CN115722187A - High-adsorption-capacity carbon monoxide complex adsorbent and preparation method and application thereof - Google Patents
High-adsorption-capacity carbon monoxide complex adsorbent and preparation method and application thereof Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 75
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 61
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 65
- 229910052802 copper Inorganic materials 0.000 claims abstract description 32
- 239000002808 molecular sieve Substances 0.000 claims abstract description 30
- 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 30
- 238000000034 method Methods 0.000 claims abstract description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 18
- 238000000746 purification Methods 0.000 claims abstract description 18
- 238000011068 loading method Methods 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 15
- 238000005342 ion exchange Methods 0.000 claims abstract description 14
- 230000000536 complexating effect Effects 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims description 48
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 46
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 46
- 238000002156 mixing Methods 0.000 claims description 12
- 229910052727 yttrium Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000004537 pulping Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 29
- 230000035515 penetration Effects 0.000 abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 239000002994 raw material Substances 0.000 description 12
- 238000011065 in-situ storage Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
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- 238000011946 reduction process Methods 0.000 description 2
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- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
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- 239000007790 solid phase Substances 0.000 description 1
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Abstract
The invention discloses a carbon monoxide complexing adsorbent with high adsorption capacity and a preparation method and application thereof. The invention takes Y or X type molecular sieve as carrier, and adopts ion exchange combined with solid heat dispersion method to obtain carbon monoxide complexing adsorbent with high copper loading after reduction. The carbon monoxide adsorption capacity of the adsorbent is remarkably improved to 4.8mmol/g. The penetration test result of trace CO shows that compared with the existing copper-based adsorbent, the adsorbent provided by the invention has obviously improved purification depth and penetration capacity, and is particularly suitable for purification occasions containing trace CO gas.
Description
Technical Field
The invention relates to a carbon monoxide adsorbent, in particular to a carbon monoxide complexing adsorbent with high adsorption capacity and a preparation method and application thereof.
Background
In some gas-solid phase catalytic reactions with important application value, trace amount of carbon monoxide often causes poisoning of catalysts, such as noble metal catalysts for fuel cells and propylene polymerization catalysts, and therefore must be removed. Temperature and pressure swing adsorption is an effective purification means, and carbon monoxide is adsorbed by using an adsorbent at a lower temperature, normal pressure or pressure, and then is desorbed in vacuum at a higher temperature. The adsorbent is the core of the temperature and pressure swing purification process, and the carbon monoxide adsorption capacity is the key performance index of the adsorbent. Generally speaking, the adsorption capacity is positively correlated with the amount of gas purified by unit weight of adsorbent, and higher adsorption capacity means less adsorbent is filled, which is beneficial to reducing one-time investment and operation energy consumption of the device. Therefore, the development of the high-capacity carbon monoxide adsorbent has important significance for purifying trace carbon monoxide by the temperature and pressure swing process.
The carbon monoxide adsorption capacity of the traditional adsorbent such as 5A, 13X, alumina, activated carbon and the like is not more than 1.0mmol/g at normal temperature and normal pressure. If the adsorbent is used for purifying trace CO, the loading amount is large and the economical efficiency is poor. In the eighties of the last century, carbon monoxide adsorbents based on monovalent copper-containing compounds have appeared, wherein pi complexation can be formed between the d orbitals of monovalent copper ions and the p orbitals of carbon monoxide molecules, and the weak chemical adsorption can effectively improve the adsorption capacity of the copper adsorbents on CO. There are three types of pi complex adsorbents:
(1) A single or near single layer salt-supported porous matrix;
(2) An ion-exchanged zeolite molecular sieve;
(3) Ion exchange resins.
The first and second types of adsorbents, or a combination of the two, are more studied because of the large specific surface area and many exchangeable sites of the porous matrix and zeolite molecular sieves, which tend to achieve high copper loadings. The first type of adsorbent is based on the principle that metal oxides and salts proposed by Xie et al can be dispersed on the solid surface in the form of a monolayer, and the effective adsorption sites of the adsorbent are cuprous salts such as CuCl which are loaded on a carrier and are in a highly dispersed state. The second type of adsorbent is prepared by introducing univalent copper ions as effective adsorption sites in an ion exchange mode by utilizing the exchangeable characteristic of cations outside a framework in a three-dimensional pore channel structure of the zeolite molecular sieve.
EP0224150 carries out ion exchange on NaY zeolite molecular sieve to obtain Cu (II) Y with bivalent copper as framework external cation, and then carries CuCl by solution impregnation method 2 And finally, reducing all bivalent copper into monovalent copper in a reducing atmosphere to obtain the CuCl-loaded Cu (I) Y adsorbent, wherein the CO adsorption capacity of the Cu (I) Y adsorbent is 2.0mmol/g. In the preparation method related by the patent, the CuCl is loaded by adopting solution impregnation, so that the CuCl loading is influenced by the CuCl 2 The limitation of saturation solubility, in turn, limits further improvement of CO adsorption capacity. Chinese patent CN86102838B directly mixes and heats solid copper salt and NaY or NaX zeolite molecular sieve to make the copper salt load on the molecular sieve. Compared with the solution impregnation method, the solid thermal dispersion method is adopted, the amount of the loaded copper salt can not be limited by the saturation solubility, and therefore, higher adsorption capacity can be obtained compared with the impregnation method. For example, the patent uses a NaX zeolite molecular Sieve (SiO) 2 /Al 2 O 3 = 2-3) as a carrier, the CO adsorption capacity of the obtained adsorbent was increased to 3.8mmol/g by thermally dispersing the supported CuCl to the carrier by its own weight ratio to 0.5. However, in the preparation method, when the molecular sieve is heated, a part of Na ions outside the framework of the molecular sieve can be subjected to solid-state ion exchange with CuCl, so that not only is part of dispersed CuCl lost, but also NaCl generated by the solid-state ion exchange is an ineffective component and causes pore blocking, and the performance of the adsorbent is adversely affected. Chinese patent application CN112755956A uses a molecular Sieve (SiO) with a high silica-alumina ratio 2 /Al 2 O 3 Not less than 200, and the content of cations outside the framework is not more than 0.1 mmol/g), and CuCl is loaded in a thermal dispersion mode, so that the quantity of cations outside the framework is greatly reduced, the loss of dispersed CuCl is avoided, the generation of ineffective salts caused by solid-state ion exchange is also greatly reduced, and the CO adsorption capacity of the obtained adsorbent reaches 4.3mmol/g.
Disclosure of Invention
The invention aims to provide an adsorbent with high adsorption capacity for removing trace carbon monoxide in gas. The invention takes Y or X type molecular sieve as carrier, and adopts ion exchange and solid heat dispersion method to obtain the carbon monoxide complex adsorbent with high copper loading after reduction.
The technical scheme of the invention is as follows:
an adsorbent for purifying and removing trace carbon monoxide is a carbon monoxide complexing adsorbent with high copper loading capacity, which is obtained by taking a Y-type or X-type molecular sieve as a carrier, firstly obtaining Cu (II) Y or Cu (II) X exchanged by divalent copper by an ion exchange method, then loading CuCl by a solid-state thermal dispersion method and then reducing.
Preferably, the Y-type or X-type molecular sieves include, but are not limited to, naY molecular sieves, 13X molecular sieves, and the like.
The specific preparation method of the high-copper-loading carbon monoxide complexing adsorbent comprises the following steps:
(1) Mixing Y-type or X-type molecular sieve raw powder with CuCl 2 Mixing the solutions, adjusting the pH value to 4-6, and performing pulping exchange for multiple times to obtain Cu (II) Y or Cu (II) X exchanged by bivalent copper;
(2) Mixing and grinding the Cu (II) Y or Cu (II) X and CuCl solid powder, vacuumizing and heating the obtained mixture for a period of time in an auxiliary way, and loading CuCl on a molecular sieve through thermal dispersion;
(3) And (3) reducing the mixture obtained in the step (2) in a reducing atmosphere to obtain the carbon monoxide complexing adsorbent.
The technical characteristics of the invention are as follows:
1) Adopting a molecular sieve such as NaY or 13X type and the like as a carrier, and adopting an ion exchange method in the first step to obtain Cu (II) Y or Cu (II) X exchanged by bivalent copper;
2) On the basis of Cu (II) Y or Cu (II) X, a solid-state thermal dispersion method is adopted in the second step to obtain Cu (II) Y or Cu (II) X loaded with CuCl;
3) Cu (II) Y or Cu (II) X loaded with CuCl is added into CO or H 2 Reducing in reducing atmosphere to obtain the carbon monoxide complexing adsorbent.
4) The carbon monoxide complexing adsorbent is prepared by adopting a method of combining ion exchange with solid state thermal dispersion, has high copper loading capacity, thus having large adsorption capacity and being suitable for purifying trace CO.
The preparation process of the carbon monoxide complex adsorbent with high adsorption capacity comprises an ion exchange process, a solid heat dispersion process and a reduction process, wherein:
in the ion exchange process of step (1), preferably, cuCl 2 The concentration of the solution is 0.5-2.0 mol/L, Y-type or X-type molecular sieve and CuCl 2 The solid-liquid mass ratio of the solution is 1; adjusting the pH value to 4-6 with ammonia water; the exchange temperature is 70-100 ℃; the exchange times are 3-6 times, and each time is 1-5 h.
In the solid-state thermal dispersion process of step (2), the weight ratio of Cu (II) Y or Cu (II) X to CuCl solid is preferably 1; mixing the two, grinding for 0.5-3 h, and then carrying out thermal dispersion; the heat dispersion temperature is preferably 300-550 ℃, the auxiliary vacuum pressure is 20-50 KPa, and the heat dispersion time is 3-10 h.
In the reduction process of step (3), it is preferably carried out in CO or H 2 Reducing for 2-6 h at 150-300 ℃ under the atmosphere and the pressure of 50-200Kpa.
The carbon monoxide complex adsorbent is particularly suitable for purifying and removing trace carbon monoxide in gas, and the purification process conditions are preferably as follows: the concentration range of carbon monoxide in the raw material gas can be 10-1000 ppm, and the purification airspeed is 300-3000 h -1 (ii) a The temperature is 0-120 ℃, and the pressure is 0.1-2 MPa.
The invention uses Y or X type molecular sieve as carrier, and adopts ion exchange combined with solid heat dispersion method to obtain carbon monoxide complex adsorbent with high copper loading. The CO adsorption capacity of the adsorbent obtained by the preparation method provided by the invention reaches 4.8mmol/g. The penetration test result of trace CO shows that compared with the existing copper-based adsorbent, the adsorbent prepared by the invention has obviously improved purification depth and penetration capacity. Compared with the prior art, the carbon monoxide adsorption capacity of the adsorbent prepared by the invention is obviously improved, and the adsorbent is particularly suitable for purification occasions containing trace CO gas.
Detailed Description
The invention is further illustrated by the following examples, but the scope of protection of the invention is not limited to the examples.
Preparation example 1
Using NaY molecular sieve raw powder and 0.8mol/L CuCl 2 Mixing the solution according to a solid-to-liquid ratio of 1; adjusting the pH to 4.2 by ammonia water; the exchange was carried out 5 times at 70 ℃ for 2h each time. Mixing and grinding the obtained Cu (II) Y and CuCl for 0.5h according to the solid weight ratio of 1; heating at 450 deg.C and 35KPa for 3h. The mixture was reduced for 6h at 150 ℃ under CO atmosphere at 100 KPa. The adsorbent obtained had a CO adsorption capacity of 4.6mmol/g at 30 ℃ and 100 KPa.
Preparation example 2
Using 13X molecular sieve raw powder and 1.5mol/L CuCl 2 Mixing the solution according to a solid-to-liquid ratio of 1; adjusting the pH value to 5.5 by ammonia water; the exchange was carried out 5 times at 90 ℃ for 3h each time. Mixing and grinding the obtained Cu (II) X and CuCl for 1.5h according to the solid weight ratio of 1; heating at 550 deg.C and 20KPa for 6h. Mixing the mixture in H 2 Reducing for 5h at the temperature of 250 ℃ under the atmosphere of 150 KPa. The adsorbent obtained had a CO adsorption capacity of 4.8mmol/g at 25 ℃ and 100 KPa.
Cleaning example one
3.0g of CuCl \ Cu (II) Y adsorbent in 20-40 meshes of preparation example I is filled in a fixed bed and reduced in situ for 6h at 100KPa and 150 ℃ under the atmosphere of CO. Introducing raw material gas (1000 ppm of carbon monoxide, and the rest gas is nitrogen) at 25 ℃ and normal pressure at a space velocity of 1500h -1 And detecting the adsorbed tail gas by using a Thermo Model 48i carbon monoxide analyzer, wherein the CO concentration in the tail gas in the first 16h is lower than 0.05ppm, and then the CO concentration slowly rises until the CO concentration reaches a penetration point of 1ppm in 36h, and the penetration capacity is 3.2mmol/g.
Purification example II
3.0g of CuCl \ Cu (II) Y adsorbent in 20-40 meshes preparation example I is filled in a fixed bed and subjected to in-situ reduction for 6h at 100KPa and 150 ℃ under the atmosphere of CO. Introducing raw material gas (1000 ppm of carbon monoxide and nitrogen as the rest) at 25 deg.C and 1.5MPa at space velocity of 1500 hr -1 Detecting the CO concentration in the tail gas after adsorption for the first 18h by adopting a Thermo Model 48i carbon monoxide analyzerBelow 0.03ppm, the CO concentration then slowly increased until 41h reached a breakthrough of 1ppm with a breakthrough capacity of 3.6mmol/g.
Purification example III
3.0g of CuCl \ Cu (II) X adsorbent in 20-40 mesh preparation example II was loaded in a fixed bed and subjected to H 2 Reducing in situ for 5h at 250 ℃ under 150KPa in the atmosphere. Introducing raw material gas (1000 ppm of carbon monoxide, and the rest gas is nitrogen) at 25 ℃ and normal pressure at a space velocity of 1500h -1 After adsorption, the CO concentration in the tail gas is detected by a Thermo Model 48i carbon monoxide analyzer, the CO concentration in the tail gas is lower than 0.04ppm in the first 18h, and then the CO concentration slowly rises until the CO concentration reaches a penetration point of 1ppm in 38h, and the penetration capacity is 3.4mmol/g.
Purification example four
Taking 3.0g of CuCl \ Cu (II) X adsorbent in 20-40 meshes preparation example II, filling the CuCl \ Cu (II) X adsorbent in a fixed bed and adsorbing the CuCl \ Cu (II) X adsorbent in H 2 Reducing in situ for 5h at the temperature of 250 ℃ under the atmosphere of 150 KPa. Introducing raw material gas (1000 ppm of carbon monoxide and nitrogen as residual gas) at 25 deg.C and 1.5MPa at space velocity of 1500 hr -1 And detecting the adsorbed tail gas by using a Thermo Model 48i carbon monoxide analyzer, wherein the CO concentration in the tail gas in the first 20h is lower than 0.02ppm, and then the CO concentration slowly rises until the CO concentration reaches a penetration point of 1ppm in 43h, and the penetration capacity is 3.8mmol/g.
Purification example five
Taking 3.0g of CuCl \ Cu (II) X adsorbent in 20-40 meshes preparation example II, filling the CuCl \ Cu (II) X adsorbent in a fixed bed and adsorbing the CuCl \ Cu (II) X adsorbent in H 2 Reducing in situ for 5h at the temperature of 250 ℃ under the atmosphere of 150 KPa. Introducing raw material gas (1000 ppm of carbon monoxide, 5% of carbon dioxide and nitrogen as residual gas) at 25 ℃ under normal pressure at a space velocity of 1500h -1 And detecting the adsorbed tail gas by using a Thermo Model 48i carbon monoxide analyzer, wherein the CO concentration in the tail gas in the first 15h is lower than 0.08ppm, and then the CO concentration slowly rises until the CO concentration reaches a penetration point of 1ppm in 32h, and the penetration capacity is 2.8mmol/g.
Purification example five
Taking 3.0g of CuCl \ Cu (II) X adsorbent in 20-40 meshes preparation example II, filling the CuCl \ Cu (II) X adsorbent in a fixed bed and adsorbing the CuCl \ Cu (II) X adsorbent in H 2 Reducing in situ for 5h at 250 ℃ under 150KPa in the atmosphere. Introducing raw material gas (1000 ppm of oxygen) at 25 deg.C under normal pressureCarbon conversion, 5 percent of carbon dioxide, 5 percent of methane and the balance of nitrogen), and the space velocity is 1500h -1 And detecting the adsorbed tail gas by using a Thermo Model 48i carbon monoxide analyzer, wherein the CO concentration in the tail gas in the first 15h is lower than 0.08ppm, and then the CO concentration slowly rises until the CO concentration reaches a penetration point of 1ppm in 32h, and the penetration capacity is 2.8mmol/g.
Example six for purification
3.0g of CuCl \ Cu (II) X adsorbent in 20-40 mesh preparation example II was loaded in a fixed bed and subjected to H 2 Reducing in situ for 5h at 250 ℃ under 150KPa in the atmosphere. Introducing raw material gas (1000 ppm of carbon monoxide, 5% of carbon dioxide, 5% of methane and nitrogen as the rest) at 120 ℃ and 2.0MPa at the space velocity of 2500h -1 And detecting the adsorbed tail gas by using a Thermo Model 48i carbon monoxide analyzer, wherein the CO concentration in the tail gas in the first 10h is lower than 0.08ppm, and then the CO concentration slowly rises until the CO concentration reaches a penetration point of 1ppm in 16h, and the penetration capacity is 1.4mmol/g.
Example seven purification
Taking 3.0g of CuCl \ Cu (II) X adsorbent in 20-40 meshes preparation example II, filling the CuCl \ Cu (II) X adsorbent in a fixed bed and adsorbing the CuCl \ Cu (II) X adsorbent in H 2 Reducing in situ for 5h at 250 ℃ under 150KPa in the atmosphere. Introducing raw material gas (1000 ppm of carbon monoxide, 5% of carbon dioxide, 5% of methane and nitrogen as residual gas) at 25 ℃ and 1.0MPa at a space velocity of 1500h -1 After adsorption, the CO concentration in the tail gas is detected by a Thermo Model 48i carbon monoxide analyzer, the CO concentration in the tail gas is lower than 0.06ppm in the first 19h, and then the CO concentration slowly rises until the CO concentration reaches a penetration point of 1ppm in 37h, and the penetration capacity is 3.3mmol/g.
Comparative purification example 1
The adsorbent was prepared as provided in EP0224150 by collecting 3.0g of 20-40 mesh adsorbent, packing in a fixed bed and introducing into H 2 Reducing in situ for 5h at 250 ℃ under 150KPa in the atmosphere. Introducing raw material gas (1000 ppm of carbon monoxide, and the rest gas is nitrogen) at 25 ℃ and normal pressure at a space velocity of 1500h -1 After adsorption, the CO concentration in the tail gas is lower than 0.07ppm in the first 7h, and then the CO concentration slowly rises until the tail gas reaches a penetration point of 1ppm in 12h and the penetration capacity is 1.0mmol/g by adopting a Thermo Model 48i carbon monoxide analyzer.
Comparative example 2
Preparing adsorbent according to the method provided in CN86102838B, collecting 3.0g of 20-40 mesh adsorbent, filling in fixed bed, and introducing into H 2 Reducing in situ for 5h at 250 ℃ under 150KPa in the atmosphere. Introducing raw material gas (1000 ppm of carbon monoxide, and the rest gas is nitrogen) at 25 ℃ and normal pressure at a space velocity of 1500h -1 After adsorption, the CO concentration in the tail gas is detected by a Thermo Model 48i carbon monoxide analyzer, the CO concentration in the tail gas is lower than 0.06ppm in the first 15h, and then the CO concentration slowly rises until the CO concentration reaches a penetration point of 1ppm in 22h, and the penetration capacity is 1.9mmol/g.
Comparative example C
Preparing adsorbent according to the method provided in CN112755956A, taking 3.0g of 20-40 mesh adsorbent, filling in a fixed bed and placing in H 2 Reducing in situ for 5h at 250 ℃ under 150KPa in the atmosphere. Introducing raw material gas (1000 ppm of carbon monoxide, and the rest gas is nitrogen) at 25 ℃ and normal pressure at a space velocity of 1500h -1 And detecting the adsorbed tail gas by using a Thermo Model 48i carbon monoxide analyzer, wherein the CO concentration in the tail gas in the first 18h is lower than 0.06ppm, and then the CO concentration slowly rises until the CO concentration reaches a penetration point of 1ppm in 32h, and the penetration capacity is 2.8mmol/g.
Claims (10)
1. A carbon monoxide adsorbent is a carbon monoxide complex adsorbent with high copper loading, which is obtained by taking a Y-type or X-type molecular sieve as a carrier, firstly obtaining Cu (II) Y or Cu (II) X exchanged by divalent copper by an ion exchange method, then loading CuCl by a solid thermal dispersion method, and then reducing.
2. The carbon monoxide adsorbent of claim 1, wherein the Y-type or X-type molecular sieve is selected from NaY molecular sieve and 13X molecular sieve.
3. A preparation method of a carbon monoxide complexing adsorbent with high copper loading capacity comprises the following steps:
1) Mixing Y-type or X-type molecular sieve raw powder with CuCl 2 Mixing the solutions, adjusting the pH value to 4-6, and performing pulping exchange for multiple times to obtain Cu (II) Y or Cu (II) X exchanged by bivalent copper;
2) Mixing and grinding Cu (II) Y or Cu (II) X and CuCl solid powder, vacuumizing and heating the obtained mixture for a period of time in an auxiliary way, and loading CuCl on a molecular sieve through thermal dispersion;
3) Reducing the mixture obtained in the step 2) in a reducing atmosphere to prepare the carbon monoxide complexing adsorbent.
4. The method of claim 3, wherein the CuCl is present in step 1) 2 The concentration of the solution is 0.5-2.0 mol/L, Y-type or X-type molecular sieve and CuCl 2 The solid-liquid mass ratio of the solution is 1.
5. The process according to claim 3, wherein in step 1) the pH is adjusted to 4 to 6 with aqueous ammonia at a temperature of 70 to 100 ℃ and for 3 to 6 exchanges, each time for 1 to 5 hours.
6. The method according to claim 3, wherein the weight ratio of Cu (II) Y or Cu (II) X to CuCl solid in step 2) is 1.
7. The method according to claim 3, wherein the heat dispersion temperature in the step 2) is 300 to 550 ℃, the auxiliary vacuum pressure is 20 to 50KPa, and the heat dispersion time is 3 to 10 hours.
8. The method according to claim 3, wherein the reducing atmosphere in step 3) is CO or H 2 Reducing for 2-6 h under the atmosphere and the pressure of 50-200Kpa at the temperature of 150-300 ℃.
9. Use of the carbon monoxide adsorbent of claim 1 in the purification of gases for the removal of trace amounts of carbon monoxide from the gases.
10. The use according to claim 9, wherein the carbon monoxide concentration of the gas to be purified is in the range of 10 to 1000ppm and the purification space velocity is in the range of 300 to 3000h -1 The temperature is 0-120 ℃, and the pressure is 0.1-2 MPa.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86102838A (en) * | 1986-04-26 | 1987-09-02 | 北京大学 | High-efficiency adsorbent and its production and application |
| US4783433A (en) * | 1985-11-19 | 1988-11-08 | Nippon Kokan Kabushiki Kaisha | Selective adsorbent for CO and method of manufacturing the same |
| CN101927152A (en) * | 2010-03-12 | 2010-12-29 | 大连海鑫化工有限公司 | High-strength gas purifying and separating adsorbent as well as preparation and application thereof |
| CN105749858A (en) * | 2016-01-11 | 2016-07-13 | 昆明理工大学 | Preparation method of carbon monoxide absorbent |
| CN106315613A (en) * | 2016-08-19 | 2017-01-11 | 西南化工研究设计院有限公司 | Novel 13X-type molecular sieve for CO adsorption as well as preparation method and application thereof |
| CN108704609A (en) * | 2018-05-30 | 2018-10-26 | 太原理工大学 | Monolayer CuCl/ acticarbon preparation methods for CO adsorbing separations |
| KR20210039808A (en) * | 2019-10-02 | 2021-04-12 | 한국에너지기술연구원 | Zeolite-based adsorbent for carbon monoxide selective adsoprtion and the manufacturing method thereof |
-
2021
- 2021-08-31 CN CN202111011122.7A patent/CN115722187A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4783433A (en) * | 1985-11-19 | 1988-11-08 | Nippon Kokan Kabushiki Kaisha | Selective adsorbent for CO and method of manufacturing the same |
| CN86102838A (en) * | 1986-04-26 | 1987-09-02 | 北京大学 | High-efficiency adsorbent and its production and application |
| CN101927152A (en) * | 2010-03-12 | 2010-12-29 | 大连海鑫化工有限公司 | High-strength gas purifying and separating adsorbent as well as preparation and application thereof |
| CN105749858A (en) * | 2016-01-11 | 2016-07-13 | 昆明理工大学 | Preparation method of carbon monoxide absorbent |
| CN106315613A (en) * | 2016-08-19 | 2017-01-11 | 西南化工研究设计院有限公司 | Novel 13X-type molecular sieve for CO adsorption as well as preparation method and application thereof |
| CN108704609A (en) * | 2018-05-30 | 2018-10-26 | 太原理工大学 | Monolayer CuCl/ acticarbon preparation methods for CO adsorbing separations |
| KR20210039808A (en) * | 2019-10-02 | 2021-04-12 | 한국에너지기술연구원 | Zeolite-based adsorbent for carbon monoxide selective adsoprtion and the manufacturing method thereof |
Non-Patent Citations (2)
| Title |
|---|
| YOUCHANG XIE ET AL.: "Zeolites Modified by CuCI for Separating CO from Gas Mixtures Containing CO2", 《ADSORPTION-JOURNAL OF THE INTERNATIONAL ADSORPTION SOCIETY》, vol. 3, no. 1, pages 27 - 32 * |
| 谢有畅等: "一氧化碳高效吸附剂CuCl/分子筛", 《高等学校化学学报》, vol. 18, no. 7, pages 1159 - 1165 * |
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