CN113441110A - Method for preparing adsorbent for adsorbing and separating carbon monoxide - Google Patents
Method for preparing adsorbent for adsorbing and separating carbon monoxide Download PDFInfo
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- CN113441110A CN113441110A CN202110934006.6A CN202110934006A CN113441110A CN 113441110 A CN113441110 A CN 113441110A CN 202110934006 A CN202110934006 A CN 202110934006A CN 113441110 A CN113441110 A CN 113441110A
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- activated carbon
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 58
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 175
- 238000001035 drying Methods 0.000 claims abstract description 90
- 238000001179 sorption measurement Methods 0.000 claims abstract description 33
- 150000001879 copper Chemical class 0.000 claims abstract description 31
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 7
- 238000005470 impregnation Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 20
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 238000005485 electric heating Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000000274 adsorptive effect Effects 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 claims description 3
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000011068 loading method Methods 0.000 abstract description 5
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000007598 dipping method Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000001976 improved effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 238000013021 overheating Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- -1 copper complex salt Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention provides a preparation method of an adsorbent for carbon monoxide adsorption separation, which takes activated carbon as a carrier, prepares copper salt and/or other additives into solution, then impregnates the solution onto the activated carbon carrier, places the impregnated activated carbon in a rotary kiln, and leads current into the impregnated activated carbon, thereby leading the activated carbon to generate heat to finish the drying process of the adsorbent preparation. The obtained adsorbent has large copper salt loading capacity, uniform distribution between the inner surface of the activated carbon and different particles of the activated carbon, difficult loss, convenient unloading after drying, less copper salt adhesion on the surface of the activated carbon and higher adsorption capacity than the traditional drying method.
Description
Technical Field
The invention relates to the technical field of carbon monoxide adsorbents, in particular to a preparation method of an adsorbent for carbon monoxide adsorption separation, which is used for separating and purifying carbon monoxide gas through pressure swing adsorption or temperature swing adsorption.
Background
The pressure swing adsorption or temperature swing adsorption separation and purification process of gas is widely applied due to low energy consumption, normal temperature operation, high automation degree, simple flow and changeable size of the device. In 1985, 410Nm was built in Japan by Kawasaki iron-making, Japan and United states carbide3A pressure swing adsorption CO purification device. The capacity of a single set of large-scale CO pressure swing adsorption and hydrogen pressure swing adsorption separation and purification devices in the carbon-chemical industry and the petrochemical industry is achievedTo the scale of tens of thousands of cubic meters of gas produced per hour.
Currently, adsorbents used for pressure swing adsorption separation of hydrogen and CO in industry generally use activated carbon, molecular sieves, silicon oxide or aluminum oxide as carriers, and load cuprous as adsorbents.
Guan Ying et al (natural gas chemical industry: C1 chemical and chemical industry, 2010, 35(6): 49-52) examined a Cu (I)/activated carbon CO adsorbent, the first adsorption capacity of which reaches 46 ml/g. Can separate high-purity CO gas and can be operated at normal temperature.
Liu Shi et al (Natural gas chemical industry: C1 chemical and chemical industry, 2007, 32(1):14) investigated a Cu (I)/activated carbon CO adsorbent and also obtained high-purity CO gas. However, the above two documents do not relate to the problem of preparing Cu (I)/activated carbon adsorbent.
Yihong et al (environmental science, 2004,25(5): 24-29) used PU1 adsorbent of Beijing university to obtain high CO recovery and purity, and the adsorbent was Cu (I)/molecular sieve.
Na in Y-type molecular sieve is adsorbed by NaY-type adsorbent adopted by Nippon Steel tube Co+And Cu2+Exchange, and then reduce, etc., the CO adsorption capacity at 25 ℃ is about 60 ml/g.
Wangzong et al (Natural gas chemical industry, 1991,16(2): 8-13) have studied Cu (I)/activated carbon adsorbents. The preparation method comprises the steps of dipping copper salt on active carbon by a dipping method, and drying by air blowing.
Sunshi et al (Proc. of higher school chemistry, 2011,32 (8): 1794-1798) prepared CuCl/NaY molecular sieve adsorbent by glucose reduction. At 25 ℃ and a CO partial pressure of 100kPa, the adsorption capacity reached 59 ml/g.
Chinese patent CN1050403 discloses a Cu/activated carbon CO adsorbent, which is dried with inert gas or under vacuum in the drying process, unlike the drying method of the present invention.
Chinese patent CN1085114C discloses an adsorbent prepared from copper chloride, activated carbon, rare earth and attapulgite, but it does not describe the drying manner and the influence of the drying manner.
Representative chinese patent CN101890332A discloses a molecular sieve adsorbent for pressure swing adsorption, which is different from the adsorbent of the present invention.
Chinese patent CN103506070A discloses a method for preparing a copper/activated carbon adsorbent. The method adopts a mode of directly electrifying the impregnated activated carbon for drying, but the drying process is finished in a drying tower. The drying process is carried out in tower drying equipment, the cross section through which current flows in the drying tower is large, activated carbon particles are not stirred or turned over in the drying process, and the resistivity of the activated carbon or adsorbent material pile is continuously reduced along with the evaporation of water, so that the activated carbon at different positions in the drying tower is heated unevenly. Finally, part of the adsorbent is overheated, so that the activity of the adsorbent is reduced and the adsorbent is deactivated, even the activated carbon is burnt, and safety accidents are caused. In addition, if the impregnation process is also completed in the drying tower, a long-time draining process is required, otherwise the liquid loading of the activated carbon at the lower part of the drying tower is too much, a large amount of copper salt crystal grains are still attached to the outer surface of the part of the adsorbent activated carbon particles after drying, and the adsorbent is difficult to discharge from the drying tower. However, in the long-time draining process, the temperature of the adsorbent material pile in the drying tower is reduced, and the copper salt in the solution in the inner hole of the activated carbon is crystallized and separated out, so that the activity of the adsorbent is reduced, and the copper salt component is more easily lost and blocks the lower part of the adsorption tower in the using process of the adsorbent. In fact, once the temperature of the adsorbent pile drops after impregnation and before drying or a large amount of copper salt is crystallized out due to other reasons, the prepared adsorbent needs to be added with a screening process to screen out the crystallized copper salt crystal grains.
As described above, the conventional adsorbent documents do not disclose a method for producing an adsorbent similar to that of the present invention, and the most similar documents do not achieve the technical effects of the present invention.
Disclosure of Invention
The invention provides a preparation method of an adsorbent for carbon monoxide adsorption separation, aiming at solving the technical problems that: the active components in the adsorbent are uniformly distributed on the inner surface of the carrier active carbon, and the crystallization of the active components on the outer surface of the carrier active carbon is reduced as much as possible; and the problem that the local overheating and local drying degree of the activated carbon material pile is insufficient in the drying process is avoided.
In view of the above problems of the prior art, according to one aspect of the present disclosure, the following technical solutions are adopted in the present invention:
a method for preparing an adsorbent for adsorptive separation of carbon monoxide, comprising:
step i) impregnation Process
Preparing a copper salt and/or other additives into a solution, then impregnating an activated carbon carrier with the solution, and impregnating the copper salt and/or other additives onto the activated carbon;
step ii) drying process
Heating and drying the impregnated activated carbon, and subjecting the copper salt and/or other auxiliary agents loaded on the impregnated activated carbon to a heating, drying, decomposing and/or reducing process;
wherein, the dipping process of the step i) and the drying process of the step ii) are sequentially carried out in the same device;
and the drying process of the step ii) is to introduce current into the impregnated activated carbon to heat the activated carbon, and stir-fry the activated carbon in the process to finish the drying process.
In order to better realize the invention, the further technical scheme is as follows:
further, the copper salt is one or more of copper chloride, copper nitrate, copper acetate, copper formate, copper oxalate, copper sulfate and salts of copper complexes.
Further, the impregnation process of the step i) and the drying process of the step ii) are realized by a rotary kiln.
Further, in step ii):
the electrode of the power supply is directly in conductive connection with the impregnated activated carbon material pile in the electric heating impregnation drying device, and then current flows through the activated carbon between the electrode and the electrode, so that the activated carbon generates heat to complete the heating process of the adsorbent.
Further, in step ii):
induced current is generated in the impregnated activated carbon in an alternating current induction mode, so that the current is introduced into the impregnated activated carbon in the electric heating impregnation drying device, and the activated carbon generates heat to complete heating and drying of the adsorbent.
Further, in step ii):
introducing inert gas or vacuum sucking to take the evaporated solvent out of the drying device.
Further, after the first drying process is completed, the dipping and drying process is repeated one or more times.
Further, in the drying process, carbon monoxide and/or hydrogen is introduced into the activated carbon material pile to reduce the cupric salt into the cuprous salt.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a method for preparing an adsorbent for carbon monoxide adsorption separation, which comprises the following steps:
1) compared with a drying tower which directly supplies electricity to the heated material for heating, the drying tower reduces the draining time of the impregnated activated carbon material pile, obviously improves the labor productivity, and avoids the loss of the adsorption capacity caused by the crystallization and precipitation of the active components due to the reduction of the temperature of the material pile caused by long-time draining after hot solution impregnation; in a drying tower, if the material pile is not drained for a long time, the liquid content at the bottom of the material pile is higher than that at the upper part, more active components are loaded on the active carbon at the bottom after drying than that at the upper part, and active component grains which are not loaded among active carbon particles at the bottom are also loaded, so that the active component is unevenly loaded, and the unloaded active component grains need to be screened after drying;
2) compared with a drying tower which directly supplies electricity to the heated material for heating, the problem that the local overheating and local drying degree of the activated carbon material pile is insufficient in the drying process is avoided; because the resistivity of the activated carbon particles is continuously reduced along with the evaporation of the solvent in the drying process of the activated carbon material pile, when the activated carbon material pile is dried by a directly electrified drying tower, the material cannot be turned over, so that the local resistance of a passage through which current flows is preferentially reduced, then more current flows through the passage, and then the material in the passage is preferentially heated and even burnt out due to overheating;
3) compared with a steam coil or a jacket heating mode or a hot air blast drying and heating mode, the technical scheme of the invention avoids a great deal of precipitation of active components of the adsorbent on the outer surface of the carrier active carbon, and improves the loading capacity of the active components; and as the heat conduction process is omitted, the heating and drying speed is faster and more uniform, and the labor productivity is greatly improved.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
A method for preparing an adsorbent for adsorptive separation of carbon monoxide, comprising:
step i) impregnation Process
Preparing a copper salt and/or other additives into a solution, then impregnating an activated carbon carrier with the solution, and impregnating the copper salt and/or other additives onto the activated carbon;
step ii) drying process
Heating and drying the impregnated activated carbon, and subjecting the copper salt and/or other auxiliary agents loaded on the impregnated activated carbon to a heating, drying, decomposing and/or reducing process;
wherein, the dipping process of the step i) and the drying process of the step ii) are sequentially carried out in the same device;
and the drying process of the step ii) is to introduce current into the impregnated activated carbon to heat the activated carbon, and stir-fry the activated carbon in the process to finish the drying process.
The copper salt may be one or more of copper chloride, copper nitrate, copper acetate, copper formate, copper oxalate, copper sulfate, and copper complex salt. In a preferred embodiment, the copper salt used is copper chloride.
Typically, the impregnation process for carrying out step i) above and the drying process for said step ii) are carried out in a rotary kiln. I.e. without transfer after impregnation, followed by drying.
In step ii) of the above example, one embodiment of the method for applying current to the impregnated activated carbon is to directly electrically connect the electrode of the power source to the impregnated activated carbon stack in the electrically heated impregnation drying device, and then to apply current to the activated carbon between the electrode and the electrode, so that the activated carbon itself generates heat to complete the heating process for the adsorbent. Or, the method for introducing the current into the impregnated activated carbon is to generate induction current in the impregnated activated carbon in an alternating current induction mode, so that the current is introduced into the impregnated activated carbon in the electric heating impregnation drying device, and the activated carbon generates heat to finish the heating process of the adsorbent.
In the drying process of step ii), the evaporated solvent can be taken out of the drying device by introducing inert gas or by vacuum suction. The drying device mentioned in this embodiment or other parts may be a rotary kiln.
In general, the impregnation and drying process may be repeated one or more times after the first described drying process is completed.
And in the drying process, introducing carbon monoxide gas into the activated carbon material pile to reduce the cupric salt into cuprous salt.
The adsorbent impregnation and dry reduction in the present invention are both carried out in an electrically heated impregnation drying rotary kiln. The evaluation of the adsorption separation ability can be carried out in a fixed bed adsorption tower which is a glass tube with an inner diameter of 2cm and a length of 50cm, and which is CO/H2、CO/N2And CO/CH4And (3) characterizing the separation capacity of the gas subjected to pressure swing adsorption. The CO partial pressure in the mixed gas is 35kPa, the total pressure of the mixed gas is 101kPa gauge pressure, and after saturated adsorption is carried out at room temperature, the equilibrium adsorption quantity of CO is obtained by the volume difference of gas entering and leaving the adsorption bed layer-the dead volume of the adsorption bed layer. Vacuum was applied to-90 kPa gauge to regenerate the adsorbent. The CO content was analyzed by gas chromatography using about 100ml of the gas desorbed during regeneration.
The invention is further illustrated by the following specific examples:
carrier carbon: activated carbon, bulk density 0.40g/ml, BET specific surface area 1050m2Particles/g, particle diameter 2.5mm, particle sizeThe particle length is 2-6 mm.
Electric heating dipping drying rotary kiln: the rotary pipe of the rotary kiln is an epoxy resin circular pipe with the length of 4m and the inner diameter of 1.6m, 6 frying plates are uniformly arranged on the inner wall of the rotary pipe along the circumferential direction, and the frying plates and the two ends of the cylinder of the rotary pipe form an angle of 75 degrees. The rotary pipe is provided with an immersion liquid inlet, an immersion liquid outlet, a carrier carbon inlet and a carrier carbon outlet. The impregnation liquid outlet is also the outlet for solvent vapour during drying. The inside of the rotary tube is provided with a positive electrode and a negative electrode which are respectively fixed on the two end cover plates of the rotary tube cylinder and are in conductive connection with the positive electrode and the negative electrode of the power supply outside the rotary tube.
Impregnating solution: 25% copper chloride solution by mass.
Adding the carrier carbon of 3m into the electric heating dipping drying rotary kiln3And circularly soaking with 90 deg.C soaking solution for 1 hr, and allowing 90 deg.C soaking solution to enter from the inlet of the rotary kiln and to flow back from the outlet. And (3) draining for 10 minutes after the impregnation is finished, then rotating the rotary kiln, applying 380V alternating current to positive and negative electrodes of the electric heating impregnation drying rotary kiln, gradually heating the carrier carbon loaded with the impregnation liquid to 200 ℃ within 1 hour, simultaneously introducing nitrogen containing 10% of carbon monoxide into the rotary pipe, then stopping the energization heating, continuously introducing nitrogen to cool to 50 ℃, and discharging the prepared adsorbent. The surface of the adsorbent is black of the activated carbon.
The equilibrium adsorption capacity of the adsorbent was tested as described above, with a first equilibrium adsorption capacity of CO of 61 ml/g. The second and third adsorption amounts were 49 and 48 ml/g. The CO content in the desorbed gas is 99 percent during regeneration. It is estimated that some non-CO gas is due to bed voids. The three mixed gases have little influence on the equilibrium adsorption quantity of CO.
In summary, the technical principle of the invention is that the drying mode in the preparation process of the adsorbent is improved, crystallization or agglomeration behaviors of the copper salt and/or the auxiliary agent on the inner and outer surfaces of the activated carbon particle and in the micropore are inhibited, migration and enrichment of the copper salt and/or the auxiliary agent to the surface of the activated carbon particle in the drying process of the adsorbent are inhibited, so that the distribution condition of the copper salt and/or the auxiliary agent on the surface of the activated carbon carrier is effectively improved, and the adsorbent has higher adsorption capacity and longer service life under the condition of the same loading amount of the copper salt and/or the auxiliary agent; and the copper salt and/or the auxiliary agent can be uniformly distributed on the surface of the activated carbon under the condition of obviously improving the loading capacity of the copper salt and/or the auxiliary agent on the activated carbon. The method of the invention can also lead the copper salt and/or the auxiliary agent loaded on the activated carbon carrier to undergo further decomposition oxidation or reduction processes. And after the decomposition, oxidation or reduction process has occurred, the impregnation, drying, and further decomposition, oxidation or reduction processes are repeated again. By adopting the electric heating, dipping and drying integrated rotary kiln device, the draining time after dipping is shortened, the active carbon material pile is stir-fried in the drying process, the heating is uniform, and the residual liquid in the material pile is also uniformly distributed.
The embodiments are described in a progressive manner in the specification, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
Reference throughout this specification to "one embodiment," "another embodiment," "an embodiment," etc., means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment described generally in this application. The appearances of the same phrase in various places in the specification are not necessarily all referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with any embodiment, it is submitted that it is within the scope of the invention to effect such feature, structure, or characteristic in connection with other embodiments.
Although the invention has been described herein with reference to a number of illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure. More specifically, various variations and modifications are possible in the component parts and/or arrangements of the subject combination arrangement within the scope of the disclosure and claims of this application. In addition to variations and modifications in the component parts and/or arrangements, other uses will also be apparent to those skilled in the art.
Claims (8)
1. A method for preparing an adsorbent for adsorptive separation of carbon monoxide, comprising:
step i) impregnation Process
Preparing a copper salt and/or other additives into a solution, then impregnating an activated carbon carrier with the solution, and impregnating the copper salt and/or other additives onto the activated carbon;
step ii) drying process
Heating and drying the impregnated activated carbon, and subjecting the copper salt and/or other auxiliary agents loaded on the impregnated activated carbon to a heating, drying, decomposing and/or reducing process;
characterized in that the impregnation process of step i) and the drying process of step ii) are carried out sequentially in the same apparatus;
and the drying process of the step ii) is to introduce current into the impregnated activated carbon to heat the activated carbon, and stir-fry the activated carbon in the process to finish the drying process.
2. The method according to claim 1, wherein the copper salt is one or more selected from the group consisting of copper chloride, copper nitrate, copper acetate, copper formate, copper oxalate, copper sulfate, and salts of copper complexes.
3. The method according to any one of claims 1 to 2, wherein the impregnation step of step i) and the drying step of step ii) are performed by a rotary kiln.
4. The method according to any one of claims 1 to 3, wherein in step ii):
the electrode of the power supply is directly in conductive connection with the impregnated activated carbon material pile in the electric heating impregnation drying device, and then current flows through the activated carbon between the electrode and the electrode, so that the activated carbon generates heat to complete the heating process of the adsorbent.
5. The method according to any one of claims 1 to 3, wherein in step ii):
induced current is generated in the impregnated activated carbon in an alternating current induction mode, so that the current is introduced into the impregnated activated carbon in the electric heating impregnation drying device, and the activated carbon generates heat to complete heating and drying of the adsorbent.
6. The method according to any one of claims 1 to 5, wherein in step ii):
introducing inert gas or vacuum sucking to take the evaporated solvent out of the drying device.
7. The method for producing an adsorbent for carbon monoxide adsorption separation according to any one of claims 1 to 6, characterized in that:
after the first drying process is completed, the impregnation and drying process is repeated one or more times.
8. The method for producing an adsorbent for carbon monoxide adsorption separation according to any one of claims 1 to 7, characterized in that:
and in the drying process, introducing carbon monoxide and/or hydrogen into the activated carbon material pile to reduce the cupric salt into cuprous salt.
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| CN116139666A (en) * | 2023-04-18 | 2023-05-23 | 大庆德斯曼环保设备有限公司 | Environmental protection exhaust emission treatment equipment |
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