烷化催化剂,包括载体和催化剂活性成分,所述催化剂活性成分包括催化剂主活性成分和催化剂助剂,所述催化剂主活性成分为NiO,催化剂助剂为La2O3,所述载体为Al2O3,其中,催化剂各组份质量百分含量为:NiO为25~45%,La2O3为0.75~1.5wt%,Al2O3为47~63wt%,石墨为1.5~2.5wt%。
本发明还提供了一种制备上述煤制天然气高温甲烷化催化剂的制备工艺,包含以下步骤:
(1)采用共沉淀法制备催化剂半成品 :按比例称取Ni(NO3)2、La(NO3)3、Al(NO3)3,向其中加入去离子水,将各组分溶液混合搅拌,并加入适量的水泥粘合剂、碳酸钠或者碳酸氢钠、硝酸、石墨,混合均匀后加热至60-70℃并保温;
(2)干燥:将步骤(1)中反应好的浆料水洗达到指标后,在100℃下干燥3h;
(3)焙烧:将步骤(2)中干燥好的催化剂半成品在780-820℃转炉焙烧4h;
(4)压制成型:将烧好的半成品由斗式提升机送至混料岗位,按比例配料,向焙烧后的物料中加入石墨粉作为润滑剂,在球磨机内混料球磨,使物料细度≤200目,磨好的物料由斗式提升机送至压环岗位储斗,料从下料斗出口送至螺旋输送器,与喷入适量的软水混合,按物料总重量加入重量百分比为10%的去离子水,经预压造粒压制成环状或压片;
(5)养护烘干:将压制成型的催化剂先喷入热水进行初养护,再送入养护罐用蒸汽养护6-8h;再经烘干即得到催化剂成品。
本发明的上述树脂加氢催化剂,其应用在工业生产焦炉煤气甲烷化过程中。
具体的,工业生产焦炉煤气甲烷化过程的条件为:压强为2~2.5MPa,反应温度为600~800℃,空速为4000h-1~8000h-1。
与现有技术相比,本发明提供的一种煤制天然气高温甲烷化催化剂含有较低含量的Ni和稀土元素La,降低了催化剂成本,且本发明制备该催化剂的方法相应的缩短了净化流程,同时通过方法制备的催化剂能在较高温度条件下反应,显著提高了甲烷化性能的稳定性。
具体实施方式
为了使本发明的目的、技术方案及优点显得更加清晰明了,以下结合具体实施例,对本发明进行进一步的详细说明。应当理解,此处的所描述的实施例仅仅是为了解释本发明,而不是用于限制本发明的保护范围。
实施例1
按比例称取催化剂主活性成分NiO、催化剂助剂La2O3、催化剂载体Al2O3的硝酸盐,向其中加入去离子水,称取硝酸镍水合物1820.04 kg、硝酸镧水合物121.99 kg、碳酸钠/碳酸氢钠1530.62 kg、硝酸82.48 kg、水泥粘结剂127.55 kg、水106292.52 kg、石墨34.01 kg;将所得的溶液进行混合,混合后加热至60-70℃并保温,在100 ℃温度下干燥3 h,然后于800(±20) ℃焙烧4 h;向焙烧后的物料中加入石墨粉作为润滑剂,在球磨混料机内磨混3 h,使物料细度≤200目,将磨好的物料由斗式提升机送至压环岗位储斗,料从下料斗出口送至螺旋输送器,与喷入适量的软水混合,按物料总重量加入重量百分比为10%的去离子水,经预压造粒压制成环状或压片;再将压制成型的催化剂先喷入热水进行初养护,再送入养护罐用蒸汽养护6-8h;再经烘干即得到催化剂成品。
以上方法制备所得的催化剂外观:圆柱状,光滑完整无破损;外形尺寸:实心圆柱状,φ3.4*3.5mm;堆密度:1.4~1.45g/mL;侧压强度:最大方向>100N/粒,最小方向>50N/粒;氧化钠含量<0.5wt%;NiO含量:28.83wt%;La2O3含量:1.26wt%。
实施例2
按比例称取催化剂主活性成分NiO、催化剂助剂La2O3、催化剂载体Al2O3的硝酸盐,向其中加入去离子水,称取硝酸镍水合物1935.04 kg、硝酸镧水合物101.76 kg、碳酸钠/碳酸氢钠1450.74kg、硝酸84.65 kg、水泥粘结剂132.78 kg、水116285.57 kg、石墨36.55 kg;将所得的溶液进行混合,混合后加热至60-70℃并保温,在100 ℃温度下干燥3 h,然后于800(±20) ℃焙烧4 h;向焙烧后的物料中加入石墨粉作为润滑剂,在球磨混料机内磨混3 h,使物料细度≤200目,将磨好的物料由斗式提升机送至压环岗位储斗,料从下料斗出口送至螺旋输送器,与喷入适量的软水混合,按物料总重量加入重量百分比为10%的去离子水,经预压造粒压制成环状或压片;再将压制成型的催化剂先喷入热水进行初养护,再送入养护罐用蒸汽养护6-8h;再经烘干即得到催化剂成品。
以上方法制备所得的催化剂外观:圆柱状,光滑完整无破损;外形尺寸:实心圆柱状,φ3.4*3.5mm;堆密度:1.4~1.45g/mL;侧压强度:最大方向>100N/粒,最小方向>50N/粒;氧化钠含量<0.5wt%;NiO含量:38.83wt%;La2O3含量:1.06wt%。
实施例3
按比例称取催化剂主活性成分NiO、催化剂助剂La2O3、催化剂载体Al2O3的硝酸盐,向其中加入去离子水,称取硝酸镍水合物2783.04 kg、硝酸镧水合物195.28 kg、碳酸钠/碳酸氢钠1582.77kg、硝酸83.56 kg、水泥粘结剂144.82 kg、水112654.57 kg、石墨38.74 kg;将所得的溶液进行混合,混合后加热至60-70℃并保温,在100 ℃温度下干燥3 h,然后于800(±20) ℃焙烧4 h;向焙烧后的物料中加入石墨粉作为润滑剂,在球磨混料机内磨混3 h,使物料细度≤200目,将磨好的物料由斗式提升机送至压环岗位储斗,料从下料斗出口送至螺旋输送器,与喷入适量的软水混合,按物料总重量加入重量百分比为10%的去离子水,经预压造粒压制成环状或压片;再将压制成型的催化剂先喷入热水进行初养护,再送入养护罐用蒸汽养护6-8h;再经烘干即得到催化剂成品。
以上方法制备所得的催化剂外观:圆柱状,光滑完整无破损;外形尺寸:实心圆柱状,φ3.4*3.5mm;堆密度:1.4~1.45g/mL;侧压强度:最大方向>100N/粒,最小方向>50N/粒;氧化钠含量<0.5wt%;NiO含量:44.87wt%;La2O3含量:0.76wt%。
催化剂的应用
在温度600~800 ℃、压力2.0~2.5 MPa、空速4000~8000 h-1的工艺条件下,催化剂不经预硫化而直接进行甲烷化,先进行初始活性测定,再进行150 h运转试验;其中,催化剂进行反应时的还原条件具体为:介质为H2、温度为600 ℃、空速为6000 h-1、压力为2.0MPa、时间为2 h。
催化剂初始活性测定时,反应器出口设定温度为800 ℃,进口温度测温点为催化剂床层上部,预热器温度为室温。
其中:从反应器出口取样阀取样检测,CO+CO2转化率%及CnHm转化率%按下式进行计算:
其中,CnHm为烯烃,(CO+CO2)出口、CnHm出口为通过体积换算后与入口同等标准的摩尔数,然后进行计算转化率。气体中无H2S气体,CnHm和CO+CO2转化率均为100%,表明催化剂的初始催化活性极高。
然后,催化剂150 h运转试验,试验条件为反应器出口初始设定温度:800 ℃、反应压力:2.0 MPa、反应空速:6000 h-1。同样,在运转150 h后从反应器出口取样阀取样检测,在催化剂经过150 h的催化后,卸出催化剂经碳。
试验结果表明催化剂经还原完毕投入原料焦炉气后催化剂进、出口均有不同程度的温升,随着运转时间的延长,温升不断的提高,结果表明催化剂的耐高温性能及甲烷化性能在所做试验阶段较为良好。原料气中配入2%的CnHm,催化剂经150 h运转。经分析,催化剂无结炭的现象,表明催化剂具有良好的抗结炭性能。
以上所述仅为本发明的实施例,并非因此而限制本发明的专利保护范围,凡是利用本发明说明书及其附图内容所作的等效结构或等效改造,或直接或间接运用本发明以外的其他相关领域,均可视为在本发明的专利保护范围内。
Claims (4)
1.一种煤制天然气高温甲烷化催化剂,包括载体和催化剂活性成分,所述催化剂活性成分包括催化剂主活性成分和催化剂助剂,其特征在于,所述催化剂主活性成分为NiO,催化剂助剂为La2O3,所述载体为Al2O3,其中,催化剂各组份质量百分含量为:NiO为25~45%,La2O3为0.75~1.5wt%,Al2O3为47~63wt%,石墨为1.5~2.5wt%。
2.一种制备如权利要求1所述的煤制天然气高温甲烷化催化剂的制备工艺,其特征在于,包含以下步骤:
采用共沉淀法制备催化剂半成品 :按比例称取Ni(NO3)2、La(NO3)3、Al(NO3)3,向其中加入去离子水,将各组分溶液混合搅拌,并加入适量的水泥粘合剂、碳酸钠或者碳酸氢钠、硝酸、石墨,混合均匀后加热至60-70℃并保温;
干燥:将步骤(1)中反应好的浆料水洗达到指标后,在100℃下干燥3h;
焙烧:将步骤(2)中干燥好的催化剂半成品在780-820℃转炉焙烧4h;
压制成型:将烧好的半成品由斗式提升机送至混料岗位,按比例配料,向焙烧后的物料中加入石墨粉作为润滑剂,在球磨机内混料球磨,使物料细度≤200目,磨好的物料由斗式提升机送至压环岗位储斗,料从下料斗出口送至螺旋输送器,与喷入适量的软水混合,按物料总重量加入重量百分比为10%的去离子水,经预压造粒压制成环状或压片;
养护烘干:将压制成型的催化剂先喷入热水进行初养护,再送入养护罐用蒸汽养护6-8h;再经烘干即得到催化剂成品。
3.一种如权利要求1或2任一项所述的树脂加氢催化剂,其应用在工业生产焦炉煤气甲烷化过程中。
4.根据权利要求3所述的树脂加氢催化剂,其特征在于,工业生产焦炉煤气甲烷化过程的条件为:压强为2~2.5MPa,反应温度为600~800℃,空速为4000h-1~8000h-1。
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