CN114471441A - 一种co吸附剂及其制备方法和应用 - Google Patents
一种co吸附剂及其制备方法和应用 Download PDFInfo
- Publication number
- CN114471441A CN114471441A CN202011159400.9A CN202011159400A CN114471441A CN 114471441 A CN114471441 A CN 114471441A CN 202011159400 A CN202011159400 A CN 202011159400A CN 114471441 A CN114471441 A CN 114471441A
- Authority
- CN
- China
- Prior art keywords
- adsorbent
- copper
- molecular sieve
- preparation
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003463 adsorbent Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002808 molecular sieve Substances 0.000 claims abstract description 22
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 17
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000005749 Copper compound Substances 0.000 claims abstract description 9
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 14
- 150000001879 copper Chemical class 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000011268 mixed slurry Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000002594 sorbent Substances 0.000 claims 4
- 239000012670 alkaline solution Substances 0.000 claims 1
- 238000010304 firing Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 29
- 230000004913 activation Effects 0.000 abstract description 6
- 238000011112 process operation Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000005751 Copper oxide Substances 0.000 abstract 1
- 229910000431 copper oxide Inorganic materials 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000013078 crystal Substances 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000005997 Calcium carbide Substances 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Images
Classifications
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3071—Washing or leaching
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/25—Coated, impregnated or composite adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/502—Carbon monoxide
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明公开了一种CO吸附剂及其制备方法和应用。本发明吸附剂含有碱式氯化铜和氧化铜。利用二价铜化合物与碱溶液在分子筛表面原位合成出碱式氯化铜为前驱体制备CO吸附剂。该技术方案过程操作简单。所制备吸附剂在使用时无需活化或显著缩短活化时间,并能够有效提高CO吸附容量和选择性。
Description
技术领域
本发明属于化工气体分离技术领域,特别涉及一种CO吸附剂及其制备方法和应用。
背景技术
随着C1化学的快速发展,CO的应用日益广泛,除其是合成许多重要有机化工产品的原料气体外,还可作为燃料和金属还原气,具有重要的工业应用价值。但中国CO原料气主要来自石油、天然气的合成,水煤气及工业尾气,如电石尾气、焦炉尾气和钢厂废气等。这些工业尾气中虽含有大量的CO组分,但组成较为复杂,吸附提纯相对困难,因此需开发和采用成本低、效率高的气体分离提纯技术。
变压吸附(PSA)技术因其操作简单和环境友好等优点,广泛应用于气体吸附提纯领域。其原理是利用不同分压下吸附剂对吸附质具有不同的吸附容量,且对于目标组分具有选择吸附的特性。PSA技术的核心在于吸附剂性能,目前CO吸附剂的开发大都集中在过渡金属负载型吸附剂,其机理是利于CO能够与过渡金属离子(如Cu(Ⅰ)、Ag(Ⅰ)或Ni(Ⅰ))间形成共轭Π键,能够大幅提高吸附剂对CO的吸附性能。其中,大部分的研究都集中在含铜类吸附剂,例如谢有畅等依据自发单层分散原理,将Cu(Ⅰ)负载到载体上可有效提高CO的吸附量及选择性。但传统采用CuCl制备吸附剂时,原料需预纯化处理,操作繁琐,且条件相对苛刻。如CN106315613A提供了一种用于CO吸附的新型13X型分子筛及其制备方法和应用,其加入铜源后需在460~550℃及氮气氛围下进行3~5小时的还原。CN110545481A公开了Y型分子筛包覆纳米铜盐的中空结构CO吸附剂及其制备方法和应用,该吸附剂虽然能够有效提高CO吸附容量和选择性,但其操作压力为0.8MPa,操作温度为40℃。王磊(工业催化2016 11(24)62)采用干混法制备了Cu(Ⅰ)-分子筛吸附剂,其虽然能够满足工业CO提纯要求,但吸附温度相对较高(60℃)且穿透吸附量相对较低(37.5ml/g)。
CN110270303A公开了一种CO吸附剂及其制备方法,以氯化铜和碱式铜盐混合体与高比表面载体为原料,加水加粘结剂成型,烘干并活化后制得CO吸附剂。该方法虽避免了直接采用氯化亚铜时的一些弊端,但其吸附剂吸附性能较低。
因此针对目前现阶段CO吸附剂制备时操作繁琐、条件苛刻和吸附容量相对较小等缺点,开发高效、环保类型吸附剂具有重要的现实意义。
发明内容
针对现有技术的弊端,本发明目的之一在于提供一种高效、环保的CO吸附剂,并进一步提高吸附剂的吸附容量,以高效吸附CO。本发明另一目的在于提供一种CO吸附剂的制备方法,以简化制备程序、改进制备条件苛刻的问题,解决现有技术中制备困难、制备过程复杂等问题。
所述CO吸附剂由二价铜化合物与碱溶液在分子筛表面原位合成而制得。所述二价铜化合物优选为可溶性无机铜盐,更优选为氯化铜、硝酸铜和硫酸铜的一种或多种或其与其它无机铜盐的混合物,最优选为氯化铜或其与其它无机铜盐的混合物。所述分子筛优选为选自Y、USY、13X、ZSM-5、MCM和β分子筛中的一种或多种。
本发明第二方面在于提供一种CO吸附剂的制备方法,包括以下步骤:
a)将二价铜化合物溶解得到含铜溶液,将碱溶解得到碱溶液;
b)将所述含铜溶液与碱溶液滴加到盛有分子筛的水溶液中,得到混合浆液;
c)将所述混合浆液晶化,洗涤、干燥后焙烧得到CO吸附剂。
上述技术方案中,所述二价铜化合物和分子筛的投料质量比为0.1~1.9:1,优选为0.7~1.7:1。所述碱液浓度范围为0.1~1mol/L(以OH-浓度计),优选为0.2~0.5mol/L。碱溶液的加入量使得混合浆液的pH值为6~8。
上述技术方案中,步骤a)中所述二价铜化合物优选为可溶性无机铜盐,更优选为氯化铜、硝酸铜和硫酸铜的一种或多种或其与其它无机铜盐的混合物,最优选为氯化铜或其与其它无机铜盐的混合物。所述的碱优选为氢氧化钠。
上述技术方案中,步骤b)中所述分子筛优选为选自Y、USY、13X、ZSM-5、MCM和β分子筛中的一种或多种。
上述技术方案中,步骤c)中所述的晶化为:60~150℃下晶化8~24小时,优选12~24小时。所述的焙烧为:在无氧条件下,于400~600℃焙烧2~10小时。
本发明第三方面在于提供一种CO吸附剂在吸附CO中的应用。所述应用优选采用固定床吸附技术进行。所述固定床吸附优选为:在100~180℃下用CO吹扫0~4小时进行活化处理,待在线色谱分析仪的基线稳定后通入混合气体进行吸附。
与现有技术相比,本发明具有如下有益效果:
1.本发明是通过在一定pH值下,利用二价铜盐与碱液在分子筛表面原位合成并经焙烧制得。上述制备技术方案中,采用二价铜盐作为铜源,过程操作简单。该吸附剂在使用时无需活化或显著缩短活化时间。
2.本发明制备的CO吸附剂具有高的CO吸附量、选择性和再生性,可用于各种含CO气体的分离与净化。
3.本发明制备的CO吸附剂,使用条件范围较宽,能够在室温及常压下进行CO吸附,一定程度上能够减小能耗。
附图说明
图1为实施例2中合成的CO吸附剂XRD谱图;
图2为实施例2中合成的CO吸附剂SEM谱图。
具体实施方式
以下通过实施例对本发明作进一步详细描述。但应当理解具体实施方式并不构成对本发明的保护范围限制。
XRD谱图:采用日本理学Rigaku Ultima IV型X-射线粉末衍射仪分析样品的物相,Cu Kα线为射线源镍滤光片,2θ扫描范围5~70°,操作电压40KV,电流40mA,扫描速率10°/min,获得XRD谱图。
同时利用X'Pert High Score软件通过谢乐公式进行晶粒尺寸计算。
SEM谱图:采用日立公司的Hitachi S-4800冷场发射高分辨率扫描电子显微镜获得SEM谱图。
【实施例1】
准确称取CuCl2·2H2O晶体1.705g,溶于100ml去离子水中配制成盐溶液;另将1.6000g的NaOH溶于100ml去离子水中配制成碱溶液。在剧烈搅拌下将上述两溶液缓慢滴加到盛有1g Y分子筛与20ml去离子水的三口烧瓶中,滴加完成后继续搅拌0.5h,将成核浆液于60℃下静置晶化24h,随后将所得沉淀过滤洗涤至中性,产物于80℃干燥12h。然后将所得固体至于管式炉中,在N2气氛保护下,于400℃焙烧8小时,冷却后得到CO吸附剂A1。吸附剂在常温和CO压力为0.6MPa下测得吸附量,随后吸附剂于100℃进行脱附处理。
本实施例合成的CO吸附剂的XRD谱图如图1所示(a.未经焙烧的CO吸附剂,b.CO吸附剂)。谱图中表明,利用该方法能够在载体表面原位合成出Cu2(OH)3Cl。以Cu2(OH)3Cl为前躯体制备出的CO吸附剂的谱图(b)中,归属于Cu2(OH)3Cl的特征衍射峰减弱,同时出现归属于CuO的特征峰。
本实施例合成的CO吸附剂的SEM谱图如图2所示。该方法制备出的CO吸附剂表面相对粗糙,能够提供较多的附着位点,有利于CO在其表面的化学吸附。
【实施例2】
准确称取CuCl2·2H2O晶体和Cu(NO3)·3H2O晶体0.6819g和0.1876g,溶于100ml去离子水中配制成混合盐溶液;另将0.4000g NaOH溶于100ml去离子水中配制成混合碱溶液。在剧烈搅拌下将上述两混合溶液缓慢滴加到盛有1g Y分子筛与20ml去离子水的三口烧瓶中,滴加完成后继续搅拌0.5h,将成核浆液于80℃下静置晶化20h,随后将所得沉淀过滤洗涤至中性,产物于80℃干燥12h。然后将所得固体至于管式炉中,在N2气氛保护下,于600℃焙烧4小时,冷却后得到CO吸附剂A2。具有与实施例1相似的XRD谱图。
【实施例3】
准确称取CuCl2·2H2O晶体和Cu(NO3)·3H2O晶体0.8524g和0.9378g,溶于100ml去离子水中配制成混合盐溶液;另将0.8000g NaOH溶于100ml去离子水中配制成混合碱溶液。在剧烈搅拌下将上述两混合溶液缓慢滴加到盛有1g Y分子筛与20ml去离子水的三口烧瓶中,滴加完成后继续搅拌0.5h,将成核浆液于100℃下静置晶化12h,随后将所得沉淀过滤洗涤至中性,产物于80℃干燥12h。然后将所得固体至于管式炉中,在N2气氛保护下,于450℃焙烧6小时,冷却后得到CO吸附剂A3。具有与实施例1相似的XRD谱图。
【实施例4】
准确称取CuCl2·2H2O晶体和CuSO4晶体1.1934g和0.4788g,溶于100ml去离子水中配制成混合盐溶液;另将1.6000g NaOH溶于100ml去离子水中配制成混合碱溶液。在剧烈搅拌下将上述两混合溶液缓慢滴加到盛有1g Y分子筛与20ml去离子水的三口烧瓶中,滴加完成后继续搅拌0.5h,将成核浆液于120℃下静置晶化8h,随后将所得沉淀过滤洗涤至中性,产物于80℃干燥12h。然后将所得固体至于管式炉中,在N2气氛保护下,于550℃焙烧3小时,冷却后得到CO吸附剂A4。具有与实施例1相似的XRD谱图。
【对比例1】
准确称取1.0gY型分子筛,CuCl2·2H2O晶体和Cu2(OH)3CO3晶体1.1365g和0.7371g混合均匀,在N2气氛保护下,于400℃焙烧8小时,冷却后得到对比剂A5。
【实施例5】应用实施例
将前面实施例及对比例所制备的CO吸附剂用于固定床吸附CO实验,在常温和CO压力为0.6MPa采用气相色谱进行检测,随后吸附剂于100℃进行脱附处理。实验过程中,将吸附剂(质量为m)安装于固定床反应器中,在常温~180℃下用CO吹扫2~4小时进行活化处理,待在线色谱分析仪的基线稳定后通入混合气体(CO混合气,混合气流量为Q,CO体积分数为C),从固定床出口端流出气体经色谱不间断检测。吸附剂吸附饱和前,CO在出口端不会被色谱检测到或浓度很低,若色谱中出现CO组分或浓度迅速上升时,则认为达到吸附饱和,计时(t)。以式(1)计算吸附剂吸附容量X:
X=CQt/m (1)
各实施例及对比例样品的吸附剂吸附量列于表1。
【实施例6】重复利用性
将实施例1制备的CO吸附剂分别通过升温脱附进行再生,再生后的吸附剂于同样条件下考察其CO吸附性能。重复3次其吸附容量都保持稳定。
表1吸附剂吸附测试结果
编号 | 吸附剂 | 吸附容量,ml/g<sub>吸附剂</sub> | CO选择性,% |
1 | A1 | 69.7 | 99 |
2 | A2 | 56.3 | 98 |
3 | A3 | 59.8 | 98 |
4 | A4 | 61.8 | 98 |
5 | A5 | 43.2 | 97 |
6 | Recycle-A1-1 | 69.7 | 99 |
7 | Recycle-A1-2 | 69.7 | 99 |
Claims (10)
1.一种CO吸附剂,其特征在于,该吸附剂含有碱式氯化铜(Cu2(OH)3Cl)和氧化铜(CuO)。
3.根据权利要求1所述的吸附剂,其特征在于,所述CO吸附剂由二价铜化合物与碱溶液在分子筛表面原位合成而制得。
4.根据权利要求3所述的吸附剂,其特征在于,所述二价铜化合物为可溶性无机铜盐,优选为氯化铜、硝酸铜和硫酸铜的一种或多种或其与其它无机铜盐的混合物;进一步优选为氯化铜或其与其它无机铜盐的混合物。
5.根据权利要求3所述的吸附剂,其特征在于,所述分子筛为选自Y、USY、13X、ZSM-5、MCM和β分子筛中的一种或多种。
6.一种权利要求1-5任一项所述吸附剂的制备方法,其特征在于,包括以下步骤:
a)将二价铜化合物溶解得到含铜溶液,将碱溶解得到碱溶液;
b)将所述含铜溶液与碱溶液滴加到盛有分子筛的水溶液中,得到混合浆液;
c)将所述混合浆液晶化,洗涤、干燥后焙烧得到CO吸附剂。
7.根据权利要求6所述的制备方法,其特征在于,所述二价铜化合物和分子筛的投料质量比为0.1~1.9:1,优选为0.7~1.7:1;所述碱液浓度范围为0.1~1mol/L,优选为0.2~0.5mol/L,碱溶液的加入量使得混合浆液的pH值为6~8。
8.根据权利要求6所述的制备方法,其特征在于,步骤c)中所述的晶化为:60~150℃下晶化8~24小时,优选12~24小时。
9.根据权利要求6所述的制备方法,其特征在于,步骤c)中所述的焙烧为:在无氧条件下,于400~600℃焙烧2~10小时。
10.一种权利要求1-5任一项所述吸附剂或者权利要求6-9任一项制备方法所制备的吸附剂在吸附CO中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011159400.9A CN114471441A (zh) | 2020-10-26 | 2020-10-26 | 一种co吸附剂及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011159400.9A CN114471441A (zh) | 2020-10-26 | 2020-10-26 | 一种co吸附剂及其制备方法和应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114471441A true CN114471441A (zh) | 2022-05-13 |
Family
ID=81470611
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011159400.9A Pending CN114471441A (zh) | 2020-10-26 | 2020-10-26 | 一种co吸附剂及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114471441A (zh) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62113710A (ja) * | 1985-11-13 | 1987-05-25 | Kansai Coke & Chem Co Ltd | Co分離回収用吸着剤の製造方法 |
US4713090A (en) * | 1985-09-17 | 1987-12-15 | Kansai Netsukagaku Kabushiki Kaisha | Adsorbent for separation-recovery of CO, preparing method thereof and process for separation-recovery of high purity CO, using the adsorbent |
JPH11137993A (ja) * | 1997-11-10 | 1999-05-25 | Cosmo Sogo Kenkyusho Kk | 一酸化炭素吸着剤及びその製造方法 |
JP2010269264A (ja) * | 2009-05-22 | 2010-12-02 | Kansai Coke & Chem Co Ltd | Co吸脱着剤の製造方法 |
CN108704609A (zh) * | 2018-05-30 | 2018-10-26 | 太原理工大学 | 用于CO吸附分离的单分子层CuCl/活性炭吸附剂制备方法 |
CN110270303A (zh) * | 2019-04-28 | 2019-09-24 | 大英达科特化工科技有限公司 | 一种高效co吸附剂及其制备方法 |
-
2020
- 2020-10-26 CN CN202011159400.9A patent/CN114471441A/zh active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4713090A (en) * | 1985-09-17 | 1987-12-15 | Kansai Netsukagaku Kabushiki Kaisha | Adsorbent for separation-recovery of CO, preparing method thereof and process for separation-recovery of high purity CO, using the adsorbent |
JPS62113710A (ja) * | 1985-11-13 | 1987-05-25 | Kansai Coke & Chem Co Ltd | Co分離回収用吸着剤の製造方法 |
JPH11137993A (ja) * | 1997-11-10 | 1999-05-25 | Cosmo Sogo Kenkyusho Kk | 一酸化炭素吸着剤及びその製造方法 |
JP2010269264A (ja) * | 2009-05-22 | 2010-12-02 | Kansai Coke & Chem Co Ltd | Co吸脱着剤の製造方法 |
CN108704609A (zh) * | 2018-05-30 | 2018-10-26 | 太原理工大学 | 用于CO吸附分离的单分子层CuCl/活性炭吸附剂制备方法 |
CN110270303A (zh) * | 2019-04-28 | 2019-09-24 | 大英达科特化工科技有限公司 | 一种高效co吸附剂及其制备方法 |
Non-Patent Citations (8)
Title |
---|
LAKSHMINARAYANA KUDINALLI GOPALAKRISHNA BHATTA ET AL: "An experimental study on thermal decomposition of microwave synthesized Cu2(OH)3Cl to copper oxide nanoparticles", 《MATER. RES.》, 31 December 2019 (2019-12-31) * |
LORIANNE R. SHULTZ ET AL: "Nickel foam supported porous copper oxide catalysts with noble metal-like activity for aqueous phase reactions", 《CATALYSIS SCIENCE & TECHNOLOGY》, vol. 12, no. 12, 1 April 2022 (2022-04-01), pages 3084 - 3016 * |
O. GARCA-MARTINEZ ET AL: "γ-Cu2(OH)3Cl as precursor in the preparation of copper (I) and (11) oxides and copper powder", 《JOURNAL OF MATERIALS SCIENCE》, vol. 21, 31 December 1986 (1986-12-31), pages 4411 - 4418 * |
温炎燊等: "Botallackite碱式氯化铜的显微形态及 热分析表征", 《中国石油和化工标准与质量》, no. 201903, pages 182 - 184 * |
祝立群, 涂晋林, 施亚钧: "活性炭负载氯化铜吸附CO的研究", 燃料化学学报, no. 03 * |
蒋晓原, 丁光辉, 刘琪, 楼莉萍, 陈英旭, 郑小明: "CuO在CeO_2和γ-Al_2O_3上的表面性质及对NO+CO反应性能的研究", 浙江大学学报(理学版), no. 03, pages 1023 * |
邓凡政等: "CuO/Cu2(OH)3Cl的制备及其光催化降解染料光谱性能研究", 《光谱学与光谱分析》, vol. 26, no. 2, pages 299 * |
陈志刚;于雷;陈丰;张玉珠;徐政;: "CuO/Ce_(1-x)Al_xO_2催化剂的制备及其催化性能研究", 材料导报, no. 20 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8377842B2 (en) | Adsorbent for selective adsorption of carbon monoxide and process for preparation thereof | |
CN100377776C (zh) | 一种高吸附量分子筛吸附剂的制备方法 | |
KR100827788B1 (ko) | 하이드로탈사이트-제올라이트 복합체 및 이를 이용한 질소산화물 흡장형 촉매 | |
CN107262145B (zh) | 一种沸石碳氢吸附重整催化剂的制备方法 | |
JP2002500094A (ja) | 炭化水素流からの痕跡量除去用吸着剤とその使用方法 | |
CN111375373B (zh) | 一种以活性炭为载体的吸附剂及其制备方法 | |
CN112044401A (zh) | 一种多孔有机笼吸附材料及其制备方法 | |
CN111377443B (zh) | 一种铜掺杂活性炭复合材料及其制备方法 | |
CN110193378B (zh) | 一种CuM/SAPO-34分子筛的制备方法及其应用 | |
CN114225910B (zh) | 一种具有NO吸附分离性能的胺基化改性Co-MOFs材料 | |
CN111530424A (zh) | 一种高效脱除气态苯系物的负载铜改性的碳材料吸附剂及其制备方法和应用 | |
CN111375375B (zh) | 一种脱硫吸附剂及其制备方法 | |
CN114471441A (zh) | 一种co吸附剂及其制备方法和应用 | |
CN115646500B (zh) | 一种氨分解制氢催化剂及其制备方法与应用 | |
CN111375374B (zh) | 一种负载型铜基吸附剂及其制备方法 | |
CN112387251B (zh) | 一种含铁螯合剂内嵌的mof材料、合成方法及应用 | |
CN110496594B (zh) | 一种高分离系数一氧化碳吸附剂的制备方法及吸附剂 | |
CN113663649A (zh) | 一种mof成型材料应用于低温二氧化碳捕获 | |
CN114590818B (zh) | 一种薄片状mor分子筛及其制备方法、利用合成气制备乙醇的催化剂和方法 | |
CN113522011B (zh) | 脱硫化氢的方法 | |
CN111378148B (zh) | 一种二元金属MOFs材料的制备方法及其在香烟烟气减害中的应用 | |
CN114260023B (zh) | 一种氨气纯化催化剂 | |
CN111530417B (zh) | 一种亚铜离子负载介孔碳粉末的制备方法 | |
CN113522302B (zh) | 硫化氢脱除剂及其制备方法和应用 | |
CN116712972A (zh) | 一种用于CO吸附的含Cu+吸附剂及其制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |