CN114471441A - CO adsorbent and preparation method and application thereof - Google Patents
CO adsorbent and preparation method and application thereof Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002808 molecular sieve Substances 0.000 claims abstract description 22
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 17
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000005749 Copper compound Substances 0.000 claims abstract description 9
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 14
- 150000001879 copper Chemical class 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000011268 mixed slurry Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 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
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000002594 sorbent Substances 0.000 claims 4
- 239000012670 alkaline solution Substances 0.000 claims 1
- 238000010304 firing Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 29
- 230000004913 activation Effects 0.000 abstract description 6
- 238000011112 process operation Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000005751 Copper oxide Substances 0.000 abstract 1
- 229910000431 copper oxide Inorganic materials 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000013078 crystal Substances 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000005997 Calcium carbide Substances 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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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
- B01J20/0203—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
- B01J20/02—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
- B01J20/0274—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 characterised by the type of anion
- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
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- 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
- B01J20/3071—Washing or leaching
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- 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
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- 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
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/25—Coated, impregnated or composite adsorbents
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention discloses a CO adsorbent and a preparation method and application thereof. The adsorbent contains basic copper chloride and copper oxide. The method comprises the step of synthesizing basic copper chloride in situ on the surface of a molecular sieve by utilizing a divalent copper compound and an alkali solution to prepare the CO adsorbent. The technical scheme has simple process operation. The prepared adsorbent does not need to be activated or the activation time is obviously shortened when in use, and the CO adsorption capacity and selectivity can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of chemical gas separation, and particularly relates to a CO adsorbent and a preparation method and application thereof.
Background
With the rapid development of C1 chemistry, CO is increasingly widely applied, can be used as a fuel and a metal reducing gas besides being a raw material gas for synthesizing a plurality of important organic chemical products, and has important industrial application value. However, the Chinese CO raw material gas mainly comes from the synthesis of petroleum and natural gas, water gas and industrial tail gas, such as calcium carbide tail gas, coke oven tail gas, steel mill waste gas and the like. Although these industrial exhaust gases contain a large amount of CO components, the compositions are complex, and the adsorption and purification are relatively difficult, so that a low-cost and high-efficiency gas separation and purification technology needs to be developed and adopted.
The Pressure Swing Adsorption (PSA) technology is widely applied to the field of gas adsorption and purification due to the advantages of simple operation, environmental friendliness and the like. The principle is that the adsorbents under different partial pressures have different adsorption capacities on adsorbates and have the characteristic of selective adsorption on target components. The core of PSA technology lies in adsorbent performance, most of the development of CO adsorbents at present focuses on transition metal supported adsorbents, and the mechanism of the CO adsorbent is favorable for forming conjugated pi bonds between CO and transition metal ions (such as Cu (I), Ag (I) or Ni (I)) and greatly improving the adsorption performance of the adsorbent on CO. Most of the research focuses on copper-containing adsorbents, for example, the Cu (I) is loaded on a carrier according to a spontaneous monolayer dispersion principle, so that the adsorption quantity and selectivity of CO can be effectively improved. However, when CuCl is traditionally used for preparing the adsorbent, raw materials need to be pre-purified, the operation is complicated, and the conditions are relatively harsh. For example, CN106315613A provides a novel 13X type molecular sieve for CO adsorption, a preparation method and an application thereof, and reduction is carried out for 3-5 hours at 460-550 ℃ under a nitrogen atmosphere after a copper source is added. CN110545481A discloses a hollow structure CO adsorbent of Y-type molecular sieve coated nano copper salt, a preparation method and application thereof, wherein the adsorbent can effectively improve CO adsorption capacity and selectivity, but the operation pressure is 0.8MPa, and the operation temperature is 40 ℃. Wanglie (Industrial catalysis 201611 (24)62) prepared Cu (I) -molecular sieve adsorbent by dry mixing method, which can satisfy the requirement of industrial CO purification, but has relatively high adsorption temperature (60 ℃) and relatively low breakthrough adsorption amount (37.5 ml/g).
CN110270303A discloses a CO adsorbent and a preparation method thereof, wherein a mixture of copper chloride and basic copper salt and a carrier with a high specific surface area are used as raw materials, water is added, a binder is added for forming, and the CO adsorbent is prepared after drying and activation. Although the method avoids some disadvantages when cuprous chloride is directly adopted, the adsorbent has lower adsorption performance.
Therefore, aiming at the defects of complex operation, harsh conditions, relatively small adsorption capacity and the like in the preparation of the CO adsorbent at the present stage, the development of the efficient and environment-friendly adsorbent has important practical significance.
Disclosure of Invention
In view of the disadvantages of the prior art, an object of the present invention is to provide an efficient and environment-friendly CO adsorbent, and further improve the adsorption capacity of the adsorbent to efficiently adsorb CO. The invention also aims to provide a preparation method of the CO adsorbent, which aims to simplify the preparation procedure, improve the problem of harsh preparation conditions and solve the problems of difficult preparation, complex preparation process and the like in the prior art.
In order to solve the foregoing problems, a first aspect of the present invention is to provide a CO adsorbent containing Cu2(OH)3Cl and CuO. Wherein, Cu2(OH)3Cl average grain size of
CuO has an average grain size of
The CO adsorbent is prepared by in-situ synthesis of a divalent copper compound and an alkali solution on the surface of a molecular sieve. The cupric compound is preferably a soluble inorganic copper salt, more preferably one or more of copper chloride, copper nitrate and copper sulfate or a mixture thereof with other inorganic copper salts, and most preferably copper chloride or a mixture thereof with other inorganic copper salts. The molecular sieve is preferably one or more selected from Y, USY, 13X, ZSM-5, MCM and beta molecular sieves.
The second aspect of the present invention provides a method for preparing a CO adsorbent, comprising the steps of:
a) dissolving a divalent copper compound to obtain a copper-containing solution, and dissolving alkali to obtain an alkali solution;
b) dripping the copper-containing solution and the alkali solution into an aqueous solution containing the molecular sieve to obtain mixed slurry;
c) and crystallizing the mixed slurry, washing, drying and roasting to obtain the CO adsorbent.
In the above technical schemeThe feeding mass ratio of the divalent copper compound to the molecular sieve is 0.1-1.9: 1, and preferably 0.7-1.7: 1. The concentration range of the alkali liquor is 0.1-1 mol/L (by OH)-Concentration meter), preferably 0.2 to 0.5 mol/L. The addition amount of the alkali solution enables the pH value of the mixed slurry to be 6-8.
In the above technical scheme, the divalent copper compound in step a) is preferably a soluble inorganic copper salt, more preferably one or more of copper chloride, copper nitrate and copper sulfate or a mixture thereof with other inorganic copper salts, and most preferably copper chloride or a mixture thereof with other inorganic copper salts. The base is preferably sodium hydroxide.
In the above technical solution, the molecular sieve in step b) is preferably one or more selected from Y, USY, 13X, ZSM-5, MCM and beta molecular sieves.
In the above technical solution, the crystallization in step c) is: crystallizing at 60-150 ℃ for 8-24 hours, preferably 12-24 hours. The roasting comprises the following steps: roasting for 2-10 hours at 400-600 ℃ under an oxygen-free condition.
In a third aspect, the invention provides the use of a CO adsorbent for adsorbing CO. The application is preferably carried out using fixed bed adsorption technology. The fixed bed adsorption is preferably: and (3) purging with CO for 0-4 hours at 100-180 ℃ for activation treatment, and introducing mixed gas for adsorption after the baseline of the online chromatographic analyzer is stable.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention is prepared by in-situ synthesis of cupric salt and alkali liquor on the surface of a molecular sieve at a certain pH value and roasting. In the preparation technical scheme, the cupric salt is used as the copper source, and the process operation is simple. The adsorbent is used without activation or with significantly reduced activation time.
2. The CO adsorbent prepared by the invention has high CO adsorption capacity, selectivity and regenerability, and can be used for separating and purifying various CO-containing gases.
3. The CO adsorbent prepared by the invention has wider range of use conditions, can adsorb CO at room temperature and normal pressure, and can reduce energy consumption to a certain extent.
Drawings
FIG. 1 is an XRD spectrum of the CO adsorbent synthesized in example 2;
fig. 2 is an SEM spectrum of the CO adsorbent synthesized in example 2.
Detailed Description
The present invention is described in further detail below by way of examples. It should be understood that the detailed description is not intended to limit the scope of the invention.
An XRD spectrogram: analyzing the phase of the sample by using a Nippon Rigaku Ultima IV type X-ray powder diffractometer, and taking Cu Ka line as a radiation source
And (3) scanning the nickel filter in a2 theta scanning range of 5-70 degrees, operating voltage of 40KV, current of 40mA, and scanning speed of 10 degrees/min to obtain an XRD spectrogram.
Meanwhile, the grain size calculation is carried out by using X' Pert High Score software through the Scherrer formula.
SEM spectrogram: SEM spectrogram is obtained by Hitachi S-4800 cold field emission high resolution scanning electron microscope of Hitachi corporation.
[ example 1 ]
Accurately weighing CuCl2·2H2Dissolving 1.705g of O crystal in 100ml of deionized water to prepare a salt solution; 1.6000g of NaOH was dissolved in 100ml of deionized water to prepare an alkali solution. Slowly dripping the two solutions into a three-neck flask containing 1g Y molecular sieve and 20ml deionized water under vigorous stirring, continuing stirring for 0.5h after dripping is finished, standing and crystallizing the nucleating slurry at 60 ℃ for 24h, filtering and washing the obtained precipitate to be neutral, and drying the product at 80 ℃ for 12 h. The resulting solid was then placed in a tube furnace at N2Roasting at 400 ℃ for 8 hours under the protection of atmosphere, and cooling to obtain the CO adsorbent A1. The adsorbent was measured for adsorption capacity at ambient temperature and a CO pressure of 0.6MPa, and then the adsorbent was subjected to desorption treatment at 100 ℃.
The XRD spectrum of the CO adsorbent synthesized in this example is shown in fig. 1 (a. unfired CO adsorbent, b. CO adsorbent). The spectrogram shows that the method can be used for loadingIn-situ synthesis of Cu on surface of body2(OH)3And (4) Cl. With Cu2(OH)3The spectrum (b) of the CO adsorbent prepared by taking Cl as a precursor belongs to Cu2(OH)3The characteristic diffraction peak of Cl weakens, and a characteristic peak attributed to CuO appears at the same time.
The component of the adsorbent contains Cu2(OH)3Cl and CuO. Wherein, Cu2(OH)3Cl average grain size of
CuO has an average grain size of
The SEM spectrum of the CO adsorbent synthesized in this example is shown in FIG. 2. The CO adsorbent prepared by the method has a relatively rough surface, can provide more attachment sites, and is beneficial to chemical adsorption of CO on the surface.
[ example 2 ]
Accurately weighing CuCl2·2H2O crystal and Cu (NO)3)·3H20.6819g of O crystal and 0.1876g of O crystal are dissolved in 100ml of deionized water to prepare a mixed salt solution; 0.4000g of NaOH was dissolved in 100ml of deionized water to prepare a mixed alkali solution. Slowly dripping the two mixed solutions into a three-neck flask containing 1g Y molecular sieve and 20ml of deionized water under vigorous stirring, continuing stirring for 0.5h after dripping is finished, standing and crystallizing the nucleating slurry at 80 ℃ for 20h, filtering and washing the obtained precipitate to be neutral, and drying the product at 80 ℃ for 12 h. The resulting solid was then placed in a tube furnace under N2Roasting at 600 ℃ for 4 hours under the protection of atmosphere, and cooling to obtain the CO adsorbent A2. Has a similar XRD spectrum as example 1.
[ example 3 ]
Accurately weighing CuCl2·2H2O crystal and Cu (NO)3)·3H2O crystals 0.8524g and 0.9378g dissolved inPreparing a mixed salt solution in 100ml of deionized water; 0.8000g of NaOH is dissolved in 100ml of deionized water to prepare a mixed alkali solution. Slowly dripping the two mixed solutions into a three-neck flask containing 1g Y molecular sieve and 20ml of deionized water under vigorous stirring, continuing stirring for 0.5h after dripping is finished, standing and crystallizing the nucleating slurry at 100 ℃ for 12h, filtering and washing the obtained precipitate to be neutral, and drying the product at 80 ℃ for 12 h. The resulting solid was then placed in a tube furnace at N2Roasting at 450 ℃ for 6 hours under the protection of atmosphere, and cooling to obtain the CO adsorbent A3. Has a similar XRD spectrum as example 1.
[ example 4 ]
Accurately weighing CuCl2·2H2O crystal and CuSO41.1934g and 0.4788g of crystals are dissolved in 100ml of deionized water to prepare a mixed salt solution; 1.6000g of NaOH was dissolved in 100ml of deionized water to prepare a mixed alkali solution. Slowly dripping the two mixed solutions into a three-neck flask containing 1g Y molecular sieve and 20ml of deionized water under vigorous stirring, continuing stirring for 0.5h after dripping is finished, standing and crystallizing the nucleating slurry at 120 ℃ for 8h, filtering and washing the obtained precipitate to be neutral, and drying the product at 80 ℃ for 12 h. The resulting solid was then placed in a tube furnace at N2Roasting at 550 ℃ for 3 hours under the protection of atmosphere, and cooling to obtain the CO adsorbent A4. Has a similar XRD spectrum as example 1.
Comparative example 1
Accurately weighing 1.0gY type molecular sieve and CuCl2·2H2O crystal and Cu2(OH)3CO31.1365g and 0.7371g of crystal are mixed uniformly in N2And roasting at 400 ℃ for 8 hours under the protection of atmosphere, and cooling to obtain the contrast agent A5.
[ example 5 ] application example
The CO adsorbents prepared in the previous examples and comparative examples were used in a fixed bed CO adsorption experiment, and were measured by gas chromatography at room temperature and a CO pressure of 0.6MPa, followed by desorption treatment of the adsorbent at 100 ℃. In the experimental process, an adsorbent (mass m) is arranged in a fixed bed reactor, CO is used for purging for 2-4 hours at normal temperature-180 ℃ for activation treatment, mixed gas (CO mixed gas, the flow of the mixed gas is Q, the volume fraction of CO is C) is introduced after the base line of an online chromatographic analyzer is stable, and the gas flowing out of the outlet end of the fixed bed is subjected to continuous chromatographic detection. Before the adsorbent is adsorbed and saturated, CO is not detected by the chromatogram at the outlet end or the concentration is very low, if CO components appear in the chromatogram or the concentration rises rapidly, the adsorption saturation is considered to be reached, and time (t) is counted. The adsorbent adsorption capacity X was calculated by formula (1):
X＝CQt/m (1)
the adsorbent adsorption amounts of the respective examples and comparative examples are shown in table 1.
[ example 6 ] reusability
The CO adsorbent prepared in example 1 was regenerated by temperature-rising desorption, and the regenerated adsorbent was examined for CO adsorption performance under the same conditions. The adsorption capacity of the adsorbent remained stable after 3 times of repetition.
Table 1 adsorbent adsorption test results
| Numbering | Adsorbent and process for producing the same | Adsorption capacity, ml/gAdsorbent and process for producing the same | CO selectivity,% |
| 1 | A1 | 69.7 | 99 |
| 2 | A2 | 56.3 | 98 |
| 3 | A3 | 59.8 | 98 |
| 4 | A4 | 61.8 | 98 |
| 5 | A5 | 43.2 | 97 |
| 6 | Recycle-A1-1 | 69.7 | 99 |
| 7 | Recycle-A1-2 | 69.7 | 99 |
Claims (10)
1. A CO adsorbent, characterized in that the adsorbent comprises basic copper chloride (Cu)2(OH)3Cl) and copper oxide (CuO).
2. The sorbent of claim 1, wherein Cu2(OH)3Cl average grain size of
CuO has an average grain size of
3. The sorbent according to claim 1, wherein the CO sorbent is prepared by in situ synthesis of a divalent copper compound and an alkaline solution on the surface of a molecular sieve.
4. The adsorbent according to claim 3, wherein the divalent copper compound is a soluble inorganic copper salt, preferably one or more of copper chloride, copper nitrate and copper sulfate or a mixture thereof with other inorganic copper salts; further preferred is copper chloride or a mixture thereof with other inorganic copper salts.
5. The sorbent of claim 3, wherein the molecular sieve is one or more selected from the group consisting of Y, USY, 13X, ZSM-5, MCM, and beta molecular sieve.
6. A method for preparing the adsorbent according to any one of claims 1 to 5, comprising the steps of:
a) dissolving a divalent copper compound to obtain a copper-containing solution, and dissolving alkali to obtain an alkali solution;
b) dripping the copper-containing solution and the alkali solution into an aqueous solution containing the molecular sieve to obtain mixed slurry;
c) and crystallizing the mixed slurry, washing, drying and roasting to obtain the CO adsorbent.
7. The preparation method according to claim 6, wherein the feeding mass ratio of the divalent copper compound to the molecular sieve is 0.1-1.9: 1, preferably 0.7-1.7: 1; the concentration range of the alkali liquor is 0.1-1 mol/L, preferably 0.2-0.5 mol/L, and the addition amount of the alkali liquor enables the pH value of the mixed slurry to be 6-8.
8. The method according to claim 6, wherein the crystallization in step c) is: crystallizing at 60-150 ℃ for 8-24 hours, preferably 12-24 hours.
9. The method of claim 6, wherein the firing in step c) is: roasting for 2-10 hours at 400-600 ℃ under an oxygen-free condition.
10. Use of the adsorbent according to any one of claims 1 to 5 or the adsorbent prepared by the preparation method according to any one of claims 6 to 9 for adsorbing CO.
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