[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

CN109012008B - Preparation of calcium-based CO by doping rare earth waste2Method for producing adsorbent - Google Patents

Preparation of calcium-based CO by doping rare earth waste2Method for producing adsorbent Download PDF

Info

Publication number
CN109012008B
CN109012008B CN201810843925.0A CN201810843925A CN109012008B CN 109012008 B CN109012008 B CN 109012008B CN 201810843925 A CN201810843925 A CN 201810843925A CN 109012008 B CN109012008 B CN 109012008B
Authority
CN
China
Prior art keywords
calcium
rare earth
adsorbent
waste
cao
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.)
Active
Application number
CN201810843925.0A
Other languages
Chinese (zh)
Other versions
CN109012008A (en
Inventor
陕绍云
金帅
贾庆明
蒋丽红
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kunming University of Science and Technology
Original Assignee
Kunming University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kunming University of Science and Technology filed Critical Kunming University of Science and Technology
Priority to CN201810843925.0A priority Critical patent/CN109012008B/en
Publication of CN109012008A publication Critical patent/CN109012008A/en
Application granted granted Critical
Publication of CN109012008B publication Critical patent/CN109012008B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B01J20/04—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
    • 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
    • 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

Landscapes

  • 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)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a method for preparing calcium-based CO by doping rare earth waste2Method of making adsorbent of calcium-based CO2The technical field of adsorbents. The method comprises the steps of cleaning impurities on the surface of rare earth waste, and pretreating to obtain rare earth dopant powder, wherein the mass percentage content of oxides of rare earth elements in the rare earth dopant is more than 50%; cleaning impurities on the surface of the waste calcium-based precursor, drying, crushing, and calcining at 800-950 ℃ for 3-6 h to obtain a calcium-based precursor; and uniformly mixing the rare earth dopant and the calcium-based precursor, and grinding to obtain the doped calcium-based adsorbent, wherein the molar ratio of the rare earth element in the rare earth dopant to the calcium element in the calcium-based precursor is (0.01-0.2): 1. The doped calcium-based CO of the invention2The adsorbent can prevent sintering of calcium oxide (CaO) powder and increase content of calcium-based CO2Cyclic adsorption performance of the adsorbent.

Description

Preparation of calcium-based CO by doping rare earth waste2Method for producing adsorbent
Technical Field
The invention relates to a method for preparing calcium-based CO by doping rare earth waste2Method of making adsorbent of calcium-based CO2The technical field of adsorbents.
Background
High CO content2The serious consequences of a series of negative effects on the environment caused by the level are serious problems which people must face. Annual CO released according to authoritative sector2Horizontal, global CO in recent years2Emissions have reached 9.795 million tons and are continuing to increase. In the light of current research, sorbent adsorption is to reduce CO2An efficient method of discharge, capture and reuse, with the concept of "treating waste with waste" producing more efficient, environmentally friendly and low cost adsorbents from waste materials being currently the most efficient method. Wherein the calcium-based adsorbent has simple adsorption principle, large adsorption capacity and CO2Simple separation and CO desorption2High purity, cheap and easily available raw materials and the like, and is widely concerned by scholars at home and abroad.
The industrial waste gas containsA certain amount of SO2、H2O, dust, etc., small amount of H2O can activate the calcium-based adsorbent, and SO2Can be irreversibly combined with calcium-based adsorbent to form calcium sulfate, and dust can block the pores of the adsorbent, hinder the diffusion of gas, influence the adsorption of the adsorbent and have a poisoning effect on the adsorbent. In addition, the biggest limiting factor of the large-scale industrial application of the calcium-based adsorbent is the talman phenomenon, and as the number of cycles increases, sintering between CaO powders becomes more severe, thereby preventing the next adsorption of internal CaO and reducing the adsorption effect.
Disclosure of Invention
The invention aims to overcome the existing calcium-based CO2The deficiency of the adsorbent provides a method for preparing calcium-based CO by doping rare earth wastes2The method of the adsorbent, the invention is from the viewpoint of treating waste with waste, the calcium source adopts waste with high calcium content, and contains a certain amount of compounds which have promoting effect on the adsorbent, and can improve the performance of the adsorbent; the doped calcium-based CO of the invention2The rare earth doped in the adsorbent exists in the calcium-based adsorbent in the form of rare earth metal oxide crystal grains, and the doped calcium-based CO2The adsorbent doping agent contains two or more rare earth element compounds, and also contains trace sodium/potassium compounds, aluminum oxide, silicon oxide and the like, all of which can act with calcium oxide to form a supporting framework structure with high specific surface area, and can effectively prevent the sintering of CaO powder under the combined action with rare earth metal oxide crystal grains, thereby improving the cycle stability of the adsorbent.
Preparation of calcium-based CO by doping rare earth waste2The method of the adsorbent comprises the following specific steps:
(1) cleaning impurities on the surface of the rare earth waste, and then pretreating to obtain rare earth dopant powder, wherein the mass percentage content of oxides of rare earth elements in the rare earth dopant is more than 50%;
(2) cleaning impurities on the surface of the waste calcium-based precursor, drying, crushing, and calcining at 800-950 ℃ for 3-6 h to obtain a calcium-based precursor;
(3) uniformly mixing the rare earth dopant in the step (1) and the calcium-based precursor in the step (2) and grinding to obtain a doped calcium-based adsorbent, wherein the molar ratio of rare earth elements in the rare earth dopant to calcium elements in the calcium-based precursor is (0.01-0.2): 1;
the pretreatment in the step (1) is a purification pretreatment by adopting a conventional method in the prior art, and comprises a pretreatment method of alkali dissolution, water washing, acid dissolution, precipitation, filtration and calcination or a pretreatment method of acid dissolution, precipitation, drying and calcination;
the rare earth waste in the step (1) is waste containing rare earth elements, and preferably one or more of waste rare earth polishing powder, waste rare earth fluorescent agent, waste rare earth magnetic material devices and waste nickel-hydrogen batteries;
the calcium-based precursor of the waste in the step (2) is waste with high calcium content, preferably one or more of marble powder, carbide slag and egg shells;
the doped calcium-based CO of the invention2The conditions for detecting the adsorption performance of the adsorbent are as follows: the adsorption temperature is 700-900 ℃, the adsorption time is 10-20 min, and the adsorption atmosphere is 15-50% CO2The balance being N2An atmosphere; the desorption temperature is 700-900 ℃, the desorption time is 10-20 min, and the desorption atmosphere is 100% N2An atmosphere.
The invention has the beneficial effects that:
(1) in the invention, from the viewpoint of treating wastes with wastes, the calcium source adopts wastes with high calcium content; series trace elements contained in the waste calcium source have a promoting effect on the adsorbent, and can improve the performance of the adsorbent;
(2) doped calcium-based CO2The rare earth element doped in the adsorbent exists in the calcium-based adsorbent in the form of rare earth metal oxide crystal grains, and the doped calcium-based CO2The adsorbent doping agent contains two or more rare earth element compounds, and also contains trace sodium/potassium compounds, aluminum oxide, silicon oxide and the like, and the rare earth element compounds and the silicon oxide can act with calcium oxide to form a supporting framework structure with high specific surface area, and can effectively prevent CaO powder from sintering under the combined action of the calcium oxide and the rare earth metal oxide crystal grains, so that the cycle stability of the adsorbent is improved; dopant rare earth waste and waste calcium-based precursorThe price of the body is low, the preparation process is simple, and the adsorption effect is obvious;
(3) the doped calcium-based CO of the invention2The adsorbent solves the problem of the existing calcium-based CO2The adsorbent has the problems of easy sintering, low cyclic adsorption performance, poor stability and the like.
Drawings
Fig. 1 is an SEM image of a calcium-based adsorbent prepared by doping marble powder with rare earth waste according to example 1;
FIG. 2 shows doped calcium-based CO in examples 1, 4 and 7 and comparative examples 1, 4, 5 and 62The change curve of the cycle conversion rate of the adsorbent along with the increase of the cycle times;
fig. 3 is a TG diagram of the calcined marble powder as it is carbonized-calcined ten times.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Comparative example 1: directly adopting calcium source obtained by marble powder pretreatment as CaO precursor to prepare CO without doping2The calcium-based adsorbent comprises the following specific steps:
(1) cleaning to remove impurities attached to the surface of the marble, then placing the marble in an oven for drying, and crushing the marble by using a high-grade crusher;
(2) placing the crushed marble powder obtained in the step (1) in a muffle furnace at the temperature of 900 ℃ and calcining for 3h to obtain a calcium-based adsorbent prepared from the marble powder; the components of the calcium-based sorbent prepared from marble powder are shown in table 1:
Figure 920773DEST_PATH_IMAGE001
(3) placing the calcium-based adsorbent obtained in the step (2) in a thermogravimetric analyzer for circulating CO2Adsorption investigation;
CO2and (3) testing the cyclic adsorption performance: the obtained adsorbent is placed in a thermogravimetric analyzer for cyclic adsorption/desorption (see FIG. 3) at 100ml/min N2Increasing the temperature from 25 deg.C to 760 deg.C at a rate of 15 deg.C/min under an atmosphere, and changing the atmosphere at 50ml/minCO2And 50ml/minN2Adsorbing at constant temperature for 20min and 100ml/min N2Desorbing for 10min in the atmosphere, the conversion rate of the first adsorbed CaO is 79.18%, and obtaining CO after 10 times of circulation2The conversion of (a) was 38.36% (see FIG. 2).
Comparative example 2: directly adopting calcium source obtained by extracting carbide slag as CaO precursor to prepare CO without doping2The calcium-based adsorbent comprises the following specific steps:
(1) cleaning to remove impurities attached to the surface of the carbide slag, then placing the carbide slag in an oven for drying, and crushing the carbide slag by using a high-grade crusher;
(2) calcining the carbide slag powder crushed in the step (1) in a muffle furnace at the temperature of 900 ℃ for 4 hours to obtain a calcium-based adsorbent prepared from the carbide slag; the components of the calcium-based adsorbent prepared from the carbide slag are shown in table 2:
Figure 369072DEST_PATH_IMAGE003
(3) placing the product obtained in the step (2) in a thermogravimetric analyzer for circulating CO2Adsorption investigation;
CO2the results of the cyclic adsorption performance test method are the same as that of comparative example 1, and show that: the conversion rate of CaO absorbed for the first time is 54.28 percent, and after 10 times of CO absorption2The CaO conversion rate after the adsorption/desorption cycle was 35.03%, and it can be seen that the cyclic adsorption performance of the calcium-based adsorbent prepared from the carbide slag after 10 cycles was inferior to that of the calcium-based adsorbent prepared from the marble powder in comparative example 1.
Comparative example 3: directly adopting calcium source obtained by extracting eggshells as a CaO precursor to prepare calcium-based CO without doping2The adsorbent comprises the following specific steps:
(1) cleaning to remove impurities attached to the surface of the egg shell, then placing the egg shell in an oven for drying, and crushing the egg shell by using a high-grade crusher;
(2) calcining the eggshell powder crushed in the step (1) in a muffle furnace at the temperature of 900 ℃ for 5 hours to obtain a calcium-based adsorbent prepared from the eggshell; the ingredients of the calcium-based adsorbent prepared from eggshell are shown in table 3:
Figure 430700DEST_PATH_IMAGE004
(3) placing the product obtained in the step (2) in a thermogravimetric analyzer for circulating CO2Adsorption investigation;
CO2the results of the cyclic adsorption performance test method are the same as that of comparative example 1, and show that: the conversion rate of absorbing CaO for the first time is 55.31 percent, and after 10 times of CO absorption2The CaO conversion rate after the adsorption/desorption cycle was 32.76%, and it can be seen that the cyclic adsorption performance of the calcium-based adsorbent prepared from eggshells after 10 cycles was inferior to that of the calcium-based adsorbent prepared from marble powder in comparative example 1.
Comparative example 4: rare earth oxide (cerium oxide (CeO)2) Production of calcium-based CO by doping with calcium oxide2The method of the adsorbent comprises the following specific steps:
mixing rare earth oxide (CeO)2) Mixing with calcium oxide, and grinding in agate mortar to obtain doped calcium-based adsorbent containing CeO2The molar ratio of the rare earth element cerium (Ce) in the (1) to the calcium oxide is 0.01:1, 0.05:1, 0.1:1 and 0.2:1, and 0.01/1 cerium oxide doped calcium-based adsorbent, 0.05/1 cerium oxide doped calcium-based adsorbent, 0.1/1 cerium oxide doped calcium-based adsorbent and 0.2/1 cerium oxide doped calcium-based adsorbent are respectively obtained;
CO2the results of the cyclic adsorption performance test method are the same as that of comparative example 1, and show that: 0.01/1 (CeO)2) The conversion rate of CaO absorbed by the doped calcium-based adsorbent for the first time is 91.21 percent, and the CO is absorbed for 10 times2The CaO conversion after adsorption/desorption cycles was 55.01%; 0.05/1 (CeO)2) The conversion rate of CaO absorbed by the doped calcium-based adsorbent for the first time is 91.79 percent, and the CO is absorbed for 10 times2The CaO conversion after adsorption/desorption cycles was 56.02%; 0.1/1 (CeO)2) The conversion rate of CaO absorbed by the doped calcium-based adsorbent for the first time is 92.31 percent, and the CO is absorbed for 10 times2The CaO conversion after adsorption/desorption cycles was 57.11%; 0.2/1 (CeO)2) The conversion rate of CaO absorbed by the doped calcium-based adsorbent for the first time is 91.04% after 10 passes of CO2The CaO conversion after the adsorption/desorption cycle was 55.43% (see fig. 2).
Example 1: in the embodiment, the rare earth waste is waste rare earth polishing powder, and the waste calcium-based precursor is marble powder in comparative example 1;
preparation of calcium-based CO by doping rare earth waste2The method of the adsorbent comprises the following specific steps:
(1) cleaning impurities on the surface of rare earth waste (waste rare earth polishing powder), and performing pretreatment such as dissolving with sodium hydroxide (NaOH), roasting, drying, grinding, dissolving with concentrated hydrochloric acid, precipitating with oxalic acid, filtering, and roasting to obtain rare earth dopant powder, wherein the components of the waste rare earth polishing powder are shown in Table 4, and the rare earth dopant contains rare earth oxide (CeO)2) The mass percentage content is 51.979%;
Figure 357067DEST_PATH_IMAGE005
(2) cleaning impurities on the surface of a waste calcium-based precursor (waste marble), drying, crushing, and calcining at 800 ℃ for 3 hours to obtain a calcium-based precursor; the composition of the calcium-based precursor is shown in table 1 of comparative example 1;
(3) uniformly mixing the rare earth dopant in the step (1) and the calcium-based precursor in the step (2), placing the mixture in an agate mortar, and grinding the mixture to obtain the doped calcium-based adsorbent, wherein the molar ratio of the rare earth element in the rare earth dopant to the calcium element in the calcium-based precursor is 0.05:1 and 0.1:1, and respectively obtaining the 0.05/1 type waste rare earth polishing powder doped with calcium-based CO2Calcium-based CO doped with adsorbent and 0.1/1 type waste rare earth polishing powder2An adsorbent;
CO2the results of the cyclic adsorption performance test method are the same as that of comparative example 1, and show that: the 0.05/1 type waste rare earth polishing powder of the embodiment is doped with calcium-based CO2The conversion rate of CaO absorbed by the adsorbent for the first time is 90.23%, and the conversion rate of CaO absorbed by the adsorbent for the first time is 10 times of CO absorption2The CaO conversion after the adsorption/desorption cycle was 71.07% (see fig. 2); compared with the calcium-based adsorbent of comparative example 1, the conversion rate of CaO adsorbed for the first time is increased by 11.05 percentPassing through CO for 10 times2The CaO conversion rate is improved by 32.71 percent after the adsorption/desorption circulation; compared with comparative example 4, the conversion rate of CaO adsorbed for the first time is reduced by 1.56 percent, and CO is absorbed for 10 times2The CaO conversion rate is improved by 15.05 percent after the adsorption/desorption circulation;
the 0.1/1 type waste rare earth polishing powder of the embodiment is doped with calcium-based CO2The conversion rate of CaO absorbed by the adsorbent for the first time is 91.67%, and the CO is absorbed for 10 times2The CaO conversion rate after adsorption/desorption circulation is 72.31 percent; compared with the calcium-based adsorbent of comparative example 1, the conversion rate of CaO adsorbed for the first time is improved by 12.49 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 33.95 percent after the adsorption/desorption circulation; compared with comparative example 4, the conversion rate of CaO adsorbed for the first time is reduced by 0.64 percent, and CO is adsorbed for 10 times2The CaO conversion rate is improved by 15.2 percent after adsorption/desorption circulation;
because of the rare earth element oxides (CeO) in the rare earth dopants2) 41.98 percent of mass percentage and CeO2、La2O3、Na2O、MgO、Al2O3、SiO2、P2O5、SO3、K2O、CaO、Fe2O3The calcium-based precursor contains calcium oxide 92.783%, and trace amount of MgO and P2O5、SO3、SiO2、SrO、Fe2O3、Al2O3Oxides of rare earth elements (CeO)2) With La in the rare earth dopant2O3、Na2O、MgO、Al2O3、SiO2And trace amount of MgO and SiO in calcium-based precursor2、SrO、Al2O3CO-doping with calcium oxide to form doped calcium-based CO with more complex and stable structure2Adsorbent, synergistic effect of making doped calcium-based CO2The adsorbent has higher CaO adsorption conversion rate and better cycle performance.
Example 2: the rare earth waste of the embodiment is the same as the embodiment 1, and the waste calcium-based precursor is calcium-based carbide slag of a comparative example 2;
preparation of calcium-based CO by doping rare earth waste2Method for preparing adsorbent, and concrete stepsThe following were used:
(1) cleaning impurities on the surface of the rare earth waste (waste rare earth polishing powder), and then performing pretreatment of dissolving with sodium hydroxide (NaOH), roasting, drying, grinding, dissolving with concentrated hydrochloric acid, precipitating with oxalic acid, filtering, and roasting to obtain rare earth dopant powder, the composition of which is shown in Table 4 of example 1, wherein the rare earth dopant powder contains rare earth element oxide (CeO)2) The mass percentage content is 51.979%;
(2) cleaning impurities on the surface of a waste calcium-based precursor (waste carbide slag), drying, crushing, and calcining at 950 ℃ for 6 hours to obtain a calcium-based precursor; the composition of the calcium-based precursor is shown in table 2 of comparative example 2;
(3) uniformly mixing the rare earth dopant in the step (1) and the calcium-based precursor in the step (2), placing the mixture in an agate mortar, and grinding the mixture to obtain the doped calcium-based adsorbent, wherein the molar ratio of the rare earth element in the rare earth dopant to the calcium element in the calcium-based precursor is 0.01:1 and 0.2:1, and respectively obtaining the 0.01/1 type waste rare earth polishing powder doped with calcium-based CO2Calcium-based CO doped with adsorbent and 0.2/1 type waste rare earth polishing powder2An adsorbent;
CO2the results of the cyclic adsorption performance test method are the same as that of comparative example 1, and show that: the 0.01/1 type waste rare earth polishing powder of the embodiment is doped with calcium-based CO2The conversion rate of CaO absorbed by the adsorbent for the first time is 89.98 percent, and the conversion rate of the CaO absorbed by the adsorbent is 10 times of CO2The CaO conversion after adsorption/desorption cycles was 71.23%; compared with the calcium-based adsorbent of comparative example 2, the conversion rate of CaO adsorbed for the first time is increased by 35.7 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 36.2 percent after the adsorption/desorption circulation; compared with comparative example 4, the conversion rate of CaO adsorbed for the first time is reduced by 1.23%, and CO is adsorbed for 10 times2The CaO conversion rate is improved by 16.22 percent after the adsorption/desorption circulation;
the 0.2/1 type waste rare earth polishing powder of the embodiment is doped with calcium-based CO2The conversion rate of CaO absorbed by the adsorbent for the first time is 91.34%, and after 10 times of CO absorption2The CaO conversion after adsorption/desorption cycles was 71.07%; compared with the calcium-based adsorbent of comparative example 2, the conversion rate of CaO adsorbed for the first time is improved by 37.06 percent, and the CO is adsorbed for 10 times2CaO transfer after adsorption/desorption cyclesThe chemical conversion rate is improved by 36.04 percent; compared with comparative example 4, the conversion rate of CaO adsorbed for the first time is improved by 0.3 percent, and CO is adsorbed for 10 times2The CaO conversion rate is improved by 15.64 percent after the adsorption/desorption circulation;
because of the rare earth element oxides (CeO) in the rare earth dopants2) 41.98 percent of mass percentage and CeO2、La2O3、Na2O、MgO、Al2O3、SiO2、P2O5、SO3、K2O、CaO、Fe2O3The calcium-based precursor contains calcium oxide 85.12%, and trace amount of MgO and P2O5、SO3、SiO2、SrO、Fe2O3、Al2O3Oxides of rare earth elements (CeO)2) With La in the rare earth dopant2O3、Na2O、MgO、Al2O3、SiO2And trace amount of MgO, SrO and K in calcium-based precursor2O、Al2O3CO-doping with calcium oxide to form doped calcium-based CO with more complex and stable structure2Adsorbent, synergistic effect of making doped calcium-based CO2The adsorbent has higher CaO adsorption conversion rate and better cycle performance.
Example 3: the rare earth waste of the embodiment is the same as the embodiment 1, and the waste calcium-based precursor is the eggshell of the comparative example 3;
preparation of calcium-based CO by doping rare earth waste2The method of the adsorbent comprises the following specific steps:
(1) cleaning impurities on the surface of the rare earth waste (waste rare earth polishing powder), and then performing pretreatment of dissolving with sodium hydroxide (NaOH), roasting, drying, grinding, dissolving with concentrated hydrochloric acid, precipitating with oxalic acid, filtering, and roasting to obtain rare earth dopant powder, the composition of which is shown in Table 4 of example 1, wherein the rare earth dopant powder contains rare earth element oxide (CeO)2) The mass percentage content is 51.979%;
(2) cleaning impurities on the surface of a waste calcium-based precursor (egg shell), drying, crushing, and calcining at 900 ℃ for 5 hours to obtain a calcium-based precursor; the composition of the calcium-based precursor is shown in table 3 of comparative example 3;
(3) uniformly mixing the rare earth dopant in the step (1) and the calcium-based precursor in the step (2), placing the mixture in an agate mortar, and grinding the mixture to obtain the doped calcium-based adsorbent, wherein the molar ratio of the rare earth element in the rare earth dopant to the calcium element in the calcium-based precursor is 0.05:1 and 0.2:1, and respectively obtaining the 0.05/1 type waste rare earth polishing powder doped with calcium-based CO2Calcium-based CO doped with adsorbent and 0.2/1 type waste rare earth polishing powder2An adsorbent;
CO2the results of the cyclic adsorption performance test method are the same as that of comparative example 1, and show that: the 0.05/1 type waste rare earth polishing powder of the embodiment is doped with calcium-based CO2The conversion rate of CaO absorbed by the adsorbent for the first time is 90.56%, and the conversion rate of CaO absorbed by the adsorbent for the first time is 10 times of CO absorption2The CaO conversion rate after adsorption/desorption circulation is 72.05 percent; compared with the calcium-based adsorbent of comparative example 2, the conversion rate of CaO adsorbed for the first time is increased by 35.25 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 39.29 percent after the adsorption/desorption circulation; compared with comparative example 4, the conversion rate of CaO adsorbed for the first time is reduced by 1.23%, and CO is adsorbed for 10 times2The CaO conversion rate is improved by 16.03 percent after adsorption/desorption circulation;
the 0.2/1 type waste rare earth polishing powder of the embodiment is doped with calcium-based CO2The conversion rate of CaO absorbed by the adsorbent for the first time is 90.76%, and the conversion rate of the CaO absorbed by the adsorbent for the first time is 10 times of CO absorption2The CaO conversion after adsorption/desorption cycles was 71.36%; compared with the calcium-based adsorbent of comparative example 2, the conversion rate of CaO adsorbed for the first time is increased by 35.45 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 38.6 percent after the adsorption/desorption circulation; compared with comparative example 4, the conversion rate of CaO adsorbed for the first time is reduced by 0.28 percent, and CO is adsorbed for 10 times2The CaO conversion rate is improved by 15.93 percent after the adsorption/desorption circulation;
because of the rare earth element oxides (CeO) in the rare earth dopants2) 41.98 percent of mass percentage and CeO2、La2O3、Na2O、MgO、Al2O3、SiO2、P2O5、SO3、K2O、CaO、Fe2O3The content of calcium oxide in the calcium-based precursor is 92.56%, andcontaining a trace amount of MgO and P2O5Organic matter, rare earth element oxide (CeO)2) With La in the rare earth dopant2O3、Na2O、MgO、Al2O3、SiO2The trace MgO in the calcium-based precursor is jointly doped with calcium oxide to form doped calcium-based CO with more complex and stable structure2Adsorbent, synergistic effect of making doped calcium-based CO2The adsorbent has higher CaO adsorption conversion rate and better cycle performance.
Comparative example 5: rare earth oxide (yttrium oxide (Y)2O3) Production of calcium-based CO by doping with calcium oxide2The method of the adsorbent comprises the following specific steps:
mixing rare earth oxide (Y)2O3) Mixing with calcium oxide, and grinding in agate mortar to obtain doped calcium-based adsorbent containing rare earth oxide (Y)2O3) The molar ratio of the rare earth element (yttrium (Y)) to calcium in calcium oxide was 0.01:1, 0.03:1, and 0.05:1, respectively, to obtain 0.01/1 (Y)2O3) Doped calcium-based sorbent, 0.03/1 (Y)2O3) Doped calcium-based sorbent, 0.05/1 (Y)2O3) A doped calcium-based sorbent;
CO2the results of the cyclic adsorption performance test method are the same as that of comparative example 1, and show that: 0.01/1 (Y)2O3) The CaO conversion rate of the doped calcium-based adsorbent is 92.56 percent after the first adsorption of CaO for 10 times2CaO conversion after adsorption/desorption cycle was 56.43% (see fig. 2); 0.03/1 (Y)2O3) The CaO conversion rate of the doped calcium-based adsorbent is 93.01 percent after the first adsorption of CaO for 10 times2The CaO conversion after adsorption/desorption cycles was 55.26%; 0.05/1 (Y)2O3) The CaO conversion rate of the doped calcium-based adsorbent is 93.64 percent after the first adsorption of the CaO for 10 times2The CaO conversion after the adsorption/desorption cycle was 57.04%.
Example 4: in the embodiment, the rare earth waste is the waste rare earth fluorescent agent, and the waste calcium-based precursor is marble powder in comparative example 1;
utilize tombarthite uselessPreparation of calcium-based CO by doping waste2The method of the adsorbent comprises the following specific steps:
(1) cleaning impurities on the surface of rare earth waste (waste rare earth fluorescer), and pretreating by dissolving with concentrated hydrochloric acid, precipitating with oxalic acid, filtering, and calcining to obtain rare earth dopant powder, wherein the components of the waste rare earth fluorescer powder are shown in Table 5, and oxide (Y) of rare earth element in the rare earth dopant2O3) The mass percentage content is 53.21%;
Figure 437019DEST_PATH_IMAGE006
(2) cleaning impurities on the surface of a waste calcium-based precursor (waste marble), drying, crushing, and calcining at 900 ℃ for 5 hours to obtain a calcium-based precursor; the composition of the calcium-based precursor is shown in table 1 of comparative example 1;
(3) uniformly mixing the rare earth dopant in the step (1) and the calcium-based precursor in the step (2), placing the mixture in an agate mortar, and grinding the mixture to obtain the doped calcium-based adsorbent, wherein the molar ratio of the rare earth element in the rare earth dopant to the calcium element in the calcium-based precursor is 0.01:1 and 0.03:1, and respectively obtaining the 0.01/1 type waste rare earth polishing powder doped with calcium-based CO2Calcium-based CO doped with adsorbent and 0.03/1 type waste rare earth polishing powder2An adsorbent;
CO2the results of the cyclic adsorption performance test method are the same as that of comparative example 1, and show that: the 0.01/1 type waste rare earth fluorescent agent of the embodiment is doped with calcium-based CO2The conversion rate of CaO absorbed by the adsorbent for the first time is 90.06%, and after 10 times of CO absorption2The CaO conversion after the adsorption/desorption cycle was 72.34% (see fig. 2); compared with the calcium-based adsorbent of comparative example 1, the conversion rate of CaO adsorbed for the first time is improved by 10.88 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 33.98 percent after the adsorption/desorption circulation; compared with the comparative example 5, the conversion rate of the CaO adsorbed for the first time is reduced by 2.51 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 15.81 percent after the adsorption/desorption circulation;
the waste rare earth fluorescer of type 0.03/1 of the embodiment is doped with calcium-based CO2First CaO adsorption converter of adsorbentConversion rate of 91.03%, after 10 CO cycles2The CaO conversion after adsorption/desorption cycles was 73.06%; compared with the calcium-based adsorbent of comparative example 1, the conversion rate of CaO adsorbed for the first time is increased by 11.85 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 34.69 percent after the adsorption/desorption circulation; compared with the comparative example 5, the conversion rate of the CaO adsorbed for the first time is reduced by 2.61 percent, and the CO is absorbed for 10 times2The CaO conversion rate is improved by 16.02 percent after the adsorption/desorption circulation;
because of the oxide (Y) of the rare earth element in the rare earth dopant2O3) 53.213 percent of mass percentage and CeO2、La2O3、Eu2O3、Tb4O7、La2O3、Al2O3、P2O5CaO, BaO, the content of calcium oxide in the calcium-based precursor is 92.783%, and the calcium-based precursor also contains trace amounts of MgO and P2O5、SO3、SiO2、SrO、Fe2O3、Al2O3Oxide of rare earth element (Y)2O3) With CeO in a rare earth dopant2、La2O3、Eu2O3、Tb4O7、La2O3、Al2O3CaO, Ca-based precursor, and trace amounts of MgO and SiO2、SrO、Al2O3CO-doping with calcium oxide to form doped calcium-based CO with more complex and stable structure2Adsorbent, synergistic effect of making doped calcium-based CO2The adsorbent has higher CaO adsorption conversion rate and better cycle performance.
Example 5: in the embodiment, the rare earth waste is the waste rare earth fluorescent agent, and the waste calcium-based precursor is the calcium-based carbide slag in the comparative example 2;
preparation of calcium-based CO by doping rare earth waste2The method of the adsorbent comprises the following specific steps:
(1) cleaning impurities on the surface of rare earth waste (waste rare earth fluorescent agent), and then carrying out pretreatment of concentrated hydrochloric acid dissolution, oxalic acid precipitation, filtration and roasting to obtain rare earth dopant powder, wherein the components of the rare earth dopant powder are as in the examples4, wherein the rare earth dopant is an oxide of a rare earth element (Y)2O3) The mass percentage content is 53.21%;
(2) cleaning impurities on the surface of a waste calcium-based precursor (waste carbide slag), drying, crushing, and calcining at 950 ℃ for 4 hours to obtain a calcium-based precursor; the composition of the calcium-based precursor is shown in table 2 of comparative example 2;
(3) uniformly mixing the rare earth dopant in the step (1) and the calcium-based precursor in the step (2), placing the mixture in an agate mortar, and grinding the mixture to obtain the doped calcium-based adsorbent, wherein the molar ratio of the rare earth element in the rare earth dopant to the calcium element in the calcium-based precursor is 0.03:1 and 0.05:1, and respectively obtaining the 0.03/1 type waste rare earth polishing powder doped with calcium-based CO2Calcium-based CO doped with adsorbent and 0.05/1 type waste rare earth polishing powder2An adsorbent;
CO2the results of the cyclic adsorption performance test method are the same as that of comparative example 1, and show that: the waste rare earth fluorescer of type 0.03/1 of the embodiment is doped with calcium-based CO2The conversion rate of CaO absorbed by the adsorbent for the first time is 91.68 percent, and after 10 times of CO absorption2The CaO conversion rate after adsorption/desorption cycle is 71.96%; compared with the calcium-based adsorbent of comparative example 2, the conversion rate of CaO adsorbed for the first time is increased by 37.5 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 36.93 percent after the adsorption/desorption circulation; compared with the comparative example 5, the conversion rate of the CaO adsorbed for the first time is reduced by 1.33 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 16.7 percent after the adsorption/desorption circulation;
the 0.05/1 type waste rare earth fluorescent agent of the embodiment is doped with calcium-based CO2The conversion rate of CaO absorbed by the adsorbent for the first time is 91.02%, and after 10 times of CO absorption2The CaO conversion after adsorption/desorption cycles was 72.07%; compared with the calcium-based adsorbent of comparative example 2, the conversion rate of CaO adsorbed for the first time is improved by 36.74 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 37.04 percent after the adsorption/desorption circulation; compared with the comparative example 5, the conversion rate of the CaO adsorbed for the first time is reduced by 2.66 percent, and the CO is absorbed for 10 times2The CaO conversion rate is improved by 15.03 percent after adsorption/desorption circulation;
because of the oxide (Y) of the rare earth element in the rare earth dopant2O3) In mass percent of53.213% and CeO2、Eu2O3、Tb4O7、La2O3、Al2O3、P2O5CaO, BaO, the content of calcium oxide in the calcium-based precursor is 85.12 percent, and trace MgO and P are also contained2O5、SO3、SiO2、SrO、Fe2O3、Al2O3Oxide of rare earth element (Y)2O3) With CeO in a rare earth dopant2、Eu2O3、Tb4O7、La2O3、Al2O3CaO, and trace amounts of MgO, SrO, and K in calcium-based precursor2O、Al2O3CO-doping with calcium oxide to form doped calcium-based CO with more complex and stable structure2Adsorbent, synergistic effect of making doped calcium-based CO2The adsorbent has higher CaO adsorption conversion rate and better cycle performance.
Example 6: in the embodiment, the rare earth waste is the waste rare earth fluorescent agent, and the waste calcium-based precursor is the eggshell in the comparative example 3;
preparation of calcium-based CO by doping rare earth waste2The method of the adsorbent comprises the following specific steps:
(1) cleaning impurities on the surface of rare earth waste (waste rare earth fluorescent agent), and pretreating by dissolving with concentrated hydrochloric acid, precipitating with oxalic acid, filtering, and calcining to obtain rare earth dopant powder with the composition shown in Table 5 of example 4, wherein the rare earth dopant contains oxide of rare earth element (Y)2O3) The mass percentage content is 53.213%;
(2) cleaning impurities on the surface of a waste calcium-based precursor (egg shell), drying, crushing, and calcining at 850 ℃ for 4 hours to obtain a calcium-based precursor; the composition of the calcium-based precursor is shown in table 3 of comparative example 3;
(3) uniformly mixing the rare earth dopant in the step (1) and the calcium-based precursor in the step (2), and grinding the mixture in an agate mortar to obtain the doped calcium-based adsorbent, wherein rare earth elements in the rare earth dopantThe molar ratio of the element to the calcium element in the calcium-based precursor is 0.01:1 and 0.05:1, and the 0.01/1 type waste rare earth polishing powder doped with calcium-based CO is obtained respectively2Calcium-based CO doped with adsorbent and 0.05/1 type waste rare earth polishing powder2An adsorbent;
CO2the results of the cyclic adsorption performance test method are the same as that of comparative example 1, and show that: the 0.01/1 type waste rare earth fluorescent agent of the embodiment is doped with calcium-based CO2The conversion rate of CaO absorbed by the adsorbent for the first time is 91.54 percent, and after 10 times of CO absorption2The CaO conversion after adsorption/desorption cycles was 71.64%; compared with the calcium-based adsorbent of comparative example 3, the conversion rate of CaO adsorbed for the first time is improved by 36.23 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 38.88 percent after the adsorption/desorption circulation; compared with the comparative example 5, the conversion rate of CaO adsorbed for the first time is reduced by 1.02 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 15.21 percent after the adsorption/desorption circulation;
the 0.05/1 type waste rare earth fluorescent agent of the embodiment is doped with calcium-based CO2The conversion rate of CaO absorbed by the adsorbent for the first time is 92.03 percent, and after 10 times of CO absorption2The CaO conversion rate after adsorption/desorption cycle is 71.94%; compared with the calcium-based adsorbent of comparative example 3, the conversion rate of CaO adsorbed for the first time is improved by 36.72 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 38.88 percent after the adsorption/desorption circulation; compared with the comparative example 5, the conversion rate of the CaO adsorbed for the first time is reduced by 1.61 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 14.9 percent after the adsorption/desorption circulation;
because of the oxide (Y) of the rare earth element in the rare earth dopant2O3) 53.213 percent of mass percentage and CeO2、Eu2O3、Tb4O7、La2O3、Al2O3、P2O5CaO, BaO, the content of calcium oxide in the calcium-based precursor is 92.56%, and the calcium-based precursor also contains trace amounts of MgO and P2O5Organic matter, oxide (Y) of rare earth element2O3) With CeO in a rare earth dopant2、Eu2O3、Tb4O7、La2O3、Al2O3Calcium oxide co-doped with trace MgO in CaO and calcium-based precursorForm doped calcium-based CO with more complex and stable structure2Adsorbent, synergistic effect of making doped calcium-based CO2The adsorbent has higher CaO adsorption conversion rate and better cycle performance.
Comparative example 6: rare earth oxide (rubidium oxide (Nd)2O3) Production of calcium-based CO by doping with calcium oxide2The method of the adsorbent comprises the following specific steps:
mixing rare earth oxide (Nd)2O3) Mixing with calcium oxide, and grinding in agate mortar to obtain doped calcium-based adsorbent containing rare earth oxide (Nd)2O3) The molar ratio of the rare earth element (rubidium (Nd)) to calcium in calcium oxide was 0.1:1, 0.15:1, 0.18:1, and 0.20:1, respectively, to obtain 0.1/1 (Nd)2O3) Doped calcium-based adsorbent, 0.15/1 (Nd)2O3) Doped calcium-based adsorbent, 0.18/1 (Nd)2O3) Doped calcium-based adsorbent, 0.20/1 (Nd)2O3) A doped calcium-based sorbent;
CO2the results of the cyclic adsorption performance test method are the same as that of comparative example 1, and show that: 0.1/1 (Nd)2O3) The CaO conversion rate of the doped calcium-based adsorbent is 91.46 percent after the first adsorption of CaO for 10 times2The CaO conversion rate after adsorption/desorption circulation is 55.07 percent; 0.15/1 (Nd)2O3) The CaO conversion rate of the doped calcium-based adsorbent is 91.76 percent after the first adsorption of CaO for 10 times2The CaO conversion after adsorption/desorption cycles was 55.76%; 0.18/1 (Nd)2O3) The conversion rate of CaO absorbed by the doped calcium-based adsorbent for the first time is 92.03 percent, and the CO is absorbed for 10 times2The CaO conversion after the adsorption/desorption cycle was 56.33% (see fig. 2); 0.20/1 (Nd)2O3) The conversion rate of CaO absorbed by the doped calcium-based adsorbent for the first time is 91.81 percent, and the CO is absorbed for 10 times2The CaO conversion after the adsorption/desorption cycle was 55.94%.
Example 7: in the embodiment, the rare earth waste is a waste rare earth magnetic material device, and the waste calcium-based precursor is marble powder in comparative example 1;
preparation of calcium-based CO by doping rare earth waste2The method of the adsorbent comprises the following specific steps:
(1) cleaning impurities on the surface of rare earth waste (waste rare earth magnetic material device), and performing pretreatment of dissolving with concentrated hydrochloric acid, precipitating with oxalic acid, filtering, and calcining to obtain rare earth dopant powder, wherein the components of the waste rare earth magnetic material device powder are shown in Table 6, and the rare earth dopant contains rare earth element oxide (Nd)2O3) The mass percentage content is 69.892%;
Figure 790640DEST_PATH_IMAGE007
(2) cleaning impurities on the surface of a waste calcium-based precursor (waste marble), drying, crushing, and calcining at 900 ℃ for 3 hours to obtain a calcium-based precursor; the composition of the calcium-based precursor is shown in table 1 of comparative example 1;
(3) uniformly mixing the rare earth dopant in the step (1) and the calcium-based precursor in the step (2), and grinding the mixture in an agate mortar to obtain a doped calcium-based adsorbent, wherein the molar ratio of the rare earth element in the rare earth dopant to the calcium element in the calcium-based precursor is 0.1:1, 0.15:1, 0.18:1 and 0.20:1, so as to respectively obtain a doped calcium-based adsorbent for a 0.1/1 waste rare earth magnetic material device, a doped calcium-based adsorbent for a 0.15/1 waste rare earth magnetic material device, a doped calcium-based adsorbent for a 0.18/1 waste rare earth magnetic material device and a doped calcium-based adsorbent for a 0.20/1 waste rare earth magnetic material device;
CO2the results of the cyclic adsorption performance test method are the same as that of comparative example 1, and show that: the 0.1/1 type waste rare earth magnetic material device of the embodiment is doped with calcium-based CO2The conversion rate of CaO absorbed by the adsorbent for the first time is 90.57 percent, and after 10 times of CO absorption2The CaO conversion after the adsorption/desorption cycle was 72.06% (see fig. 2); compared with the calcium-based adsorbent of comparative example 1, the conversion rate of CaO adsorbed for the first time is increased by 11.39 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 33.7 percent after the adsorption/desorption circulation; compared with the comparative example 6, the conversion rate of CaO adsorbed for the first time is reduced by 0.89%, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 16.99 percent after the adsorption/desorption circulation;
this example0.15/1 type waste rare earth magnetic material device doped with calcium-based CO2The conversion rate of CaO absorbed by the adsorbent for the first time is 90.54%, and after 10 times of CO absorption2The CaO conversion rate after adsorption/desorption cycle was 72.46%; compared with the calcium-based adsorbent of comparative example 1, the conversion rate of CaO adsorbed for the first time is increased by 11.36 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 34.04 percent after the adsorption/desorption circulation; compared with the comparative example 6, the conversion rate of the CaO adsorbed for the first time is reduced by 1.22 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 16.7 percent after the adsorption/desorption circulation;
the 0.18/1 type waste rare earth magnetic material device of the embodiment is doped with calcium-based CO2The conversion rate of CaO absorbed by the adsorbent for the first time is 90.99 percent, and the conversion rate is 10 times of CO absorption2The CaO conversion rate after adsorption/desorption circulation is 71.97 percent; compared with the calcium-based adsorbent of comparative example 1, the conversion rate of CaO adsorbed for the first time is increased by 11.81 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 33.61 percent after the adsorption/desorption circulation; compared with the comparative example 6, the conversion rate of CaO adsorbed for the first time is reduced by 1.04 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 15.64 percent after the adsorption/desorption circulation;
the 0.20/1 type waste rare earth magnetic material device of the embodiment is doped with calcium-based CO2The conversion rate of CaO absorbed by the adsorbent for the first time is 90.44%, and after 10 times of CO absorption2The CaO conversion after adsorption/desorption cycles was 71.57%; compared with the calcium-based adsorbent of comparative example 1, the conversion rate of CaO adsorbed for the first time is increased by 11.26 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 33.21 percent after the adsorption/desorption circulation; compared with the comparative example 6, the conversion rate of the CaO adsorbed for the first time is reduced by 1.37 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 15.63 percent after the adsorption/desorption circulation;
because of the oxide (Nd) of the rare earth element in the rare earth dopant2O3) 69.892 percent of mass percentage content and Pr6O11、Gd2O3、Tb4O7、Dy2O3、Ho2O3、Fe2O3、Nb2O5The calcium-based precursor contains calcium oxide 92.783%, and trace amount of MgO and P2O5、SO3、SiO2、SrO、Fe2O3、Al2O3Oxide of rare earth element (Nd)2O3) With Pr in rare earth dopants6O11、Gd2O3、Tb4O7、Dy2O3、Ho2O3And trace amount of MgO and SiO in calcium-based precursor2、SrO、Al2O3CO-doping with calcium oxide to form doped calcium-based CO with more complex and stable structure2Adsorbent, synergistic effect of making doped calcium-based CO2The adsorbent has higher CaO adsorption conversion rate and better cycle performance.
Example 8: in the embodiment, the rare earth waste is a waste rare earth magnetic material device, and the waste calcium-based precursor is carbide slag in comparative example 2;
preparation of calcium-based CO by doping rare earth waste2The method of the adsorbent comprises the following specific steps:
(1) cleaning impurities on the surface of rare earth waste (waste rare earth magnetic material device), and performing pretreatment such as dissolution in concentrated hydrochloric acid, precipitation in oxalic acid, filtration, and calcination to obtain rare earth dopant powder, wherein the composition of the rare earth dopant powder is shown in table 6 of example 7, wherein the rare earth dopant powder contains rare earth oxide (Nd)2O3) The mass percentage content is 69.892%;
(2) cleaning impurities on the surface of a waste calcium-based precursor (waste carbide slag), drying, crushing, and calcining at 950 ℃ for 3 hours to obtain a calcium-based precursor; the composition of the calcium-based precursor is shown in table 2 of comparative example 2;
(3) uniformly mixing the rare earth dopant in the step (1) and the calcium-based precursor in the step (2), placing the mixture in an agate mortar, and grinding the mixture to obtain a doped calcium-based adsorbent, wherein the molar ratio of rare earth elements in the rare earth dopant to calcium elements in the calcium-based precursor is 0.15:1 and 0.18:1, so as to respectively obtain a doped calcium-based adsorbent for a 0.15/1 type waste rare earth magnetic device and a doped calcium-based adsorbent for a 0.18/1 type waste rare earth magnetic device;
CO2the results of the cyclic adsorption performance test method are the same as that of comparative example 1, and show that: type 0.15/1 waste rare earth of this exampleMagnetic material device doped with calcium-based CO2The conversion rate of CaO absorbed by the adsorbent for the first time is 90.44%, and after 10 times of CO absorption2The CaO conversion after adsorption/desorption cycles was 72.36%; compared with the calcium-based adsorbent of comparative example 2, the conversion rate of CaO adsorbed for the first time is improved by 36.16 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 37.33 percent after the adsorption/desorption circulation; compared with the comparative example 6, the conversion rate of the CaO adsorbed for the first time is reduced by 1.32 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 16.6 percent after the adsorption/desorption circulation;
the 0.18/1 type waste rare earth magnetic material device of the embodiment is doped with calcium-based CO2The conversion rate of CaO absorbed by the adsorbent for the first time is 91.36%, and after 10 times of CO absorption2The CaO conversion after adsorption/desorption cycles was 71.24%; compared with the calcium-based adsorbent of comparative example 2, the conversion rate of CaO adsorbed for the first time is improved by 37.08 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 36.31 percent after the adsorption/desorption circulation; compared with the comparative example 6, the conversion rate of the CaO adsorbed for the first time is reduced by 0.57 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 15.01 percent after adsorption/desorption circulation;
because of the oxide (Nd) of the rare earth element in the rare earth dopant2O3) 69.892 percent of mass percentage content and Pr6O11、Gd2O3、Tb4O7、Dy2O3、Ho2O3、Fe2O3、Nb2O5The calcium-based precursor contains calcium oxide 85.12%, and trace amount of MgO and P2O5、SO3、SiO2、SrO、Fe2O3、Al2O3Oxide of rare earth element (Nd)2O3) With Pr in rare earth dopants6O11、Gd2O3、Tb4O7、Dy2O3、Ho2O3And trace amount of MgO, SrO and K in calcium-based precursor2O、Al2O3CO-doping with calcium oxide to form doped calcium-based CO with more complex and stable structure2Adsorbent, synergistic effect of making doped calcium-based CO2The adsorbent has higher CaO adsorption conversion rate andbetter cycle performance.
Example 9: in the embodiment, the rare earth waste is a waste rare earth magnetic material device, and the waste calcium-based precursor is the eggshell in the comparative example 2;
preparation of calcium-based CO by doping rare earth waste2The method of the adsorbent comprises the following specific steps:
(1) cleaning impurities on the surface of rare earth waste (waste rare earth magnetic material device), and performing pretreatment such as dissolution in concentrated hydrochloric acid, precipitation in oxalic acid, filtration, and calcination to obtain rare earth dopant powder, wherein the composition of the rare earth dopant powder is shown in table 6 of example 7, wherein the rare earth dopant powder contains rare earth oxide (Nd)2O3) The mass percentage content is 69.892%;
(2) cleaning waste calcium-based precursor (impurities on the surface of the waste egg shell, drying, crushing, and calcining at 800 ℃ for 6h to obtain the calcium-based precursor, wherein the components of the calcium-based precursor are shown in the table 2 of the comparative example 2;
(3) uniformly mixing the rare earth dopant in the step (1) and the calcium-based precursor in the step (2), placing the mixture in an agate mortar, and grinding the mixture to obtain a doped calcium-based adsorbent, wherein the molar ratio of rare earth elements in the rare earth dopant to calcium elements in the calcium-based precursor is 0.1:1 and 0.20:1, so as to respectively obtain a doped calcium-based adsorbent for a 0.1/1 type waste rare earth magnetic device and a doped calcium-based adsorbent for a 0.20/1 type waste rare earth magnetic device;
CO2the results of the cyclic adsorption performance test method are the same as that of comparative example 1, and show that: the 0.1/1 type waste rare earth magnetic material device of the embodiment is doped with calcium-based CO2The conversion rate of CaO absorbed by the adsorbent for the first time is 91.2%, and the conversion rate of the CaO absorbed by the adsorbent is 10 times of CO2The CaO conversion after adsorption/desorption cycles was 70.34%; compared with the calcium-based adsorbent of comparative example 3, the conversion rate of CaO adsorbed for the first time is improved by 35.89 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 37.58 percent after the adsorption/desorption circulation; compared with the comparative example 6, the conversion rate of the CaO adsorbed for the first time is reduced by 0.16 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 15.27 percent after the adsorption/desorption circulation;
the 0.20/1 type waste rare earth magnetic material device of the embodiment is doped with calcium-based CO2The conversion rate of CaO absorbed by the adsorbent for the first time is 90.34%, and after 10 times of CO absorption2The CaO conversion rate after adsorption/desorption cycle is 71.47%; compared with the calcium-based adsorbent of comparative example 3, the conversion rate of CaO adsorbed for the first time is increased by 35.03 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 38.71 percent after the adsorption/desorption circulation; compared with the comparative example 6, the conversion rate of the CaO adsorbed for the first time is reduced by 1.47 percent, and the CO is adsorbed for 10 times2The CaO conversion rate is improved by 15.53 percent after the adsorption/desorption circulation;
because of the oxide (Nd) of the rare earth element in the rare earth dopant2O3) 69.892 percent of mass percentage content and Pr6O11、Gd2O3、Tb4O7、Dy2O3、Ho2O3、Fe2O3、Nb2O5The calcium-based precursor contains calcium oxide 92.56%, and trace amount of MgO and P2O5Organic matter, oxide of rare earth element (Nd)2O3) With Pr in rare earth dopants6O11、Gd2O3、Tb4O7、Dy2O3、Ho2O3The trace MgO in the calcium-based precursor is jointly doped with calcium oxide to form doped calcium-based CO with more complex and stable structure2Adsorbent, synergistic effect of making doped calcium-based CO2The adsorbent has higher CaO adsorption conversion rate and better cycle performance.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.

Claims (2)

1. Preparation of calcium-based CO by doping rare earth waste2The method of the adsorbent is characterized by comprising the following specific steps:
(1) cleaning impurities on the surface of the rare earth waste, and then pretreating to obtain rare earth dopant powder, wherein the mass percentage content of oxides of rare earth elements in the rare earth dopant is more than 50%; the pretreatment is a pretreatment method of alkali dissolution, water washing, acid dissolution, precipitation, filtration and calcination or a pretreatment method of acid dissolution, precipitation, drying and calcination; the rare earth waste is one or more of waste rare earth polishing powder, waste rare earth fluorescent agent, waste rare earth magnetic material device and waste nickel-hydrogen battery;
(2) cleaning impurities on the surface of the waste calcium-based precursor, drying, crushing, and calcining at 800-950 ℃ for 3-6 h to obtain a calcium-based precursor;
(3) and (3) uniformly mixing the rare earth dopant in the step (1) and the calcium-based precursor in the step (2) and grinding to obtain the doped calcium-based adsorbent, wherein the molar ratio of the rare earth element in the rare earth dopant to the calcium element in the calcium-based precursor is (0.01-0.2): 1.
2. The method for preparing calcium-based CO by doping rare earth wastes according to claim 12A method of making an adsorbent, characterized by: and (3) the waste calcium-based precursor in the step (2) is one or more of marble powder, carbide slag and egg shells.
CN201810843925.0A 2018-07-27 2018-07-27 Preparation of calcium-based CO by doping rare earth waste2Method for producing adsorbent Active CN109012008B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810843925.0A CN109012008B (en) 2018-07-27 2018-07-27 Preparation of calcium-based CO by doping rare earth waste2Method for producing adsorbent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810843925.0A CN109012008B (en) 2018-07-27 2018-07-27 Preparation of calcium-based CO by doping rare earth waste2Method for producing adsorbent

Publications (2)

Publication Number Publication Date
CN109012008A CN109012008A (en) 2018-12-18
CN109012008B true CN109012008B (en) 2021-06-18

Family

ID=64647205

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810843925.0A Active CN109012008B (en) 2018-07-27 2018-07-27 Preparation of calcium-based CO by doping rare earth waste2Method for producing adsorbent

Country Status (1)

Country Link
CN (1) CN109012008B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114904481B (en) * 2022-04-25 2024-05-31 沈阳工业大学 Tubular porous high-activity calcium-based absorbent and preparation method thereof
CN117101400B (en) * 2023-08-25 2024-10-11 北京予知环保科技有限公司 Calcium-based desulfurizing agent, composition and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102553516A (en) * 2012-01-18 2012-07-11 厦门大学 Chemical adsorbent for treating arsenic-containing wastewater and preparation method for chemical adsorbent
CN103418336A (en) * 2013-08-20 2013-12-04 昆明理工大学 Preparation method of high-temperature calcium-based CO2 absorbing material
CN104785195A (en) * 2015-04-03 2015-07-22 天津大学 Calcium oxide based high-temperature carbon dioxide adsorbent material doped with inert component and preparation method
WO2015191962A1 (en) * 2014-06-12 2015-12-17 Arizona Board Of Regents On Behalf Of Arizona State University Carbon dioxide adsorbents
CN106334517A (en) * 2015-07-07 2017-01-18 云南民族大学 Method for preparation of carbon dioxide adsorbent through modification of sediment simultaneously by rare earth and microwave heating

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102553516A (en) * 2012-01-18 2012-07-11 厦门大学 Chemical adsorbent for treating arsenic-containing wastewater and preparation method for chemical adsorbent
CN103418336A (en) * 2013-08-20 2013-12-04 昆明理工大学 Preparation method of high-temperature calcium-based CO2 absorbing material
WO2015191962A1 (en) * 2014-06-12 2015-12-17 Arizona Board Of Regents On Behalf Of Arizona State University Carbon dioxide adsorbents
CN104785195A (en) * 2015-04-03 2015-07-22 天津大学 Calcium oxide based high-temperature carbon dioxide adsorbent material doped with inert component and preparation method
CN106334517A (en) * 2015-07-07 2017-01-18 云南民族大学 Method for preparation of carbon dioxide adsorbent through modification of sediment simultaneously by rare earth and microwave heating

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
掺杂Ce、Zr 对CO2 钙基吸附剂循环特性的影响;张雷等;《化工学报》;20150228;第66卷(第2期);第612-617页，摘要部分，第1.1节和第2.1节 *
高温钙基CO2吸收剂的制备及其性能测试;杨仕梅;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20140215(第2期);B015-106，第5.1-5.4节 *

Also Published As

Publication number Publication date
CN109012008A (en) 2018-12-18

Similar Documents

Publication Publication Date Title
US11332380B2 (en) Method for aluminum-enhanced dealkalization of red mud and separation and recovery of aluminum and iron
CN103418336B (en) Preparation method of high-temperature calcium-based CO2 absorbing material
CN108212074A (en) It is a kind of can the metatitanic acid type lithium ion sieve of Magnetic Isolation, preparation method and applications
CN104492372B (en) A kind of preparation method and applications for adsorbing heavy metal in waste water material
CN109012008B (en) Preparation of calcium-based CO by doping rare earth waste2Method for producing adsorbent
CN107879366B (en) Activation method for extracting aluminum oxide from fly ash
CN108499515B (en) Doped CO2Preparation method of calcium-based adsorbent
CN103769045B (en) A kind of preparation method of fly ash base high-performance adsorbing material
CN104941586B (en) A kind of modified mesoporous silicon material and its preparation method and application
CN102101686B (en) Process method for ultra-high purity alumina preparation by utilizing coal ash and comprehensive utilization of ultra-high purity alumina
CN102600818B (en) Preparation method and application of calcium oxide based absorbing material using diatomite as carrier
CN104971690A (en) Method for preparing high-temperature CO2 calcium-based adsorbent from papermaking white mud
CN108325501A (en) One kind can heat safe gaseous iodine sorbing material and preparation method thereof
CN110577847A (en) Synergistic removal of sulfide and CO in blast furnace gas by composite calcium ferrite2Method (2)
CN105903458A (en) Preparation method and application of calcium-based adsorbent
CN103816863B (en) For diatomite-nickel slag composite adsorbing material and the preparation thereof for the treatment of of Phosphorus Containing Waste Water
CN113750961A (en) Carbon dioxide adsorbent and preparation method thereof
CN103816862B (en) Diatomite-nickel slag the composite adsorbing material of recyclable heavy metal ion and preparation thereof
CN100566815C (en) Remove the preparation method of the high-temperature adsorbing agent of the portion gas in the flue gas simultaneously
CN104162403B (en) A kind of mixed acid modified calcium-based adsorbent and its preparation method and application
WO2020155245A1 (en) Method for using magnesite microwave activation to prepare highly reactive magnesium oxide
CN111603906B (en) Carbon dioxide magnesium-based adsorbent and preparation method thereof
CN101982414A (en) Method for preparing doped nano ceria powder by utilizing solvent-thermal method
CN115557720A (en) Cement clinker mineralization reinforcing agent
CN106563415A (en) Method for preparing MIL-100Al-based porous carbon material for carbon dioxide adsorption and separation

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
GR01 Patent grant
GR01 Patent grant