CN105597659B - One kind prepares CO using oil shale or dirty coal2The method of high-temperature adsorbing agent - Google Patents
One kind prepares CO using oil shale or dirty coal2The method of high-temperature adsorbing agent Download PDFInfo
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- 239000004058 oil shale Substances 0.000 title claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 53
- 239000003245 coal Substances 0.000 claims abstract description 48
- 239000011575 calcium Substances 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 28
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 25
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 22
- 239000012190 activator Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000013021 overheating Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 33
- 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
- 239000007789 gas Substances 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
- 238000002156 mixing Methods 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 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
- 238000001816 cooling Methods 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000004579 marble Substances 0.000 claims description 4
- 230000008569 process Effects 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
- 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
- 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
- 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
- 239000004575 stone Substances 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 47
- 239000003463 adsorbent Substances 0.000 abstract description 23
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 238000004458 analytical method Methods 0.000 description 22
- 239000002585 base Substances 0.000 description 21
- 239000012298 atmosphere Substances 0.000 description 20
- 238000010521 absorption reaction Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000002956 ash Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000000921 elemental analysis Methods 0.000 description 10
- 229910052681 coesite Inorganic materials 0.000 description 9
- 229910052906 cristobalite Inorganic materials 0.000 description 9
- 239000011148 porous material Substances 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
- 230000001276 controlling effect Effects 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000003610 charcoal Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000009286 beneficial effect Effects 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
- 239000012299 nitrogen atmosphere Substances 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
- 238000012827 research and development Methods 0.000 description 4
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000005431 greenhouse gas Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000003079 shale oil Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 241000124033 Salix Species 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
- 230000008901 benefit Effects 0.000 description 2
- 159000000007 calcium salts Chemical group 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
- 230000005611 electricity Effects 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
- 230000007935 neutral effect Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000007420 reactivation Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 238000000926 separation method 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
- ZVKPGHYZRCHUJO-UHFFFAOYSA-N 4-ethenoxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=C(C(=O)OC=C)C=C1 ZVKPGHYZRCHUJO-UHFFFAOYSA-N 0.000 description 1
- 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000007707 calorimetry Methods 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
- 238000005253 cladding Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000011285 coke tar Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 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
- 238000000227 grinding Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 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
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000003014 reinforcing 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
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming Methods 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
One kind prepares CO using oil shale or dirty coal2The method of high-temperature adsorbing agent, oil shale or dirty coal are crushed to, be sieved into 70~180 μm of particle, be then 1 according to the mass ratio of oil shale particle, activator, calcium base reagent or dirty coal particle, activator, calcium base reagent:(0.1~10):(1~20) dispensing is carried out, and is well mixed, forms mixture；By mixture at 500~950 DEG C, pressure is under 0~2MPa, is heat-treated 1~10h, mixture is cooled into less than 100 DEG C in the residue formed after Overheating Treatment, then is washed to neutrality, after drying, obtains CO2High-temperature adsorbing agent.The present invention is wider with the raw material scope of application, and prepared adsorbent has larger specific surface area, excellent CO2The features such as adsorption capacity and recycling stability.
Description
Technical field
The invention belongs to the trans-utilization field of oil shale or dirty coal, and in particular to one kind utilizes oil shale or dirty coal
Prepare CO2The method of high-temperature adsorbing agent.
Background technology
Global oil shale resources very abundant, according to incompletely statistics its contain stock number and there are about 10,000,000,000,000 tons, provided than coal
Source amount more 40%.Oil Shale Resources in China rich reserves, the world the 4th is occupied by stock number sequence is verified, verifies stock number 315
Hundred million tons, 452,000,000,000 tons of prognostic resources.In addition, a large amount of oil shales are also generated in progress of coal mining.Develop oily page
Rock can not only alleviate contradiction between oil supply and demand, can also solve the environmental problem caused by discarded oil shale, improve the utilization of resources
Rate.
Oil shale (also known as oil shale) is a kind of high-ash sedimentary rock containing flammable organic matter, the main region of it and coal
Be not ash content more than 40%, the mineral matter in oil shale often uniformly compactly mixes with organic matter, it is difficult to the side of general coal separation
Method carries out ore dressing.Dirty coal has the property similar with oil shale.
Country variant is different to the purposes of oil shale.In Estonia, oil shale is mainly used to the shale oil that generates electricity and refine；
In Brazil, oil shale is mainly used as transporting fuel；In Germany, oil shale is mainly for the manufacture of cement and construction material；In China
And Australia, oil shale are mainly used in refining shale oil and as fuel；It is mainly used in Russia and Israel, oil shale
Generate electricity.
In recent years, the Global Environmental Problems getting worse using climate change as core, cuts down with CO2For the greenhouse gas of representative
Body discharge turns into the focus of current international community concern.Research and development CO2Efficient trapping with using technology to China control
It is significant with reducing greenhouse gas emission, responding actively the climatic issues such as global warming.And research and development are inexpensive
And efficient CO2Adsorbent turns into the current key scientific problems urgently to be resolved hurrily in the field, and research and development at this stage
Important directions.
, can be by CO according to adsorbent and the difference of adsorbate interactive property2Adsorption separation technology be divided into physics suction
Echo chemisorbed.CO2Physical absorption generally use pressure swing adsorption method, the selectivity of adsorbent is poor, adsorption capacity is small, but
Adsorbent reactivation is easy, simple to operate, energy consumption is relatively low.Relatively, CO2Chemisorbed generally use temp.-change adsorptive process, absorption
The selectivity of agent is preferable, adsorption capacity is larger, but adsorbent reactivation is relatively difficult, energy consumption is higher.Industrial common CO2Absorption
Agent majority has larger specific surface area, main to include being used for low temperature CO2The porous carbon materials such as the activated carbon of absorption, natural boiling
The materials such as stone, molecular sieve, silica gel, and for high temperature CO2The metal oxides such as the CaO of absorption, alkali carbonate, hydrotalcite
With the material such as lithium salts.Low temperature adsorbent using porous charcoal as representative depends on pore passage structure feature, mostly under low-temperature condition
Physical absorption category, and its surface functional group effect under chemical adsorption capacity it is weaker.Therefore, the absorption property of porous charcoal according to
So show the problems such as selectivity is poor, adsorption capacity is smaller, it would be highly desirable to improve and break through.
Due to each side factor, CaO and its modifier quilt such as raw material sources are extensive, cost is relatively low and preparation technology is simple
It is considered as presently preferred CO2High-temperature adsorbing agent, have broad application prospects.Wu Su virtues seminar of Zhejiang University inhales in CaO bases
Attached dose of aspect done substantial amounts of research work (Industrial＆Engineering Chemistry Research, 2008,47:
180-184；Chemical Engineering&Technology,2014, 37(4):580-586.), TiO is prepared in succession2、
MgO or Al2O3The nano-calcium carbonate of cladding, there is the nanometer CaO adsorbents of inertia support frame so as to obtain surface, prevent or
The generation of CaO sintering or agglomeration is slow down, improves the stability of CaO base adsorbents recycling；Higher adsorbance
Up to 6mol CO2/ kg adsorbents；However, after the adsorption-regeneration cycles of 30 times, the attenuation rate of adsorbent adsorbance reaches
About 30%, i.e., cyclical stability is up for improving.Chen etc. (Science of Advanced Materials, 2014,6
(8):1799-1805) with Ca-Al-CO3Composite oxides are as CO2Adsorbent, find its adsorption capacity accessibility theory value
53.1%, adsorption rate may remain in 95% after 40 adsorption-regeneration cycles, show excellent cyclical stability, but its
Adsorbance is far below the level of similar adsorbent, only 0.63mol CO2/ kg adsorbents.(the Journal such as Przepi ó rski
of Thermal Analysis and Calorimetry,2013, 111:357-364；International Journal
of Greenhouse Gas Control,2012,10:The Ca-base adsorbent of skeleton containing charcoal 164-168.) is prepared, i.e., with poly-
Vinyl terephthalate supports MgO/CaO composite for the porous carbon material of carbon source, finds this composite simultaneously
With physics and the dual adsorption function of chemistry, the larger specific surface area of porous charcoal skeleton improves MgO/CaO decentralization, can had
Effect alleviates the generation of adsorbent sintering and agglomeration, but the stability during recycling of its long period needs further improvement
Or improve.
Up to now, there is not yet " preparing CO using oil shale or dirty coal2Technique or technology report in terms of adsorbent "
Road.
The content of the invention
To overcome the problems of the prior art, prepared it is an object of the invention to provide one kind using oil shale or dirty coal
CO2The method of high-temperature adsorbing agent, this method is using oil shale (or dirty coal) while has higher carbon content and content of ashes
(Al in ash content2O3And SiO2The property of usual reachable more than 50%) of the gross mass content of both compositions, with reference to CaO to CO2's
High temperature adsorption, by building and regulating and controlling charcoal skeleton, Al2O3-SiO2Inertia skeleton and CaO crystal grain three are on a microscopic scale
Organically combine and act synergistically system, designs and prepare " charcoal-Al2O3-SiO2" compound skeleton CO2Sorbing material, so as to reach
To reinforcing with improving CO2The purpose of absorption property.
To achieve the above object, the technical solution adopted by the present invention is as follows：
One kind prepares CO using oil shale or dirty coal2The method of high-temperature adsorbing agent, comprises the following steps：
Step 1: oil shale or dirty coal to be crushed to, be sieved into 70~180 μm of particle, then according to oil shale particle,
Activator, the mass ratio of calcium base reagent are 1:(0.1~10):(1~20) or according to dirty coal particle, activator, calcium base reagent
Mass ratio be 1:(0.1~10):(1~20) dispensing is carried out, and is well mixed, forms mixture；
Step 2: mixture obtained by step 1 is heat-treated, the condition of heat treatment is：Temperature range be 500~
950 DEG C, pressure is 0~2MPa, and heat treatment time is 1~10h, and mixture is cooled down in the residue formed after Overheating Treatment
To less than 100 DEG C, then neutrality is washed to, after drying, obtains CO2High-temperature adsorbing agent.
The activator is K2CO3、Na2CO3、KOH、NaOH、KHCO3、NaHCO3、ZnCl2Middle one or more of or dense sulphur
One or both of acid, phosphoric acid.
The mass fraction of the concentrated sulfuric acid is 70%~98%, and the mass fraction of phosphoric acid is 80%~98%.
The calcium base reagent is calcium salt and/or calcium ore deposit.
The calcium salt is CaO, Ca (OH)2、CaCO3、CaCl2、Ca(NO3)2In one or more.
The calcium ore deposit is the one or more in marble, lime stone, dolomite.
It is described to be well mixed the hybrid mode progress for mixing or being placed in by mechanical agitation and mixed in solution.
Described be placed in solution is combined by being placed in water and ethanol volume ratio as 5:Stirred in 1 water-ethanol binary solution
Mix realization.
The heat treatment is in nitrogen, argon gas, helium, CO2, air, carry out under one or more of gases in vapor
's.
The residue cooling uses cold water spray process, vapor heat-exchanging method, inert gas heat-exchanging method or inertia
What the natural cooling under gas shield was carried out.
Compared with prior art, the device have the advantages that：
The present invention can be by oil shale or the higher value application and high temperature CO of dirty coal2The preparation of adsorbent is combined together,
Higher carbon content and the property of the content of ashes (ash content of oil shale or dirty coal are had based on oil shale or dirty coal simultaneously
In, Al2O3And SiO2The gross mass contents of both compositions is generally up to more than 50%), using CaO crystal grain on nanoscale with
" charcoal-Al2O3-SiO2" compound skeleton combination, the CO of research and development NEW TYPE OF COMPOSITE skeleton2Sorbing material, structure collaboration
Suction-operated system, realizes CO2The purpose that mass transfer enhancement, adsorbance and the cyclical stability of absorption effectively improve.Surveyed through experiment
, the CO prepared according to technical scheme provided by the invention2Sorbing material, BET specific surface area is up to 165~572m2/ g (tradition
The typically smaller than 100m of preparation method2/ g), total pore volume is up to 0.272~0.585cm3/ g, the CO at 600~850 DEG C2Absorption
Capacity is up to 0.55gCO2/gCaO(about the 70% of theoretical value, convert into 8.75mol CO2/ kg adsorbents), by 50 times absorption-
After de-adsorption cycle use, adsorption capacity is still maintained at more than the 80% of initial adsorption amount.
In addition, technical scheme provided by the invention has further the advantage that：
1) primary raw material abundance of the invention, cheap, is applicable not only to oil shale or dirty coal, equally applicable
In flying dust etc. caused by the semi-coke or coal tar of high ash content, coal directly-liquefied residue, Coal Gasification or coking.
2) " charcoal-Al prepared by the present invention2O3-SiO2" compound skeleton supporting ca O grain type adsorbents, not only using charcoal
The larger specific surface area of skeleton (after heat treatment being formed by the carbon component in raw shale oil or dirty coal), effectively improves CaO
Crystal grain (i.e. CO2Adsorption activity center) decentralization, improve adsorption reaction activity；And using Al2O3-SiO2Skeleton it is lazy
Property, suppress or prevent the sintering or agglomeration at adsorption activity center, strengthen CO2Absorption property and sorbent circulation use steady
It is qualitative.
3) CO of compound skeleton prepared by the present invention2High-temperature adsorbing agent has more rich pore passage structure, relative to tradition
Calcium base CO2Adsorbent (usual duct limited configurations, specific surface area are smaller), can effectively shorten CO2The road of molecule transmission and diffusion
Footpath, help to reduce the resistance to mass tranfer of adsorption reaction, and then improve the utilization rate and action effect of adsorbent active ingredient.
Embodiment
With reference to specific embodiment, the present invention is described in further detail, but is not limited to the following example.
Embodiment 1
Taking willow river oil shale, (Industrial Analysis of the sample is shown in Table 1 with Elemental analysis data, ash packet as material sample
Into being shown in Table 2), through the particle for crushing, being sieved into 70~180 μm.According to 1:1:1 mass ratio, weigh respectively oil shale particle,
K2CO3(analysis is pure, as activator) and CaO (analysis is pure, as calcium base reagent), and water-ethanol binary solution is added to simultaneously
(water is 5 with ethanol volume ratio:1) in, after being stirred mixing 10h, vacuum drying forms mixture A.
Then, mixture A is placed under nitrogen atmosphere protection and heated, the condition for regulating and controlling heat treatment is：Temperature
Spend for 500 DEG C, pressure is normal pressure, heat treatment time 8h.Again by the residue C formed after heat treatment under nitrogen atmosphere protection
Less than 100 DEG C are naturally cooled to, after being washed to neutrality, dry, obtains CO2High-temperature adsorbing agent.
The CO2The BET specific surface area of high-temperature adsorbing agent is 165m2/ g, total pore volume is up to 0.272cm3/g；600 DEG C,
20%CO2- 80%N2Under the atmosphere of composition, by 20min adsorption reactions, CO2The capacity of absorption is up to 0.25gCO2/gCaO。
Embodiment 2
Taking willow river oil shale, (Industrial Analysis of the sample is shown in Table 1 with Elemental analysis data, ash packet as material sample
Into being shown in Table 2), through the particle for crushing, being sieved into 70~180 μm.According to 1:2:3 mass ratio, weigh respectively oil shale particle,
K2CO3(analysis is pure, as activator) and CaO (analysis is pure, as calcium base reagent), and water-ethanol binary solution is added to simultaneously
(water is 5 with ethanol volume ratio:1) in, after being stirred mixing 10h, vacuum drying forms mixture A.
Then, mixture A is placed under steam atmosphere protection and heated, the condition for regulating and controlling heat treatment is：
Temperature is 600 DEG C, pressure 1MPa, heat treatment time 5h.The residue C formed after heat treatment is protected in steam atmosphere again
After 150 DEG C are cooled under shield, switch to and naturally cool to less than 100 DEG C under nitrogen protection, after being washed to neutrality, dry,
Obtain CO2High-temperature adsorbing agent.
The CO2The BET specific surface area of high-temperature adsorbing agent is 568m2/ g, total pore volume is up to 0.579cm3/g；600 DEG C,
20%CO2- 80%N2Under the atmosphere of composition, by 20min adsorption reactions, CO2The capacity of absorption is up to 0.55gCO2/gCaO, then
In 650 DEG C, N2Under atmosphere, by 15min desorption reactions and then secondary carry out adsorption reaction, circulate successively, by 50 suctions
After attached-de-adsorption cycle use, adsorption capacity is still maintained at the excellent beneficial effect of initial adsorption amount 83%.
Embodiment 3
Taking Estonia's oil shale, (Industrial Analysis of the sample is shown in Table 1 with Elemental analysis data, ash as material sample
It is grouped into and is shown in Table 2), through the particle for crushing, being sieved into 70~180 μm.According to 1:5:9 mass ratio, weighs oil shale respectively
Grain, NaOH (analysis is pure, as activator) and CaCO3(analysis is pure, as calcium base reagent), and ball mill grinding is added to simultaneously
In tank, after carrying out mechanical lapping, stirring 15min, mixture A is formed.
Then, mixture A is placed under nitrogen atmosphere protection and heated, the condition for regulating and controlling heat treatment is：Temperature
It is 700 DEG C to spend scope, and pressure is normal pressure, heat treatment time 8h.Again by the residue C formed after heat treatment in nitrogen atmosphere protection
Under naturally cool to less than 100 DEG C, through being washed to it is neutral, dry after, obtain CO2High-temperature adsorbing agent.
The CO2The BET specific surface area of high-temperature adsorbing agent is 283m2/ g, total pore volume is up to 0.319cm3/g；650 DEG C,
20%CO2- 80%N2Under the atmosphere of composition, by 20min adsorption reactions, CO2The capacity of absorption is up to 0.45gCO2/gCaO, so
Afterwards in 700 DEG C, N2Under atmosphere, by 15min desorption reactions and then secondary carry out adsorption reaction, circulate successively, by 50 suctions
After attached-de-adsorption cycle use, adsorption capacity is still maintained at the excellent beneficial effect of initial adsorption amount 81%.
Embodiment 4
Take Shengli coal (dirty coal sample 1) as material sample (Industrial Analysis of the sample is shown in Table 1 with Elemental analysis data,
2) ash composition is shown in Table, through the particle for crushing, being sieved into 70~180 μm.According to 1:9:15 mass ratio, weighs oil shale respectively
Particle, KHCO3(analysis is pure, as activator) and lime stone (analysis is pure, as calcium base reagent), and water-second is added to simultaneously
(water is 5 with ethanol volume ratio to alcohol binary solution:1) in, after being stirred mixing 10h, vacuum drying forms mixture A.
Then, mixture A is placed under steam atmosphere protection and heated, the condition for regulating and controlling heat treatment is：
Temperature is 800 DEG C, pressure 0.5MPa, heat treatment time 4h.Again by the residue C formed after heat treatment in steam atmosphere
After 150 DEG C are cooled under protection, switch to and naturally cool to less than 100 DEG C under nitrogen protection, it is neutral, dry by being washed to
Afterwards, CO is obtained2High-temperature adsorbing agent.
The CO2The BET specific surface area of high-temperature adsorbing agent is 517m2/ g, total pore volume is up to 0.387cm3/g；650 DEG C,
20%CO2- 80%N2Under the atmosphere of composition, by 20min adsorption reactions, CO2The capacity of absorption is up to 0.53gCO2/gCaO, then
In 700 DEG C, N2Under atmosphere, by 15min desorption reactions and then secondary carry out adsorption reaction, circulate successively, by 50 suctions
After attached-de-adsorption cycle use, adsorption capacity is still maintained at the excellent beneficial effect of initial adsorption amount 81%.
Embodiment 5
Take Pingshuo Coal (dirty coal sample 2) as material sample (Industrial Analysis of the sample is shown in Table 1 with Elemental analysis data,
2) ash composition is shown in Table, through the particle for crushing, being sieved into 70~180 μm.According to 1:2:7 mass ratio, weighs oil shale respectively
Particle, ZnCl2(analysis is pure, as activator) and lime stone (analysis is pure, as calcium base reagent), and water-second is added to simultaneously
(water is 5 with ethanol volume ratio to alcohol binary solution:1) in, after being stirred mixing 10h, vacuum drying forms mixture A.
Then, mixture A is placed under steam atmosphere protection and heated, the condition for regulating and controlling heat treatment is：
Temperature is 900 DEG C, and pressure is normal pressure, heat treatment time 4h.The residue C formed after heat treatment is protected in steam atmosphere again
After 150 DEG C are cooled under shield, switch to and naturally cool to less than 100 DEG C under nitrogen protection, after being washed to neutrality, dry,
Obtain CO2High-temperature adsorbing agent.
The CO2The BET specific surface area of high-temperature adsorbing agent is 572m2/ g, total pore volume is up to 0.585cm3/g；650 DEG C,
20%CO2- 80%N2Under the atmosphere of composition, by 20min adsorption reactions, CO2The capacity of absorption is up to 0.53gCO2/gCaO, then
In 700 DEG C, N2Under atmosphere, by 15min desorption reactions and then secondary carry out adsorption reaction, circulate successively, by 50 suctions
After attached-de-adsorption cycle use, adsorption capacity is still maintained at the excellent beneficial effect of initial adsorption amount 80%.
Embodiment 6
Take Shenhua direct coal liquefaction residue as material sample (Industrial Analysis of the sample is shown in Table 1 with Elemental analysis data,
2) ash composition is shown in Table, through the particle for crushing, being sieved into 70~180 μm.According to 1:2:7 mass ratio, weighs oil shale respectively
Particle, KOH (analysis is pure, as activator) and lime stone (analysis is pure, as calcium base reagent), and water-ethanol is added to simultaneously
(water is 5 with ethanol volume ratio to binary solution:1) in, after being stirred mixing 10h, vacuum drying forms mixture A.
Then, mixture A is placed under steam atmosphere protection and heated, the condition for regulating and controlling heat treatment is：
Temperature is 900 DEG C, and pressure is normal pressure, heat treatment time 4h.Again by the residue C formed after heat treatment under nitrogen atmosphere protection
Less than 100 DEG C are naturally cooled to, after being washed to neutrality, dry, obtains CO2High-temperature adsorbing agent.
The CO2The BET specific surface area of high-temperature adsorbing agent is 557m2/ g, total pore volume is up to 0.534cm3/g；650 DEG C,
20%CO2- 80%N2Under the atmosphere of composition, by 20min adsorption reactions, CO2The capacity of absorption is up to 0.52gCO2/gCaO, then
In 700 DEG C, N2Under atmosphere, by 15min desorption reactions and then secondary carry out adsorption reaction, circulate successively, by 50 suctions
After attached-de-adsorption cycle use, adsorption capacity is still maintained at the excellent beneficial effect of initial adsorption amount 83%.
The Industrial Analysis of the sample such as the oil shale of table 1 or coal and Elemental analysis data table
*Minusing obtains
Ash composition analytical data (the unit of the sample such as the oil shale of table 2 or coal：Wt.%)
Embodiment 7
Step 1: by Jincheng Anthracite, (dirty coal sample 3,1) Industrial Analysis and the Elemental analysis data of the sample, which are shown in Table, to be broken
Particle that is broken, being sieved into 70~180 μm, it is then 1 according to the mass ratio of Jincheng Anthracite particle, activator, calcium base reagent:
0.1:20 carry out dispensing, and are well mixed using mechanical agitation mode, form mixture；Wherein, activator ZnCl2、NaHCO3
With K2CO3The mixture of three；Calcium base reagent is Ca (OH)2With CaCO3Mixture；
Step 2: by mixture obtained by step 1 in air with being heat-treated under nitrogen mixed gas, the bar of heat treatment
Part is：Temperature is 950 DEG C, and pressure is 0MPa (i.e. gauge pressure), heat treatment time 1h, and mixture is being formed after Overheating Treatment
Residue be cooled to less than 100 DEG C using cold water spray process, then be washed to neutrality, after drying, obtain CO2High-temperature adsorbing agent.
Embodiment 8
Step 1: by western bent coking coal, (dirty coal sample 4,1) Industrial Analysis and the Elemental analysis data of the sample, which are shown in Table, to be broken
Particle that is broken, being sieved into 70~180 μm, it is then 1 according to the mass ratio of western bent coking coal particle, activator, calcium base reagent:10:
12 carry out dispensing, and are well mixed using mechanical agitation mode, form mixture；Wherein, activator is that mass fraction is 98%
The concentrated sulfuric acid and mass fraction be 80% phosphoric acid mixture；Calcium base reagent is CaCO3、CaCl2With Ca (NO3)2Mixing
Thing；
Step 2: by mixture obtained by step 1 in CO2It is heat-treated under atmosphere, the condition of heat treatment is：Temperature is
550 DEG C, pressure 1.5MPa, heat treatment time 10h, mixture is steamed in the residue formed after Overheating Treatment using water
Gas heat-exchanging method is cooled to less than 100 DEG C, then is washed to neutrality, after drying, obtains CO2High-temperature adsorbing agent.
Embodiment 9
Step 1: by western bent coking coal, (dirty coal sample 4,1) Industrial Analysis and the Elemental analysis data of the sample, which are shown in Table, to be broken
Particle that is broken, being sieved into 70~180 μm, it is then 1 according to the mass ratio of western bent coking coal particle, activator, calcium base reagent:7:2
Dispensing is carried out, and is well mixed using mechanical agitation mode, forms mixture；Wherein, activator is that mass fraction is 98%
Mixture of the phosphoric acid with mass fraction for 70% concentrated sulfuric acid；Calcium base reagent is CaCl2, marble and dolomite mixture；
Step 2: by mixture obtained by step 1 in argon gas with being heat-treated under helium mix gas, the bar of heat treatment
Part is：Temperature is 700 DEG C, pressure 2MPa, heat treatment time 3h, by mixture in the residue formed after Overheating Treatment
Less than 100 DEG C are cooled to using inert gas heat-exchanging method, then is washed to neutrality, after drying, obtains CO2High-temperature adsorbing agent.
Embodiment 10
Step 1: oil shale to be crushed to, is sieved into 70~180 μm of particle, then according to oil shale particle, activator,
The mass ratio of calcium base reagent is 1:9:5 carry out dispensing, and are well mixed using mechanical agitation mode, form mixture；Wherein, it is living
Agent is the phosphoric acid that mass fraction is 90%；Calcium base reagent is CaCO3, marble and lime stone mixture；
Step 2: mixture obtained by step 1 is heat-treated in air atmosphere, the condition of heat treatment is：Temperature is
800 DEG C, pressure 1.7MPa, heat treatment time 7h, by mixture in the residue natural cooling formed after Overheating Treatment
To less than 100 DEG C, then neutrality is washed to, after drying, obtains CO2High-temperature adsorbing agent.
The present invention has higher carbon content and the property of content of ashes simultaneously using oil shale or dirty coal, with reference to CaO
To CO2High temperature adsorption, by building and regulating and controlling charcoal skeleton, Al2O3-SiO2Inertia skeleton is with CaO crystal grain threes microcosmic
Combination and synergy system on yardstick, design and prepare " charcoal-Al2O3-SiO2" compound skeleton CO2Adsorption material
Material, strengthen so as to reach with improving CO2The purpose of absorption property.It has wider, the prepared adsorbent of the raw material scope of application
With larger specific surface area, excellent CO2The features such as adsorption capacity and recycling stability.
Claims (8)
1. one kind prepares CO using oil shale or dirty coal2The method of high-temperature adsorbing agent, it is characterised in that comprise the following steps：
Step 1: oil shale or dirty coal are crushed to, are sieved into 70~180 μm of particle, then according to oil shale particle, activation
Agent, the mass ratio of calcium base reagent are 1:(0.1~10):(1~20) or according to dirty coal particle, activator, calcium base reagent matter
Amount is than being 1:(0.1~10):(1~20) dispensing is carried out, and is well mixed, forms mixture；
Step 2: mixture obtained by step 1 is heat-treated, the condition of heat treatment is：Temperature range is 500~950 DEG C,
Pressure is 0~2MPa, and heat treatment time is 1~10h, and mixture is cooled into 100 in the residue formed after Overheating Treatment
Below DEG C, then neutrality is washed to, after drying, obtains CO2High-temperature adsorbing agent.
2. one kind according to claim 1 prepares CO using oil shale or dirty coal2The method of high-temperature adsorbing agent, its feature
It is, the activator is K2CO3、Na2CO3、KOH、NaOH、KHCO3、NaHCO3、ZnCl2The middle one or more of or concentrated sulfuric acid,
One or both of phosphoric acid.
3. one kind according to claim 2 prepares CO using oil shale or dirty coal2The method of high-temperature adsorbing agent, its feature
It is, the mass fraction of the concentrated sulfuric acid is 70%~98%, and the mass fraction of phosphoric acid is 80%~98%.
4. one kind according to claim 1 prepares CO using oil shale or dirty coal2The method of high-temperature adsorbing agent, its feature
It is, the calcium base reagent is CaO, Ca (OH)2、CaCO3、CaCl2、Ca(NO3)2In one or more and/or marble, stone
One or more in lime stone, dolomite.
5. one kind according to claim 1 prepares CO using oil shale or dirty coal2The method of high-temperature adsorbing agent, its feature
It is, it is described to be well mixed the hybrid mode progress for mixing or being placed in by mechanical agitation and mixed in solution.
6. one kind according to claim 5 prepares CO using oil shale or dirty coal2The method of high-temperature adsorbing agent, its feature
It is, described be placed in solution is combined by being placed in water and ethanol volume ratio as 5:Stirred in 1 water-ethanol binary solution real
Existing.
7. one kind according to claim 1 prepares CO using oil shale or dirty coal2The method of high-temperature adsorbing agent, its feature
It is, the heat treatment is in nitrogen, argon gas, helium, CO2, air, carry out under one or more of gases in vapor.
8. one kind according to claim 1 prepares CO using oil shale or dirty coal2The method of high-temperature adsorbing agent, its feature
It is, the residue cooling uses cold water spray process, vapor heat-exchanging method, inert gas heat-exchanging method or inert gas
What the natural cooling under protection was carried out.
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| 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 |
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| 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 |
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