CN101371979B - Sorbent for absorbing carbon dioxide in trace amounts of ethylene and preparation method thereof - Google Patents
Sorbent for absorbing carbon dioxide in trace amounts of ethylene and preparation method thereof Download PDFInfo
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- CN101371979B CN101371979B CN2008101523006A CN200810152300A CN101371979B CN 101371979 B CN101371979 B CN 101371979B CN 2008101523006 A CN2008101523006 A CN 2008101523006A CN 200810152300 A CN200810152300 A CN 200810152300A CN 101371979 B CN101371979 B CN 101371979B
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Abstract
The invention discloses an absorbent which is used for the removal of trace ethylene and comprises the following components by weight percentage: 10-50 percent of active component, 20-80 percent of carrier and 10-30 percent of bonding agent. The active component comprises cuprous compound, manganous compound and divalent zinc compound. The carrier comprises an HY molecular sieve, an HBeta molecular sieve and an HZSM-5 molecular sieve. The bonding agent is alumina sol. The absorbent has perfect absorption property on trace ethylene in carbon dioxide. And the absorbent has the advantages of simple preparation process, low price, uneasy pulverization and long service life. In the preparation method, a solid phase mechanical hybrid method which has the advantages of simple operation and shortprocess is adopted. After an absorption device is arranged, a process of low temperature reduction first and then high temperature calcination are adopted to realize continuous operation, thereby saving cost while lowering the operational strength and difficulty of the reduction and calcination.
Description
Technical field
The present invention relates to a kind of adsorbent and preparation method thereof, more particularly, relate to a kind of adsorbent that microscale ethylene removes and preparation method thereof that is used in the carbon dioxide production field.
Background technology
. at present, the method that removes lighter hydrocarbons in gaseous mixture or the unstripped gas has Production by Catalytic Combustion Process and adsorption method of separation.Even Production by Catalytic Combustion Process ethene and oxygen carry out chemical reaction under catalyst action, generate water and carbon dioxide, often make catalyst with platinum, palladium, reaction needed is carried out under high temperature (usually〉350 ℃).The problem that this technology exists is: the hydrocarbon of burning high-load can be emitted a large amount of heat, for caloric restriction too much, need to carry out at multiple combustion phases, like this system the operation on more complicated and costliness, in addition because not necessarily contain enough oxygen in the unstripped gas, excessive oxygen is added in the feed stream usually, with the assurance sufficient combustion, and the not only owning cost of the introducing of oxygen own also increases the later separation task.
Adsorption method of separation is low because of its energy consumption, degree of purification is high, equipment is simple, be easy to advantages such as automation mechanized operation is used widely.Chinese patent " removes microscale ethylene adsorbent in the carbon dioxide ", and (applying date is on November 6th, 2003, open day is on November 3rd, 2004, application number is 200310105015.6) reported a kind of adsorbent that is used for removing the carbon dioxide microscale ethylene, this adsorbent is main active component with the silver salt, HZSM-5, HY and γ-Al2O3 are complex carrier, add multiple auxiliary agent and adopt incipient impregnation-thermodynamics individual layer process for dispersing to make, performance of the adsorbent is good, its shortcoming is the preparation process complexity, and the ratio that precious metal salt accounts for is higher, has improved preparation cost.(applying date is on April 26th, 1986 to Chinese patent " high-efficiency adsorbent and its production and use ", the authorization day for announcing is on September 9th, 1987, application number is 86102838) a kind of " adsorbent that is made by monovalence copper or cupric compound and high surface area carrier Hybrid Heating " disclosed, contain cupprous adsorbent and take first roasting as last in absorption, the pretreating process of filling back reduction, it is cupric by partial oxidation easily that elder generation's roasting causes the monovalence copper-base, the requirement secluding air stores, the condition harshness, and make the action mode complexity of copper and carrier, increase the weight of the difficulty of absorption pre reduction operation, and then influenced absorption property.
Summary of the invention
It is not high that the present invention is intended to overcome existing ethene adsorbent adsorption capacity, the preparation cost height, the low and high deficiency of restoring operation difficulty of intensity, a kind of ethene adsorbent is provided, this adsorbent can not only have good absorption property to microscale ethylene in the carbon dioxide, and preparation process is simple, low price, be difficult for efflorescence, the life-span is long.
A kind of adsorbent that is used for the absorbing carbon dioxide microscale ethylene of the present invention is characterized in that, is made up of 10%-50% active component, 20%-80% carrier and 10%-30% adhesive according to mass percent; Described active component is made up of 50%-95% monovalence copper compound, 1%-30% manganous compound and 1%-30% divalent zinc compound according to mass percent; Described carrier is HY type molecular sieve or is made up of 50%-90% HY type molecular sieve and 10-50% HZSM-5 type molecular sieve for the H beta molecular sieve or according to mass percent, perhaps form by 50%-90% H beta molecular sieve and 10-50% HZSM-5 type molecular sieve, perhaps form by 50%-80% HY type molecular sieve, 10%-25% H beta molecular sieve and 10-25% HZSM-5 type molecular sieve according to mass percent according to mass percent; Wherein said monovalence copper compound is a kind of among CuCl, CuBr or the CuI; Described manganous compound is MnCl
2, MnSO
4Perhaps Mn (CH
3COO)
2In a kind of; Described divalent zinc compound is ZnCl
2, ZnBr
2, ZnSO
4Perhaps Zn (NO
3)
2In a kind of; Described adhesive is an aluminium colloidal sol.
A kind of adsorbent that is used for the absorbing carbon dioxide microscale ethylene of the present invention, it is characterized in that, described adsorbent is made up of active component, carrier and adhesive according to mass percent, described active component is 20%-30%, described carrier is 60-70%, described adhesive is 10%-20%, and described active component is made up of the monovalence copper compound of 60%-90%, the manganous compound of 5%-20% and the divalent zinc compound of 5%-20% according to mass percent; Described carrier is a HY type molecular sieve or for the H beta molecular sieve or be made up of the HY type molecular sieve of 60%-80% and the HZSM-5 type molecular sieve of 20-40% according to mass percent, perhaps form by the H beta molecular sieve of 60%-80% and the HZSM-5 type molecular sieve of 20-40%, perhaps form by the HY type molecular sieve of 60%-70%, the H beta molecular sieve of 15%-20% and the HZSM-5 type molecular sieve of 15%-20% according to mass percent according to mass percent; Described adhesive is an aluminium colloidal sol.The specific area of described adsorbent is 250-400m
2/ g, pore volume are 0.05-0.6mL/g, and bulk density is 0.8-1.5g/cm
3
A kind of adsorbent that is used for the absorbing carbon dioxide microscale ethylene of the present invention, carry out according to following step:
(1) utilizes the solid phase mechanical mixing will account for the active component of the mass percent 10%-50% of adsorbent oeverall quality, the carrier of 20%-80% and the adhesive of 10%-30% and fully mix 3-10h;
(2) with the abundant mixed mixture moulding of step (1), vacuum drying then;
(3) adsorbent after step (2) moulding is seated in the adsorbent equipment, reduces with nitrogen hydrogen mixeding gas, the percentage by volume of hydrogen is 0.5%-10% in the mist, and reduction temperature is 120-190 ℃, and the recovery time is 10-48h;
(4) after the reduction, be full of inert gas at adsorbent equipment, then wherein adsorbent carried out roasting, roasting time is 1-24h, and sintering temperature is 250-400 ℃.
The active component of described step (1) is made up of the monovalence copper compound of 50%-95%, the manganous compound of 1%-30% and the divalent zinc compound of 1%-30% according to mass percent; Described carrier is a HY type molecular sieve or for the H beta molecular sieve or be made up of the HY type molecular sieve of 50%-90% and the HZSM-5 type molecular sieve of 10-50% according to mass percent, perhaps form by the H beta molecular sieve of 50%-90% and the HZSM-5 type molecular sieve of 10-50%, perhaps form by the HY type molecular sieve of 50%-80%, the H beta molecular sieve of 10%-25% and the HZSM-5 type molecular sieve of 10-25% according to mass percent according to mass percent; Wherein said monovalence copper compound is a kind of among CuCl, CuBr or the CuI; Described manganous compound is MnCl
2, MnSO
4Perhaps Mn (CH
3COO)
2In a kind of; Described divalent zinc compound is ZnCl
2, ZnBr
2, ZnSO
4Perhaps Zn (NO
3)
2In a kind of; Described adhesive is an aluminium colloidal sol.
The active component of described step (1) is preferably 20%-30%, described carrier is preferably 60-70%, described adhesive is preferably 10%-20%, and described active component is made up of the monovalence copper compound of 60%-90%, the manganous compound of 5%-20% and the divalent zinc compound of 5%-20% according to mass percent; Described carrier is a HY type molecular sieve or for the H beta molecular sieve or be made up of the HY type molecular sieve of 60%-80% and the HZSM-5 type molecular sieve of 20-40% according to mass percent, perhaps form by the H beta molecular sieve of 60%-80% and the HZSM-5 type molecular sieve of 20-40%, perhaps form by the HY type molecular sieve of 60%-70%, the H beta molecular sieve of 15%-20% and the HZSM-5 type molecular sieve of 15%-20% according to mass percent according to mass percent; Wherein said monovalence copper compound is a kind of among CuCl, CuBr or the CuI; Described manganous compound is MnCl
2, MnSO
4Perhaps Mn (CH
3COO)
2In a kind of; Described divalent zinc compound is ZnCl
2, ZnBr
2, ZnSO
4Perhaps Zn (NO
3)
2In a kind of; Described adhesive is an aluminium colloidal sol.
The percentage by volume of hydrogen is 1%-5% in the middle mist of described step (3), and reduction temperature is 160-180 ℃, and the recovery time is 10-24h.
The inert gas of described step (4) is a kind of in nitrogen, helium or the argon gas.
The roasting time of described step (4) is 4-15h, and sintering temperature is 300-350 ℃.The specific area of described adsorbent is 250-400m
2/ g, pore volume are 0.05-0.6mL/g, and bulk density is 0.8-1.5g/cm
3
The carrier that adsorbent of the present invention adopts can be HY type molecular sieve, also can be the mixture of HY type molecular sieve and HZSM-5 type molecular sieve.The character of H beta molecular sieve and HY type molecular sieve is close, for example both apertures, main aperture road are approximate, also can select the H beta molecular sieve for use, the mixture of H beta molecular sieve and HZSM-5 type molecular sieve, the perhaps mixture of HY type molecular sieve, H beta molecular sieve and HZSM-5 type molecular sieve.
Active component low price not only can effectively remove microscale ethylene in the carbon dioxide in the adsorbent of the present invention, and manganese, being added with of zinc compound are beneficial to cupprous stable existence; The use of H type molecular sieve carrier not only has high-specific surface area, and weakens the absorption of carbon dioxide sour gas, promotes ethylene absorption, improves degree of purification; Adhesive is selected the inorganic matter that has identical element with carrier for use, helps cohering between carrier and carrier and carrier and active component, improves the intensity of adsorbent.Adsorbent of the present invention has good absorption property to microscale ethylene in the carbon dioxide, preparation and use are simple, low price, be difficult for efflorescence, long service life, be the superior adsorbent of purification of carbon dioxide, be applicable to remove and contain microscale ethylene in one or more nonpolar sources of the gas (as carbon dioxide, alkane (carbon number is greater than 2), nitrogen etc.), be with a wide range of applications.
Another object of the present invention is to overcome monovalence copper adsorbent elder generation roasting in the prior art, the secluding air that the treatment process of filling back reduction brings stores and adsorbs the difficulty of pre reduction operation, provide a kind of and can lower carrying cost, can conveniently reduce again and the preparation method of baking operation.
A kind of preparation of the present invention is used for the method for the adsorbent of absorbing carbon dioxide microscale ethylene, carries out according to following step:
(1) utilize the solid phase mechanical mixing that the active component of mass percent 10%-50%, the carrier of 20%-80% and the adhesive of 10%-30% are fully mixed 3-10h;
(2) with the abundant mixed mixture moulding of step (1), vacuum drying then;
(3) adsorbent after step (2) moulding is seated in the adsorbent equipment, reduces with nitrogen hydrogen mixeding gas, the percentage by volume of hydrogen is 0.5%-10% in the mist, and reduction temperature is 120-190 ℃, and the recovery time is 10-48h;
(4) after the reduction, be full of inert gas at adsorbent equipment, then wherein adsorbent carried out roasting, roasting time is 1-24h, and sintering temperature is 250-400 ℃.
The active component of described step (1) is made up of the monovalence copper compound of 50%-95%, the manganous compound of 1%-30% and the divalent zinc compound of 1%-30% according to mass percent; Described carrier is a HY type molecular sieve or for the H beta molecular sieve or be made up of the HY type molecular sieve of 50%-90% and the HZSM-5 type molecular sieve of 10-50% according to mass percent, perhaps form by the H beta molecular sieve of 50%-90% and the HZSM-5 type molecular sieve of 10-50%, perhaps form by the HY type molecular sieve of 50%-80%, the H beta molecular sieve of 10%-25% and the HZSM-5 type molecular sieve of 10-25% according to mass percent according to mass percent; Wherein said monovalence copper compound is a kind of among CuCl, CuBr or the CuI; Described manganous compound is MnCl
2, MnSO
4Perhaps Mn (CH
3COO)
2In a kind of; Described divalent zinc compound is ZnCl
2, ZnBr
2, ZnSO
4Perhaps Zn (NO
3)
2In a kind of; Described adhesive is an aluminium colloidal sol.
The active component of described step (1) is preferably 20%-30%, described carrier is preferably 60-70%, described adhesive is preferably 10%-20%, and described active component is made up of the monovalence copper compound of 60%-90%, the manganous compound of 5%-20% and the divalent zinc compound of 5%-20% according to mass percent; Described carrier is a HY type molecular sieve or for the H beta molecular sieve or be made up of the HY type molecular sieve of 60%-80% and the HZSM-5 type molecular sieve of 20-40% according to mass percent, perhaps form by the H beta molecular sieve of 60%-80% and the HZSM-5 type molecular sieve of 20-40%, perhaps form by the HY type molecular sieve of 60%-70%, the H beta molecular sieve of 15%-20% and the HZSM-5 type molecular sieve of 15%-20% according to mass percent according to mass percent; Wherein said monovalence copper compound is a kind of among CuCl, CuBr or the CuI; Described manganous compound is MnCl
2, MnSO
4Perhaps Mn (CH
3COO)
2In a kind of; Described divalent zinc compound is ZnCl
2, ZnBr
2, ZnSO
4Perhaps Zn (NO
3)
2In a kind of; Described adhesive is an aluminium colloidal sol.
The percentage by volume of hydrogen is 1%-5% in the middle mist of described step (3), and reduction temperature is 160-180 ℃, and the recovery time is 10-24h.
The inert gas of described step (4) is a kind of in nitrogen, helium or the argon gas.
The roasting time of described step (4) is 4-15h, and sintering temperature is 300-350 ℃.
Adsorbent profile of the present invention and size can be determined according to instructions for use, can make sheet, sphere, honeycombed, bar shaped, cloverleaf pattern, irregular shape etc.
Preparation method of the present invention, solid phase mechanical mixing (for example ball milling) is adopted in preparation, and is simple to operate, and flow process is short; Because do not carry out roasting before the filling, monovalence copper is more stable,, saved storage cost so the adsorbent after the moulding can conventional airtight preservation; Behind the filling adsorbent equipment, adopt the first low-temperature reduction technology of high-temperature roasting again.As shown in Figure 3, whole device can adopt pipe valve cooperation sensor or computer reduces and the control of roasting technique, realize continued operation, promptly close the pipeline of the carbon dioxide that contains microscale ethylene earlier, open the pipeline of nitrogen and hydrogen, in adsorbent equipment, carry out earlier low-temperature reduction, close the hydrogen pipeline and the temperature that raises then, in nitrogen or other inert gas atmosphere, carry out high-temperature roasting, after high-temperature roasting, close the pipeline of nitrogen, open the mist pipeline that needs processing, in adsorbent equipment, adsorb, thereby save cost, reduce the manipulation strength and the difficulty of reduction and roasting simultaneously.Technical process does not have corrosiveness to production equipment simultaneously, and non-environmental-pollution is fit to suitability for industrialized production.When the continuous use of adsorbent reaches capacity, can adopt pipe valve to cooperate sensor or computer that adsorbent is regenerated, regeneration uses hot nitrogen to be regeneration gas, and temperature is 180-250 ℃.
Adsorbent of the present invention is carried out the test of physicochemical properties, and the specific area of adsorbent is 300-380m as can be known
2/ g, pore volume are 0.05-0.1mL/g, and bulk density is 0.8-1.2g/cm
3, edge strength is 12-15N, has higher specific surface area, bulk density, pore volume and blade mechanical strength.H
2The experimental result of-TPR shows, is reduced to monovalence copper (Cu by cupric on the adsorbent
2+→ Cu
+The reduction peak temperature is 255 ℃) and the monovalence copper reduction be zerovalent copper (Cu
+→ Cu
0The reduction peak temperature is 480 ℃) the temperature difference bigger, illustrate that adsorbent of the present invention restoring operation in actual use controls easily, adsorbent has lower reduction peak area simultaneously, illustrates that adsorbent provided by the invention is difficult for being oxidized to cupric, reduce the consumption of hydrogen, be convenient to conventional the storage.
The PU-1 type adsorbent of selling on adsorbent of the present invention and the market is carried out the ethylene absorption experiment, and testing process is adsorbent preliminary treatment-absorption-regeneration.The normal pressure restoring operation is taked in preliminary treatment behind the PU-1 type adsorbent motion device, and reducing gases is hydrogen nitrogen mixed gas (0.5%～2% a hydrogen), about 160 ℃ of reduction temperatures, air speed 815h
-1, carrying out normal temperature absorption afterwards, pressure is controlled at 2.15MPa, and the CO 2 raw material gas air speed is 2173h
-1, adsorb and utilize hot nitrogen to carry out desorption and regeneration after saturated, nitrogen air speed 815h
-1, 200 ℃ of temperature; Adsorbent of the present invention carries out low-temperature reduction and high-temperature roasting earlier, and reducing condition is with PU-1 type adsorbent, and high-temperature roasting is 4h under the flow of warm nitrogen gas about 350 ℃, and absorption after this and regeneration condition are with PU-1 type adsorbent.Measure the breakthrough curve that ethene is depressed in six components in the gaseous mixture respectively, obtain penetrating adsorbance, the adsorption isotherm of its match as shown in Figure 2, the adsorption capacity of adsorbent provided by the invention as can be seen and PU-1 type adsorbent all improves with the increase of ethylene partial pressure, under the identical ethylene partial pressure, the adsorption capacity of adsorbent of the present invention is higher 20～40 percentage points than the adsorption capacity of PU-1 type adsorbent.
Description of drawings
Fig. 1 this patent preparation method flow chart
The adsorption isotherm of ethene in Fig. 2 gaseous mixture
Fig. 3 adsorbent equipment structural representation
The specific embodiment
Further specify technical scheme of the present invention below in conjunction with specific embodiment.
Embodiment 1
(1) 16g stannous chloride, 2g manganese chloride, 2g zinc chloride, 70gHY type molecular sieve and 10g aluminium colloidal sol are mixed, carry out ball milling, ball milling 6h;
(2) the abundant mixed mixture of step (1) is shaped to sphere, vacuum drying then;
(3) adsorbent after step (2) moulding is seated in the adsorbent equipment, reduces with nitrogen hydrogen mixeding gas, wherein the percent by volume of hydrogen is 2%, and reduction temperature is 160 ℃, reduction 12h;
(4) after the reduction, be full of nitrogen, then adsorbent carried out roasting, roasting time 6h, 350 ℃ of sintering temperatures at adsorbent equipment.
Embodiment 2
(1) 47.5g stannous chloride, 0.5g manganese chloride, 2g zinc chloride, 20gHY type molecular sieve, 20gHZSM-5 type molecular sieve and 10g aluminium colloidal sol are mixed, carry out ball milling, ball milling 8h;
(2) the abundant mixed mixture of step (1) is shaped to bar shaped, vacuum drying then;
(3) adsorbent after step (2) moulding is seated in the adsorbent equipment, reduces with nitrogen hydrogen mixeding gas, the percentage by volume of hydrogen is 0.5% in the mist, and reduction temperature is 150 ℃, reduction 48h;
(4) after the reduction, be full of nitrogen, then adsorbent carried out roasting, roasting time 4h, 400 ℃ of sintering temperatures at adsorbent equipment.
Embodiment 3
(1) 20g stannous chloride, 12g manganese chloride, 8g zinc chloride, 27gH beta molecular sieve, 3gHZSM-5 type molecular sieve and 30g aluminium colloidal sol are mixed, carry out ball milling, ball milling 8h;
(2) the abundant mixed mixture of step (1) is shaped to honeycomb shape, vacuum drying then;
(3) adsorbent after step (2) moulding is seated in the adsorbent equipment, reduces with nitrogen hydrogen mixeding gas, the percentage by volume of hydrogen is 5% in the mist, and reduction temperature is 180 ℃, reduction 10h;
(4) after the reduction, be full of nitrogen, then adsorbent carried out roasting, roasting time 8h, 300 ℃ of sintering temperatures at adsorbent equipment.
Embodiment 4
(1) 12g cuprous bromide, 4g manganese sulfate, 4g zinc nitrate, 36gHY type molecular sieve, 12gH beta molecular sieve, 12gHZSM-5 type molecular sieve and 20g aluminium colloidal sol are mixed, carry out ball milling, ball milling 10h;
(2) the abundant mixed mixture of step (1) is shaped to bar, vacuum drying then;
(3) adsorbent after step (2) moulding is seated in the adsorbent equipment, reduces with nitrogen hydrogen mixeding gas, wherein the percent by volume of hydrogen is 3%, and reduction temperature is 190 ℃, reductase 12 0h;
(4) after the reduction, be full of argon gas, then adsorbent carried out roasting, roasting time 10h, 250 ℃ of sintering temperatures at adsorbent equipment.
Embodiment 5
(1) 18g cuprous iodide, 1g manganese acetate, 1g zinc sulfate, 49gHY type molecular sieve, 10.5gH beta molecular sieve, 10.5gHZSM-5 type molecular sieve and 10g aluminium colloidal sol are mixed, carry out ball milling, ball milling 10h;
(2) the abundant mixed mixture of step (1) is shaped to honeycomb shape, vacuum drying then;
(3) adsorbent after step (2) moulding is seated in the adsorbent equipment, reduces with nitrogen hydrogen mixeding gas, wherein the percent by volume of hydrogen is 5%, and reduction temperature is 185 ℃, reduction 10h;
(4) after the reduction, be full of helium, then adsorbent carried out roasting, roasting time 15h, 400 ℃ of sintering temperatures at adsorbent equipment.
Embodiment 6
(1) 24g cuprous bromide, 3g manganese sulfate, 3g zinc bromide, 48gH beta molecular sieve, 12gHZSM-5 type molecular sieve and 10g aluminium colloidal sol are mixed, carry out ball milling, ball milling 3h;
(2) the abundant mixed mixture of step (1) is shaped to sphere, vacuum drying then;
(3) adsorbent after step (2) moulding is seated in the adsorbent equipment, reduces with nitrogen hydrogen mixeding gas, wherein the percent by volume of hydrogen is 4%, and reduction temperature is 150 ℃, reduction 35h;
(4) after the reduction, be full of nitrogen, then adsorbent carried out roasting, roasting time 2h, 300 ℃ of sintering temperatures at adsorbent equipment.
Embodiment 7
(1) 25g stannous chloride, 15g manganese chloride, 10g zinc sulfate, 27gHY type molecular sieve, 3gHZSM-5 type molecular sieve and 20g aluminium colloidal sol are mixed, carry out ball milling, ball milling 4h;
(2) the abundant mixed mixture of step (1) is shaped to irregular shape, vacuum drying then;
(3) adsorbent after step (2) moulding is seated in the adsorbent equipment, reduces with nitrogen hydrogen mixeding gas, wherein the percent by volume of hydrogen is 1%, and reduction temperature is 175 ℃, reduction 40h;
(4) after the reduction, be full of nitrogen, then adsorbent carried out roasting, roasting time 12h, 250 ℃ of sintering temperatures at adsorbent equipment.
Embodiment 8
(1) 32g cuprous bromide, 4g manganese sulfate, 4g zinc chloride, 24gH beta molecular sieve, 16gHZSM-5 type molecular sieve and 20g aluminium colloidal sol are mixed, carry out ball milling, ball milling 5h;
(2) the abundant mixed mixture of step (1) is shaped to honeycomb shape, vacuum drying then;
(3) adsorbent after step (2) moulding is seated in the adsorbent equipment, reduces with nitrogen hydrogen mixeding gas, wherein the percent by volume of hydrogen is 3%, and reduction temperature is 165 ℃, reduction 30h;
(4) after the reduction, be full of nitrogen, then adsorbent carried out roasting, roasting time 20h, 350 ℃ of sintering temperatures at adsorbent equipment.
Embodiment 9
(1) 25g stannous chloride, 10g manganous bromide, 15g zinc nitrate, 20gH beta molecular sieve and 30g aluminium colloidal sol are mixed, carry out ball milling, ball milling 10h;
(2) the abundant mixed mixture of step (1) is shaped to irregular shape, vacuum drying then;
(3) adsorbent after step (2) moulding is seated in the adsorbent equipment, reduces with nitrogen hydrogen mixeding gas, wherein the percent by volume of hydrogen is 2%, and reduction temperature is 150 ℃, reductase 12 4h;
(4) after the reduction, be full of nitrogen, then adsorbent carried out roasting, roasting time 24h, 300 ℃ of sintering temperatures at adsorbent equipment.
Embodiment 10
(1) 28g cuprous bromide, 8g manganese acetate, 4g zinc sulfate, 30gHY type molecular sieve, 20gHZSM-5 type molecular sieve and 10g aluminium colloidal sol are mixed, carry out ball milling, ball milling 8h;
(2) the abundant mixed mixture of step (1) is shaped to honeycomb shape, vacuum drying then;
(3) adsorbent after step (2) moulding is seated in the adsorbent equipment, reduces with nitrogen hydrogen mixeding gas, wherein the percent by volume of hydrogen is 10%, and reduction temperature is 180 ℃, reduction 10h;
(4) after the reduction, be full of argon gas, then adsorbent carried out roasting, roasting time 20h, 400 ℃ of sintering temperatures at adsorbent equipment.
Embodiment 11
(1) 21g cuprous iodide, 3g manganese chloride, 6g zinc bromide, 30gHY type molecular sieve, 15gH beta molecular sieve, 15gHZSM-5 type molecular sieve and 10g aluminium colloidal sol are mixed, carry out ball milling, ball milling 4h;
(2) the abundant mixed mixture of step (1) is shaped to bar shaped, vacuum drying then;
(3) adsorbent after step (2) moulding is seated in the adsorbent equipment, reduces with nitrogen hydrogen mixeding gas, wherein the percent by volume of hydrogen is 5%, and reduction temperature is 190 ℃, reduction 10h;
(4) after the reduction, be full of helium, then adsorbent carried out roasting, roasting time 7h, 250 ℃ of sintering temperatures at adsorbent equipment.
Embodiment 12
(1) 18g stannous chloride, 4.5g manganese chloride, 7.5g zinc chloride, 48gHY type molecular sieve, 6gH beta molecular sieve, 6gHZSM-5 type molecular sieve and 10g aluminium colloidal sol are mixed, carry out ball milling, ball milling 6h;
(2) the abundant mixed mixture of step (1) is shaped to sphere, vacuum drying then;
(3) adsorbent after step (2) moulding is seated in the adsorbent equipment, reduces with nitrogen hydrogen mixeding gas, wherein the percent by volume of hydrogen is 6%, and reduction temperature is 160 ℃, reduction 40h;
(4) after the reduction, be full of nitrogen, then adsorbent carried out roasting, roasting time 10h, 350 ℃ of sintering temperatures at adsorbent equipment.
Embodiment 13
(1) 6g stannous chloride, 2g manganese sulfate, 2g zinc sulfate, 64gH beta molecular sieve, 16gHZSM-5 type molecular sieve and 10g aluminium colloidal sol are mixed, carry out ball milling, ball milling 6h;
(2) the abundant mixed mixture of step (1) is shaped to sphere, vacuum drying then;
(3) adsorbent after step (2) moulding is seated in the adsorbent equipment, reduces with nitrogen hydrogen mixeding gas, wherein the percent by volume of hydrogen is 7%, and reduction temperature is 160 ℃, reduction 35h;
(4) after the reduction, be full of nitrogen, then adsorbent carried out roasting, roasting time 10h, 350 ℃ of sintering temperatures at adsorbent equipment.
Embodiment 14
(1) 24g stannous chloride, 4.5g manganese acetate, 1.5g zinc nitrate, 28gHY type molecular sieve, 4gH beta molecular sieve, 8gHZSM-5 type molecular sieve and 30g aluminium colloidal sol are mixed, carry out ball milling, ball milling 6h;
(2) the abundant mixed mixture of step (1) is shaped to sphere, vacuum drying then;
(3) adsorbent after step (2) moulding is seated in the adsorbent equipment, reduces with nitrogen hydrogen mixeding gas, wherein the percent by volume of hydrogen is 9%, and reduction temperature is 160 ℃, reduction 35h;
(4) after the reduction, be full of nitrogen, then adsorbent carried out roasting, roasting time 10h, 350 ℃ of sintering temperatures at adsorbent equipment.
Embodiment 15
(1) 21g stannous chloride, 6g manganese sulfate, 3g zinc sulfate, 28gHY type molecular sieve, 8gH beta molecular sieve, 4gHZSM-5 type molecular sieve and 30g aluminium colloidal sol are mixed, carry out ball milling, ball milling 6h;
(2) the abundant mixed mixture of step (1) is shaped to sphere, vacuum drying then;
(3) adsorbent after step (2) moulding is seated in the adsorbent equipment, reduces with nitrogen hydrogen mixeding gas, wherein the percent by volume of hydrogen is 8%, and reduction temperature is 160 ℃, reduction 35h;
(4) after the reduction, be full of nitrogen, then adsorbent carried out roasting, roasting time 10h, 350 ℃ of sintering temperatures at adsorbent equipment.
The carrier that adsorbent of the present invention adopts can be HY type molecular sieve, also can be the mixture of HY type molecular sieve and HZSM-5 type molecular sieve.The character of H beta molecular sieve and HY type molecular sieve is close, for example both apertures, main aperture road are approximate, also can select the H beta molecular sieve for use, the mixture of H beta molecular sieve and HZSM-5 type molecular sieves, the perhaps mixture of HY type molecular sieve, H beta molecular sieve and HZSM-5 type molecular sieve.
The adsorbent that the foregoing description is made, specific area are 300-380m
2/ g, pore volume are 0.05-0.1cc/g, and bulk density is 0.8-1.2g/cm
3, the blade mechanical strength is 10N-16N, and (normal temperature and pressure, flow: 50ml/min, ethylene contents 252ppm) under the same conditions tests the adsorbent of the foregoing description preparation, and test result is as shown in the table:
| The embodiment numbering | Saturated extent of adsorption (mg/g) | Time of break-through (h) |
| 1 | 2.2 | 9 |
| 2 | 2.0 | 7 |
| 3 | 2.1 | 6 |
| 4 | 1.8 | 8 |
| 5 | 2.4 | 9 |
| 6 | 2.1 | 10 |
| 7 | 2.0 | 8 |
| 8 | 1.9 | 8 |
| 9 | 2.5 | 9 |
| 10 | 2.3 | 10 |
| 11 | 2.1 | 9 |
| 12 | 2.2 | 10 |
| 13 | 2.3 | 8 |
| 14 | 2.3 | 9 |
| 15 | 2.4 | 7 |
This shows that ethene adsorbent of the present invention has higher saturated extent of adsorption and long time of break-through, this explanation adsorbent has good absorption property and service life.
More than the present invention has been done exemplary description; should be noted that; under the situation that does not break away from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (12)
1. an adsorbent that is used for the absorbing carbon dioxide microscale ethylene is characterized in that, is made up of the active component of 10%-50%, the carrier of 20%-80% and the adhesive of 10%-30% according to mass percent; Described active component is made up of the monovalence copper compound of 50%-95%, the manganous compound of 1%-30% and the divalent zinc compound of 1%-30% according to mass percent; Described carrier is a HY type molecular sieve or for the H beta molecular sieve or be made up of the HY type molecular sieve of 50%-90% and the HZSM-5 type molecular sieve of 10-50% according to mass percent, perhaps form by the H beta molecular sieve of 50%-90% and the HZSM-5 type molecular sieve of 10-50%, perhaps form by the HY type molecular sieve of 50%-80%, the H beta molecular sieve of 10%-25% and the HZSM-5 type molecular sieve of 10-25% according to mass percent according to mass percent; Wherein said monovalence copper compound is a kind of among CuCl, CuBr or the CuI; Described manganous compound is MnCl
2, MnSO
4Perhaps Mn (CH
3COO)
2In a kind of; Described divalent zinc compound is ZnCl
2, ZnBr
2, ZnSO
4Perhaps Zn (NO
3)
2In a kind of; Described adhesive is an aluminium colloidal sol.
2. a kind of adsorbent that is used for the absorbing carbon dioxide microscale ethylene according to claim 1, it is characterized in that, described adsorbent is made up of active component, carrier and adhesive according to mass percent, described active component is 20%-30%, described carrier is 60-70%, described adhesive is 10%-20%, and described active component is made up of the monovalence copper compound of 60%-90%, the manganous compound of 5%-20% and the divalent zinc compound of 5%-20% according to mass percent; Described carrier is a HY type molecular sieve or for the H beta molecular sieve or be made up of the HY type molecular sieve of 60%-80% and the HZSM-5 type molecular sieve of 20-40% according to mass percent, perhaps form by the H beta molecular sieve of 60%-80% and the HZSM-5 type molecular sieve of 20-40%, perhaps form by the HY type molecular sieve of 60%-70%, the H beta molecular sieve of 15%-20% and the HZSM-5 type molecular sieve of 15%-20% according to mass percent according to mass percent; Wherein said monovalence copper compound is a kind of among CuCl, CuBr or the CuI; Described manganous compound is MnCl
2, MnSO
4Perhaps Mn (CH
3COO)
2In a kind of; Described divalent zinc compound is ZnCl
2, ZnBr
2, ZnSO
4Perhaps Zn (NO
3)
2In a kind of; Described adhesive is an aluminium colloidal sol.
3. according to claim 1 or 2 described a kind of adsorbents that are used for the absorbing carbon dioxide microscale ethylene, it is characterized in that the specific area of described adsorbent is 250-400m
2/ g, pore volume are 0.05-0.6mL/g, and bulk density is 0.8-1.5g/cm
3
4. an adsorbent that is used for the absorbing carbon dioxide microscale ethylene is characterized in that, carries out according to following step:
(1) utilizes the solid phase mechanical mixing will account for the active component of the mass percent 10%-50% of adsorbent oeverall quality, the carrier of 20%-80% and the adhesive of 10%-30% and fully mix 3-10h;
(2) with the abundant mixed mixture moulding of step (1), vacuum drying then;
(3) adsorbent after step (2) moulding is seated in the adsorbent equipment, reduces with nitrogen hydrogen mixeding gas, the percentage by volume of hydrogen is 0.5%-10% in the mist, and reduction temperature is 120-190 ℃, and the recovery time is 10-48h;
(4) after the reduction, be full of inert gas at adsorbent equipment, then wherein adsorbent carried out roasting, roasting time is 1-24h, and sintering temperature is 250-400 ℃;
The active component of described step (1) is made up of the monovalence copper compound of 50%-95%, the manganous compound of 1%-30% and the divalent zinc compound of 1%-30% according to mass percent; Described carrier is a HY type molecular sieve or for the H beta molecular sieve or be made up of the HY type molecular sieve of 50%-90% and the HZSM-5 type molecular sieve of 10-50% according to mass percent, perhaps form by the H beta molecular sieve of 50%-90% and the HZSM-5 type molecular sieve of 10-50%, perhaps form by the HY type molecular sieve of 50%-80%, the H beta molecular sieve of 10%-25% and the HZSM-5 type molecular sieve of 10-25% according to mass percent according to mass percent; Wherein said monovalence copper compound is a kind of among CuCl, CuBr or the CuI; Described manganous compound is MnCl
2, MnSO
4Perhaps Mn (CH
3COO)
2In a kind of; Described divalent zinc compound is ZnCl
2, ZnBr
2, ZnSO
4Perhaps Zn (NO
3)
2In a kind of; Described adhesive is an aluminium colloidal sol.
5. a kind of adsorbent that is used for the absorbing carbon dioxide microscale ethylene according to claim 4, it is characterized in that, the active component of described step (1) is 20%-30%, described carrier is 60-70%, described adhesive is 10%-20%, and described active component is made up of the monovalence copper compound of 60%-90%, the manganous compound of 5%-20% and the divalent zinc compound of 5%-20% according to mass percent; Described carrier is a HY type molecular sieve or for the H beta molecular sieve or be made up of the HY type molecular sieve of 60%-80% and the HZSM-5 type molecular sieve of 20-40% according to mass percent, perhaps form by the H beta molecular sieve of 60%-80% and the HZSM-5 type molecular sieve of 20-40%, perhaps form by the HY type molecular sieve of 60%-70%, the H beta molecular sieve of 15%-20% and the HZSM-5 type molecular sieve of 15%-20% according to mass percent according to mass percent; Wherein said monovalence copper compound is a kind of among CuCl, CuBr or the CuI; Described manganous compound is MnCl
2, MnSO
4Perhaps Mn (CH
3COO)
2In a kind of; Described divalent zinc compound is ZnCl
2, ZnBr
2, ZnSO
4Perhaps Zn (NO
3)
2In a kind of; Described adhesive is an aluminium colloidal sol.
6. a kind of adsorbent that is used for the absorbing carbon dioxide microscale ethylene according to claim 4 is characterized in that, the percentage by volume of hydrogen is 1%-5% in the middle mist of described step (3), and reduction temperature is 160-180 ℃, and the recovery time is 10-24h; The inert gas of described step (4) is a kind of in nitrogen, helium or the argon gas; The roasting time of described step (4) is 4-15h, and sintering temperature is 300-350 ℃.
7. a kind of adsorbent that is used for the absorbing carbon dioxide microscale ethylene according to claim 4 is characterized in that the specific area of described adsorbent is 250-400m
2/ g, pore volume are 0.05-0.6mL/g, and bulk density is 0.8-1.5g/cm
3
8. one kind prepares as claim 1 or the 4 described methods that are used for the adsorbent of absorbing carbon dioxide microscale ethylene, it is characterized in that, carries out according to following step:
(1) utilize the solid phase mechanical mixing that the active component of mass percent 10%-50%, the carrier of 20%-80% and the adhesive of 10%-30% are fully mixed 3-10h;
(2) with the abundant mixed mixture moulding of step (1), vacuum drying then;
(3) adsorbent after step (2) moulding is seated in the adsorbent equipment, reduces with nitrogen hydrogen mixeding gas, the percentage by volume of hydrogen is 0.5%-10% in the mist, and reduction temperature is 120-190 ℃, and the recovery time is 10-48h;
(4) after the reduction, be full of inert gas at adsorbent equipment, then wherein adsorbent carried out roasting, roasting time is 1-24h, and sintering temperature is 250-400 ℃;
The active component of described step (1) is made up of the monovalence copper compound of 50%-95%, the manganous compound of 1%-30% and the divalent zinc compound of 1%-30% according to mass percent; Described carrier is a HY type molecular sieve or for the H beta molecular sieve or be made up of the HY type molecular sieve of 50%-90% and the HZSM-5 type molecular sieve of 10-50% according to mass percent, perhaps form by the H beta molecular sieve of 50%-90% and the HZSM-5 type molecular sieve of 10-50%, perhaps form by the HY type molecular sieve of 50%-80%, the H beta molecular sieve of 10%-25% and the HZSM-5 type molecular sieve of 10-25% according to mass percent according to mass percent; Wherein said monovalence copper compound is a kind of among CuCl, CuBr or the CuI; Described manganous compound is MnCl
2, MnSO
4Perhaps Mn (CH
3COO)
2In a kind of; Described divalent zinc compound is ZnCl
2, ZnBr
2, ZnSO
4Perhaps Zn (NO
3)
2In a kind of; Described adhesive is an aluminium colloidal sol.
9. a kind of preparation according to claim 8 is as claim 1 or the 4 described methods that are used for the adsorbent of absorbing carbon dioxide microscale ethylene, it is characterized in that, the active component of described step (1) is 20%-30%, described carrier is 60-70%, described adhesive is 10%-20%, and described active component is made up of the monovalence copper compound of 60%-90%, the manganous compound of 5%-20% and the divalent zinc compound of 5%-20% according to mass percent; Described carrier is a HY type molecular sieve or for the H beta molecular sieve or be made up of the HY type molecular sieve of 60%-80% and the HZSM-5 type molecular sieve of 20-40% according to mass percent, perhaps form by the H beta molecular sieve of 60%-80% and the HZSM-5 type molecular sieve of 20-40%, perhaps form by the HY type molecular sieve of 60%-70%, the H beta molecular sieve of 15%-20% and the HZSM-5 type molecular sieve of 15%-20% according to mass percent according to mass percent; Wherein said monovalence copper compound is a kind of among CuCl, CuBr or the CuI; Described manganous compound is MnCl
2, MnSO
4Perhaps Mn (CH
3COO)
2In a kind of; Described divalent zinc compound is ZnCl
2, ZnBr
2, ZnSO
4Perhaps Zn (NO
3)
2In a kind of; Described adhesive is an aluminium colloidal sol.
10. a kind of preparation according to claim 8 is as claim 1 or the 4 described methods that are used for the adsorbent of absorbing carbon dioxide microscale ethylene, it is characterized in that, the percentage by volume of hydrogen is 1%-5% in the middle mist of described step (3), reduction temperature is 160-180 ℃, and the recovery time is 10-24h; The inert gas of described step (4) is a kind of in nitrogen, helium or the argon gas; The roasting time of described step (4) is 4-15h, and sintering temperature is 300-350 ℃.
11. according to claim 1 or the 4 described adsorbents that are used for the absorbing carbon dioxide microscale ethylene, it is characterized in that, adsorbent be shaped as a kind of in sheet, sphere, honeycombed, bar shaped or the cloverleaf pattern.
12. the application of microscale ethylene in absorbing carbon dioxide as claim 1 or 4 described adsorbents.
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