CN105597659A - Method for utilizing oil shale or ash coal to prepare CO2 high-temperature adsorbent - Google Patents
Method for utilizing oil shale or ash coal to prepare CO2 high-temperature adsorbent Download PDFInfo
- Publication number
- CN105597659A CN105597659A CN201610107965.XA CN201610107965A CN105597659A CN 105597659 A CN105597659 A CN 105597659A CN 201610107965 A CN201610107965 A CN 201610107965A CN 105597659 A CN105597659 A CN 105597659A
- Authority
- CN
- China
- Prior art keywords
- oil shale
- prepare
- temperature
- agentmethod
- dirty coal
- 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.)
- Granted
Links
- 239000004058 oil shale Substances 0.000 title claims abstract description 54
- 239000003245 coal Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000003463 adsorbent Substances 0.000 title abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 60
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 29
- 239000011575 calcium Substances 0.000 claims abstract description 28
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 18
- 239000012190 activator Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 235000019738 Limestone Nutrition 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 239000006028 limestone Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 238000013021 overheating Methods 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 159000000007 calcium salts Chemical group 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000010459 dolomite Substances 0.000 claims description 3
- 229910000514 dolomite Inorganic materials 0.000 claims description 3
- 238000013467 fragmentation Methods 0.000 claims description 3
- 238000006062 fragmentation reaction Methods 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004579 marble Substances 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000011435 rock Substances 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 40
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 2
- 230000007935 neutral effect Effects 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 20
- 239000012298 atmosphere Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000002585 base Substances 0.000 description 16
- 239000002956 ash Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 229910052681 coesite Inorganic materials 0.000 description 9
- 229910052906 cristobalite Inorganic materials 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 229910052682 stishovite Inorganic materials 0.000 description 9
- 229910052905 tridymite Inorganic materials 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000003610 charcoal Substances 0.000 description 8
- 230000004087 circulation Effects 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 6
- 238000002336 sorption--desorption measurement Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- 150000001875 compounds Chemical group 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- 241000124033 Salix Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000003079 shale oil Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000015076 Shorea robusta Nutrition 0.000 description 1
- 244000166071 Shorea robusta Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000009671 shengli Substances 0.000 description 1
- 239000010117 shenhua Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid 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
-
- 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
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
Abstract
Provided is a method for utilizing oil shale or ash coal to prepare a CO2 high-temperature adsorbent. Oil shale or ash coal is crushed and screened into particles of 70-180 [mu]m, burdening is performed according to a mass ratio of 1:(0.1-10):(1-20) of oil shale particles, an activating agent and a calcium-based reagent or ash coal particles, an activating agent and a calcium-based reagent, and uniform mixing is performed to form mixture; the mixture undergoes heat treatment for 1-10 h at 500-950 DEG C at 0-2 MPa, residue formed by the mixture after the heat treatment is cooled to below 100 DEG C and then is washed to be neutral; and after the residue is dried, the CO2 high-temperature adsorbent is obtained. The method has the advantages that the raw material application range is wide and the prepared adsorbent has large specific surface area and excellent CO2 adsorption capacity and recycling stability.
Description
Technical field
The invention belongs to the trans-utilization field of oil shale or dirty coal, be specifically related to one and utilize oil shale or heightCulm is prepared CO2The method of high-temperature adsorbing agent.
Background technology
Whole world oil shale resources are very abundant, and it contains stock number according to incompletely statistics approximately 10,000,000,000,000 tons, thanCoal resources many 40%. Oil Shale Resources in China reserves are abundant, occupy the world the 4th by verifying stock number sequence,Verify 31,500,000,000 tons of stock numbers, 4,520 hundred million tons of prognostic resources. In addition in progress of coal mining, also produce,A large amount of oil shales. Develop oil shale and not only can alleviate contradiction between oil supply and demand, can also solve because of discardedThe environmental problem that oil shale causes, improves resource utilization.
Oil shale (claiming again oil shale) is a kind of high-ash sedimentary rock containing flammable organic matter, it and coalThe main distinction is that ash content exceedes 40%, and the mineral matter in oil shale often evenly compactly mixes with organic matter, is difficult toCarry out ore dressing by the method for general coal separation. Dirty coal has and the similar character of oil shale.
The purposes difference of country variant to oil shale. In Estonia, oil shale is mainly used to generating and refines pageRock oil; In Brazil, oil shale is mainly as transport fuel; In Germany, oil shale mainly for the manufacture of cement andConstruction material; In China and Australian, oil shale is mainly used in refining shale oil and is used as fuel; At Russia sieveThis and Israel, oil shale is mainly used in generating.
In recent years, the Global Environmental Problems taking climate change as core was day by day serious, cut down with CO2For representativeGreenhouse gas emission become current international community pay close attention to focus. Research and development CO2Efficient trapping withUtilize technology China is controlled and reduce greenhouse gas emission, respond actively the Climatic issues such as global warming and have heavilyLarge meaning. And research and development low cost and efficiently CO2It is current urgently to be resolved hurrily that adsorbent becomes this fieldKey scientific problems is also the important directions of present stage research and development.
According to the difference of adsorbent and adsorbate interactive property, can be by CO2Adsorption separation technology be divided intoPhysical absorption and chemisorbed. CO2Physical absorption conventionally adopt pressure swing adsorption method, adsorbent selectivelyPoor, adsorption capacity is little, but adsorbent reactivation is easy, simple to operate, energy consumption is lower. Relatively, CO2ChangeLearn absorption and conventionally adopt Temp .-change adsorptive process, adsorbent selective better, adsorption capacity is larger, but adsorbent is againLife is more difficult, energy consumption is higher. Industrial common CO2Adsorbent majority has larger specific area,Mainly comprise for low temperature CO2Porous carbon material, natural zeolite, molecular sieve, the silica gel such as the active carbon of absorptionDeng material, and for high temperature CO2Metal oxide, alkali carbonate, the hydrotalcites such as the CaO of absorptionWith materials such as lithium salts. Low temperature adsorbent taking porous charcoal as representative mainly depends on pore passage structure feature, mostly is lowPhysical absorption category under temperature state, and chemical adsorption capacity under its surface functional group effect a little less than. Therefore,The absorption property of porous charcoal still shows selectively the problems such as poor, adsorption capacity is less, urgently improves with prominentBroken.
Due to raw material sources extensively, the each side factor such as the lower and preparation technology of cost is simple, CaO and changingProperty thing be regarded as at present first-selected CO2High-temperature adsorbing agent, has broad application prospects. The Wu Su of Zhejiang UniversityA large amount of research work (Industrial&Engineering is being in virtue seminar aspect CaO base adsorbentChemistryResearch,2008,47:180-184；ChemicalEngineering&Technology,2014,37 (4): 580-586.), in succession prepare TiO2, MgO or Al2O3Coated nano-calcium carbonate, thus obtainSurface has the nanometer CaO adsorbent of inertia support frame, stops or has slowed down CaO sintering or agglomerationGeneration, improved the stability that CaO base adsorbent recycles; Higher adsorbance can reach 6molCO2/ kg adsorbent; But after the adsorption-regeneration circulation of 30 times, the attenuation rate of adsorbent adsorbance reachesApproximately 30%, cyclical stability await improve. Chen etc. (ScienceofAdvancedMaterials,2014,6 (8): 1799-1805) with Ca-Al-CO3Composite oxides are as CO2Adsorbent, find its absorptionCapacity can reach 53.1% of theoretical value, and after 40 adsorption-regeneration circulations, adsorption rate still can remain on 95%, tableReveal good cyclical stability, but its adsorbance is far below the level of similar adsorbent, is only 0.63molCO2/ kg adsorbent. Przepi ó rski etc. (JournalofThermalAnalysisandCalorimetry, 2013,111:357-364；InternationalJournalofGreenhouseGasControl,2012,10:164-168.)Prepare containing charcoal skeleton Ca-base adsorbent, i.e. the load of the porous carbon material taking polyvinyl terephthalate as carbon sourceCarry the composite of MgO/CaO, find that this composite has the dual adsorption function of physics and chemistry simultaneously,The specific area that porous charcoal skeleton is larger has improved the decentralization of MgO/CaO, can effectively alleviate adsorbent sinteringWith the generation of agglomeration, but the stability of its long period while recycling needs further improvement or improves.
Up to now, there is not yet and " utilize oil shale or dirty coal to prepare CO2Adsorbent " technique or the skill of aspectArt report.
Summary of the invention
For overcoming the problems of the prior art, the object of the present invention is to provide one to utilize oil shale or dirty coalPreparation CO2The method of high-temperature adsorbing agent, the method utilizes oil shale (or dirty coal) to have higher simultaneouslyCarbon content and content of ashes (Al in ash content2O3And SiO2The gross mass content of these two kinds of compositions can reach 50% conventionallyCharacter above), in conjunction with CaO to CO2High temperature adsorption, by build and regulate and control charcoal skeleton,Al2O3-SiO2Inertia skeleton and CaO crystal grain three combination and the synergy system on micro-scale,Design & preparation goes out " charcoal-Al2O3-SiO2" CO of compound skeleton2Sorbing material, thus reach strengthening and improveCO2The object of absorption property.
For achieving the above object, the technical solution used in the present invention is as follows:
One utilizes oil shale or dirty coal to prepare CO2The method of high-temperature adsorbing agent, comprises the following steps:
Step 1, by oil shale or dirty coal fragmentation, be sieved into the particle of 70～180 μ m, then according to oil pageThe mass ratio of rock particle, activator, calcium base reagent is 1:(0.1～10): (1～20) or according to dirty coal particle, workThe mass ratio of agent, calcium base reagent is 1:(0.1～10): prepare burden (1～20), and mix, and forms and mixThing;
Step 2, step 1 gained mixture is heat-treated, heat treated condition is: temperature range is500～950 DEG C, pressure is 0～2MPa, and heat treatment time is 1～10h, by mixture after Overheating TreatmentThe residue forming is cooled to below 100 DEG C, then is washed to neutrality, after being dried, obtains CO2High-temperature adsorbing agent.
Described activator is K2CO3、Na2CO3、KOH、NaOH、KHCO3、NaHCO3、ZnCl2In one or both in one or more or the concentrated sulfuric acid, phosphoric acid.
The mass fraction of the described concentrated sulfuric acid is 70%～98%, and the mass fraction of phosphoric acid is 80%～98%.
Described calcium base reagent is calcium salt and/or calcium ore deposit.
Described calcium salt is CaO, Ca (OH)2、CaCO3、CaCl2、Ca(NO3)2In one or more.
Described calcium ore deposit is one or more in marble, lime stone, dolomite.
Described mixing mixed or is placed in by mechanical agitation the hybrid mode that solution mixes and carry out.
Described be placed in solution mix be by being placed in the water-ethanol binary solution that water and ethanol volume ratio are 5:1Middle stirring realizes.
Described heat treatment is at nitrogen, argon gas, helium, CO2, one or more gas in air, steamUnder body, carry out.
The cooling employing cold water of described residue spray process, steam heat-exchanging method, inert gas heat-exchanging method orNatural cooling under inert gas shielding carries out.
Compared with prior art, the beneficial effect that the present invention has:
The present invention can be by the higher value application of oil shale or dirty coal and high temperature CO2The preparation of adsorbent combinesGet up, based on oil shale or dirty coal have simultaneously higher carbon content and the character of content of ashes (oil shale orIn the ash content of dirty coal, Al2O3And SiO2The gross mass content of these two kinds of compositions can reach more than 50% conventionally),Utilize CaO crystal grain and " charcoal-Al on nanoscale2O3-SiO2" combination of compound skeleton, research and developmentThe CO of NEW TYPE OF COMPOSITE skeleton2Sorbing material, builds synergic sorption system, realizes CO2The mass transfer of absorptionThe object that strengthening, adsorbance and cyclical stability effectively improve. Record through experiment, according to skill provided by the inventionCO prepared by art scheme2Sorbing material, BET specific area can reach 165～572m2/ g (traditional preparation methodBe conventionally less than 100m2/ g), total pore volume can reach 0.272～0.585cm3/ g, CO at 600～850 DEG C2InhaleAttached capacity can reach 0.55gCO2/gCaO(approximately reach 70% of theoretical value, amount to 8.75molCO2/ kg adsorbent),After 50 adsorption-desorptions recycle, adsorption capacity still remains on the more than 80% of initial adsorption amount.
In addition, technical scheme provided by the invention also has the following advantages:
1) primary raw material of the present invention source is abundant, cheap, is not only applicable to oil shale or dirty coal,Be equally applicable to the blue charcoal of high ash content or flying of coal tar, coal directly-liquefied residue, Coal Gasification or coking generationAsh etc.
2) " charcoal-Al that prepared by the present invention2O3-SiO2" compound skeleton supporting ca O grain type adsorbent, not only canUtilize the larger specific surface of charcoal skeleton (after heat treatment being formed by the carbon component in raw shale oil or dirty coal)Long-pending, effectively improving CaO crystal grain (is CO2Adsorption activity center) decentralization, improve adsorption reaction activity;And can utilize Al2O3-SiO2The inertia of skeleton, suppresses or stops the sintering at adsorption activity center or reunite existingResemble strengthening CO2The stability that absorption property and sorbent circulation are used.
3) CO of the compound skeleton that prepared by the present invention2High-temperature adsorbing agent has more rich pore passage structure, relativelyIn traditional calcium base CO2Adsorbent (pore passage structure is limited conventionally, specific area is less), can effectively shorten CO2Molecule transmits the path with diffusion, contributes to reduce the resistance to mass tranfer of adsorption reaction, and then improves adsorbent activityThe utilization rate of composition and action effect.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, but be not limited to the following example.
Embodiment 1
Get willow river oil shale as material sample (Industrial Analysis of this sample and elementary analysis data are in table 1,Ash composition is in table 2), through particle broken, that be sieved into 70～180 μ m. According to the mass ratio of 1:1:1, pointAnother name is got oil shale particle, K2CO3(analyze pure, as activator) and CaO (analyze pure, as calcium baseReagent), and join in water-ethanol binary solution (water and ethanol volume ratio are 5:1), stir. simultaneouslyMix after 10h, vacuum drying forms mixture A.
Then, mixture A is placed in to nitrogen atmosphere protection and descends and carry out heat treated, regulate and control heat treatedPart is: temperature is 500 DEG C, and pressure is normal pressure, and heat treatment time is 8h. Residual by what form after heat treatment againStay thing C to naturally cool to below 100 DEG C under nitrogen atmosphere protection, through being washed to neutrality, dry after,To CO2High-temperature adsorbing agent.
This CO2The BET specific area of high-temperature adsorbing agent is 165m2/ g, total pore volume can reach 0.272cm3/g；At 600 DEG C, 20%CO2-80％N2Under the atmosphere of composition, through 20min adsorption reaction, CO2The appearance of absorptionAmount can reach 0.25gCO2/gCaO。
Embodiment 2
Get willow river oil shale as material sample (Industrial Analysis of this sample and elementary analysis data are in table 1,Ash composition is in table 2), through particle broken, that be sieved into 70～180 μ m. According to the mass ratio of 1:2:3, pointAnother name is got oil shale particle, K2CO3(analyze pure, as activator) and CaO (analyze pure, as calcium baseReagent), and join in water-ethanol binary solution (water and ethanol volume ratio are 5:1), stir. simultaneouslyMix after 10h, vacuum drying forms mixture A.
Then, mixture A is placed in to steam atmosphere protection and descends and carry out heat treated, regulate and control heat treatedCondition is: temperature is 600 DEG C, and pressure is 1MPa, and heat treatment time is 5h. To after heat treatment, form againResidue C under steam atmosphere protection, be cooled to after 150 DEG C, switch under nitrogen protection and naturally cool toBelow 100 DEG C, through being washed to neutrality, dry after, obtain CO2High-temperature adsorbing agent.
This CO2The BET specific area of high-temperature adsorbing agent is 568m2/ g, total pore volume can reach 0.579cm3/g；At 600 DEG C, 20%CO2-80％N2Under the atmosphere of composition, through 20min adsorption reaction, CO2The appearance of absorptionAmount can reach 0.55gCO2/gCaO, then at 650 DEG C, N2Under atmosphere, after 15min desorption reaction,Again carry out adsorption reaction, circulation successively, after 50 adsorption-desorptions recycle, adsorption capacity is stillRemain on the excellent beneficial effect of initial adsorption amount 83%.
Embodiment 3
(Industrial Analysis of this sample and elementary analysis data are in Table as material sample to get Estonia's oil shale1, ash composition is in table 2), through particle broken, that be sieved into 70～180 μ m. According to the mass ratio of 1:5:9,Take respectively oil shale particle, NaOH (analyze pure, as activator) and CaCO3(analyze pure, asCalcium base reagent), and join in ball mill grinding tank, carry out mechanical lapping, stir after 15min shape. simultaneouslyResulting mixture A.
Then, mixture A is placed in to nitrogen atmosphere protection and descends and carry out heat treated, regulate and control heat treatedPart is: temperature range is 700 DEG C, and pressure is normal pressure, and heat treatment time is 8h. To after heat treatment, form againResidue C under nitrogen atmosphere protection, naturally cool to below 100 DEG C, through being washed to neutrality, dry after,Obtain CO2High-temperature adsorbing agent.
This CO2The BET specific area of high-temperature adsorbing agent is 283m2/ g, total pore volume can reach 0.319cm3/g；At 650 DEG C, 20%CO2-80％N2Under the atmosphere of composition, through 20min adsorption reaction, CO2The appearance of absorptionAmount can reach 0.45gCO2/gCaO, then at 700 DEG C, N2Under atmosphere, after 15min desorption reaction,Again carry out adsorption reaction, circulation successively, after 50 adsorption-desorptions recycle, adsorption capacity is stillRemain on the excellent beneficial effect of initial adsorption amount 81%.
Embodiment 4
Get Shengli coal (dirty coal sample 1) as material sample (Industrial Analysis of this sample and elementary analysis dataIn table 1, ash composition is in table 2), through particle broken, that be sieved into 70～180 μ m. According to 1:9:15'sMass ratio, takes respectively oil shale particle, KHCO3(analyze pure, as activator) and lime stone (pointAnalyse pure, as calcium base reagent), and join water-ethanol binary solution (water and ethanol volume ratio are 5:1) simultaneouslyIn, being uniformly mixed after 10h, vacuum drying forms mixture A.
Then, mixture A is placed in to steam atmosphere protection and descends and carry out heat treated, regulate and control heat treatedCondition is: temperature is 800 DEG C, and pressure is 0.5MPa, and heat treatment time is 4h. To after heat treatment, form againResidue C under steam atmosphere protection, be cooled to after 150 DEG C, switch under nitrogen protection and naturally cool toBelow 100 DEG C, through being washed to neutrality, dry after, obtain CO2High-temperature adsorbing agent.
This CO2The BET specific area of high-temperature adsorbing agent is 517m2/ g, total pore volume can reach 0.387cm3/g；At 650 DEG C, 20%CO2-80％N2Under the atmosphere of composition, through 20min adsorption reaction, CO2The appearance of absorptionAmount can reach 0.53gCO2/gCaO, then at 700 DEG C, N2Under atmosphere, after 15min desorption reaction,Again carry out adsorption reaction, circulation successively, after 50 adsorption-desorptions recycle, adsorption capacity is stillRemain on the excellent beneficial effect of initial adsorption amount 81%.
Embodiment 5
Get Pingshuo Coal (dirty coal sample 2) as material sample (Industrial Analysis of this sample and elementary analysis dataIn table 1, ash composition is in table 2), through particle broken, that be sieved into 70～180 μ m. According to the matter of 1:2:7Amount ratio, takes respectively oil shale particle, ZnCl2(analyze pure, as activator) and lime stone (it is analyze pure,As calcium base reagent), and join in water-ethanol binary solution (water and ethanol volume ratio are 5:1), simultaneouslyBe uniformly mixed after 10h, vacuum drying forms mixture A.
Then, mixture A is placed in to steam atmosphere protection and descends and carry out heat treated, regulate and control heat treatedCondition is: temperature is 900 DEG C, and pressure is normal pressure, and heat treatment time is 4h. To after heat treatment, form againResidue C is cooled to after 150 DEG C under steam atmosphere protection, switches under nitrogen protection and naturally cools toBelow 100 DEG C, through being washed to neutrality, dry after, obtain CO2High-temperature adsorbing agent.
This CO2The BET specific area of high-temperature adsorbing agent is 572m2/ g, total pore volume can reach 0.585cm3/g；At 650 DEG C, 20%CO2-80％N2Under the atmosphere of composition, through 20min adsorption reaction, CO2The appearance of absorptionAmount can reach 0.53gCO2/gCaO, then at 700 DEG C, N2Under atmosphere, after 15min desorption reaction,Again carry out adsorption reaction, circulation successively, after 50 adsorption-desorptions recycle, adsorption capacity is stillRemain on the excellent beneficial effect of initial adsorption amount 80%.
Embodiment 6
(Industrial Analysis of this sample and elementary analysis data are shown in as material sample to get Shenhua direct coal liquefaction residueTable 1, ash composition is in table 2), through particle broken, that be sieved into 70～180 μ m. According to the quality of 1:2:7Ratio, take respectively oil shale particle, KOH (analyze pure, as activator) and lime stone (analyze pure,As calcium base reagent), and join in water-ethanol binary solution (water and ethanol volume ratio are 5:1), simultaneouslyBe uniformly mixed after 10h, vacuum drying forms mixture A.
Then, mixture A is placed in to steam atmosphere protection and descends and carry out heat treated, regulate and control heat treatedCondition is: temperature is 900 DEG C, and pressure is normal pressure, and heat treatment time is 4h. To after heat treatment, form againResidue C naturally cools to below 100 DEG C under nitrogen atmosphere protection, through being washed to neutrality, dry after,To CO2High-temperature adsorbing agent.
This CO2The BET specific area of high-temperature adsorbing agent is 557m2/ g, total pore volume can reach 0.534cm3/g；At 650 DEG C, 20%CO2-80％N2Under the atmosphere of composition, through 20min adsorption reaction, CO2The appearance of absorptionAmount can reach 0.52gCO2/gCaO, then at 700 DEG C, N2Under atmosphere, after 15min desorption reaction,Again carry out adsorption reaction, circulation successively, after 50 adsorption-desorptions recycle, adsorption capacity is stillRemain on the excellent beneficial effect of initial adsorption amount 83%.
Industrial Analysis and the elementary analysis tables of data of the samples such as table 1 oil shale or coal
*Minusing obtains.
The ash composition analytical data (unit: wt.%) of the samples such as table 2 oil shale or coal
Embodiment 7
Step 1, by Jincheng Anthracite, (dirty coal sample 3, the Industrial Analysis of this sample and elementary analysis data are shown inTable 1) broken, the particle that is sieved into 70～180 μ m, then according to Jincheng Anthracite particle, activator, calciumThe mass ratio of base reagent is that 1:0.1:20 prepares burden, and adopts mechanical agitation mode to mix, and forms and mixesThing; Wherein, activator is ZnCl2、NaHCO3With K2CO3Three's mixture; Calcium base reagent is Ca (OH)2With CaCO3Mixture;
Step 2, step 1 gained mixture is heat-treated under air and nitrogen mixture body to heat treatmentCondition be: temperature is 950 DEG C, and pressure is 0MPa (being gauge pressure), and heat treatment time is 1h, will mixThing adopts cold water spray process to be cooled to below 100 DEG C at the residue forming after Overheating Treatment, then in being washed toProperty, after being dried, obtain CO2High-temperature adsorbing agent.
Embodiment 8
Step 1, by bent west coking coal, (dirty coal sample 4, the Industrial Analysis of this sample and elementary analysis data are in Table1) broken, the particle that is sieved into 70～180 μ m, then according to the bent coking coal particle in west, activator, the examination of calcium baseThe mass ratio of agent is that 1:10:12 prepares burden, and adopts mechanical agitation mode to mix, and forms mixture;Wherein, activator is that mass fraction is the mixture of 98% the concentrated sulfuric acid and the mass fraction phosphoric acid that is 80%;Calcium base reagent is CaCO3、CaCl2With Ca (NO3)2Mixture;
Step 2, by step 1 gained mixture at CO2Under atmosphere, heat-treat, heat treated condition is:Temperature is 550 DEG C, and pressure is 1.5MPa, and heat treatment time is 10h, by mixture after Overheating TreatmentThe residue forming adopts steam heat-exchanging method to be cooled to below 100 DEG C, then is washed to neutrality, after being dried,Obtain CO2High-temperature adsorbing agent.
Embodiment 9
Step 1, by bent west coking coal, (dirty coal sample 4, the Industrial Analysis of this sample and elementary analysis data are in Table1) broken, the particle that is sieved into 70～180 μ m, then according to the bent coking coal particle in west, activator, the examination of calcium baseThe mass ratio of agent is that 1:7:2 prepares burden, and adopts mechanical agitation mode to mix, and forms mixture; ItsIn, activator is that mass fraction is the mixture of 98% phosphoric acid and the mass fraction concentrated sulfuric acid that is 70%; CalciumBase reagent is CaCl2, marble and dolomite mixture;
Step 2, step 1 gained mixture is heat-treated under argon gas and helium mix gas to heat treatmentCondition be: temperature is 700 DEG C, and pressure is 2MPa, and heat treatment time is 3h, by mixture through overheatedThe residue forming after processing adopts inert gas heat-exchanging method to be cooled to below 100 DEG C, then is washed to neutrality,After dry, obtain CO2High-temperature adsorbing agent.
Embodiment 10
Step 1, by oil shale fragmentation, be sieved into the particle of 70～180 μ m, then according to oil shale particle,The mass ratio of activator, calcium base reagent is that 1:9:5 prepares burden, and adopts mechanical agitation mode to mix,Form mixture; Wherein, activator is that mass fraction is 90% phosphoric acid; Calcium base reagent is CaCO3, largeThe mixture of reason stone and lime stone;
Step 2, step 1 gained mixture is heat-treated under air atmosphere, heat treated condition is:Temperature is 800 DEG C, and pressure is 1.7MPa, and heat treatment time is 7h, by mixture shape after Overheating TreatmentThe residue becoming naturally cools to below 100 DEG C, then is washed to neutrality, after being dried, obtains CO2High temperature adsorptionAgent.
The present invention utilizes oil shale or dirty coal to have higher carbon content and the character of content of ashes simultaneously, in conjunction withCaO is to CO2High temperature adsorption, by building and regulating and controlling charcoal skeleton, Al2O3-SiO2Inertia skeleton and CaOCombination and the synergy system of crystal grain three on micro-scale, Design & preparation goes out " charcoal-Al2O3-SiO2" CO of compound skeleton2Sorbing material, thus reach strengthening and improve CO2The order of absorption property. It is wider that it has the raw material scope of application, and prepared adsorbent has larger specific area, excellentCO2Adsorption capacity and recycle the features such as stability.
Claims (10)
1. one kind is utilized oil shale or dirty coal to prepare CO2The method of high-temperature adsorbing agent, is characterized in that, comprisesFollowing steps:
Step 1, by oil shale or dirty coal fragmentation, be sieved into the particle of 70～180 μ m, then according to oil pageThe mass ratio of rock particle, activator, calcium base reagent is 1:(0.1～10): (1～20) or according to dirty coal particle, workThe mass ratio of agent, calcium base reagent is 1:(0.1～10): prepare burden (1～20), and mix, and forms and mixThing;
Step 2, step 1 gained mixture is heat-treated, heat treated condition is: temperature range is500～950 DEG C, pressure is 0～2MPa, and heat treatment time is 1～10h, by mixture after Overheating TreatmentThe residue forming is cooled to below 100 DEG C, then is washed to neutrality, after being dried, obtains CO2High-temperature adsorbing agent.
2. one according to claim 1 utilizes oil shale or dirty coal to prepare CO2The side of high-temperature adsorbing agentMethod, is characterized in that, described activator is K2CO3、Na2CO3、KOH、NaOH、KHCO3、NaHCO3、ZnCl2In one or both in one or more or the concentrated sulfuric acid, phosphoric acid.
3. one according to claim 2 utilizes oil shale or dirty coal to prepare CO2The side of high-temperature adsorbing agentMethod, is characterized in that, the mass fraction of the described concentrated sulfuric acid is 70%～98%, and the mass fraction of phosphoric acid is80％～98％。
4. one according to claim 1 utilizes oil shale or dirty coal to prepare CO2The side of high-temperature adsorbing agentMethod, is characterized in that, described calcium base reagent is calcium salt and/or calcium ore deposit.
5. one according to claim 4 utilizes oil shale or dirty coal to prepare CO2The side of high-temperature adsorbing agentMethod, is characterized in that, described calcium salt is CaO, Ca (OH)2、CaCO3、CaCl2、Ca(NO3)2In oneKind or several.
6. utilize oil shale or dirty coal to prepare CO according to the one described in claim 4 or 52High-temperature adsorbing agentMethod, it is characterized in that, described calcium ore deposit is one or more in marble, lime stone, dolomite.
7. one according to claim 1 utilizes oil shale or dirty coal to prepare CO2The side of high-temperature adsorbing agentMethod, is characterized in that, described in mix by mechanical agitation and mix or be placed in the hybrid mode that solution mixesCarry out.
8. one according to claim 7 utilizes oil shale or dirty coal to prepare CO2The side of high-temperature adsorbing agentMethod, is characterized in that, described in be placed in solution mix be by be placed in the water that water and ethanol volume ratio are 5:1-In ethanol binary solution, stirring realizes.
9. one according to claim 1 utilizes oil shale or dirty coal to prepare CO2The side of high-temperature adsorbing agentMethod, is characterized in that, described heat treatment is at nitrogen, argon gas, helium, CO2, in air, steamUnder one or more gases, carry out.
10. one according to claim 1 utilizes oil shale or dirty coal to prepare CO2High-temperature adsorbing agentMethod, is characterized in that, the cooling employing cold water of described residue spray process, steam heat-exchanging method, indifferent gasNatural cooling under body heat exchange process or inert gas shielding carries out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610107965.XA CN105597659B (en) | 2016-02-26 | 2016-02-26 | One kind prepares CO using oil shale or dirty coal2The method of high-temperature adsorbing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610107965.XA CN105597659B (en) | 2016-02-26 | 2016-02-26 | One kind prepares CO using oil shale or dirty coal2The method of high-temperature adsorbing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105597659A true CN105597659A (en) | 2016-05-25 |
| CN105597659B CN105597659B (en) | 2018-01-16 |
Family
ID=55978325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610107965.XA Active CN105597659B (en) | 2016-02-26 | 2016-02-26 | One kind prepares CO using oil shale or dirty coal2The method of high-temperature adsorbing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105597659B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110404930A (en) * | 2019-07-24 | 2019-11-05 | 中国科学院兰州化学物理研究所 | A method of black oil shale semi-coke is turned white |
| CN111013527A (en) * | 2019-11-26 | 2020-04-17 | 中国矿业大学(北京) | Method for preparing heavy metal cadmium adsorption fixing agent from oil shale ash and coal ash |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102600818A (en) * | 2012-03-29 | 2012-07-25 | 昆明理工大学 | Preparation method and application of calcium oxide based absorbing material using diatomite as carrier |
| CN102815926A (en) * | 2012-08-31 | 2012-12-12 | 南开大学 | High-temperature calcium-based coal ash absorbent for CO2 and preparation method of high-temperature calcium-based coal ash absorbent |
| US8545781B1 (en) * | 2012-10-08 | 2013-10-01 | King Fahd University Of Petroleum And Minerals | Carbon dioxide adsorbent composition |
| CN104740995A (en) * | 2015-03-02 | 2015-07-01 | 中国矿业大学 | Fly-ash-based carbon dioxide curing agent and preparation method thereof |
-
2016
- 2016-02-26 CN CN201610107965.XA patent/CN105597659B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102600818A (en) * | 2012-03-29 | 2012-07-25 | 昆明理工大学 | Preparation method and application of calcium oxide based absorbing material using diatomite as carrier |
| CN102815926A (en) * | 2012-08-31 | 2012-12-12 | 南开大学 | High-temperature calcium-based coal ash absorbent for CO2 and preparation method of high-temperature calcium-based coal ash absorbent |
| US8545781B1 (en) * | 2012-10-08 | 2013-10-01 | King Fahd University Of Petroleum And Minerals | Carbon dioxide adsorbent composition |
| CN104740995A (en) * | 2015-03-02 | 2015-07-01 | 中国矿业大学 | Fly-ash-based carbon dioxide curing agent and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110404930A (en) * | 2019-07-24 | 2019-11-05 | 中国科学院兰州化学物理研究所 | A method of black oil shale semi-coke is turned white |
| CN110404930B (en) * | 2019-07-24 | 2021-09-14 | 中国科学院兰州化学物理研究所 | Method for turning black oil shale semicoke into white |
| CN111013527A (en) * | 2019-11-26 | 2020-04-17 | 中国矿业大学(北京) | Method for preparing heavy metal cadmium adsorption fixing agent from oil shale ash and coal ash |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105597659B (en) | 2018-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dindi et al. | Applications of fly ash for CO2 capture, utilization, and storage | |
| Chen et al. | The effect of fly ash on reactivity of calcium based sorbents for CO2 capture | |
| CN104437355B (en) | Preparation method of coal ash-based CuO-CeO2/FAU desulfurizer | |
| CN101367529B (en) | Method for synthesis of 4A molecular sieve with coal ash alkali melting method | |
| Boycheva et al. | Comparative studies of carbon capture onto coal fly ash zeolites Na-X and Na–Ca-X | |
| Wang et al. | Solid‐waste‐derived carbon dioxide‐capturing materials | |
| Zou et al. | Sorption capacity and mechanism of Cr3+ on tobermorite derived from fly ash acid residue and carbide slag | |
| Han et al. | Relevant influence of alkali carbonate doping on the thermochemical energy storage of Ca-based natural minerals during CaO/CaCO3 cycles | |
| Xu et al. | Glycine tailored effective CaO-based heat carriers for thermochemical energy storage in concentrated solar power plants | |
| KR101150920B1 (en) | Method for manufacturing carbon dioxide absorbent | |
| CN102674346A (en) | Process for preparing high-specific surface area composite pore structure coal-based activated carbon by using low dosage of KOH | |
| CN103331096A (en) | Preparation method of modified carbon dioxide calcium-based absorbent | |
| CN105152340A (en) | Red mud phosphate-removing filling material for constructed wetland and preparation method thereof | |
| CN106984266A (en) | A kind of method that VOC molecular sieve adsorption materials are prepared by raw material of flyash | |
| CN103769045B (en) | A kind of preparation method of fly ash base high-performance adsorbing material | |
| CN105597659A (en) | Method for utilizing oil shale or ash coal to prepare CO2 high-temperature adsorbent | |
| CN103349891B (en) | Calcium magnesium double salt CO2 absorbent prepared from modified dolomite and preparation method thereof | |
| CN101890331A (en) | High strength dried regenerative CO2 adsorbent taking coal gangue as carrier and preparation thereof | |
| Na et al. | Pyrolysis of low-density polyethylene using synthetic catalysts produced from fly ash | |
| Gao et al. | Trends and advances in the development of coal fly ash-based materials for application in hydrogen-rich gas production: A review | |
| CN106693880A (en) | Calcium-based CO2 adsorbent and preparation method for same | |
| US20160271586A1 (en) | Dechlorinating Agent for Blast Furnace Top Gas | |
| Li et al. | Cigarette butt-assisted combustion synthesis of dolomite-derived sorbents with enhanced cyclic CO2 capturing capability for direct solar-driven calcium looping | |
| CN103537177A (en) | Modified calcium-based desulfurizing agent for dry desulfurization of sintering gas and preparation method of modified calcium-based desulfurizing agent | |
| CN101837279A (en) | Dry-type CO2 adsorbent using lake sediment and fly ash together as carrier and preparation thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |