CN105817198A - Method for preparing high-stability calcium oxide-based adsorbent - Google Patents

Method for preparing high-stability calcium oxide-based adsorbent Download PDF

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Publication number
CN105817198A
CN105817198A CN201610292480.2A CN201610292480A CN105817198A CN 105817198 A CN105817198 A CN 105817198A CN 201610292480 A CN201610292480 A CN 201610292480A CN 105817198 A CN105817198 A CN 105817198A
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perlite
calcium oxide
adsorbent
calcium
beaker
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陈建峰
孟浩影
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04Solid 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
    • B01J20/041Oxides or hydroxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/02Separation 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06Solid 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
    • B01J20/08Solid 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 comprising aluminium oxide or hydroxide; comprising bauxite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B01J20/106Perlite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/50Carbon oxides
    • B01D2257/504Carbon dioxide
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/40Capture or disposal of greenhouse gases of CO2

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treating Waste Gases (AREA)

Abstract

The invention discloses a method for preparing a high-stability calcium oxide-based adsorbent and belongs to the field of adsorbents. Calcium citrate is used as the precursor and forms colloid in deionized water together with perlite solution containing cationic polyacrylamide and alumina sol, then dehydration is conducted, and a dehydrated sample is subjected to high-temperature calcination to generate the adsorbent with perlite wrapped in calcium oxide; due to the fact that perlite expands at high temperature, calcium oxide in which perlite is wrapped expands at high temperature through the expansion of perlite, and then pores of calcium oxide become larger and adsorption capacity becomes higher; besides, aluminum oxide and alumina sol in perlite both can react with calcium oxide at high temperature to generate calcium-aluminate higher in high temperature resistance so as to support the adsorbent and isolate calcium oxide molecules, sintering of the adsorbent is effectively prevented, and the stability of the adsorbent is improved.

Description

A kind of preparation method of the calcium oxide-based adsorbent of high stability
Technical field
The invention discloses the preparation method of the calcium oxide-based adsorbent of a kind of high stability, belong to absorbent fields.
Background technology
CO2It is the predominant gas causing greenhouse effect, whole world CO2Discharge capacity be 20,000,000,000 t/, wherein Fossil fuel thermal power plant CO2Discharge capacity account for 1/3, and continuing to increase of this discharge capacity, bring serious impact to the existence of the sustainable development of the energy, the protection of ecological environment and the mankind.AssociatingGovernment of stateBetween climate change specialCommitteeUsing CO2 emission trapping and the Plugging Technology Applied for coal-burning power plant as the most important technique direction of the year two thousand fifty reduction of greenhouse gas discharge.Controlling at 2.0~2.4 DEG C compared with 2000 if the year two thousand fifty whole world mean temperature raises, the whole world takes around minimizing 50~80%CO2Discharge.Therefore, China must vigorously advocate CO2Reduction of discharging cause, to reaching the CO of the year two thousand twenty per GDP2Discharge capacity decline 40~the target of 50%.Absorption method is applicable to low concentration CO2Occasion.Owing to flue gas has, temperature is high, discharge capacity is big, therefore researchs and develops the high temperature CO of economical and efficient2Separation and collection technology has important practical significance.
At present, more CO is studied both at home and abroad2High-temperature adsorbing agent is houghite compound, lithio and Ca-base adsorbent.Wherein, first as the CO in absorption enhanced hydrogen making by natural gas reformation reaction2The houghite compound of adsorbent is industrial important adsorbing separation, catalysis and ion exchange material, but its adsorption capacity is relatively low;Lithio and Ca-base adsorbent are circulated trapping CO2, wherein on lithio adsorbent carbonation rate and regeneration rate, there is advantage, but it is relatively costly, and Ca-base adsorbent source is wide, low cost, decarburization efficiency is high, the most industrially it is used widely, but in use find, it is slow that CaO adsorbent also exists the rate of adsorption, burning is easily tied on surface, the problem that cyclical stability is poor, trace it to its cause, the mainly surface texture of CaO is undesirable, specific surface area and porosity is not high enough, and it is unstable caused under high temperature, therefore prepare a kind of high temperature and be difficult to knot burning, adsorption rate is high, the calcium oxide-based adsorbent of good stability has important practical significance.
Summary of the invention
nullThe technical problem that present invention mainly solves: the most easily shrink sintering for current calcium oxide and cause less stable,Along with the increase adsorption capacity of cycle-index declines problem faster,Provide the preparation method of the calcium oxide-based adsorbent of a kind of high stability,The present invention is with calcium citrate as presoma,With the perlite solution with PAMC、Alumina gel forms slurry in deionized water,Then it is dehydrated,Again by the high-temperature sample calcining after dehydration,Form a kind of calcium oxide and wrap up perlitic adsorbent,Perlite has the characteristic at high temperature expanded,Expand so making to be wrapped in outer calcium oxide by perlitic expansion during high temperature,So that the hole of calcium oxide becomes big,Absorption affinity becomes strong,And perlite the most all can generate more resistant to elevated temperatures calcium-aluminate with calcium oxide containing aluminium oxide and Alumina gel,Calcium-aluminate can not absorbing carbon dioxide,But adsorbent can be supported,And take blocking effect calcium oxide is intermolecular,Effectively stop adsorbent sintering,Strengthen the stability of adsorbent,The present invention utilizes calcium citrate、Perlite is possible not only to improve the absorbability of calcium oxide,But also calcium oxide can well be solved and at high temperature sinter、The problem of poor stability.
In order to solve above-mentioned technical problem, the technical solution adopted in the present invention is:
(1) weighing 10~20g calcium citrates to pulverize, sieve, collection cut size is 100~200 mesh powder, by standby for the calcium citrate powder smashed;
(2) weighing 5~7g perlites to pulverize, sieve, collection cut size is the perlite powder of 100~200 mesh;
(3) above-mentioned perlite is soaked 12~14h with 200~300mL0.1mol/L hydrochloric acid solutions, filter, filtering residue is washed with deionized 3~5 times, perlite after washing and 0.1~0.3g PAMC are added sequentially in the 250mL beaker containing 150~200mL deionized waters, beaker is placed in sonic oscillation 20~30min in 180~200W ultrasound wave, obtains colloid mixture;
(4) standby calcium citrate powder and above-mentioned colloid mixture are joined in the 1000mL beaker equipped with 100~200mL deionized waters, 50~100mL Alumina gel are added again in beaker, with 180~200W ultrasonic echographies 10~20min, then temperature controlled water baths is at 80~90 DEG C, reaction 5~7h, obtains grayish serosity;
(5) above-mentioned serosity is placed in 150~200 DEG C of baking ovens, it is dried 2~3h, the sample of drying is smashed, being crushed to particle diameter is 100~200 mesh, the sample smashed is put in Muffle furnace, at 700~800 DEG C, calcine 2~3h, naturally cool to room temperature, obtain stable calcium oxide-based adsorbent.
The method of the application of the present invention: weigh in calcium oxide-based uniform paving prepared by the 1~3g present invention is sprinkled upon corundum boat and form thin layer (thickness≤2mm), adsorb at ambient pressure, corundum boat is placed on 700~800 DEG C, adsorbs in the flue of continued emissions carbon dioxide, it is adsorbed to saturated, adsorbent takes out and regenerates, after circulating 20 times, carbon dioxide absorption rate is more than 50%;The calcium oxide of the present invention is the most fluffy, has preferable anti-caking power.
The invention has the beneficial effects as follows:
(1) present invention utilize calcium citrate, perlite be possible not only to improve calcium oxide absorbability, but also can well solve calcium oxide at high temperature sinter, the problem of poor stability;
(2) calcium oxide-based adsorbent prepared by the present invention at high temperature can expand, and strengthens absorption property, obtains higher surface area and repeat usage height.
Detailed description of the invention
First weighing 10~20g calcium citrates to pulverize, sieve, collection cut size is 100~200 mesh powder, by standby for the calcium citrate powder smashed;Weighing 5~7g perlites again to pulverize, sieve, collection cut size is the perlite powder of 100~200 mesh;Above-mentioned perlite is soaked 12~14h with 200~300mL0.1mol/L hydrochloric acid solutions, filter, filtering residue is washed with deionized 3~5 times, perlite after washing and 0.1~0.3g PAMC are added sequentially in the 250mL beaker containing 150~200mL deionized waters, beaker is placed in sonic oscillation 20~30min in 180~200W ultrasound wave, obtains colloid mixture;Standby calcium citrate powder and above-mentioned colloid mixture are joined in the 1000mL beaker equipped with 100~200mL deionized waters, 50~100mL Alumina gel are added again in beaker, with 180~200W ultrasonic echographies 10~20min, then temperature controlled water baths is at 80~90 DEG C, reaction 5~7h, obtains grayish serosity;Above-mentioned serosity is placed in 150~200 DEG C of baking ovens, is dried 2~3h, the sample of drying is smashed, being crushed to particle diameter is 100~200 mesh, puts in Muffle furnace by the sample smashed, and calcines 2~3h at 700~800 DEG C, naturally cool to room temperature, obtain stable calcium oxide-based adsorbent.
Example 1
First weighing 10g calcium citrate to pulverize, sieve, collection cut size is 100 mesh powder, by standby for the calcium citrate powder smashed;Weighing 5 perlites again to pulverize, sieve, collection cut size is the perlite powder of 100 mesh;Above-mentioned perlite 200mL0.1mol/L hydrochloric acid solution is soaked 12h, filter, filtering residue is washed with deionized 3 times, perlite after washing and 0.1g PAMC are added sequentially in the 250mL beaker containing 200mL deionized water, beaker is placed in sonic oscillation 20min in 180W ultrasound wave, obtains colloid mixture;Standby calcium citrate powder and above-mentioned colloid mixture are joined equipped with in the 1000mL beaker of 100mL deionized water, adding 50mL Alumina gel again in beaker, with 180W ultrasonic echography 10min, then temperature controlled water baths is at 80 DEG C, reaction 5h, obtains grayish serosity;Being placed in by above-mentioned serosity in 150 DEG C of baking ovens, be dried 2h, smashed by the sample of drying, being crushed to particle diameter is 100 mesh, puts in Muffle furnace by the sample smashed, and calcines 2h, naturally cool to room temperature, obtain stable calcium oxide-based adsorbent at 700 DEG C.
Weigh in calcium oxide-based uniform paving prepared by the 1g present invention is sprinkled upon corundum boat and form thin layer (thickness is 1.9mm), adsorb at ambient pressure, corundum boat is placed on 700 DEG C, adsorbs in the flue of continued emissions carbon dioxide, it is adsorbed to saturated, adsorbent takes out and regenerates, circulating 20 times, carbon dioxide absorption rate is 50.3%;The calcium oxide of the present invention is the most fluffy, has preferable anti-caking power;The present invention utilize calcium citrate, perlite be possible not only to improve calcium oxide absorbability, but also can well solve calcium oxide at high temperature sinter, the problem of poor stability;Calcium oxide-based adsorbent prepared by the present invention at high temperature can expand, and strengthens absorption property, obtains higher surface area and repeat usage height.
Example 2
First weighing 15g calcium citrate to pulverize, sieve, collection cut size is 150 mesh powder, by standby for the calcium citrate powder smashed;Weighing 6g perlite again to pulverize, sieve, collection cut size is the perlite powder of 150 mesh;Above-mentioned perlite 250mL0.1mol/L hydrochloric acid solution is soaked 13h, filter, filtering residue is washed with deionized 4 times, perlite after washing and 0.2g PAMC are added sequentially in the 250mL beaker containing 175mL deionized water, beaker is placed in sonic oscillation 25min in 190W ultrasound wave, obtains colloid mixture;Standby calcium citrate powder and above-mentioned colloid mixture are joined equipped with in the 1000mL beaker of 150mL deionized water, adding 75mL Alumina gel again in beaker, with 190W ultrasonic echography 15min, then temperature controlled water baths is at 85 DEG C, reaction 6h, obtains grayish serosity;Being placed in by above-mentioned serosity in 175 DEG C of baking ovens, be dried 2.5h, smashed by the sample of drying, being crushed to particle diameter is 150 mesh, puts in Muffle furnace by the sample smashed, and calcines 2.5h, naturally cool to room temperature, obtain stable calcium oxide-based adsorbent at 750 DEG C.
Weigh in calcium oxide-based uniform paving prepared by the 2g present invention is sprinkled upon corundum boat and form thin layer (thickness is 1.6mm), adsorb at ambient pressure, corundum boat is placed on 675 DEG C, adsorbs in the flue of continued emissions carbon dioxide, it is adsorbed to saturated, adsorbent takes out and regenerates, circulating 20 times, carbon dioxide absorption rate is 52.1%;The calcium oxide of the present invention is the most fluffy, has preferable anti-caking power;The present invention utilize calcium citrate, perlite be possible not only to improve calcium oxide absorbability, but also can well solve calcium oxide at high temperature sinter, the problem of poor stability;Calcium oxide-based adsorbent prepared by the present invention at high temperature can expand, and strengthens absorption property, obtains higher surface area and repeat usage height.
Example 3
First weighing 20g calcium citrate to pulverize, sieve, collection cut size is 200 mesh powder, by standby for the calcium citrate powder smashed;Weighing 7g perlite again to pulverize, sieve, collection cut size is the perlite powder of 200 mesh;Above-mentioned perlite 300mL0.1mol/L hydrochloric acid solution is soaked 14h, filter, filtering residue is washed with deionized 5 times, perlite after washing and 0.3g PAMC are added sequentially in the 250mL beaker containing 200mL deionized water, beaker is placed in sonic oscillation 30min in 200W ultrasound wave, obtains colloid mixture;Calcium citrate and above-mentioned colloid mixture being joined equipped with in the 1000mL beaker of 200mL deionized water, then add 100mL Alumina gel in beaker, with 200W ultrasonic echography 20min, then temperature controlled water baths is at 90 DEG C, reacts 7h, obtains grayish serosity;Being placed in by above-mentioned serosity in 200 DEG C of baking ovens, be dried 3h, smashed by the sample of drying, being crushed to particle diameter is 200 mesh, puts in Muffle furnace by the sample smashed, and calcines 3h, naturally cool to room temperature, obtain stable calcium oxide-based adsorbent at 800 DEG C.
Weigh in calcium oxide-based uniform paving prepared by the 3g present invention is sprinkled upon corundum boat and form thin layer (thickness is 1.3mm), adsorb at ambient pressure, corundum boat is placed on 700 DEG C, adsorbs in the flue of continued emissions carbon dioxide, it is adsorbed to saturated, adsorbent takes out and regenerates, circulating 20 times, carbon dioxide absorption rate is 54%;The calcium oxide of the present invention is the most fluffy, has preferable anti-caking power;The present invention utilize calcium citrate, perlite be possible not only to improve calcium oxide absorbability, but also can well solve calcium oxide at high temperature sinter, the problem of poor stability;Calcium oxide-based adsorbent prepared by the present invention at high temperature can expand, and strengthens absorption property, obtains higher surface area and repeat usage height.

Claims (1)

1. the preparation method of the calcium oxide-based adsorbent of high stability, it is characterised in that concrete preparation process is:
(1) weighing 10~20g calcium citrates to pulverize, sieve, collection cut size is 100~200 mesh powder, by standby for the calcium citrate powder smashed;
(2) weighing 5~7g perlites to pulverize, sieve, collection cut size is the perlite powder of 100~200 mesh;
(3) above-mentioned perlite is soaked 12~14h with 200~300mL0.1mol/L hydrochloric acid solutions, filter, filtering residue is washed with deionized 3~5 times, perlite after washing and 0.1~0.3g PAMC are added sequentially in the 250mL beaker containing 150~200mL deionized waters, beaker is placed in sonic oscillation 20~30min in 180~200W ultrasound wave, obtains colloid mixture;
(4) standby calcium citrate powder and above-mentioned colloid mixture are joined in the 1000mL beaker equipped with 100~200mL deionized waters, 50~100mL Alumina gel are added again in beaker, with 180~200W ultrasonic echographies 10~20min, then temperature controlled water baths is at 80~90 DEG C, reaction 5~7h, obtains grayish serosity;
(5) above-mentioned serosity is placed in 150~200 DEG C of baking ovens, it is dried 2~3h, the sample of drying is smashed, being crushed to particle diameter is 100~200 mesh, the sample smashed is put in Muffle furnace, at 700~800 DEG C, calcine 2~3h, naturally cool to room temperature, obtain stable calcium oxide-based adsorbent.
CN201610292480.2A 2016-05-05 2016-05-05 Method for preparing high-stability calcium oxide-based adsorbent Withdrawn CN105817198A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106281603A (en) * 2016-08-05 2017-01-04 宁波金特信钢铁科技有限公司 A kind of preparation method of antioxidant wear-resistant self-restoring lubricating oil
CN109621925A (en) * 2019-01-24 2019-04-16 长江师范学院 A kind of collecting carbonic anhydride agent and its application
CN113024313A (en) * 2021-04-28 2021-06-25 上海乾界生物科技有限公司 Mycorrhizal fungi agent and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106281603A (en) * 2016-08-05 2017-01-04 宁波金特信钢铁科技有限公司 A kind of preparation method of antioxidant wear-resistant self-restoring lubricating oil
CN109621925A (en) * 2019-01-24 2019-04-16 长江师范学院 A kind of collecting carbonic anhydride agent and its application
CN109621925B (en) * 2019-01-24 2021-09-28 长江师范学院 Carbon dioxide trapping agent and application thereof
CN113024313A (en) * 2021-04-28 2021-06-25 上海乾界生物科技有限公司 Mycorrhizal fungi agent and preparation method thereof

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