WO2019042158A1 - Calcium oxide-based high temperature co2 adsorbent, and preparation method therefor - Google Patents

Calcium oxide-based high temperature co2 adsorbent, and preparation method therefor Download PDF

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WO2019042158A1
WO2019042158A1 PCT/CN2018/100992 CN2018100992W WO2019042158A1 WO 2019042158 A1 WO2019042158 A1 WO 2019042158A1 CN 2018100992 W CN2018100992 W CN 2018100992W WO 2019042158 A1 WO2019042158 A1 WO 2019042158A1
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temperature
adsorbent
based high
calcium oxide
carrier
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Chinese (zh)
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胡燕
周云龙
李蒙
梅慧
蒯平宇
王大祥
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武汉丰盈长江生态科技研究总院有限公司
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    • 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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • 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
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the invention relates to a CO 2 adsorbent in a steam reforming hydrogen production technology, in particular to a calcium oxide based high temperature CO 2 adsorbent and a preparation method thereof.
  • reaction temperature higher than 800 ° C reaction temperature higher than 800 ° C
  • low hydrogen concentration a relatively high concentration of CO 2 in the equilibrium gas
  • high energy consumption for reaction and purification high energy consumption for reaction and purification.
  • the principle of SERP technology is to add CO 2 adsorbent together in the reactor based on the existing SMR process, and use the adsorbent to adsorb CO 2 to remove the CO 2 continuously generated in the reaction, breaking the reaction equilibrium and making the reaction
  • the direction of hydrogen production is continuously carried out, that is, the reforming reaction and the adsorption reaction of CO 2 occur simultaneously in the reactor.
  • This technology not only greatly reduces the reaction temperature, but also reduces the energy consumption, and the purity of hydrogen produced in a single pass can be as high as 95. %, thereby reducing the energy consumption of hydrogen purification.
  • the high purity CO 2 produced by the CO 2 desorption regeneration process can be comprehensively utilized.
  • Lithium compounds such as Li 2 ZrO 3 , Li 4 SiO 4
  • hydrotalcites such as Mg 6 Al 2 (OH) 16 [CO 3 ] ⁇ 4H 2 O/K 2 CO 3
  • CaO are commonly used at present.
  • the lithium compound has a poor adsorption capacity, and the hydrotalcite adsorption rate is too slow, so it is not suitable for industrial large-scale adsorption of CO 2 .
  • CaO as it has the advantages of high adsorption capacity and fast adsorption speed, has become a suitable adsorbent for high-temperature CO 2 adsorption (Esther Ochoa-Fernández et al.
  • the development of high-stability, high-abrasion, easily fluidized spherical high-temperature CaO sorbent particles is critical for adsorption-enhanced hydrogen production technology.
  • the method commonly used by researchers is to dope the CaO with a suitable inert metal to inhibit its sintering and improve its thermal stability.
  • Janewit Phromprasit et al. added 20% by weight of Al 2 O 3 sol to the CaO suspension, and dried and calcined to obtain a powdered CO 2 adsorbent.
  • the adsorbent was subjected to 10 cycles of adsorption-desorption.
  • the calcium carbonate raw material and the doped raw material are mixed into a slurry, and then the sprayed granulation or other molding method is used to obtain the modified adsorbent particles; the process is cumbersome and involves various solutions.
  • the post-treatment of the solvent the most important thing is that the adsorbent product obtained by such a method is difficult to meet the requirements of the circulating fluidized bed process in terms of strength, wear resistance and particle morphology.
  • the object of the present invention is to provide a calcium oxide-based high-temperature CO 2 adsorbent and a preparation method thereof, which have high wear resistance, high heat stability and high activity.
  • the technical solution adopted by the present invention is: a calcium oxide-based high-temperature CO 2 adsorbent comprising a carrier M and a main active component CaO supported on the carrier M, characterized in that the carrier M The structure is further loaded with a structural stabilizer A; the composition of the calcium oxide-based high-temperature CO 2 adsorbent is:
  • x is the mass percentage of CaO
  • a is the mass percentage of A, 5% ⁇ x ⁇ 60%, and 0.1% ⁇ a ⁇ 50%.
  • the structural stabilizing aid A is a metal and/or a metal oxide of one or more of Mo, Mg, V, Ti, Fe, Co, Zr, Cu, Sr, Ce, La and W.
  • the carrier M is a mixture of one or more of Al 2 O 3 , SiO 2 , magnesium aluminum spinel, molecular sieve.
  • the present invention also provides a method for preparing the above calcium oxide-based high-temperature CO 2 adsorbent, wherein the structural stabilizer A and CaO are supported on the carrier M by a step impregnation method or a co-impregnation method, and after aging treatment at 80 to
  • the calcium oxide-based high-temperature CO 2 adsorbent is obtained by drying at 200 ° C and calcining at 400 to 1000 ° C.
  • the structural stabilizer A and CaO are supported on the carrier M by a bifurcation impregnation method, including the following steps:
  • the aging time is 0.5 to 8 hours, and the aging temperature is 10 to 90 ° C; in the step 4), the aging time is 0.5 to 8 hours, and the aging temperature is 10 to 90 ° C.
  • the drying temperature is 80 to 120 ° C
  • the drying time is 1 to 24 hours
  • the baking temperature is 400 to 1000 ° C
  • the baking time is 0.1 to 6 hours.
  • the drying temperature is 100 to 200 ° C
  • the drying time is 1 to 24 hours
  • the baking temperature is 500 to 1000 ° C
  • the baking time is 0.1 to 5 hours.
  • the structural stabilizer A and CaO are supported on the carrier M by a co-impregnation method: the following steps are included:
  • the carrier M and the mixed impregnation liquid are mixed, subjected to impregnation and aging treatment, and then dried at 80 to 200 ° C, and then calcined at 400 to 1000 ° C to obtain the calcium oxide-based high-temperature CO 2 adsorbent.
  • the aging time is 1 to 8 hours
  • the aging temperature is 10 to 90 ° C
  • the drying temperature is 80 to 200 ° C
  • the drying time is 1 to 24 hours
  • the baking temperature is 400 to 1000 ° C.
  • the baking time is 0.5 to 6 hours.
  • the metal salts of the structural stabilizing aid A are Ce(NO 3 ) 3 , Mg(NO 3 ) 2 , La(NO 3 ) 3 , ZrO(NO 3 ) 2 , Fe(NO 3 ) 2 , TiO(SO 4 2, one or more of magnesium gluconate and barium acetate
  • the calcium precursor is one or more of calcium nitrate, calcium acetate, calcium gluconate, and calcium hydrogencarbonate.
  • the present invention has the following advantages:
  • the calcium oxide-based high-temperature CO 2 adsorbent obtained by the present invention has high wear resistance, high heat stability and high activity.
  • the adsorbent can promote the conversion reaction to the hydrogen generation by adsorbing the conversion product CO 2 during the steam reforming hydrogen production process of the hydrocarbon compound or the carbonaceous raw material, and the adsorbent can be in the regeneration reactor under favorable conditions. decomposition, CO 2 adsorption capacity restored, the adsorbent in the adsorption-desorption cycles 40 loss of CO 2 adsorption capacity of less than 20%, under certain conditions even no more than 10%; the adsorbent of 0.1 to wear 1 wt% / hour, no more than 0.5 wt% / hour under certain conditions.
  • the structural stabilizing aid A is doped in the CaO matrix by the formed metal oxide, and inhibits the migration of CaO, thereby improving the CaO on the surface of the carrier M. Dispersibility, while inhibiting the migration of CaO, thereby improving its thermal stability and maintaining its high adsorption capacity and adsorption rate.
  • the carrier M is a spherical carrier having a certain strength and wear resistance conforming to the fluidization characteristics of a specific circulating fluidized bed, and the CaO is loaded thereon without affecting On the basis of its adsorption performance to CO 2 , it also enhances the effective surface area of CaO particles, provides a suitable pore structure, improves the mechanical strength and anti-wear ability of CaO, and simultaneously improves the heat of CaO with additives. stability.
  • the calcium oxide-based high-temperature CO 2 adsorbent prepared by the invention has good fluidization property, good wear resistance and high strength, and meets the requirements of the adsorption-enhanced circulating fluidized bed steam reforming hydrogen production process, thereby reducing the requirement R&D and production risks and costs.
  • the invention can adopt the stepwise impregnation, or the mixed impregnation to prepare the adsorbent, the preparation method is simple, no waste water is produced, environment friendly, easy to repeat, and is particularly suitable for large-scale industrial production and application.
  • Fig. 1 is a graph showing the relationship between the adsorption capacity of the CO 2 adsorbent and the number of cycles in Examples 1 to 5.
  • thermogravimetric analyzer was used to test the stability of the cyclic adsorption-desorption CO 2 ability of the calcium oxide-based high-temperature CO 2 adsorbent prepared in each example by the method of weighing about 15 mg of the sample. Place in the sample crucible, heat up to 800 degrees under high purity N 2 for 5 minutes (the weight does not change in 5 minutes, indicating that the calcium carbonate in the sample has been decomposed), and cool down to 650 degrees. At this time, switch the gas to Adsorption was carried out under a mixed atmosphere (5% CO 2 + high purity nitrogen).
  • the gas was switched to high purity N 2 , and the temperature was raised to 800 °C for 5 minutes (the sample weight no longer changed), and then the temperature was lowered to 650. Degree, the adsorption of CO 2 was carried out, and the cycle was performed 40 times to test the thermal stability of the sample.
  • the wear resistance of the adsorbent is evaluated by using a wear meter in accordance with the measurement of the wear index of the catalytic cracking catalyst of the straight pipe method of the China National Petroleum Corporation Co., Ltd. Catalyst Branch Company Standard Q/TSH 3490 909-2006.
  • the Ce 2 O 3 /La 2 O 3 modified ⁇ -Al 2 O 3 carrier obtained in the step (2) is mixed with the immersion liquid II, and then impregnated and aged at 75 ° C by ultrasonic vibration method. After the hour, after drying at 150 ° C for 12 h and then at 800 ° C for 4 h, the composition is 10% CaO ⁇ 3% Ce 2 O 3 ⁇ 1.5% La 2 O 3 ⁇ 85.5% ⁇ -Al 2 O 3 High wear resistance and high stability calcium oxide based high temperature CO 2 adsorbent.
  • the measurement results of the wear meter showed that the wear rate of the adsorbent was 0.65 wt% / hour.
  • the MgO-modified ⁇ -Al 2 O 3 carrier obtained in the step (2) is mixed with the immersion liquid II, and then immersed in an equal volume at 70 ° C for 4 hours by ultrasonic vibration, and then dried at 110 ° C. After 12 h, it was calcined at 800 ° C for 3 h to obtain a highly wear-resistant and high-stability calcium oxide-based high-temperature CO 2 adsorbent having a composition of 20% CaO ⁇ 5% MgO ⁇ 75% ⁇ -Al 2 O 3 .
  • the measurement results of the wear meter showed that the wear rate of the adsorbent was 0.84% by weight/hour.
  • the MgO/La 2 O 3 modified ⁇ -Al 2 O 3 carrier obtained in the step (2) is mixed with the immersion liquid II, and then immersed and immersed in an equal volume at 60 ° C for 6 hours by an ultrasonic vibration method. After drying at 200 ° C for 10 h and then calcining at 800 ° C for 4 h, a high wear resistance and high stability of 20% CaO ⁇ 2% MgO ⁇ 1% La 2 O 3 ⁇ 77% ⁇ -Al 2 O 3 can be obtained. Calcium oxide based high temperature CO 2 adsorbent.
  • the measurement results of the wear meter showed that the wear rate of the adsorbent was 0.31% by weight/hour.
  • the ZrO 2 modified SiO 2 support obtained in the step (2) is mixed with the immersion liquid II, and then immersed in an equal volume at 60 ° C for 4 hours by an ultrasonic vibration method, and then dried at 100 ° C for 10 hours. After calcination at 800 ° C for 4 h, a highly wear-resistant and highly stable calcium oxide-based high-temperature CO 2 adsorbent having a composition of 15% CaO ⁇ 1.5% ZrO 2 ⁇ 83.5% SiO 2 was obtained.
  • the measurement results of the wear meter showed that the wear rate of the adsorbent was 0.95 wt% / hour.
  • the measurement results of the wear meter showed that the wear rate of the adsorbent was 1.2 wt% / hour.
  • the measurement results of the wear meter showed that the wear rate of the adsorbent was 1.1 wt% / hour.

Abstract

A calcium oxide-based high temperature CO2 adsorbent, and a preparation method therefor. The adsorbent comprises a carrier M and a main active component CaO loaded on the carrier M; a structure stabilizing assistant A is further loaded on the carrier M; the general formula of the calcium oxide-based high temperature CO2 adsorbent is x CaO•a A•(100-x-a)M, wherein x represents the mass percent of CaO, a represents the mass percent of A, 5%≤x≤60%, and 0.1%≤a≤50%. The preparation method comprises: loading the structure stabilizing assistant A and CaO on the carrier M by means of a stepped impregnation method or a common impregnation method, drying under a temperature of 80-200°C after aging, and then performing calcination under a temperature of 400-1000°C. The calcium oxide-based high temperature CO2 adsorbent has high wear resistance, high thermal stability, and high activity. Moreover, the preparation method is simple, does not generate any waste water, and is environmentally friendly, easy to repeat, and especially suitable for large-scale industrial production and application.

Description

氧化钙基高温CO 2吸附剂及其制备方法 Calcium oxide based high temperature CO       2 adsorbent and preparation method thereof      技术领域Technical field
本发明涉及水蒸汽重整制氢技术中的CO 2吸附剂，具体地指一种氧化钙基高温CO 2吸附剂及其制备方法。 The invention relates to a CO 2 adsorbent in a steam reforming hydrogen production technology, in particular to a calcium oxide based high temperature CO 2 adsorbent and a preparation method thereof.
背景技术Background technique
在燃烧相同重量的煤、汽油和氢气的情况下，氢气产生的能量最多；而且氢气燃烧的产物是水，没有灰渣和废气，不会污染环境，而煤和石油燃烧生成的主要是CO 2,同时产生大量SO 2，可分别造成温室效应和酸雨等污染，因此，氢是21世纪最理想的能源之一。迄今为止，世界上大约有48％的氢气是从甲烷水蒸汽重整工艺(SMR)制备而来，该工艺是目前最成熟的制氢工艺。甲烷水蒸汽重整制氢反应的总化学反应式如下所示： In the case of burning the same weight of coal, gasoline and hydrogen, hydrogen produces the most energy; and the product of hydrogen combustion is water, no ash and waste gas, does not pollute the environment, and coal and petroleum combustion mainly produces CO 2 At the same time, a large amount of SO 2 is produced, which can cause pollution such as greenhouse effect and acid rain. Therefore, hydrogen is one of the most ideal energy sources in the 21st century. To date, approximately 48% of the world's hydrogen has been produced from the methane steam reforming process (SMR), which is currently the most mature hydrogen production process. The total chemical reaction formula for the hydrogen production of methane steam reforming is as follows:
该制氢工艺虽然自1926年沿用至今，但是存在着反应温度高(反应温度高于800℃)，氢气浓度低(平衡气体中含有相当高浓度的CO 2)，且反应流程长，设备投资大，反应和提纯能耗高等问题。 Although the hydrogen production process has been in use since 1926, it has a high reaction temperature (reaction temperature higher than 800 ° C), a low hydrogen concentration (a relatively high concentration of CO 2 in the equilibrium gas), and a long reaction process and large equipment investment. , high energy consumption for reaction and purification.
吸附强化制氢技术即SERP技术(Sorption-enhanced reaction process)自公布以来，受到全世界范围的广泛关注。SERP技术的原理就是在现有SMR工艺的基础上，在反应器中一起加入CO 2吸附剂，利用吸附剂对CO 2的吸附来去除反应中不断产生的CO 2，打破反应平衡，使反应朝着产出氢气的方向不断进行，即在反应器中同时发生重整反应和CO 2的吸附反应，这一技术不仅大大降低了反应温度，减少了能耗，而且单程产出氢气纯度可高达95％，从而降低氢气提纯的能耗。此外，CO 2脱附再生过程产生的高纯CO 2可以得到综合利用。 Since the publication of the Sorption-enhanced reaction process, the SERP technology has received worldwide attention. The principle of SERP technology is to add CO 2 adsorbent together in the reactor based on the existing SMR process, and use the adsorbent to adsorb CO 2 to remove the CO 2 continuously generated in the reaction, breaking the reaction equilibrium and making the reaction The direction of hydrogen production is continuously carried out, that is, the reforming reaction and the adsorption reaction of CO 2 occur simultaneously in the reactor. This technology not only greatly reduces the reaction temperature, but also reduces the energy consumption, and the purity of hydrogen produced in a single pass can be as high as 95. %, thereby reducing the energy consumption of hydrogen purification. In addition, the high purity CO 2 produced by the CO 2 desorption regeneration process can be comprehensively utilized.
对于吸附强化的甲烷水蒸气重整的制氢工艺，因为涉及催化剂和吸附剂需要不断进行反应和再生的循环，所以，使用固定床反应器会带来连续性生产和催化剂、吸附剂再生操作不便的问题，而循环流化床反应器因微球颗粒催化剂的易流化特性，不仅可以强化传热、传质，而且还易于实现催化剂/吸附剂的再生和添加等，从而可以实现反应和再生的连续循环操作。如：本领域研究人员在中国专利CN106629600A中公布了一种循环 流化床的粗合成气强化制氢工艺，在此工艺中重整催化剂/吸附剂在流化床反应器和再生器中循环使用。For the hydrogen production process of adsorption-enhanced methane steam reforming, the use of a fixed-bed reactor results in continuous production and inconvenience of catalyst and adsorbent regeneration because of the cycle in which the catalyst and adsorbent are required to be continuously reacted and regenerated. The problem, while the circulating fluidized bed reactor can not only enhance heat transfer and mass transfer due to the easy fluidization characteristics of the microsphere particle catalyst, but also facilitate the regeneration and addition of the catalyst/adsorbent, thereby realizing reaction and regeneration. Continuous loop operation. For example, researchers in the field have disclosed a crude syngas-enhanced hydrogen production process in a circulating fluidized bed in Chinese patent CN106629600A, in which the reforming catalyst/adsorbent is recycled in a fluidized bed reactor and regenerator. .
锂化合物(如Li 2ZrO 3，Li 4SiO 4)、水滑石类(如Mg 6Al 2(OH) 16[CO 3]·4H 2O/K 2CO 3)和CaO等都是目前常用的CO 2吸附剂。但是其中锂化合物吸附容量差，水滑石类吸附速度太慢，因此不适合应用于工业上大规模吸附CO 2。而CaO则因具有吸附容量高、吸附速度快的优点而成为目前公认的高温CO 2吸附的合适吸附剂(Esther Ochoa-Fernández et al.Green Chem.,2007,9:654-662)。但是，CaO型吸附剂在使用过程中面临的主要问题是经过多次吸附脱附的循环操作后稳定性较差，其吸附容量会随着吸附-脱附循环次数的增多而下降，文献报道：纯CaO粉末在经过10次的吸附-脱附循环后，其吸附容量下降了大约37％(Phromprasit J et al.Chem Eng J.2016,284:1212-1223)。这是由于CaO颗粒不可避免的烧结和结块而造成的。 Lithium compounds (such as Li 2 ZrO 3 , Li 4 SiO 4 ), hydrotalcites (such as Mg 6 Al 2 (OH) 16 [CO 3 ]·4H 2 O/K 2 CO 3 ), and CaO are commonly used at present. CO 2 adsorbent. However, the lithium compound has a poor adsorption capacity, and the hydrotalcite adsorption rate is too slow, so it is not suitable for industrial large-scale adsorption of CO 2 . CaO, as it has the advantages of high adsorption capacity and fast adsorption speed, has become a suitable adsorbent for high-temperature CO 2 adsorption (Esther Ochoa-Fernández et al. Green Chem., 2007, 9: 654-662). However, the main problem faced by CaO-type adsorbents in the process of use is that after repeated cycles of adsorption and desorption, the stability is poor, and the adsorption capacity decreases with the increase of the number of adsorption-desorption cycles. The adsorption capacity of the pure CaO powder decreased by about 37% after 10 cycles of adsorption-desorption (Phromprasit J et al. Chem Eng J. 2016, 284: 1212-1223). This is due to the inevitable sintering and agglomeration of CaO particles.
综上所述，开发出高稳定性的、具有高耐磨强度的、易流化的球型高温CaO吸附剂颗粒对于吸附增强型制氢技术是至关重要的。目前，研究者们普遍采用的方法是在CaO中掺杂合适的惰性金属来抑制其烧结，提高其热稳定性。Janewit Phromprasit等在CaO悬浮液中分别加入相当于重量百分含量20％的Al 2O 3溶胶，搅拌干燥焙烧后得到粉末状的CO 2吸附剂，该吸附剂经过10次的循环吸附-脱附试验后，吸附容量下降约6.4％(Internationaljournal of hydrogen energy,2016.41:7318-7331)；在中国专利CN103657582A中，发明人通过在破碎的碳酸钙矿石粉末中加入钒酸盐和铝酸盐粉剂和去离子水制成泥浆状产品，再经过干燥、煅烧即可得到一种改进型CaO吸附剂；中国专利CN102784630A介绍的一种钙基CO 2吸附剂的制备方法是：首先把钙前驱体、惰性载体前驱体以及溶剂混合均匀后，采用喷雾干燥机对混合液进行干燥造粒得到的固体物，再经焙烧即得到钙基吸附剂；中国专利(CN103962087A)公开了一种表面包覆改性的纳米CaO基CO 2吸附剂，其表面的包覆层包括Al 2O 3、Ca 12Al 14O 33、MgO中的至少一种，采用的方法是先把纳米碳酸钙颗粒、醇类溶剂、包覆原料以及分散剂、粘结剂等搅拌均匀后，再经过成型、干燥、煅烧后得到纳米CaO基CO 2吸附剂。 In summary, the development of high-stability, high-abrasion, easily fluidized spherical high-temperature CaO sorbent particles is critical for adsorption-enhanced hydrogen production technology. At present, the method commonly used by researchers is to dope the CaO with a suitable inert metal to inhibit its sintering and improve its thermal stability. Janewit Phromprasit et al. added 20% by weight of Al 2 O 3 sol to the CaO suspension, and dried and calcined to obtain a powdered CO 2 adsorbent. The adsorbent was subjected to 10 cycles of adsorption-desorption. After the test, the adsorption capacity decreased by about 6.4% (International journal of hydrogen energy, 2016.41: 7318-7331); in Chinese patent CN103657582A, the inventors added vanadate and aluminate powder to the broken calcium carbonate ore powder and Ionized water is made into a slurry product, and then dried and calcined to obtain an improved CaO adsorbent; a calcium-based CO 2 adsorbent introduced by Chinese patent CN102784630A is prepared by firstly introducing a calcium precursor and an inert carrier. After the precursor and the solvent are uniformly mixed, the solid obtained by drying and granulating the mixed liquid by a spray dryer is calcined to obtain a calcium-based adsorbent; Chinese Patent (CN103962087A) discloses a surface-coated modified nanometer. CaO-based CO 2 adsorbent surface coating layer comprising Al 2 O 3, Ca 12 Al 14 O 33, MgO , at least one of the method used is to first nanocarbon Calcium particles, an alcohol solvent, a dispersant and a coating material, adhesive or the like after mixing, and then after molding, drying and calcining the nano-CaO-yl CO 2 adsorbent.
以上这些方法中均是采用碳酸钙原料与掺杂的原料经过混合成浆料后，再采用喷雾造粒或其他成型的方法，得到改性的吸附剂颗粒；过程繁琐，且涉及到各种溶液和溶剂的后处理，最重要的是采用此类方法得到的吸附剂产品很难在强度、耐磨度以及颗粒形 貌方面达到循环流化床工艺的要求。In the above methods, the calcium carbonate raw material and the doped raw material are mixed into a slurry, and then the sprayed granulation or other molding method is used to obtain the modified adsorbent particles; the process is cumbersome and involves various solutions. With the post-treatment of the solvent, the most important thing is that the adsorbent product obtained by such a method is difficult to meet the requirements of the circulating fluidized bed process in terms of strength, wear resistance and particle morphology.
发明内容Summary of the invention
本发明的目的就是要提供一种氧化钙基高温CO 2吸附剂及其制备方法，该吸附剂具有高耐磨性、高热稳定性及高活性。 The object of the present invention is to provide a calcium oxide-based high-temperature CO 2 adsorbent and a preparation method thereof, which have high wear resistance, high heat stability and high activity.
为实现上述目的，本发明采用的技术方案是：一种氧化钙基高温CO 2吸附剂，包括载体M和负载在所述载体M上的主活性组分CaO，其特征在于：所述载体M上还负载有结构稳定助剂A；所述氧化钙基高温CO 2吸附剂的组成通式为： In order to achieve the above object, the technical solution adopted by the present invention is: a calcium oxide-based high-temperature CO 2 adsorbent comprising a carrier M and a main active component CaO supported on the carrier M, characterized in that the carrier M The structure is further loaded with a structural stabilizer A; the composition of the calcium oxide-based high-temperature CO 2 adsorbent is:
x CaO·a A·(100-x-a)Mx CaO·a A·(100-x-a)M
其中，x为CaO的质量百分数，a为A的质量百分数，5％≤x≤60％，0.1％≤a≤50％。Where x is the mass percentage of CaO, a is the mass percentage of A, 5% ≤ x ≤ 60%, and 0.1% ≤ a ≤ 50%.
进一步地，所述结构稳定助剂A为Mo、Mg、V、Ti、Fe、Co、Zr、Cu、Sr、Ce、La和W中一种或几种的金属和/或金属氧化物。Further, the structural stabilizing aid A is a metal and/or a metal oxide of one or more of Mo, Mg, V, Ti, Fe, Co, Zr, Cu, Sr, Ce, La and W.
进一步地，所述载体M为Al 2O 3、SiO 2、镁铝尖晶石、分子筛中一种或几种的混合物。 Further, the carrier M is a mixture of one or more of Al 2 O 3 , SiO 2 , magnesium aluminum spinel, molecular sieve.
本发明还提供上述氧化钙基高温CO 2吸附剂的制备方法，将所述结构稳定助剂A和CaO通过分步浸渍法或共浸渍法负载在所述载体M上，老化处理后在80～200℃下干燥，再在400～1000℃下焙烧，即得所述氧化钙基高温CO 2吸附剂。 The present invention also provides a method for preparing the above calcium oxide-based high-temperature CO 2 adsorbent, wherein the structural stabilizer A and CaO are supported on the carrier M by a step impregnation method or a co-impregnation method, and after aging treatment at 80 to The calcium oxide-based high-temperature CO 2 adsorbent is obtained by drying at 200 ° C and calcining at 400 to 1000 ° C.
作为优选方案之一，上述氧化钙基高温CO 2吸附剂的制备方法，所述结构稳定助剂A和CaO通过分歩浸渍法负载在所述载体M上：包括以下步骤： As one of the preferred embodiments, in the preparation method of the above calcium oxide-based high-temperature CO 2 adsorbent, the structural stabilizer A and CaO are supported on the carrier M by a bifurcation impregnation method, including the following steps:
1)将结构稳定助剂A的金属盐溶于水，制得浸渍液Ⅰ；1) The metal salt of the structural stabilizing aid A is dissolved in water to prepare an immersion liquid I;
2)将载体M和浸渍液Ⅰ混合，进行浸渍和老化处理，然后在80～120℃下干燥，再在400～1000℃下焙烧，得到改性载体；2) mixing the carrier M and the immersion liquid I, performing impregnation and aging treatment, then drying at 80 to 120 ° C, and then firing at 400 to 1000 ° C to obtain a modified carrier;
3)将钙前驱体溶于水，得到浸渍液Ⅱ；3) dissolving the calcium precursor in water to obtain an immersion liquid II;
4)将所述改性载体与浸渍液Ⅱ混合，进行浸渍和老化处理，然后在100～200℃下干燥，再在600～1000℃下焙烧，即得所述氧化钙基高温CO 2吸附剂。 4) mixing the modified carrier with the impregnation liquid II, performing impregnation and aging treatment, and then drying at 100 to 200 ° C, and then calcining at 600 to 1000 ° C to obtain the calcium oxide-based high-temperature CO 2 adsorbent. .
进一步地，所述步骤2)中，老化时间为0.5～8小时，老化温度为10～90℃；所述步骤4)中，老化时间为0.5～8小时，老化温度为10～90℃。Further, in the step 2), the aging time is 0.5 to 8 hours, and the aging temperature is 10 to 90 ° C; in the step 4), the aging time is 0.5 to 8 hours, and the aging temperature is 10 to 90 ° C.
进一步地，所述步骤2)中，干燥温度为80～120℃，干燥时间为1～24小时；焙烧 温度为400～1000℃，焙烧时间为0.1～6小时。Further, in the step 2), the drying temperature is 80 to 120 ° C, the drying time is 1 to 24 hours, the baking temperature is 400 to 1000 ° C, and the baking time is 0.1 to 6 hours.
进一步地，所述步骤4)中，干燥温度为100～200℃，干燥时间为1～24小时；焙烧温度为500～1000℃，焙烧时间为0.1～5小时。Further, in the step 4), the drying temperature is 100 to 200 ° C, the drying time is 1 to 24 hours, the baking temperature is 500 to 1000 ° C, and the baking time is 0.1 to 5 hours.
作为优选方案之二，上述氧化钙基高温CO 2吸附剂的制备方法，所述结构稳定助剂A和CaO通过共浸渍法负载在所述载体M上：包括以下步骤： As a second preferred embodiment, in the above method for preparing a calcium oxide-based high-temperature CO 2 adsorbent, the structural stabilizer A and CaO are supported on the carrier M by a co-impregnation method: the following steps are included:
1)将结构稳定助剂A的金属盐和钙前驱体一起溶于水，制得混合浸渍液；1) dissolving the metal salt of the structural stabilizing aid A together with the calcium precursor to prepare a mixed impregnation liquid;
2)将载体M和混合浸渍液混合，进行浸渍和老化处理，然后在80～200℃下干燥，再在400～1000℃下焙烧，即得所述氧化钙基高温CO 2吸附剂。 2) The carrier M and the mixed impregnation liquid are mixed, subjected to impregnation and aging treatment, and then dried at 80 to 200 ° C, and then calcined at 400 to 1000 ° C to obtain the calcium oxide-based high-temperature CO 2 adsorbent.
进一步地，所述步骤2)中，老化时间为1～8小时，老化温度为10～90℃；干燥温度为80～200℃，干燥时间为1～24小时；焙烧温度为400～1000℃，焙烧时间为0.5～6小时。Further, in the step 2), the aging time is 1 to 8 hours, the aging temperature is 10 to 90 ° C, the drying temperature is 80 to 200 ° C, the drying time is 1 to 24 hours, and the baking temperature is 400 to 1000 ° C. The baking time is 0.5 to 6 hours.
上述两种优选方案中：Among the above two preferred solutions:
所述结构稳定助剂A的金属盐为Ce(NO 3) 3、Mg(NO 3) 2、La(NO 3) 3、ZrO(NO 3) 2、Fe(NO 3) 2、TiO(SO 4) 2、葡萄糖酸镁和醋酸镧中的一种或几种 The metal salts of the structural stabilizing aid A are Ce(NO 3 ) 3 , Mg(NO 3 ) 2 , La(NO 3 ) 3 , ZrO(NO 3 ) 2 , Fe(NO 3 ) 2 , TiO(SO 4 2, one or more of magnesium gluconate and barium acetate
所述钙前驱体为硝酸钙、醋酸钙、葡萄糖酸钙和碳酸氢钙中的一种或几种。The calcium precursor is one or more of calcium nitrate, calcium acetate, calcium gluconate, and calcium hydrogencarbonate.
与现有技术相比，本发明具有如下优点：Compared with the prior art, the present invention has the following advantages:
其一，本发明得到的氧化钙基高温CO 2吸附剂具有高耐磨性、高热稳定性及高活性。该吸附剂在烃类化合物或含碳的原料的水蒸气转化制氢过程中，通过吸附转化产物CO 2，促进转化反应向生成氢气的方向进行，吸附剂能够在有利条件下，在再生反应器中分解，恢复CO 2吸附能力，吸附剂在40个吸附脱附循环后对CO 2的吸附能力的损失不超过20％，特定条件下甚至不超过10％；该吸附剂的磨损率为0.1～1wt％/小时，特定条件下不超过0.5wt％/小时。 First, the calcium oxide-based high-temperature CO 2 adsorbent obtained by the present invention has high wear resistance, high heat stability and high activity. The adsorbent can promote the conversion reaction to the hydrogen generation by adsorbing the conversion product CO 2 during the steam reforming hydrogen production process of the hydrocarbon compound or the carbonaceous raw material, and the adsorbent can be in the regeneration reactor under favorable conditions. decomposition, CO 2 adsorption capacity restored, the adsorbent in the adsorption-desorption cycles 40 loss of CO 2 adsorption capacity of less than 20%, under certain conditions even no more than 10%; the adsorbent of 0.1 to wear 1 wt% / hour, no more than 0.5 wt% / hour under certain conditions.
其二，本发明得到的氧化钙基高温CO 2吸附剂中，结构稳定助剂A通过形成的金属氧化物掺杂在CaO基质中，并抑制CaO的迁移，既可提高CaO在载体M表面的分散性，同时又可抑制CaO的迁移，从而提高其热稳定性，保持其较高的吸附容量和吸附速率。 Secondly, in the calcium oxide-based high-temperature CO 2 adsorbent obtained by the present invention, the structural stabilizing aid A is doped in the CaO matrix by the formed metal oxide, and inhibits the migration of CaO, thereby improving the CaO on the surface of the carrier M. Dispersibility, while inhibiting the migration of CaO, thereby improving its thermal stability and maintaining its high adsorption capacity and adsorption rate.
其三，本发明得到的氧化钙基高温CO 2吸附剂中，载体M是具有一定强度和耐磨性能的符合特定循环流化床流化特性的球型载体，CaO负载其上，在不影响其对CO 2的吸附性能的基础上，还增强了CaO颗粒的有效表面积，提供了合适的孔径结构，提高了 CaO的机械强度和抗摩损能力，同时还与助剂一体提高了CaO的热稳定性。 Third, in the calcium oxide-based high-temperature CO 2 adsorbent obtained by the present invention, the carrier M is a spherical carrier having a certain strength and wear resistance conforming to the fluidization characteristics of a specific circulating fluidized bed, and the CaO is loaded thereon without affecting On the basis of its adsorption performance to CO 2 , it also enhances the effective surface area of CaO particles, provides a suitable pore structure, improves the mechanical strength and anti-wear ability of CaO, and simultaneously improves the heat of CaO with additives. stability.
其四，本发明制得的氧化钙基高温CO 2吸附剂流化性好，耐磨性好，强度高，符合吸附增强型循环流化床水蒸汽重整制氢工艺的要求，从而降低了研发及生产风险和成本。 Fourthly, the calcium oxide-based high-temperature CO 2 adsorbent prepared by the invention has good fluidization property, good wear resistance and high strength, and meets the requirements of the adsorption-enhanced circulating fluidized bed steam reforming hydrogen production process, thereby reducing the requirement R&D and production risks and costs.
其五，本发明可采用分步浸渍，也可采用混合浸渍制备吸附剂，制备方法简单，无废水产生，环境友好，易重复，特别适合于大规模工业生产及应用。Fifthly, the invention can adopt the stepwise impregnation, or the mixed impregnation to prepare the adsorbent, the preparation method is simple, no waste water is produced, environment friendly, easy to repeat, and is particularly suitable for large-scale industrial production and application.
附图说明DRAWINGS
图1为实施例1～5中CO 2吸附剂的吸附容量与循环次数的关系图。 Fig. 1 is a graph showing the relationship between the adsorption capacity of the CO 2 adsorbent and the number of cycles in Examples 1 to 5.
具体实施方式Detailed ways
下面结合附图和具体实施例对本发明作进一步的详细说明，便于更清楚地了解本发明，但它们不对本发明构成限定。The present invention will be further described in detail with reference to the accompanying drawings and specific embodiments.
在实施例1～5中，采用热重分析仪来测试各实施例制备的氧化钙基高温CO 2吸附剂的循环吸附-脱附CO 2能力的稳定性，测试方法为：称取大约15mg样品置于样品钵中，在高纯N 2下升温至800度，维持5分钟(5分钟重量不再变化，说明样品中的碳酸钙已分解完毕)，降温至650度，此时，切换气体到混合气氛下(5％CO 2+高纯氮气)进行吸附，吸附20分钟后，切换气体到高纯N 2，升温至800度，维持5分钟(样品重量不再变化)，接着再降温到650度，进行CO 2的吸附，如此循环40次，测试样品的热稳定性能。 In Examples 1 to 5, the thermogravimetric analyzer was used to test the stability of the cyclic adsorption-desorption CO 2 ability of the calcium oxide-based high-temperature CO 2 adsorbent prepared in each example by the method of weighing about 15 mg of the sample. Place in the sample crucible, heat up to 800 degrees under high purity N 2 for 5 minutes (the weight does not change in 5 minutes, indicating that the calcium carbonate in the sample has been decomposed), and cool down to 650 degrees. At this time, switch the gas to Adsorption was carried out under a mixed atmosphere (5% CO 2 + high purity nitrogen). After adsorption for 20 minutes, the gas was switched to high purity N 2 , and the temperature was raised to 800 °C for 5 minutes (the sample weight no longer changed), and then the temperature was lowered to 650. Degree, the adsorption of CO 2 was carried out, and the cycle was performed 40 times to test the thermal stability of the sample.
在本发明中，采用磨损仪，按照中国石油化工股份有限公司催化剂分公司企业标准Q/TSH 3490 909-2006直管法催化裂化催化剂磨损指数的测定来评价吸附剂的耐磨性能。In the present invention, the wear resistance of the adsorbent is evaluated by using a wear meter in accordance with the measurement of the wear index of the catalytic cracking catalyst of the straight pipe method of the China National Petroleum Corporation Co., Ltd. Catalyst Branch Company Standard Q/TSH 3490 909-2006.
实施例1Example 1
(1)浸渍液Ⅰ的制备：称取0.772g的Ce(NO 3) 3·6H 2O和0.388g的La(NO 3) 3·6H 2O，溶于6.6ml的去离子水中，搅拌溶解； (1) Preparation of the immersion liquid I: 0.772 g of Ce(NO 3 ) 3 ·6H 2 O and 0.388 g of La(NO 3 ) 3 ·6H 2 O were weighed and dissolved in 6.6 ml of deionized water, stirred and dissolved. ;
(2)称取已筛选过的高耐磨性能的γ-Al 2O 3载体8.55g，与上述的浸渍液Ⅰ混合后，采用超声波震荡法在60℃等体积浸渍、老化2小时后，在110℃干燥12小时后，再在600℃焙烧4小时，即得到Ce 2O 3/La 2O 3改性的γ-Al 2O 3载体； (2) 8.55 g of the γ-Al 2 O 3 carrier with high abrasion resistance which has been screened was weighed, mixed with the above-mentioned immersion liquid I, and then impregnated and immersed in an equal volume at 60 ° C for 2 hours by ultrasonic vibration method. After drying at 110 ° C for 12 hours, and then calcining at 600 ° C for 4 hours, the Ce 2 O 3 /La 2 O 3 modified γ-Al 2 O 3 carrier is obtained;
(3)浸渍液Ⅱ的制备：称取4.214g的Ca(NO 3) 3·4H 2O，溶于5.4ml的去离子水中， 搅拌溶解； (3) Preparation of the immersion liquid II: 4.214 g of Ca(NO 3 ) 3 · 4H 2 O was weighed, dissolved in 5.4 ml of deionized water, and dissolved by stirring;
(4)将步骤(2)中得到的Ce 2O 3/La 2O 3改性的γ-Al 2O 3载体与浸渍液Ⅱ混合后，采用超声波震荡法在75℃等体积浸渍、老化4小时后，在150℃下干燥12h后，再在800℃下焙烧4h，即可得到组成为10％CaO·3％Ce 2O 3·1.5％La 2O 3·85.5％γ-Al 2O 3的高耐磨高稳定的氧化钙基高温CO 2吸附剂。 (4) The Ce 2 O 3 /La 2 O 3 modified γ-Al 2 O 3 carrier obtained in the step (2) is mixed with the immersion liquid II, and then impregnated and aged at 75 ° C by ultrasonic vibration method. After the hour, after drying at 150 ° C for 12 h and then at 800 ° C for 4 h, the composition is 10% CaO · 3% Ce 2 O 3 · 1.5% La 2 O 3 · 85.5% γ-Al 2 O 3 High wear resistance and high stability calcium oxide based high temperature CO 2 adsorbent.
该吸附剂对CO 2的吸附稳定性在热重分析仪上的测试，结果如图1显示：在经过40个吸附-脱附循环测试后，其吸附容量仅下降8.2％。 The adsorption stability of the adsorbent to CO 2 was tested on a thermogravimetric analyzer. The results are shown in Figure 1. After 40 adsorption-desorption cycles, the adsorption capacity decreased by only 8.2%.
磨损仪的测定结果显示该吸附剂的磨损率为0.65wt％/小时。The measurement results of the wear meter showed that the wear rate of the adsorbent was 0.65 wt% / hour.
实施例2Example 2
(1)浸渍液Ⅰ的制备：称取3.031g的Mg(NO 3) 3·6H 2O溶于5.5ml的去离子水中，搅拌溶解； (1) Preparation of the immersion liquid I: 3.031 g of Mg(NO 3 ) 3 ·6H 2 O was weighed and dissolved in 5.5 ml of deionized water, and stirred and dissolved;
(2)称取已筛选过的高耐磨性能的γ-Al 2O 3载体7.5g，与上述的浸渍液Ⅰ混合后，采用超声波震荡法等体积在60℃浸渍、老化2小时后，在110℃干燥8小时后，再在600℃焙烧2小时，即得到MgO改性的γ-Al 2O 3载体； (2) Weigh 7.5 g of the γ-Al 2 O 3 carrier with high abrasion resistance that has been screened, and mix it with the above-mentioned immersion liquid I, and then immerse it in an equal volume at 60 ° C for 2 hours by ultrasonic vibration method. After drying at 110 ° C for 8 hours, and then calcined at 600 ° C for 2 hours, the MgO modified γ-Al 2 O 3 carrier is obtained;
(3)浸渍液Ⅱ的制备：称取5.643的醋酸钙，溶于6.8ml的去离子水中，搅拌溶解；(3) Preparation of the immersion liquid II: Weigh 5.437 of calcium acetate, dissolve in 6.8 ml of deionized water, stir and dissolve;
(4)将步骤(2)中得到的MgO改性的γ-Al 2O 3载体与浸渍液Ⅱ混合后，采用超声波震荡法在70℃等体积浸渍、老化4小时后，在110℃下干燥12h后，再在800℃下焙烧3h，即可得到组成为20％CaO·5％MgO·75％γ-Al 2O 3的高耐磨高稳定的氧化钙基高温CO 2吸附剂。 (4) The MgO-modified γ-Al 2 O 3 carrier obtained in the step (2) is mixed with the immersion liquid II, and then immersed in an equal volume at 70 ° C for 4 hours by ultrasonic vibration, and then dried at 110 ° C. After 12 h, it was calcined at 800 ° C for 3 h to obtain a highly wear-resistant and high-stability calcium oxide-based high-temperature CO 2 adsorbent having a composition of 20% CaO·5% MgO·75% γ-Al 2 O 3 .
该吸附剂对CO 2的吸附稳定性在热重分析仪上的测试，结果如图1显示：在经过40个吸附-脱附循环测试后，其吸附容量仅下降10.5％。 The adsorption stability of the adsorbent to CO 2 was tested on a thermogravimetric analyzer. The results are shown in Figure 1. After 40 adsorption-desorption cycles, the adsorption capacity decreased by only 10.5%.
磨损仪的测定结果显示该吸附剂的磨损率为0.84wt％/小时。The measurement results of the wear meter showed that the wear rate of the adsorbent was 0.84% by weight/hour.
实施例3Example 3
(1)浸渍液Ⅰ的制备：称取2.056g的葡萄糖酸镁和0.258g的La(NO 3) 3·6H 2O溶于6.8ml的去离子水中，搅拌溶解； (1) Preparation of the immersion liquid I: Weigh 2.056 g of magnesium gluconate and 0.258 g of La(NO 3 ) 3 ·6H 2 O dissolved in 6.8 ml of deionized water, and stir to dissolve;
(2)称取已筛选过的高耐磨性能的γ-Al 2O 3载体7.7g，与上述的浸渍液Ⅰ混合后，采用超声波震荡法在60℃等体积浸渍老化4小时后，再在100℃干燥10小时后，再在800℃焙烧2小时，即得到MgO/La 2O 3改性的γ-Al 2O 3载体； (2) Weighing 7.7 g of the highly wear-resistant γ-Al 2 O 3 carrier, which was mixed with the above-mentioned immersion liquid I, and then immersed in an equal volume of 60 ° C for 4 hours by ultrasonic vibration method, and then After drying at 100 ° C for 10 hours, and then calcined at 800 ° C for 2 hours, to obtain a MgO / La 2 O 3 modified γ-Al 2 O 3 carrier;
(3)浸渍液Ⅱ的制备：称取5.643g醋酸钙[Ca(CH 3COO) 2]，溶于6.8ml的去离子水中，搅拌溶解； (3) Preparation of the immersion liquid II: Weigh 5.643 g of calcium acetate [Ca(CH 3 COO) 2 ], dissolve it in 6.8 ml of deionized water, and stir to dissolve;
(4)将步骤(2)中得到的MgO/La 2O 3改性的γ-Al 2O 3载体与浸渍液Ⅱ混合后，采用超声波震荡法在60℃等体积浸渍老化6小时后，在200℃下干燥10h后，再在800℃下焙烧4h，即可得到组成为20％CaO·2％MgO·1％La 2O 3·77％γ-Al 2O 3的高耐磨高稳定的氧化钙基高温CO 2吸附剂。 (4) The MgO/La 2 O 3 modified γ-Al 2 O 3 carrier obtained in the step (2) is mixed with the immersion liquid II, and then immersed and immersed in an equal volume at 60 ° C for 6 hours by an ultrasonic vibration method. After drying at 200 ° C for 10 h and then calcining at 800 ° C for 4 h, a high wear resistance and high stability of 20% CaO·2% MgO·1% La 2 O 3 ·77% γ-Al 2 O 3 can be obtained. Calcium oxide based high temperature CO 2 adsorbent.
该吸附剂对CO 2的吸附稳定性在热重分析仪上的测试，结果如图1显示：在经过40个吸附-脱附循环测试后，其吸附容量仅下降6.3％。 The adsorption stability of the adsorbent to CO 2 was tested on a thermogravimetric analyzer. The results are shown in Figure 1. After 40 adsorption-desorption cycles, the adsorption capacity decreased by only 6.3%.
磨损仪的测定结果显示该吸附剂的磨损率为0.31wt％/小时。The measurement results of the wear meter showed that the wear rate of the adsorbent was 0.31% by weight/hour.
实施例4Example 4
(1)浸渍液Ⅰ的制备：称取0.281g的ZrO(NO 3) 2溶于5.5ml的去离子水中，搅拌溶解； (1) Preparation of the immersion liquid I: Weigh 0.281 g of ZrO(NO 3 ) 2 dissolved in 5.5 ml of deionized water, and stir to dissolve;
(2)称取已筛选过的高耐磨性能的SiO 2载体8.35g，与上述的浸渍液Ⅰ混合后，采用超声波震荡法在50℃等体积浸渍、老化4小时后，在在120℃干燥8小时后，再在800℃焙烧2小时，即得到ZrO 2改性的SiO 2载体； (2) 8.35 g of the SiO 2 support with high abrasion resistance which has been screened was weighed, mixed with the above-mentioned immersion liquid I, and then immersed in an equal volume at 50 ° C for 4 hours by ultrasonic vibration method, and then dried at 120 ° C. After 8 hours, calcination was further carried out at 800 ° C for 2 hours to obtain a ZrO 2 modified SiO 2 support;
(3)浸渍液Ⅱ的制备：称取11.518g葡萄糖酸钙溶于5.5ml的去离子水中，搅拌溶解；(3) Preparation of the immersion liquid II: 11.518 g of calcium gluconate was dissolved in 5.5 ml of deionized water and stirred to dissolve;
(4)将步骤(2)中得到的ZrO 2改性的SiO 2载体与浸渍液Ⅱ混合后，采用超声波震荡法在60℃等体积浸渍、老化4小时后，再在100℃下干燥10h后，再在800℃下焙烧4h，即可得到组成为15％CaO·1.5％ZrO 2·83.5％SiO 2的高耐磨高稳定的氧化钙基高温CO 2吸附剂。 (4) The ZrO 2 modified SiO 2 support obtained in the step (2) is mixed with the immersion liquid II, and then immersed in an equal volume at 60 ° C for 4 hours by an ultrasonic vibration method, and then dried at 100 ° C for 10 hours. After calcination at 800 ° C for 4 h, a highly wear-resistant and highly stable calcium oxide-based high-temperature CO 2 adsorbent having a composition of 15% CaO·1.5% ZrO 2 ·83.5% SiO 2 was obtained.
该吸附剂对CO 2的吸附稳定性在热重分析仪上的测试，结果如图1显示：在经过40个吸附-脱附循环测试后，其吸附容量仅下降11.7％。 The adsorption stability of the adsorbent to CO 2 was tested on a thermogravimetric analyzer. The results are shown in Figure 1. After 40 adsorption-desorption cycles, the adsorption capacity decreased by only 11.7%.
磨损仪的测定结果显示该吸附剂的磨损率为0.95wt％/小时。The measurement results of the wear meter showed that the wear rate of the adsorbent was 0.95 wt% / hour.
实施例5Example 5
(1)混合浸渍液的制备：称取0.281g的ZrO(NO 3) 2和11.518g葡萄糖酸钙溶于5.5ml的去离子水中，搅拌溶解； (1) Preparation of mixed impregnation liquid: Weigh 0.281 g of ZrO(NO 3 ) 2 and 11.518 g of calcium gluconate dissolved in 5.5 ml of deionized water, and stir to dissolve;
(2)称取已筛选过的高耐磨性能的5A分子筛8.35g，与上述的混合浸渍液混合后， 采用超声波震荡法在80℃等体积浸渍、老化4小时后，在在120℃干燥12小时后，再在800℃焙烧2小时，即可得到组成为15％CaO·1.5％ZrO 2·83.5％分子筛的高耐磨高稳定的氧化钙基高温CO 2吸附剂。 (2) Weigh 8.35g of the highly abrasion-resistant 5A molecular sieve, and mix it with the above mixed impregnation solution, then immerse it in an equal volume at 80 °C for 4 hours by ultrasonic vibration method, and then dry at 120 °C. After an hour, it was calcined at 800 ° C for 2 hours to obtain a highly wear-resistant and highly stable calcium oxide-based high-temperature CO 2 adsorbent having a composition of 15% CaO·1.5% ZrO 2 ·83.5% molecular sieve.
该吸附剂对CO 2的吸附稳定性在热重分析仪上的测试，结果如图1显示：在经过40个吸附-脱附循环测试后，其吸附容量仅下降16.2％。 The adsorption stability of the adsorbent to CO 2 was tested on a thermogravimetric analyzer. The results are shown in Figure 1. After 40 adsorption-desorption cycles, the adsorption capacity decreased by only 16.2%.
磨损仪的测定结果显示该吸附剂的磨损率为1.2wt％/小时。The measurement results of the wear meter showed that the wear rate of the adsorbent was 1.2 wt% / hour.
实施例6Example 6
(1)混合浸渍液的制备：称取0.121g的TiO(SO 4) 2和7.869g一水醋酸钙溶于6.7ml的去离子水中，搅拌溶解； (1) Preparation of mixed impregnation liquid: 0.121 g of TiO(SO 4 ) 2 and 7.869 g of calcium acetate monohydrate were weighed and dissolved in 6.7 ml of deionized water, and stirred to dissolve;
(2)称取已筛选过的高耐磨性能的γ-Al 2O 3载体10.0g，与上述的混合浸渍液混合后，采用超声波震荡法在70℃等体积浸渍老化6小时后，再在120℃干燥12小时后，再在650℃焙烧4小时，即得到组成为20％CaO·0.3％TiO 2·79.7％γ-Al 2O 3的高耐磨高稳定的氧化钙基高温CO 2吸附剂。 (2) Weigh 10.0 g of the γ-Al 2 O 3 carrier with high abrasion resistance, and mix it with the above mixed immersion liquid, and then immerse it in an equal volume of 70 ° C for 6 hours by ultrasonic vibration method, and then After drying at 120 ° C for 12 hours, and then baking at 650 ° C for 4 hours, a high wear-resistant and high-stability calcium oxide-based high-temperature CO 2 adsorption having a composition of 20% CaO·0.3% TiO 2 ·79.7% γ-Al 2 O 3 is obtained . Agent.
该吸附剂对CO 2的吸附稳定性在热重分析仪上的测试，结果如图1显示：在经过40个吸附-脱附循环测试后，其吸附容量仅下降9.5％。 The adsorption stability of the adsorbent to CO 2 was tested on a thermogravimetric analyzer. The results are shown in Figure 1. After 40 adsorption-desorption cycles, the adsorption capacity decreased by only 9.5%.
磨损仪的测定结果显示该吸附剂的磨损率为1.1wt％/小时。The measurement results of the wear meter showed that the wear rate of the adsorbent was 1.1 wt% / hour.

Claims (12)

  1. 一种氧化钙基高温CO 2吸附剂，包括载体M和负载在所述载体M上的主活性组分CaO，其特征在于：所述载体M上还负载有结构稳定助剂A；所述氧化钙基高温CO 2吸附剂的组成通式为： A calcium oxide-based high-temperature CO 2 adsorbent comprising a carrier M and a main active component CaO supported on the carrier M, wherein the carrier M is further loaded with a structural stabilizing aid A; the oxidation The composition of the calcium-based high-temperature CO 2 adsorbent is:
    x CaO·a A·(100-x-a)Mx CaO·a A·(100-x-a)M
    其中，x为CaO的质量百分数，a为A的质量百分数，5％≤x≤60％，0.1％≤a≤50％。Where x is the mass percentage of CaO, a is the mass percentage of A, 5% ≤ x ≤ 60%, and 0.1% ≤ a ≤ 50%.
  2. 根据权利要求1所述氧化钙基高温CO 2吸附剂，其特征在于：所述结构稳定助剂A为Mo、Mg、V、Ti、Fe、Co、Zr、Cu、Sr、Ce、La和W中一种或几种的金属和/或金属氧化物。 The calcium oxide-based high-temperature CO 2 adsorbent according to claim 1, wherein said structural stabilizer A is Mo, Mg, V, Ti, Fe, Co, Zr, Cu, Sr, Ce, La and W One or more of the metals and/or metal oxides.
  3. 根据权利要求1所述氧化钙基高温CO 2吸附剂，其特征在于：所述载体M为Al 2O 3、SiO 2、镁铝尖晶石、分子筛中一种或几种的混合物。 The calcium oxide-based high-temperature CO 2 adsorbent according to claim 1, wherein the carrier M is a mixture of one or more of Al 2 O 3 , SiO 2 , magnesium aluminum spinel, and molecular sieve.
  4. 一种权利要求1所述氧化钙基高温CO 2吸附剂的制备方法，其特征在于：将所述结构稳定助剂A和CaO通过分步浸渍法或共浸渍法负载在所述载体M上，老化处理后在80～200℃下干燥，再在400～1000℃下焙烧，即得所述氧化钙基高温CO 2吸附剂。 A method for preparing a calcium oxide-based high-temperature CO 2 adsorbent according to claim 1, wherein the structural stabilizer A and CaO are supported on the carrier M by a stepwise impregnation method or a co-impregnation method. After the aging treatment, it is dried at 80 to 200 ° C, and then calcined at 400 to 1000 ° C to obtain the calcium oxide-based high-temperature CO 2 adsorbent.
  5. 根据权利要求4所述氧化钙基高温CO 2吸附剂的制备方法，其特征在于：所述结构稳定助剂A和CaO通过分歩浸渍法负载在所述载体M上：包括以下步骤： The method for preparing a calcium oxide-based high-temperature CO 2 adsorbent according to claim 4, wherein the structural stabilizer A and CaO are supported on the carrier M by a bifurcation impregnation method, comprising the steps of:
    1)将结构稳定助剂A的金属盐溶于水，制得浸渍液Ⅰ；1) The metal salt of the structural stabilizing aid A is dissolved in water to prepare an immersion liquid I;
    2)将载体M和浸渍液Ⅰ混合，进行浸渍和老化处理，然后在80～120℃下干燥，再在400～1000℃下焙烧，得到改性载体；2) mixing the carrier M and the immersion liquid I, performing impregnation and aging treatment, then drying at 80 to 120 ° C, and then firing at 400 to 1000 ° C to obtain a modified carrier;
    3)将钙前驱体溶于水，得到浸渍液Ⅱ；3) dissolving the calcium precursor in water to obtain an immersion liquid II;
    4)将所述改性载体与浸渍液Ⅱ混合，进行浸渍和老化处理，然后在100～200℃下干燥，再在600～1000℃下焙烧，即得所述氧化钙基高温CO 2吸附剂。 4) mixing the modified carrier with the impregnation liquid II, performing impregnation and aging treatment, and then drying at 100 to 200 ° C, and then calcining at 600 to 1000 ° C to obtain the calcium oxide-based high-temperature CO 2 adsorbent. .
  6. 根据权利要求4所述氧化钙基高温CO 2吸附剂的制备方法，其特征在于：所述结构稳定助剂A和CaO通过共浸渍法负载在所述载体M上：包括以下步骤： The method for preparing a calcium oxide-based high-temperature CO 2 adsorbent according to claim 4, wherein the structural stabilizer A and CaO are supported on the carrier M by a co-impregnation method, comprising the steps of:
    1)将结构稳定助剂A的金属盐和钙前驱体一起溶于水，制得混合浸渍液；1) dissolving the metal salt of the structural stabilizing aid A together with the calcium precursor to prepare a mixed impregnation liquid;
    2)将载体M和混合浸渍液混合，进行浸渍和老化处理，然后在80～200℃下干燥，再在400～1000℃下焙烧，即得所述氧化钙基高温CO 2吸附剂。 2) The carrier M and the mixed impregnation liquid are mixed, subjected to impregnation and aging treatment, and then dried at 80 to 200 ° C, and then calcined at 400 to 1000 ° C to obtain the calcium oxide-based high-temperature CO 2 adsorbent.
  7. 根据权利要求4或5或6所述氧化钙基高温CO 2吸附剂的制备方法，其特征在 于：所述结构稳定助剂A的金属盐为Ce(NO 3) 3、Mg(NO 3) 2、La(NO 3) 3、ZrO(NO 3) 2、Fe(NO 3) 2、TiO(SO 4) 2、葡萄糖酸镁和醋酸镧中的一种或几种。 The method for preparing a calcium oxide-based high-temperature CO 2 adsorbent according to claim 4 or 5 or 6, wherein the metal salt of the structural stabilizer A is Ce(NO 3 ) 3 , Mg(NO 3 ) 2 One or more of La(NO 3 ) 3 , ZrO(NO 3 ) 2 , Fe(NO 3 ) 2 , TiO(SO 4 ) 2, magnesium gluconate and cesium acetate.
  8. 根据权利要求5或6所述氧化钙基高温CO 2吸附剂的制备方法，其特征在于：所述钙前驱体为硝酸钙、醋酸钙、葡萄糖酸钙和碳酸氢钙中的一种或几种。 The method for preparing a calcium oxide-based high-temperature CO 2 adsorbent according to claim 5 or 6, wherein the calcium precursor is one or more of calcium nitrate, calcium acetate, calcium gluconate and calcium hydrogencarbonate. .
  9. 根据权利要求5所述氧化钙基高温CO 2吸附剂的制备方法，其特征在于：所述步骤2)中，老化时间为0.5～8小时，老化温度为10～90℃；所述步骤4)中，老化时间为0.5～8小时，老化温度为10～90℃。 The method for preparing a calcium oxide-based high-temperature CO 2 adsorbent according to claim 5, wherein in the step 2), the aging time is 0.5 to 8 hours, and the aging temperature is 10 to 90 ° C; The aging time is 0.5 to 8 hours, and the aging temperature is 10 to 90 °C.
  10. 根据权利要求5所述氧化钙基高温CO 2吸附剂的制备方法，其特征在于：所述步骤2)中，干燥温度为80～120℃，干燥时间为1～24小时；焙烧温度为400～1000℃，焙烧时间为0.1～6小时。 The method for preparing a calcium oxide-based high-temperature CO 2 adsorbent according to claim 5, wherein in the step 2), the drying temperature is 80 to 120 ° C, the drying time is 1 to 24 hours, and the baking temperature is 400 to The calcination time is 1000 to 6 hours and the calcination time is 0.1 to 6 hours.
  11. 根据权利要求5所述氧化钙基高温CO 2吸附剂的制备方法，其特征在于：所述步骤4)中，干燥温度为100～200℃，干燥时间为1～24小时；焙烧温度为500～1000℃，焙烧时间为0.1～5小时。 The method for preparing a calcium oxide-based high-temperature CO 2 adsorbent according to claim 5, wherein in the step 4), the drying temperature is 100 to 200 ° C, the drying time is 1 to 24 hours, and the baking temperature is 500 to The calcination time is 1000 to 5 hours and the calcination time is 0.1 to 5 hours.
  12. 根据权利要求6所述氧化钙基高温CO 2吸附剂的制备方法，其特征在于：所述步骤2)中，老化时间为1～8小时，老化温度为10～90℃；干燥温度为80～200℃，干燥时间为1～24小时；焙烧温度为400～1000℃，焙烧时间为0.5～6小时。 The method for preparing a calcium oxide-based high-temperature CO 2 adsorbent according to claim 6, wherein in the step 2), the aging time is 1 to 8 hours, the aging temperature is 10 to 90 ° C, and the drying temperature is 80 ～. The drying time is 1 to 24 hours at 200 ° C; the baking temperature is 400 to 1000 ° C, and the baking time is 0.5 to 6 hours.
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