CN112090427A - 一种低汽气比一氧化碳高温变换催化剂 - Google Patents
一种低汽气比一氧化碳高温变换催化剂 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title abstract description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 title abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011701 zinc Substances 0.000 claims abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 10
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- -1 aluminum compound Chemical class 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 229910052795 boron group element Inorganic materials 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 18
- 239000007789 gas Substances 0.000 abstract description 10
- 238000007086 side reaction Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 229910021529 ammonia Inorganic materials 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 150000004677 hydrates Chemical class 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012018 catalyst precursor Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- 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
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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
- B01J23/80—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 zinc, cadmium or mercury
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Abstract
本发明属于催化技术领域，涉及一种用于低汽气比（0.45及以下）条件下进行一氧化碳高温变换反应的铜基催化剂及高温变换工艺，催化剂以铜、锌、铝为主要组份，组成(wt)：CuO25%~45%，ZnO25%~45%，Al2O35%~15%，添加碱金属助剂Me2O0.5%～5.5%。采用沉淀法制备，碱金属氧化物(Me2O)主要是K或Cs，以氧化物或氧化物的水合物加入沉淀法制得的催化剂母体中，提高了催化剂在低汽气比条件下的高变活性并消除了铁系高变催化剂的F‑T副反应，采用此种催化剂的高温变换工艺CO转化率高，出口CO达到约1%，大大提高了高温换工艺的效率，明显降低合成氨或制氢过程的能耗。
Description
技术领域：本发明属于催化技术领域，涉及一种一氧化碳和水蒸汽在低汽气比0.45或者更低（相当于转化炉水碳比2.75及以下）条件下进行高温变换反应的催化剂及其制备方法，用于合成氨厂和制氢装置，特别适用于节能型氨厂的低汽气比高温变换反应以降低合成氨或制氢工艺的能耗。
背景技术：通常，合成氨和制氢工艺都涉及进行变换反应，通常包括一步或两步工艺，即在300℃以上的高温变换和220℃左右的低温变换。高温变换催化剂通常由活性组分Fe2O3与其它助剂化合物组成，有的还含有铬氧化物助剂，铬的氧化物是一种毒性物质，在生产的使用过程中，容易造成人身伤害，因此属于避免使用的物质。同时，由于Fe3O4在使用过程中容易形成金属铁和碳化铁，在高温变换条件下对CO甲烷化和F—T合成反应有催化作用，致使H2产率下降。为了控制副反应的发生，需使用更多的蒸汽，从而增加能耗。
随着合成氨工业的节能化、大型化以及制氢行业的高效率，适用于低水碳比的节能型催化剂越来越受到普遍重视，尤其在催化剂的选择性方面还不能适应当今日益提高的环保要求。如专利CN1140630A 提供的一种低水碳比的高温变换催化剂及其制备方法，也是为了适应节能要求而进行的催化剂改进，但是仍然是铁-铬为主要成分。铁系高温变换催化剂除了添加的铬助剂有毒性之外，还会导致F-T副反应的发生，为了适应节能技术要求，采用高活性的催化剂和降低蒸汽用量时，这种铁系催化剂将严重影响整个合成氨及制氢工艺的运行。这就使铁铬系催化剂在使用上受到制约。
解决这类问题有两种方法：一种是改进传统的铁基催化剂，如加入适量的铜，以抑制F—T副反应的发生，并提高催化剂的活性，另一种是采用不含铁的铜基催化剂，不仅可以完全避免F—T副反应，而且变换效率更高。因此，开发不含铁及毒性物质铬化合物的高温变换催化剂十分必要。
技术内容：本发明的目的是提供一种不含铁及毒性物质铬氧化物的铜基低汽气比一氧化碳高温变换催化剂及其制备方法。
本发明的催化剂以铜、锌、铝为主要组份，组成(wt)：CuO25%~45%，ZnO25%~45%，Al2O35%~15%，添加碱金属助剂Me2O0.5%～5.5%。采用沉淀法制备，碱金属氧化物(Me2O)主要是K或Cs，以氧化物，氧化物的水合物或碳酸盐形式加入沉淀法制得的催化剂母体中，经适当的处理、成型得到铜基一氧化碳高温变换催化剂。
本发明的主要特征在于添加了碱金属氧化物促进剂，该促进剂可以是K或Cs中的一种氧化物或一种以上的氧化物混合物，碱金属元素氧化物的来源可以是碱金属元素氧化物的水合物或碳酸盐类。
本发明的催化剂在200~350℃，1.0~3.0Mpa下，采用添加碱金属氧化物促进剂Me2O的含锌铝的铜系催化剂进行高温变换反应时，无F-T副反应的发生。本发明的催化剂中碱金属元素氧化物促进剂Me2O的含量为0.5%~5.5%。
本发明的催化剂采用沉淀法制备，即将铜锌的可溶性盐与碱溶液按不同的加入料顺序加入沉淀槽得到铜锌的微溶或不溶化合物。这种微溶或不溶化合物再经老化得半成品。本方法的沉淀条件控制pH值在5.0~8.0，并保持在50~90℃的温度范围下进行。沉淀过程中加入计量的铝化合物进行共沉淀，计量的碱金属元素氧化物促进剂Me2O母体以湿混方式加入到沉淀产物中，经搅拌，并在30~90℃条件下老化20min到2h，老化后要进行热处理，热处理的温度为100～450℃，以保证促进剂的分布均匀。再按已公知的方法加入成型助剂，经压片成型制得催化剂产品。催化剂的比表面积，根据碱金属元素氧化物促进剂Me2O含量和控制成型条件来调整。
通过调整催化剂中碱金属元素氧化物促进剂Me2O的含量，可使汽气比～0.45条件下均无F-T副反应的发生。
Cu、Zn组份催化剂母体采用沉淀的方法制备，并通过调节沉淀温度、老化时间和温度条件从它们的可溶性盐溶液中沉淀出来，沉淀过程中加入计量的铝化合物进行共沉淀，洗去杂质离子后的半成品按所需要的量，加入碱金属元素氧化物母体水溶液进行湿混，再经热处理最后成型。
由于催化剂是从可溶于水的Cu盐、Zn盐、Al盐开始制备的，其相互之间的比例可由成品中Cu/Zn/Al的比例来决定，采用本工艺特别有利。
金属盐溶液沉淀所用的沉淀剂可以是碳酸钠、碳酸氢钠、碳铵、氨水等，采用碳酸钠更为有利，沉淀剂的浓度可在较宽的范围内变化。沉淀温度控制在50～90℃，最好是60～75℃。
沉淀所用的时间 ，可在宽范围内变动，最好是在10分钟到1小时。沉淀结束后，沉淀产物的老化要进行搅拌，老化的温度范围在30~90℃，最好是45~80℃。老化过程中的pH值应保持不变。老化后的产物用传统方法进行分离，如过滤，洗涤。老化后进行热处理，热处理的温度为100～450℃，最好是分两步处理，如先在90~120℃处理1~2h，随后在300～450℃处理0.5~1.5h。
碱金属元素氧化物母体最好是氧化物或氢氧化物，加入到上述中间产物中，并且不带入任何杂质离子。含碱金属元素氧化物的产物经热处理，温度在250~500℃，最好是350~450℃，焙烧时间为0.5~2h，最好是0.5~1h。热处理可以在固定床或流动床（如转炉）中进行，处理后的催化剂半成品加工成型。
本发明的催化剂外型最好是片剂。
制备好的催化剂成品中CuO/ZnO/Al2O3/Me2O的组成为CuO（wt）25％~45%，ZnO（wt）25％~45%，Al2O3（wt）5％~15%，Me2O（wt）0.5％~5.5%。
具体实施方式：
实施例1
485gCu(NO3)2·3H2O，625gZn(NO3)2·6H2O用水溶解后，配成溶液。710g无水碳酸钠用水溶解，配成溶液。将两种溶液加热到60℃，进行沉淀，边沉淀边搅拌，保持PH值6.0～7.0，原料混合均匀时，加入150gAl(NO3)3·9H2O配成的溶液，再进行搅拌。半小时后进行过滤，用去离子水洗涤，再在120℃下进行干燥。干燥后的物料与4.8g的KOH进行湿混，混合均匀后在400℃下焙烧2h，加入2％～2.5％的石墨，压成片剂。制得的催化剂组成(以氧化物wt%计)为CuO39.7，ZnO42.4，Al2O310.0，K2O1.9。
实施例2
将实施例1中的铜锌两种溶液与碳酸钠溶液进行沉淀，沉淀条件同对比实施例1，沉淀过程中再加入对比例等量的Al(NO3)3溶液进行共沉淀，沉淀的产物洗去杂质离子后，过滤，在滤饼中加入4.8g的KOH进行湿混，在100℃下老化干燥1h后，在400℃下焙烧1h，最后配入成型助剂石墨，压片成型同实施例1。
对比例
按专利CN1140630A 提供的一种低水碳比的高温变换催化剂，制备出含氧化铁Fe2O388%，三氧化铬Cr2O38%，氧化铜CuO 1.6%，氧化铈CeO22.4%的催化剂。
将对比例所述的催化剂与实施例催化剂样品在原粒度Ф5×4.5~5mm，入口温度220℃，压力3.0MPa，空速8000h-1，入口CO浓度14.0％～15.0％的试验条件下分别进行了汽气比0.4和0.45的低汽气比高温变换的实验，对比结果如下。
表1 低汽气比条件下高温变换活性试验结果
表2 低汽气比条件下高温变换选择性试验结果
表1、表2 中的结果可以看出，实施例催化剂在活性和降低F-T副反应的效果都明显优于对比例催化剂，其中，表2 中的CH4生成量，实施例中出口低于进口，是由于变换反应后体积增大的缘故，而对比例催化剂由于含有Fe仍然避免不了生成F-T副反应。
Claims (6)
1.一种一氧化碳高温变换催化剂，其特征在于该催化剂为不含铁铬的铜-锌-铝系催化剂，并且添加了碱金属助剂。
2.如权利要求1所述催化剂各组分的重量组成为：CuO25%~45%，ZnO25%~45%，Al2O35%~15%，碱金属元素氧化物Me2O重量含量为0.5%～5.5%，Me为K、Cs中的一种或者一种以上的混合物，余为成型助剂。
3.如权利要求1、2所述催化剂的制备方法，其特征在于采用沉淀法制备，首先将铜锌的可溶性盐用水溶性碱溶液进行沉淀得到铜锌的微溶或不溶化合物，沉淀条件控制pH值在5.0~8.0，沉淀过程中加入计量的铝化合物。
4.如权利要求3所述催化剂的制备方法，其特征在于金属盐溶液共沉淀所用的沉淀剂是碳酸钠、碳酸氢钠、碳铵或氨水。
5.如权利要求3所述催化剂的制备方法，其特征在于硼族元素氧化物母体是氧化物或氧化物的水合物；热处理可分为两步进行，先在90~120℃处理1~2h，随后在300～450℃处理0.5~1.5h。
6.如权利要求2、3、4所述催化剂的制备方法，其特征在于碱金属元素氧化物母体以湿混方式加入到沉淀产物中。
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