CN115400721B - Activation, application and regeneration method of adsorbent for deeply removing CO - Google Patents
Activation, application and regeneration method of adsorbent for deeply removing CO Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 242
- 238000011069 regeneration method Methods 0.000 title claims abstract description 62
- 230000004913 activation Effects 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 92
- 230000009467 reduction Effects 0.000 claims abstract description 86
- 239000007789 gas Substances 0.000 claims abstract description 82
- 239000010949 copper Substances 0.000 claims abstract description 77
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 56
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000001301 oxygen Substances 0.000 claims abstract description 55
- 230000008929 regeneration Effects 0.000 claims abstract description 52
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 35
- 230000003213 activating effect Effects 0.000 claims abstract description 30
- 239000005751 Copper oxide Substances 0.000 claims abstract description 19
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 111
- 239000012071 phase Substances 0.000 claims description 32
- 239000007791 liquid phase Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 9
- 230000001172 regenerating effect Effects 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 30
- 230000003647 oxidation Effects 0.000 abstract description 15
- 238000007254 oxidation reaction Methods 0.000 abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052802 copper Inorganic materials 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 9
- 230000005012 migration Effects 0.000 abstract description 4
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- 238000001994 activation Methods 0.000 description 38
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 26
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 238000010926 purge Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- XTYUEDCPRIMJNG-UHFFFAOYSA-N copper zirconium Chemical compound [Cu].[Zr] XTYUEDCPRIMJNG-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01J20/34—Regenerating or reactivating
- B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
-
- 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
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
-
- 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
- B01D2257/502—Carbon monoxide
-
- 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 discloses an activation method, application and a regeneration method of an adsorbent for deeply removing CO, which are suitable for deeply removing copper oxide and MO of CO x The composite is formed by reducing and then oxidizing and activating the CO adsorbent; the application method comprises the following steps: removing CO from the material containing trace CO through an activated CO adsorbent; the regeneration method comprises the following steps: the CO adsorbent is activated and applied, then heated and regenerated by introducing regeneration gas. The invention improves Cu by an activation method of reduction and oxidation + Content and dispersibility of (2) to precisely control Cu + And the proportion of other valence state copper, the migration capacity of lattice oxygen on the surface of copper oxide is improved, and the activity of removing CO of the activated adsorbent is improved; the activation and regeneration method provided by the invention is easy to operate, good in repeatability and convenient for industrial application, and the content, composition and distribution of the active components of the CO adsorbent are accurately regulated and controlled, so that the activity of the CO adsorbent is stably maintained in a better state.
Description
Technical Field
The invention belongs to the technical field of adsorbents, and particularly relates to an activation, application and regeneration method of a deep CO removal adsorbent.
Background
The deep removal of CO has great significance and great demands in the fields of chemical industry, fuel cells, automobile tail gas and air purification, high-purity gas preparation, closed system CO elimination and the like, wherein the catalytic oxidation method can be carried out at a lower reaction temperature and under mild reaction conditions, and the deep removal is high in depth and simple to operate, so that the method is widely applied to the electronic industry and various chemical fields, such as the purification of polyolefin monomers in petroleum and coal chemical processes. Compared with noble metal catalysts such as gold, palladium, platinum and the like, the copper-based adsorbent has low cost, can reach better removal depth at low temperature, and is a common CO removal adsorbent in the industry at present. In recent years, the application of the high-activity polymerization catalyst requires that the content of CO in monomer raw materials is lower than 30ppb, and in addition, in order to avoid the influence of gasification of propylene under the condition of a liquid-phase polymerization process on system stability, the temperature of CO removal of liquid-phase propylene monomers cannot be higher than 50 ℃, which puts higher requirements on the removal depth and the reaction activity of CO catalytic oxidation.
The oxidation of CO on copper oxide adsorbents is based on the CO being adsorbed and activated on Cu active species of variable valence to react with active lattice oxygen in the copper oxide to form carbon dioxide. Research shows that the oxidation performance of pure CuO or Cu to CO is not good under the condition of low temperature and oxygen deficiency, but Cu in the copper oxide-based adsorbent + Has a significant influence on the activity of oxidizing CO by the amount and dispersibility of lattice oxygen. Thus, the active species Cu in copper oxide adsorbents is regulated by activation and regeneration + And the amount and activity of lattice oxygen are key technologies in the adsorbent preparation and application process. A two-component copper zirconium catalyst disclosed in the publication CN101642707a and a copper zirconium-containing three-component catalyst disclosed in the publication CN101462057a can remove 0.1ppm CO to less than 30ppb in both gas and liquid phase propylene, but neither describes the adsorbent activation and regeneration process. CN104475114 discloses a CuO-ZnO-ZrO 2 The composite oxide catalyst of (2) and the method for activating the catalyst by hydrogen reduction, but the reduction of CuO has various reaction paths and intermediate products, so that the catalyst is very easy to avoid Cu + And Cu is directly produced, so that it is difficult to produce Cu as a high active component by reduction control + It is difficult to control Cu in the activated adsorbent + The content ratio, distribution and activity of lattice oxygen of Cu and CuO lead to large difference of the performance of the adsorbent after reduction and activation and poor repeatability. Therefore, further development of the activation and regeneration process of the low-temperature high-activity CO adsorbent is needed to improve the CO oxidation performance of the adsorbent, so as to meet the current industryThe need for CO removal is applied.
Disclosure of Invention
The invention aims to solve the technical problem of providing an activation method for a deep removal CO adsorbent aiming at the defects of the prior art. The method activates the CO adsorbent by a method of reducing and then oxidizing, thereby improving Cu + Content and dispersibility of (2) to precisely control Cu + And the proportion of other valence state copper, the migration capacity of lattice oxygen on the surface of the copper oxide is improved, the activity of the adsorbent for removing CO after activation is improved, and the difficult problems that the copper oxide is easy to directly generate metal copper with low activity and the activation performance is difficult to improve only by reducing and activating the CO adsorbent are solved.
In order to solve the technical problems, the invention adopts the following technical scheme: an activation method of a deep CO removal adsorbent is characterized in that the deep CO removal adsorbent is copper oxide and MO x A composite comprising one or more of M Zn, ce, zr, al, mn, cr, co and Si, and x is MO x A stoichiometric number of zero charge, the activation method comprising the steps of:
step one, heating a CO adsorbent in a reducing airflow to reduce; the temperature of the reduction is 130-230 ℃, and the heat preservation time is 1-24 h;
and step two, activating the CO adsorbent obtained after the reduction in the step one by taking inert gas containing methanol and oxygen as activating gas at the temperature of 10-320 ℃ to obtain the activated CO adsorbent.
The activation method of the deep CO removal adsorbent is characterized in that in the first step, the reducing gas flow is H 2 CO or hydrocarbons, or reducing gas streams to H 2 A mixed gas of one of CO and hydrocarbon and an inert gas, H in the mixed gas 2 The volume fraction of CO or hydrocarbon is 1-100%; the reduction temperature is 140-190 ℃, and the reduction degree of the Cu-containing component in the reduced CO adsorbent is 70-100%. Preferably, H in the mixed gas 2 The volume fraction of CO or hydrocarbon is 10%～20％。
The amount of reducing gas in the reducing gas stream, the temperature of the reduction and the degree of reduction all affect the composition of the active species in the product and their dispersibility, content and reactivity on the adsorbent surface. The invention ensures that the reduction degree of the product is not lower than 70 percent by controlling the content of the reducing gas and the reduction temperature, and simultaneously avoids the sintering deactivation of the CO adsorbent, especially copper oxide, caused by too severe reduction reaction and too high bed temperature, thereby ensuring that the CO adsorbent reaches the optimal state of CO removal performance through a subsequent activation process.
The reduction degree of the Cu-containing component in the CO adsorbent after reduction in the invention is H 2 -ratio of hydrogen consumption of copper-containing component to hydrogen consumption of copper oxide in terms of CuO in TPR.
The activation method for deeply removing the CO adsorbent is characterized in that the volume fraction of methanol in the activated gas in the second step is 0.05-6%, and the volume fraction of oxygen is 0.1-22%; the activation temperature is 40-260 ℃, and the reduction degree of the Cu-containing component in the activated CO adsorbent is 65-85%. Preferably, the volume fraction of methanol in the activated gas is 2.4% and the volume fraction of oxygen is 8%.
The oxygen and methanol content of the activating gas and the activation temperature determine the active species, in particular Cu 2 O content and dispersibility. The method ensures that Cu obtained by reduction generates highly dispersed Cu by controlling the volume fractions of methanol and oxygen in the activated gas 2 O, and controlling Cu oxidation to Cu by adjusting the volume fraction of oxygen and the activation temperature 2 The O content avoids the decrease of the activity of the CO adsorbent caused by too high or too low methanol content, and the excessive oxidation of Cu to CuO caused by too high oxygen content and activation temperature, and simultaneously avoids the failure of the oxidation of Cu to generate enough Cu caused by too low oxygen content and activation temperature 2 O, thereby reducing the CO removal performance of the CO adsorbent. Finally, cu in the activated CO adsorbent at the activation temperature and the content of methanol and oxygen in the activated gas 2 O, cu and CuO have better relative proportion and dispersion state, so that the removal performance of the water reaches better waterThe reduction degree of Cu-containing components in the activated CO adsorbent is 65-85 percent.
The reduction degree of the Cu-containing component in the activated CO adsorbent in the invention is H 2 -ratio of hydrogen consumption of copper-containing component to hydrogen consumption of copper oxide in terms of CuO in TPR.
In addition, the invention also discloses an application method of the CO adsorbent, which is characterized in that the CO adsorbent is activated firstly, and then the material containing trace CO is subjected to CO removal through the activated CO adsorbent under the conditions of the temperature of 0-120 ℃ and the pressure of 0.1-5 MPa; the material containing trace CO is gas phase, liquid phase or gas-liquid mixed phase, and is olefin, saturated hydrocarbon or inert gas, the content of CO is 0.01 ppm-3000 ppm, and the content of CO in the material after CO removal is lower than 10ppb.
The content of CO in the trace CO-containing materials before and after CO removal was analyzed by gas chromatography equipped with a methane reformer and a hydrogen flame detector, and the minimum detection limit of CO was 0.01ppm.
The application method is characterized in that the space velocity of the gas phase material containing trace CO is 10h -1 ～100000h -1 The space velocity of the material containing trace CO in the liquid phase is 0.1h -1 ～100h -1 。
The invention also discloses a regeneration method of the CO adsorbent, which is characterized in that the CO adsorbent is heated to 180-320 ℃ after being activated and applied, and then inert gas containing methanol and oxygen is introduced as regeneration gas for regeneration.
The regeneration process of the CO adsorbent in the invention comprises the reaction of CO with lattice oxygen of the adsorbent to generate CO 2 And the activation treatment of the CO adsorbent surface by oxygen and methanol, the latter being the same as the mechanism of activation.
The invention controls the regeneration temperature to enable the CO adsorbed on the CO adsorbent to be completely oxidized and removed, and adds active oxygen consumed by CO reduction to the CO adsorbent by introducing regeneration gas for treatment, so that the regenerated CO adsorbent is maintained in a reduction degree range with better activity, the CO is prevented from being difficult to be completely desorbed due to the too low regeneration temperature, the accuracy and the capacity of the regenerated CO adsorbent for removing CO are reduced, and the degradation of the performance of the adsorbent due to the sintering of an active component or the excessive oxidation of copper in a low valence state into CuO due to the too high regeneration temperature is avoided. Finally, the regeneration temperature of the invention enables the CO to be completely oxidized and desorbed and enables the CO adsorbent to recover the reduction degree range with better activity in the regeneration atmosphere.
The regeneration method is characterized in that the volume fraction of methanol in the regeneration gas is 0.001-4%, and the volume fraction of oxygen is 0.001-6%; the regeneration temperature is 200 ℃, and the reduction degree of the Cu-containing component in the regenerated CO adsorbent is 70-80%. Preferably, the volume fraction of methanol in the regeneration gas is 0.5% and the volume fraction of oxygen is 0.6%.
The invention supplements active oxygen consumed by CO reduction for the CO adsorbent by controlling the composition of the regeneration gas, so as to recover the activity of the CO adsorbent, avoid the conditions that the reduction degree is too low and Cu is excessively oxidized into CuO with low activity in the regenerated CO adsorbent due to the too high oxygen content in the regeneration gas, and the sufficient active oxygen cannot be generated on the surface of the regenerated CO adsorbent due to the too low oxygen content, and simultaneously avoid the condition that the activity of the regenerated CO adsorbent is difficult to reach the optimal state due to the too high or too low methanol content.
Compared with the prior art, the invention has the following advantages:
1. compared with the method that the CO adsorbent is activated only by reduction so that copper oxide is easy to directly generate metal copper with low activity, the method utilizes Cu to preferentially generate Cu in the oxidation process + ，Cu + Continuous oxidation to regenerate Cu 2+ Is characterized in that the activation of the activating gas containing methanol and oxygen improves the Cu of intermediate high-activity species 2 O content of Cu + And the accurate regulation and control of the copper content in other valence states; meanwhile, the copper oxide is activated by the activating gas containing methanol and oxygen, and the methanol adsorbed on the surface of the copper oxide crystal grains is used for inhibiting the growth of Cu crystal grains in the oxidation process, so that oversized Cu is avoided to be formed 2 O, improve Cu 2 The dispersibility of O greatly improves the activity of the adsorbent for removing CO after activation.
2. In the activation and regeneration process involving methanol and oxygen, the invention is carried out along with M 2x+ Dissolution from copper oxide phase, MO x The induction effect on the lattice distortion of the surface copper oxide is enhanced, and the migration capability of lattice oxygen on the surface of the copper oxide is greatly improved, so that the adsorption oxidation activity of the CO adsorbent on CO is improved.
3. Compared with the method for activating the adsorbent by reduction only, the method for activating the adsorbent by reduction first and then oxidation ensures that more lattice oxygen is distributed on the surface of the adsorbent under the same reduction degree, avoids poor initial activity of the adsorbent caused by poor migration capability of bulk lattice oxygen, and further improves the activity of the activated CO adsorbent.
4. The activation and regeneration method provided by the invention is easy to operate and good in repeatability, the content, composition and distribution of the active components of the CO absorbing agent can be accurately regulated and controlled, the activity of the CO absorbing agent is stably maintained in a better state, the CO removing depth can reach 10ppb, the CO removing capacity of each milliliter of absorbing agent is higher than 0.7mL, and the method is convenient for industrial application.
The technical scheme of the invention is further described in detail by examples.
Detailed Description
The reduction degree of Cu-containing components in the CO adsorbent at each stage in the invention is determined by the reduction degree of each CO adsorbent in H 2 Hydrogen consumption in TPR is measured.
Example 1
The deep CO removal adsorbent of this example is CuO-ZnO-ZrO 2 Three-component adsorbent, and CuO, znO, zrO 2 The mass ratio of (2) is 70:20:10; the activation method comprises the following steps:
step one, loading 3mL of CO adsorbent particles with 20-40 meshes into a stainless steel reactor of a fixed bed reaction device, and introducing hydrogen with the volume purity of more than 99.99% as a reducing gas flow under normal pressure, wherein the volume airspeed is 3000h -1 Then heating to 130 ℃ at a speed of 2 ℃/min and maintaining for 3 hours for reduction; the reduction degree of the Cu-containing component in the CO adsorbent after reduction is 70%;
step two, purging and fixing by nitrogenBed layer 0.5h, volume space velocity 3000h -1 Then at 10 ℃ N containing 6% methanol by volume and 22% oxygen by volume 2 Activating the CO adsorbent after reduction in the first step for 50min as an activating gas to obtain an activated CO adsorbent; the reduction degree of the Cu-containing component in the activated CO adsorbent is 65%.
The application process of the deep removal CO adsorbent in this embodiment is as follows: at 50 ℃ and 0.1MPa, the gas-phase propylene containing trace CO is reacted for 3000h -1 Removing CO by means of an activated CO adsorbent; the composition of the gas-phase propylene containing trace CO is as follows by volume percent: c (C) 3 H 6 99.9％，CO 201ppm，C 3 H 8 48ppm，H 2 O0.5 ppm, and the content of CO in the gas-phase propylene after CO removal is lower than 0.01ppm.
Continuing the repeated application process, when the content of CO in the gas-phase propylene after CO removal is greater than 0.1ppm in the application process of the deep CO removal adsorbent in the embodiment, regenerating the CO adsorbent, wherein the specific process is as follows: the CO adsorbent bed was warmed to 260℃under a nitrogen atmosphere and then N containing 0.001% by volume methanol and 0.001% by volume oxygen was introduced 2 Passing through CO adsorbent bed as regeneration gas and maintaining for 15min for regeneration, and using nitrogen for 3000h after regeneration -1 Purging the CO adsorbent bed for 1h at a volume space velocity; the reduction degree of the Cu-containing component in the regenerated CO adsorbent is 70%.
The activity of the regenerated CO adsorbent was detected and evaluated according to the application procedure of the deep removal CO adsorbent in this example, and the results showed that: the content of CO in the gas-phase propylene after CO removal is lower than 0.005ppm, and the CO capacity of the regenerated CO adsorbent is 1.1mL CO/mL-cat.
CuO-ZnO-ZrO of the example 2 Zn and Zr in the adsorbent can be replaced by one or more than two of Zn, ce, zr, al, mn, cr, co and Si except the two; the trace CO-containing material in this example may also be replaced by olefins other than propylene, saturated hydrocarbons or inert gases.
Comparative example 1
This comparative example differs from example 1 in that: the activation method does not comprise a second step, wherein the CO adsorbent after reduction in the first step is used as an activated CO adsorbent; the content of CO in the gas-phase propylene after CO removal in the application process is lower than 0.02ppm; the regeneration process does not comprise a regeneration gas treatment process, the reduction degree of the Cu-containing component in the regenerated CO adsorbent is 75%, and the CO capacity of the regenerated CO adsorbent is 0.6mL CO/mL-cat.
Comparing example 1 with comparative example 1, it is clear that the activated CO adsorbent obtained in example 1 using the activation method of reduction followed by oxidation has a higher depth of removal and a significantly increased CO capacity after regeneration than the activated CO adsorbent obtained in comparative example 1 using the activation method of reduction directly.
Example 2
The deep CO removal adsorbent in the embodiment is a CuO-ZnO two-component adsorbent, and the mass ratio of CuO to ZnO is 50:50; the activation method comprises the following steps:
step one, loading 3mL of CO adsorbent particles with 20-40 meshes into a stainless steel reactor of a fixed bed reaction device, and introducing hydrogen with the volume purity of more than 99.99% as a reducing gas flow under normal pressure, wherein the volume airspeed is 3000h -1 Then heating to 230 ℃ at a speed of 2 ℃/min and maintaining for 1h for reduction; the reduction degree of the Cu-containing component in the reduced CO adsorbent is 100%;
step two, purging the fixed bed layer for 0.5h by nitrogen, wherein the volume space velocity is 3000h -1 Then N containing 2% methanol by volume and 3% oxygen by volume is added at 320 DEG C 2 Activating the CO adsorbent after reduction in the first step for 20min as an activating gas to obtain an activated CO adsorbent; the reduction degree of the Cu-containing component in the activated CO adsorbent is 75%.
The application process of the deep removal CO adsorbent in this embodiment is as follows: at 120 deg.C and 0.1MPa, making gas phase ethylene containing trace CO be reacted for 3000 hr -1 Removing CO by means of an activated CO adsorbent; the composition of the gas-phase ethylene containing trace CO is as follows by volume percent: c (C) 2 H 4 99.95%, methane and ethane 250ppm,CO 100ppm,C 2 H 2 ＜1ppm，O 2 1ppm, wherein the content of CO in the gas-phase ethylene after CO removal is lower than 0.01ppm.
Continuing the repeated application process, when the content of CO in the ethylene after CO removal is greater than 0.1ppm in the application process of the deep CO removal adsorbent in the embodiment, regenerating the CO adsorbent, wherein the specific process is as follows: heating the CO adsorbent bed to 180 ℃ under nitrogen atmosphere, and then introducing N containing 4% of methanol and 6% of oxygen by volume 2 Passing through CO adsorbent bed as regeneration gas and maintaining for 50min for regeneration, and using nitrogen for 3000 hr after regeneration -1 Purging the CO adsorbent bed for 1h at a volume space velocity; the reduction degree of the Cu-containing component in the regenerated CO adsorbent is 73%.
The activity of the regenerated CO adsorbent was detected and evaluated according to the application procedure of the deep removal CO adsorbent in this example, and the results showed that: the content of CO in the gas-phase ethylene after CO removal is lower than 0.01ppm, and the CO capacity of the regenerated CO adsorbent is 0.7mL CO/mL-cat.
Comparative example 2
This comparative example differs from example 2 in that: in the second step of the activation method, N containing 3% of oxygen by volume fraction is adopted 2 As an activating gas, the activated CO adsorbent had a Cu-containing component reduction degree of 71%; the content of CO in the gas-phase propylene after CO removal in the application process is lower than 0.08ppm; n using 6% oxygen by volume during regeneration 2 As a regeneration gas, the reduction degree of the Cu-containing component in the regenerated CO adsorbent was 60%, and the CO capacity of the regenerated CO adsorbent was 0.3mL CO/mL-cat.
As can be seen from a comparison of example 2 with comparative example 2, only N containing oxygen was used in comparison with comparative example 2 2 As a regeneration gas, example 2 uses N containing methanol and oxygen 2 The removal depth of the regenerated gas is higher, and the CO capacity after regeneration is obviously increased.
Example 3
The deep CO removal adsorbent of this example is CuO-ZrO 2 The two-component adsorbent is prepared from the two components,and CuO, zrO 2 The mass ratio of (2) is 80:20; the activation method comprises the following steps:
step one, loading 3mL of CO adsorbent particles with 20-40 meshes into a stainless steel reactor of a fixed bed reaction device, and introducing the mixture into a reactor with the volume fraction of 20% H under normal pressure 2 The mixed gas composed of nitrogen and the catalyst is taken as a reducing gas flow, and the volume space velocity is 3000h -1 Then heating to 180 ℃ at a speed of 2 ℃/min and maintaining for 1h for reduction; the reduction degree of the Cu-containing component in the reduced CO adsorbent is 95%;
step two, purging the fixed bed layer for 0.5h by nitrogen, wherein the volume space velocity is 3000h -1 Then at 200 ℃, N containing 0.05 percent of methanol by volume fraction and 0.1 percent of oxygen by volume fraction is added 2 Activating the CO adsorbent after reduction in the first step for 30min as an activating gas to obtain an activated CO adsorbent; the reduction degree of the Cu-containing component in the activated CO adsorbent is 85%.
The application process of the deep removal CO adsorbent in this embodiment is as follows: at 40 ℃ and 3MPa, the liquid phase propylene containing trace CO is reacted for 0.1h -1 Removing CO by the activated CO adsorbent; the liquid-phase propylene containing trace CO comprises the following components in percentage by volume: c (C) 3 H 6 99.9% of CO 10ppm, and the content of CO in the liquid-phase propylene after CO removal is lower than 0.01ppm.
Continuing the repeated application process, when the content of CO in the liquid-phase propylene after CO removal is greater than 0.1ppm in the application process of the deep CO removal adsorbent in the embodiment, regenerating the CO adsorbent, wherein the specific process is as follows: the CO adsorbent bed was warmed to 250℃under a nitrogen atmosphere and then N containing 0.5% by volume methanol and 1% by volume oxygen was introduced 2 Passing through CO adsorbent bed as regeneration gas and maintaining for 60min for regeneration, and using nitrogen gas for 3000h after regeneration -1 Purging the CO adsorbent bed for 1h at a volume space velocity; the reduction degree of the Cu-containing component in the regenerated CO adsorbent is 78%.
The activity of the regenerated CO adsorbent was detected and evaluated according to the application procedure of the deep removal CO adsorbent in this example, and the results showed that: the content of CO in the liquid-phase propylene after CO removal is lower than 0.01ppm, and the CO capacity of the regenerated CO adsorbent is 3.5mL CO/mL-cat.
Example 4
The deep CO removal adsorbent of this embodiment is CuO-ZnO-CeO 2 Three-component adsorbent, and CuO, znO, ceO 2 The mass ratio of (2) is 75:15:10; the activation method comprises the following steps:
step one, loading 3mL of CO adsorbent particles with 20-40 meshes into a stainless steel reactor of a fixed bed reaction device, and introducing H with the volume fraction of 1% under normal pressure 2 The mixed gas composed of nitrogen and the catalyst is taken as a reducing gas flow, and the volume space velocity is 3000h -1 Then heating to 130 ℃ at a speed of 2 ℃/min and maintaining for 24 hours for reduction; the reduction degree of the Cu-containing component in the CO adsorbent after reduction is 80%;
step two, purging the fixed bed layer for 0.5h by nitrogen, wherein the volume space velocity is 3000h -1 Then N containing 2.4% methanol and 8% oxygen by volume at 250 DEG C 2 Activating the CO adsorbent after reduction in the first step for 30min as an activating gas to obtain an activated CO adsorbent; the reduction degree of the Cu-containing component in the activated CO adsorbent is 73%.
The application process of the deep removal CO adsorbent in this embodiment is as follows: at 40 ℃ and 3MPa, the liquid phase propylene containing trace CO is reacted for 8.0h -1 Removing CO by the activated CO adsorbent; the liquid-phase propylene containing trace CO comprises the following components in percentage by volume: c (C) 3 H 6 99.9% of CO 10ppm, and the content of CO in the liquid-phase propylene after CO removal is lower than 0.01ppm.
Continuing the repeated application process, when the content of CO in the liquid-phase propylene after CO removal is greater than 0.1ppm in the application process of the deep CO removal adsorbent in the embodiment, regenerating the CO adsorbent, wherein the specific process is as follows: the CO adsorbent bed was warmed to 200℃under a nitrogen atmosphere and then N containing 0.5% by volume of methanol and 0.5% by volume of oxygen was introduced 2 As a regeneration gasRegenerating by passing through CO adsorbent bed and maintaining for 100min, and adding nitrogen gas for 3000 hr after regeneration -1 Purging the CO adsorbent bed for 1h at a volume space velocity; the reduction degree of the Cu-containing component in the regenerated CO adsorbent is 76%.
The activity of the regenerated CO adsorbent was detected and evaluated according to the application procedure of the deep removal CO adsorbent in this example, and the results showed that: the content of CO in the liquid-phase propylene after CO removal is lower than 0.01ppm, and the CO capacity of the regenerated CO adsorbent is 0.8mL CO/mL-cat.
Example 5
The deep CO removal adsorbent of this embodiment is CuO-CeO 2 Two-component adsorbent, cuO and CeO 2 Is 45:55 by mass; the activation method comprises the following steps:
step one, loading 3mL of CO adsorbent particles with 20-40 meshes into a stainless steel reactor of a fixed bed reaction device, and introducing CH with the volume fraction of 20% under normal pressure 4 And N 2 The mixed gas is taken as the reducing gas flow, and the volume airspeed is 3000h -1 Then heating to 200 ℃ at a speed of 2 ℃/min and maintaining for 3 hours for reduction; the reduction degree of the Cu-containing component in the reduced CO adsorbent is 90%;
step two, purging the fixed bed layer for 0.5h by nitrogen, wherein the volume space velocity is 3000h -1 Then at 120 ℃, N containing 0.5 percent of methanol by volume and 1 percent of oxygen by volume is added 2 Activating the CO adsorbent after reduction in the first step for 50min as an activating gas to obtain an activated CO adsorbent; the reduction degree of the Cu-containing component in the activated CO adsorbent is 83%.
The application process of the deep removal CO adsorbent in this embodiment is as follows: at 50 ℃ and 0.1MPa, the gas phase ethylene containing trace CO is reacted for 3000h -1 Removing CO by means of an activated CO adsorbent; the composition of the gas-phase ethylene containing trace CO is as follows by volume percent: c (C) 2 H 4 99.95%, methane and ethane 250ppm,CO 100ppm,C 2 H 2 ＜1ppm，O 2 1ppm, the content of CO in the gas-phase ethylene after CO removal is lowAt 0.01ppm.
Continuing the repeated application process, when the content of CO in the gas-phase ethylene after CO removal is greater than 0.1ppm in the application process of the deep CO removal adsorbent in the embodiment, regenerating the CO adsorbent, wherein the specific process is as follows: the CO adsorbent bed was warmed to 200℃under a nitrogen atmosphere and then N containing 0.5% by volume of methanol and 0.5% by volume of oxygen was introduced 2 Passing through CO adsorbent bed as regeneration gas and maintaining for 180min for regeneration, and using nitrogen gas for 3000h after regeneration -1 Purging the CO adsorbent bed for 1h at a volume space velocity; the reduction degree of the Cu-containing component in the regenerated CO adsorbent is 75%.
The activity of the regenerated CO adsorbent was detected and evaluated according to the application procedure of the deep removal CO adsorbent in this example, and the results showed that: the content of CO in the gas-phase ethylene after CO removal is lower than 0.01ppm, and the CO capacity of the regenerated CO adsorbent is 0.52mL CO/mL-cat.
Example 6
The deep CO removal adsorbent of this example is CuO-ZnO-Al 2 O 3 -ZrO 2 Four component adsorbent, and CuO, znO, al 2 O 3 、ZrO 2 The mass ratio of (2) is 70:20:5:5; the activation method comprises the following steps:
step one, loading 3mL of CO adsorbent particles with 20-40 meshes into a stainless steel reactor of a fixed bed reaction device, and introducing mixed gas consisting of 10% of CO and He by volume fraction as reducing gas flow at normal pressure, wherein the volume space velocity is 3000h -1 Then heating to 160 ℃ at a speed of 2 ℃/min and maintaining for 5 hours for reduction; the reduction degree of the Cu-containing component in the reduced CO adsorbent is 85%;
step two, purging the fixed bed layer for 1h by nitrogen, wherein the volume space velocity is 3000h -1 Then at 160 ℃, N containing 3 percent of methanol by volume and 4.5 percent of oxygen by volume is added 2 Activating the CO adsorbent after reduction in the first step for 30min as an activating gas to obtain an activated CO adsorbent; the reduction degree of the Cu-containing component in the activated CO adsorbent is 81%.
The implementation isThe application process of the deep CO removal adsorbent comprises the following steps: at 40 ℃ and 0.1MPa, the gas phase nitrogen containing trace CO is reacted for 10h -1 Removing CO by means of an activated CO adsorbent; the composition of the gas phase nitrogen containing trace CO is as follows by volume percent: n (N) 2 99.9％，CO 3000ppm，O 2 0.2ppm, and the content of CO in the gas phase nitrogen after CO removal is lower than 0.01ppm.
Continuing the repeated application process, when the content of CO in the gas phase nitrogen after CO removal is greater than 0.1ppm in the application process of the deep CO removal adsorbent in the embodiment, regenerating the CO adsorbent, wherein the specific process is as follows: the CO adsorbent bed was warmed to 320℃under a nitrogen atmosphere and then N containing 0.5% by volume methanol and 0.6% by volume oxygen was introduced 2 Passing through CO adsorbent bed as regeneration gas and maintaining for 100min for regeneration, and using nitrogen gas for 3000h after regeneration -1 Purging the CO adsorbent bed for 1h at a volume space velocity; the reduction degree of the Cu-containing component in the regenerated CO adsorbent is 80%.
The activity of the regenerated CO adsorbent was detected and evaluated according to the application procedure of the deep removal CO adsorbent in this example, and the results showed that: the content of CO in the gas phase nitrogen after CO removal is lower than 0.01ppm, and the CO capacity of the regenerated CO adsorbent is 1.6mL CO/mL-cat.
Example 7
The deep CO removal adsorbent of this example is CuO-ZnO-ZrO 2 Three-component adsorbent, and CuO, znO, zrO 2 The mass ratio of (2) is 70:20:10; the activation method comprises the following steps:
step one, loading 3mL of CO adsorbent particles with 20-40 meshes into a stainless steel reactor of a fixed bed reaction device, and introducing hydrogen with the volume purity of more than 99.99% as a reducing gas flow under normal pressure, wherein the volume airspeed is 3000h -1 Then heating to 130 ℃ at a speed of 2 ℃/min and maintaining for 3 hours for reduction; the reduction degree of the Cu-containing component in the reduced CO adsorbent is 93%;
step two, purging the fixed bed layer for 0.5h by nitrogen, wherein the volume space velocity is 3000h -1 However, it isThen at 10 ℃, N containing 2.4 percent of methanol by volume and 8 percent of oxygen by volume is added 2 Activating the CO adsorbent after reduction in the first step for 50min as an activating gas to obtain an activated CO adsorbent; the reduction degree of the Cu-containing component in the activated CO adsorbent is 80%.
The application process of the deep removal CO adsorbent in this embodiment is as follows: at a temperature of 0 ℃ and a pressure of 5MPa, the liquid-phase propylene containing trace CO is reacted for 100h -1 Removing CO by the activated CO adsorbent; the liquid-phase propylene containing trace CO comprises the following components in percentage by volume: c (C) 3 H 6 99.9% of CO 10ppm, and the content of CO in the liquid-phase propylene after CO removal is lower than 0.01ppm.
Continuing the repeated application process, when the content of CO in the liquid-phase propylene after CO removal is greater than 0.1ppm in the application process of the deep CO removal adsorbent in the embodiment, regenerating the CO adsorbent, wherein the specific process is as follows: the CO adsorbent bed was warmed to 200℃under a nitrogen atmosphere and then N containing 0.5% by volume of methanol and 0.6% by volume of oxygen was introduced 2 Passing through CO adsorbent bed as regeneration gas and maintaining for 50min for regeneration, and using nitrogen for 3000 hr after regeneration -1 Purging the CO adsorbent bed for 1h at a volume space velocity; the reduction degree of the Cu-containing component in the regenerated CO adsorbent is 79%.
The activity of the regenerated CO adsorbent was detected and evaluated according to the application procedure of the deep removal CO adsorbent in this example, and the results showed that: the content of CO in the liquid-phase propylene after CO removal is lower than 0.01ppm, and the CO capacity of the regenerated CO adsorbent is 0.8mL CO/mL-cat.
Example 8
The deep CO removal adsorbent of this example is CuO-ZnO-Al 2 O 3 -ZrO 2 Four component adsorbent, and CuO, znO, al 2 O 3 、ZrO 2 The mass ratio of the four components is 70:20:5:5; the activation method comprises the following steps:
step one, loading 3mL of CO adsorbent particles with 20-40 meshes into a stainless steel reactor of a fixed bed reaction device, and in normal conditionUnder reduced pressure, 10% H by volume 2 And N 2 The mixed gas is taken as the reducing gas flow, and the volume airspeed is 3000h -1 Then heating to 140 ℃ at a speed of 2 ℃/min and maintaining for 3 hours for reduction; the reduction degree of the Cu-containing component in the CO adsorbent after reduction is 83%;
step two, purging the fixed bed layer for 1h by nitrogen, wherein the volume space velocity is 3000h -1 Then N containing 0.1% methanol by volume and 0.3% oxygen by volume is added at 160 DEG C 2 Activating the CO adsorbent after reduction in the first step for 30min as an activating gas to obtain an activated CO adsorbent; the reduction degree of the Cu-containing component in the activated CO adsorbent is 78%.
The application process of the deep removal CO adsorbent in this embodiment is as follows: under the conditions of 50 ℃ and 0.1MPa, the gas phase nitrogen containing trace CO is made to be 100000h -1 Removing CO by means of an activated CO adsorbent; the nitrogen containing trace CO comprises the following components in percentage by volume: n (N) 2 99.9％，CO 0.1ppm，O 2 0.2ppm, and the content of CO in the gas phase nitrogen after CO removal is lower than 0.01ppm.
Continuing the repeated application process, when the content of CO in the gas phase nitrogen after CO removal is greater than 0.03ppm in the application process of the deep CO removal adsorbent in the embodiment, regenerating the CO adsorbent, wherein the specific process is as follows: the CO adsorbent bed was warmed to 320℃under a nitrogen atmosphere and then N containing 0.5% by volume methanol and 0.6% by volume oxygen was introduced 2 Passing through CO adsorbent bed as regeneration gas and maintaining for 100min for regeneration, and using nitrogen gas for 3000h after regeneration -1 Purging the CO adsorbent bed for 1h at a volume space velocity; the reduction degree of the Cu-containing component in the regenerated CO adsorbent is 80%.
The activity of the regenerated CO adsorbent was detected and evaluated according to the application procedure of the deep removal CO adsorbent in this example, and the results showed that: the content of CO in the gas phase nitrogen after CO removal is lower than 0.01ppm, and the CO capacity of the regenerated CO adsorbent is 1.6mL CO/mL-cat.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (6)
1. An activation method of a deep CO removal adsorbent is characterized in that the deep CO removal adsorbent is copper oxide and MO x A composite comprising one or more of M Zn, ce, zr, al, mn, cr, co and Si, and x is MO x A stoichiometric number of zero charge, the activation method comprising the steps of:
step one, heating a CO adsorbent in a reducing airflow to reduce; the reduction temperature is 130-230 ℃, and the heat preservation time is 1-24 h; the reducing gas stream is H 2 CO or hydrocarbons, or reducing gas streams to H 2 A mixed gas of one of CO and hydrocarbon and an inert gas, H in the mixed gas 2 The volume fraction of CO or hydrocarbon is 1% -100%; the reduction temperature is 140-190 ℃, and the reduction degree of the Cu-containing component in the reduced CO adsorbent is 70-100%;
step two, activating the CO adsorbent subjected to reduction in the step one by taking inert gas containing methanol and oxygen as activating gas at the temperature of 10-320 ℃ to obtain an activated CO adsorbent; the volume fraction of methanol in the activated gas is 0.05% -6%, and the volume fraction of oxygen is 0.1% -22%; the reduction degree of the Cu-containing component in the activated CO adsorbent is 65% -85%.
2. The method for activating a deep removal CO adsorbent according to claim 1, wherein the activation temperature in the second step is 40 ℃ to 260 ℃.
3. An application method of the activated CO adsorbent obtained by the method of claim 1 or 2, which is characterized in that the CO adsorbent is activated firstly, and then a material containing trace CO is subjected to CO removal by the activated CO adsorbent under the conditions of the temperature of 0 ℃ to 120 ℃ and the pressure of 0.1MPa to 5 MPa; the material containing trace CO is gas phase, liquid phase or gas-liquid mixed phase, and is olefin, saturated hydrocarbon or inert gas, the content of CO is 0.01 ppm-3000 ppm, and the content of CO in the material after CO removal is lower than 10ppb.
4. The method according to claim 3, wherein the gas phase of the material containing trace CO has a space velocity of 10h -1 ~100000h -1 The space velocity of the material containing trace CO in the liquid phase is 0.1h -1 ~100h -1 。
5. A method for regenerating an activated CO adsorbent obtained by the method according to claim 1 or 2, wherein the CO adsorbent is activated and applied, then heated to 180 ℃ to 320 ℃, and then regenerated by introducing an inert gas containing methanol and oxygen as a regeneration gas.
6. The regeneration method according to claim 5, wherein the volume fraction of methanol in the regeneration gas is 0.001% -4%, and the volume fraction of oxygen is 0.001% -6%; the regeneration temperature is 200 ℃, and the reduction degree of the Cu-containing component in the regenerated CO adsorbent is 70% -80%.
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