CN106824201B - 一种用于甲烷二氧化碳重整制合成气的催化剂及制备方法 - Google Patents
一种用于甲烷二氧化碳重整制合成气的催化剂及制备方法 Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000002407 reforming Methods 0.000 title claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 51
- 239000004917 carbon fiber Substances 0.000 claims abstract description 51
- 238000001035 drying Methods 0.000 claims abstract description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 15
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 44
- 239000007789 gas Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000013049 sediment Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
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- 230000003197 catalytic effect Effects 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000006057 reforming reaction Methods 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
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- 230000001376 precipitating effect Effects 0.000 claims description 2
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- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- 239000002134 carbon nanofiber Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000001833 catalytic reforming Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 metal oxide compound Chemical class 0.000 description 3
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- 238000012986 modification Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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Abstract
本发明公开了一种用于甲烷二氧化碳重整制合成气的催化剂及制备方法。该催化剂将碳纤维与金属氧化物结合作为复合载体,金属镍为活性组分,制得镍/金属氧化物‑碳纤维催化剂;其中符号“/”前表示催化剂的活性组分,“/”后表示催化剂的载体,符号“‑”表示两种物质复合。制备方法是将金属(X)与Ni的硝酸盐溶液和碳酸钠溶液通过并加法滴入含纳米碳纤维的反应器进行共沉淀反应,过滤得到沉淀产物,再经水洗、烘干、煅烧、研磨等步骤制得所需催化剂。此催化剂具有较大比表面积及发达的孔结构,低温活性高,稳定性好,成本低廉,具有一定的应用前景。
Description
技术领域
本发明涉及一种碳纤维与金属氧化物复合载体金属催化剂的制备方法及其在CH4/CO2重整过程中的应用。属于复合催化剂制备及气化重整领域。
背景技术
CH4-CO2催化重整制合成气技术,既能缓解一定的能源危机也能起到改善日益严重的环境问题的作用。与此同时在甲烷二氧化碳重整反应中因产生的H2/CO比约为1,可以直接作为羰基合成或Fischer-Tropsch合成的原料,又因在此重整中具有较大反应热的可逆反应,所以又可以作为能量储存介质和运输能源。因此这是一个具有经济、环保、科学的多重价值的研究方向。
在传统的甲烷二氧化碳催化重整制合成气催化剂中,大部分都是以单一金属氧化物为载体,以单一的镍或镍加单一稀土元素为活性组份所构成的。这些类型催化剂高温易烧结,稳定性较差且价格较高,因而造成高投入、低产出的结果。
由于炭材料的优异性能,引起了学者的广泛关注并开始将其做为载体研究二氧化碳重整甲烷反应。其中纳米碳纤维作为一种新的碳材料,与金属催化剂相比,具有以下优势:①较低的成本;②耐高温性能③抗硫和原料气中其他有害物质。但也因低温时活性较低,而不能起到良好的催化作用。因此将碳纤维与金属氧化物结合作为复合载体,通过碳纤维与金属的相互作用,将碳纤维与金属材料的优势相结合,减少单一载体对催化剂造成的负面影响。
发明内容
技术问题:本发明的目的就是要提供以金属氧化物与碳纤维形成的复合物为载体,金属镍为活性组分的甲烷二氧化碳重整制合成气的催化剂,以及该催化剂的制备方法和用途。
技术方案:本发明的一种甲烷二氧化碳重整制合成气的催化剂,该催化剂将碳纤维与金属氧化物结合作为复合载体,金属镍为活性组分,制得镍/金属氧化物-碳纤维催化剂;其中符号“/”前表示催化剂的活性组分,“/”后表示催化剂的载体,符号“-”表示两种物质复合。
所述催化剂中碳纤维与金属氧化物的质量比为0.25~4,金属镍与催化剂的质量比为0.02~0.25。
本发明的的甲烷二氧化碳重整制合成气的催化剂的制备方法具体包括如下步骤:
步骤1:分别配制金属(X)硝酸盐和硝酸镍混合溶液与碳酸钠溶液;
步骤2:在40℃恒温水浴条件下,分别将金属(X)硝酸盐和硝酸镍混合溶液与碳酸钠溶液通过蠕动泵以相同流量加入装有碳纤维的烧杯中连续搅拌,其中烧杯中预先加入水和碳纤维混合搅拌,待沉淀完全后继续搅拌20-80分钟,作为沉淀的老化时间,得到沉淀物A;
步骤3:将步骤2的沉淀物A抽滤并水洗至中性,得到沉淀物B;
步骤4:将步骤3的沉淀物B置于100~120℃电热鼓风干燥箱内,干燥时间8~14h;然后将其置于管式炉中,在300~750℃,氮气保护下,恒温焙烧1.5~14h,得到焙烧样品;
步骤5:将步骤4的焙烧样品研磨,筛分出60~80目的粉粒,得到成品催化剂。
其中:
所述步骤1中的金属(X)为Al、Ca、Mg、La、Ce、Ti、Zr及其混合物。
步骤2所述碳纤维是经氢氧化钾活化的活性碳纤维,具体包括如下步骤:
步骤2.1:将碳纤维加入氢氧化钾溶液中,在40℃条件下,等体积浸渍24h;
步骤2.2:将经过浸渍如理的碳纤维在100~120℃的温度下干燥,并在800℃焙烧2h,水洗至中性,烘干得到所需活性碳纤维。
所述成品催化剂中金属镍的重量百分比为2%~25%。
所述碳纤维与氢氧化钾的质量比为1:1。
本发明的甲烷二氧化碳重整制合成气的催化剂的应用是:将所述催化剂用于固定床反应器中的甲烷二氧化碳重整制合成气反应,具体包括以下步骤:
1)取0.2~1g所述催化剂于固定床反应器内,在氮气氛围中升温至500~600℃,通入氢气还原0.5~1.5h;
2)还原结束以后,通入CH4:CO2:N2=1:1:1,总流量为150~300ml/min的混合气,在800℃进行重整反应,集气用气相色谱分析其催化效果。
有益效果:
1)本发明中的催化剂载体中的碳纤维来源广泛,价格低廉,有效降低了催化剂的制作成本。
2)金属氧化物与碳纤维复合,不仅保持了碳纤维表面发达的孔结构和高比表面积的特点,而且金属氧化物与碳纤维之间的相互作用使催化剂保持良好的催化效果和抗烧结性,体现了双功能特点。
3)将金属氧化物与碳纤维复合载体金属催化剂在固定床催化装置中对CH4/CO2反应进行催化重整反应,金属氧化物与碳纤维复合载体负载金属更有利于CH4,CO2的表面吸附,提高转化率,促进反应的进行。
附图说明
图1是温度对转化率的影响示意图。
具体实施方式
以下所述是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也视为本发明的保护范围。
实施例1
1)将碳纤维与KOH溶液在40℃条件下等体积浸渍24h,其中碳纤维与KOH质量比为1:1,烘干,800℃煅烧2h,水洗至中性,烘干得到活性碳纤维。
2)向36.774gAl(NO3)3·9H2O和4.953gNi(NO3)2·6H2O中加入去离子水配置成混合溶液与16.173gNa2CO3配置而成的溶液分别通过蠕动泵以相同流量加入称装有5g碳纤维的烧杯中持续搅拌,其中烧杯中预先加入少量水,待沉淀完全后继续搅拌40分钟,抽滤并水洗至中性,烘干。
3)将上述所得烘干后的复合物置于卧式管式炉中,在氮气流速为150mL/min,升温速率为5℃/min下升温至550℃煅烧100min,冷却后研磨成颗粒状。即可制备得到碳纤维与氧化铝质量比为1,负载10%镍的复合载体金属催化剂。
实施例2
1)将实施案例1种制得的镍/碳纤维-氧化铝催化剂1g置于固定床催化装置中,将装置在氮气气氛,升温速率为5℃/min下升温至650℃。
2)在原料气CH4、CO2、N2流速分别为50ml/min、50ml/min、100ml/min的情况下,收集650℃、700℃、750℃、800℃、850℃、900℃、950℃的产物气。
3)利用气相色谱仪检测产物气的组成及含量,由此计算甲烷、二氧化碳转化率如图1。
实施例3
1)将碳纤维与KOH溶液在40℃条件下等体积浸渍24h,其中碳纤维与KOH质量比为1:1,烘干,800℃煅烧2h,水洗至中性,烘干得到活性碳纤维。
2)向147.096gAl(NO3)3·9H2O和12.383gNi(NO3)2·6H2O中加入去离子水配置成混合溶液与63.822gNa2CO3配置而成的溶液分别通过蠕动泵以相同流量加入称装有5g碳纤维的烧杯中持续搅拌,其中烧杯中预先加入少量水,待沉淀完全后继续搅拌40分钟,抽滤并水洗至中性,烘干。
3)将上述所得烘干后的复合物置于卧式管式炉中,在氮气流速为150mL/min,升温速率为5℃/min下升温至550℃煅烧100min,冷却后研磨成颗粒状。即可制备得到碳纤维与氧化铝质量比为0.25,负载10%镍的复合载体金属催化剂。
实施例4
1)将碳纤维与KOH溶液在40℃条件下等体积浸渍24h,其中碳纤维与KOH质量比为1:1,烘干,800℃煅烧2h,水洗至中性,烘干得到活性碳纤维。
2)向18.387gAl(NO3)3·9H2O和3.715gNi(NO3)2·6H2O中加入去离子水配置成混合溶液与8.231gNa2CO3配置而成的溶液分别通过蠕动泵以相同流量加入称装有5g碳纤维的烧杯中持续搅拌,其中烧杯中预先加入少量水,待沉淀完全后继续搅拌40分钟,抽滤并水洗至中性,烘干。
3)将上述所得烘干后的复合物置于卧式管式炉中,在氮气流速为150mL/min,升温速率为5℃/min下升温至550℃煅烧100min,冷却后研磨成颗粒状。即可制备得到碳纤维与氧化铝质量比为2,负载10%镍的复合载体金属催化剂。
实施例5
1)将碳纤维与KOH溶液在40℃条件下等体积浸渍24h,其中碳纤维与KOH质量比为1:1,烘干,800℃煅烧2h,水洗至中性,烘干得到活性碳纤维。
2)向12.258gAl(NO3)3·9H2O和3.299gNi(NO3)2·6H2O中加入去离子水配置成混合溶液与5.584gNa2CO3配置而成的溶液分别通过蠕动泵以相同流量加入称装有5g碳纤维的烧杯中持续搅拌,其中烧杯中预先加入少量水,待沉淀完全后继续搅拌40分钟,抽滤并水洗至中性,烘干。
3)将上述所得烘干后的复合物置于卧式管式炉中,在氮气流速为150mL/min,升温速率为5℃/min下升温至550℃煅烧100min,冷却后研磨成颗粒状。即可制备得到碳纤维与氧化铝质量比为3,负载10%镍的复合载体金属催化剂。
实施例6
1)将碳纤维与KOH溶液在40℃条件下等体积浸渍24h,其中碳纤维与KOH质量比为1:1,烘干,800℃煅烧2h,水洗至中性,烘干得到活性碳纤维。
2)向9.194gAl(NO3)3·9H2O和3.096gNi(NO3)2·6H2O中加入去离子水配置成混合溶液与4.261gNa2CO3配置而成的溶液分别通过蠕动泵以相同流量加入称装有5g碳纤维的烧杯中持续搅拌,其中烧杯中预先加入少量水,待沉淀完全后继续搅拌40分钟,抽滤并水洗至中性,烘干。
3)将上述所得烘干后的复合物置于卧式管式炉中,在氮气流速为150mL/min,升温速率为5℃/min下升温至550℃煅烧100min,冷却后研磨成颗粒状。即可制备得到碳纤维与氧化铝质量比为4,负载10%镍的复合载体金属催化剂。
Claims (6)
1.一种甲烷二氧化碳重整制合成气的催化剂,其特征在于该催化剂将碳纤维与金属氧化物结合作为复合载体,金属镍为活性组分,制得镍/金属氧化物-碳纤维催化剂;其中符号“/”前表示催化剂的活性组分,“/”后表示催化剂的载体,符号“-”表示两种物质复合;所述催化剂中碳纤维与金属氧化物的质量比为0.25~4,金属镍与催化剂的质量比为0.02~0.25。
2.一种如权利要求1所述的甲烷二氧化碳重整制合成气的催化剂的制备方法,其特征在于该制备方法具体包括如下步骤:
步骤1:分别配制金属X硝酸盐和硝酸镍混合溶液与碳酸钠溶液;
步骤2:在40℃恒温水浴条件下,分别将金属X硝酸盐和硝酸镍混合溶液与碳酸钠溶液通过蠕动泵以相同流量加入装有碳纤维的烧杯中连续搅拌,其中烧杯中预先加入水和碳纤维混合搅拌,待沉淀完全后继续搅拌20~80分钟,作为沉淀的老化时间,得到沉淀物A;
步骤3:将步骤2的沉淀物A抽滤并水洗至中性,得到沉淀物B;
步骤4:将步骤3的沉淀物B置于100~120℃电热鼓风干燥箱内,干燥时间8~14h;然后将其置于管式炉中,在300~750℃,氮气保护下,恒温焙烧1.5~14h,得到焙烧样品;
步骤5:将步骤4的焙烧样品研磨,筛分出60~80目的粉粒,得到成品催化剂。
3.根据权利要求2所述的甲烷二氧化碳重整制合成气的催化剂的制备方法,其特征在于:所述步骤1中的金属X为Al、Ca、Mg、La、Ce、Ti、Zr及其混合物。
4.根据权利要求2所述的甲烷二氧化碳重整制合成气的催化剂的制备方法,其特征在于:步骤2所述碳纤维是经氢氧化钾活化的活性碳纤维,具体包括如下步骤:
步骤2.1:将碳纤维加入氢氧化钾溶液中,在40℃条件下,等体积浸渍24h;
步骤2.2:将经过浸渍如理的碳纤维在100~120℃的温度下干燥,并在800℃焙烧2h,水洗至中性,烘干得到所需活性碳纤维。
5.根据权利要求4所述的甲烷二氧化碳重整制合成气的催化剂的制备方法,其特征在于:所述碳纤维与氢氧化钾的质量比为1:1。
6.一种如权利要求1所述的甲烷二氧化碳重整制合成气的催化剂的应用,其特征在于:将所述催化剂用于固定床反应器中的甲烷二氧化碳重整制合成气反应,具体包括以下步骤:
1)取0.2~1g所述催化剂于固定床反应器内,在氮气氛围中升温至500~600℃,通入氢气还原0.5~1.5h;
2)还原结束以后,通入CH4:CO2:N2=1:1:2,总流量为150~300mL/min的混合气,在800℃进行重整反应,集气用气相色谱分析其催化效果。
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