CN1356155A - Adsorbent for gas separation and its preparing process - Google Patents
Adsorbent for gas separation and its preparing process Download PDFInfo
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- CN1356155A CN1356155A CN 00134120 CN00134120A CN1356155A CN 1356155 A CN1356155 A CN 1356155A CN 00134120 CN00134120 CN 00134120 CN 00134120 A CN00134120 A CN 00134120A CN 1356155 A CN1356155 A CN 1356155A
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Abstract
An adsorbent for separating out gas, especially air is prepared from A-type or X-type molecular sieve whose pore diameter is less than 20 A and inorganic oxide with mesopores whose diameter is greater than 20A. It features that the ratio of volume for mesopores to total pore volume is at least 15%.
Description
The present invention relates to a kind of adsorbent that gas separates and preparation method thereof that is used for, particularly relate to zeolite adsorbents of a kind of selective absorption nitrogen that is used for air separation and preparation method thereof.
Transformation absorption PSA (Pressure Swing Adsorption) is one of gas absorption separation means of using always, on air separation, is used to prepare oxygen rich gas and nitrogen-rich gas.The process of PSA is at for example USP4,234,322, USP4,477, be described in 267 patent documentations such as grade, be about to compressed air and demonstrate the fixed bed of sorbent layer of preferential adsorption by a kind of component in the main component to gas, obtain being rich in the gas stream of the component that does not adsorb (or less absorption) through pumping.It is miniaturization to use that PSA compares to its advantage of cryogenic separation, and equipment is simple, and maintenance is also quite easy; Separate with film and to compare and the high characteristics of separative efficiency are arranged.Critical component mainly is two for the PSA air-separating plant: the performance of adsorbent and the performance in the life-span of valve, particularly adsorbent have directly determined the separating effect and the energy consumption of package unit.So be necessary to update and develop the better adsorbent of performance.
The adsorbent that uses in the prior art on the adsorption activity constituent element mainly with A type zeolite such as CaA zeolite or with X zeolite such as LiX zeolite active component as adsorbent, the history that the former uses is longer, and technical comparatively speaking easy realization, also cheap on the cost.Two kinds of adsorbents that can also be by using simultaneously that different zeolites constitutes such as A type zeolite and X type zeolite are shared, and the subregion filling to be to reach better effect, and as USP5,885,331 is described.But " Ind.Eng.Chem.Res.2000,39,1775-1780 " literary composition of publishing thinks that the LiX zeolite is present best air separation adsorbent activity constituent element recently.Thereby the corrective measure on the adsorbents adsorb active component mainly is to adopt the silica alumina ratio that reduces zeolite to improve the air separation effect of adsorbent with the nitrogen adsorption amount that increases zeolite, as USP5,366,720, GB1580928, USP4,606,899 have reported by introducing potassium ion when the synthetic zeolite or adopting sodium aluminate that zeolite is carried out post processing and reduce the silica alumina ratio of X zeolite to increase the adsorption capacity of adsorbent.
Generally speaking present improvement mainly concentrates on the zeolite aspect of adsorbent, and notes less to the nonzeolite component in the adsorbent.General these adsorbents all are to hold concurrently binding agent to reduce cost and might adopt waterglass to handle to increase granule strength, as the forming process described in the CN1248488A with clay as carrier.
USP4,950,312 and USP5,098,448 is not to adopt natural clay as the carrier binding agent of holding concurrently, but with Ludox and waterglass in conjunction with the A zeolite is carried out granulating and forming, promptly first molecular sieve and Ludox are made smaller particles, should obtain larger particles and curing fast by adding molecular sieve powder while spray water glass than granule then, its inventive point is mainly in the molding particles process.CN1248487A has introduced secondary perforated molecular siever adsorbent and preparation method thereof, and its secondary forming hole method of introducing is to adopt alkali lye to handle adsorbent to reduce the obstruction of amorphous article confrontation microporous molecular sieve.Can learn that from these disclosed prior aries its approach that improves the adsorbents adsorb separating property mainly is by improving the performance of zeolite, absorption mainly occurs in the micropore of zeolite＜20 dusts, still there is not prior art to mention the adsorption separation performance that can improve adsorbent as second adsorption activity constituent element by the mesopore more than introducing 20 dusts on holding concurrently binding agent at the carrier of adsorbent, because it is generally acknowledged nonzeolite mesopore its to the adsorptive selectivity of non-polar gas selectivity height not as the micropore of zeolite, therefore in adsorbent, introduce the air separation coefficient that adsorbent can not be improved in the low slightly duct of this selectivity.But the inventor finds the mesopore of introducing nonzeolite in adsorbent and can improve non-polar gas such as nitrogen (the four pole span 0.31A with high four pole spans effectively
3) adsorption capacity, but to the non-polar gas such as oxygen (the four pole span 0.10A of low four pole spans
3) then adsorption capacity improve seldom, thereby improved the adsorbing separation effect of adsorbent.
The purpose of this invention is to provide a kind of gas that is used for and separate adsorbent of air separation particularly and preparation method thereof, with the further particularly adsorption separation performance of air of gas that improves.
Provided by the inventionly be used for adsorbent that gas separates and form by A type or X type molecular sieve and inorganic oxide, it is characterized in that in this adsorbent except the contained micropore of aperture of molecular sieve less than 20 dusts (being generally the 3-13 dust), said inorganic oxide has the aperture and is at least 0.3 milliliter/gram greater than the mesopore of 20 dusts and its pore volume, preferably at least 0.4 milliliter/gram (for example 0.4-1.2 milliliter/gram); Wherein said aperture is at least 15% greater than the ratio that the pore volume of the mesopore of 20 dusts accounts for the total pore volume of said adsorbent, is preferably 20-40%, more preferably 22-35%.
Said molecular sieve is a kind of or two kinds or above mixture, wherein preferably CaA or LiX or the combination of the two in them that is selected from the zeolites such as CaA, CaX, LiX, SrX in the adsorbent provided by the invention.
Said inorganic oxide can be selected from SiO in the adsorbent provided by the invention
2-Al
2O
3, Al
2O
3, SiO
2, the clay crossed of acid treatment or hydrothermal treatment consists etc., its condition is that this inorganic oxide has the aperture and is at least 0.3 milliliter/gram greater than mesopore and its pore volume of 20 dusts.
Preparation of adsorbent method provided by the present invention comprises: the molecular sieve that will be selected from CaA, CaX, LiX, SrX or their compound with have the SiO that is selected from that mesopore and its pore volume of aperture greater than 20 dusts is at least 0.3 milliliter/gram
2-Al
2O
3, Al
2O
3, SiO
2, the clay crossed of acid treatment or hydrothermal treatment consists etc. inorganic oxide mix, the ratio of mixing is according to the said molecular sieve of measuring in advance and the pore volume of said inorganic oxide, the aperture of make mixing said inorganic oxide in the gained mixture of back is at least 15% greater than the ratio that the pore volume of the mesopore of 20 dusts accounts for the total pore volume of said mixture, then with the gained mixture according to the conventional method moulding, and with the product after the moulding at 300 ℃～750 ℃ following calcination activation 0.5-8 hours, preferably at 350 ℃～550 ℃ following calcination activation 1-6 hours.
Said moulding is carried out according to the conventional method of prior art in the preparation of adsorbent method provided by the invention, the present invention has no particular limits it, for example can be in bowling machine granulating and forming, also can in banded extruder, be extruded into the bar shaped of different shape, as cylindrical, hexagonal prism shape, cloverleaf pattern and various irregular bar shapeds etc.When moulding, can add various binding agents such as aluminium colloidal sol, Ludox, sticking clay etc., also can add acid and mediate as nitric acid, hydrochloric acid, citric acid etc.
The construction features that are used for the adsorbent of gas separation provided by the invention are to have two kinds of absorption ducts, promptly except common prior art possessed＜zeolite micropore of 20 dusts (general 3～13 dusts), have also that another kind of prior art adsorbent does not possess or the content nonzeolite mesopore of the aperture of (＜10%)＞20 dusts seldom.The advantage of this adsorbent is to go up the mesopore of introducing proper proportion by the binding agent (inorganic oxide) of holding concurrently at carrier to reach raising selective absorption capacity on selected zeolite activity constituent element basis, and then improves the purpose of the air separation coefficient of whole adsorbent.
Fig. 1 is the pore size distribution curve of the mesopore scope of embodiment 1 and Comparative Examples 1 gained sample of sorbent.
To be further specified the present invention with embodiment below, but should this and limit the present invention.
Each embodiment and Comparative Examples mesopore volume and pore-size distribution adopt low-temperature nitrogen adsorption method to measure (GB/T5816-1995); Chemical composition adopts X-ray fluorescent spectrometry method to measure; Compressive resistance adopts the granule strength analyzer to measure; The still air separation is measured and is adopted following experimental condition: adopt volumetric method to record the adsorbance that sample adsorbs nitrogen and oxygen, then separation=nitrogen adsorption amount/oxygen adsorbance under 25 ℃ of temperature, pressure 0.1MPa.
Embodiment 1
(Zhengzhou, Henan snow mountain Industrial Co., Ltd. produces with commercially available NaA type molecular sieve, 8 kilograms (dry basis) down together), with the calcium chloride solution of concentration 5% (the solid calcium chloride reagent preparation of producing by the Beijing Chemical Plant) exchange 1 hour under 90 ℃ and 20: 1 condition of liquid-solid ratio, repeated exchanged is once again after filtering and washing with water, drying is 5 hours under 120 ℃, obtains CaA type molecular sieve.With 2 kilograms of (SiO of silicon aluminium microsphere Cracking catalyst
2-Al
2O
3Chang Ling oil-refining chemical factory catalyst plant is produced, its pore volume is 0.36ml/g, grinding the back down together) mixes with above-mentioned CaA type molecular sieve, and on small-sized bowling machine, make the bead of 5 millimeters of diameters according to a conventional method, and an amount of spray concentration is rare waterglass of 50g/L in the spin process, the bead of making is behind airing, obtained the adsorbent finished product in 4 hours 450 ℃ of following roastings, recording its bulk density is 0.70g/ml; Saturated water adsorptive value 22.6%; Surface area 518m
2/ g, pore volume 0.23ml/g; Chemical composition sees Table 1; Pore size distribution as shown in Figure 1, wherein to account for the ratio of total pore volume be 25% to mesopore volume; The particle compressive resistance is 65N/mm
2Nitrogen oxygen separation 3.2.
The chemical composition of table 1, embodiment 1 sample:
| Na 2O | ?SiO 2 | ?Al 2O 3 | ?CaO | ?Fe 2O 3 | ?MgO | ?H 2O | ?SiO 2/Al 2O 3(mol) | |
| Embodiment 1 sample | ????2.5 | ????46 | ????36 | ????14 | ????0.1 | ??- | ?＜1.5 | ????2.2 |
Comparative Examples 1
According to the preparation of the same procedure of embodiment 1, but with the used silicon aluminium microsphere of 2 kilograms of (dry basis) kaolin (production of Suzhou kaolin company) replacement embodiment 1, its bulk density of the adsorbent that makes is 0.75g/ml, saturated water adsorptive value 21.1%, surface area 501m
2/ g, pore volume 0.20ml/g, chemical composition sees Table 2, pore size distribution as shown in Figure 1, wherein mesopore volume account for total pore volume ratio less than 5%, the particle compressive resistance is 73N/mm
2, nitrogen oxygen separation 2.9.
The chemical composition of table 2, Comparative Examples 1 sample:
| Na 2O | ?SiO 2 | ?Al 2O 3 | ?CaO | ?Fe 2O 3 | ?MgO | ?H 2O | ?SiO 2/Al 2O 3(mol) | |
| Comparative Examples 1 sample | ??4.3 | ????41 | ????35 | ????18 | ??0.34 | ??0.19 | ??＜1.1 | ????2.0 |
Embodiment 2
According to the preparation of the same procedure of embodiment 1, but replace silicon aluminium microsphere and add 0.5 kilogram clay increase adhesive property with the silica gel after 2 kilograms of grindings (silica gel factory in Qingdao produces, and its pore volume is 0.998ml/g).Its bulk density of the adsorbent that makes is 0.65g/ml, saturated water adsorptive value 21.3%, surface area 509m
2/ g, pore volume 0.21ml/g form and to see Table 3, and pore size distribution is similar to the embodiment among Fig. 1, and wherein to account for the ratio of total pore volume be 33% to mesopore volume, and the particle compressive resistance is 60N/mm
2, nitrogen oxygen separation 3.2.
The chemical composition of table 3, embodiment 2 samples:
| Na 2O | ?SiO 2 | ?Al 2O 3 | ?CaO | ?Fe 2O 3 | ?MgO | ?H 2O | ?SiO 2/Al 2O 3(mol) | |
| Embodiment 2 samples | ??6.9 | ??50 | ??30 | ??14 | ??0.01 | ??0.01 | ??＜1.2 | ????2.7 |
Embodiment 3
Same procedure preparation according to embodiment 1, but replace silicon aluminium microsphere with the alumina powder after 2 kilograms of grindings (the Chang Ling catalyst plant is produced, and its pore volume is 0.64ml/g), its bulk density of the adsorbent that makes is 0.75g/ml, saturated water adsorptive value 22.3%, surface area 539m
2/ g, pore volume 0.23ml/g, chemical composition sees Table 4, and pore size distribution is similar to the embodiment 1 among Fig. 1, and wherein to account for the ratio of total pore volume be 31% to mesopore volume, and the particle compressive resistance is 80N/mm
2, nitrogen oxygen separation 3.2.
The chemistry of table 4, embodiment 3 samples is fine into:
| Na 2O | ?SiO 2 | ?Al 2O 3 | ?CaO | ?Fe 2O 3 | ?MgO | ?H 2O | ?SiO 2/Al 2O 3(mol) | |
| Embodiment 3 samples | 3.9 | ?30 | ?37 | ?15 | ??0.01 | ?- | ??＜1.2 | ????2.0 |
Embodiment 4
(Zhengzhou, Henan snow mountain Industrial Co., Ltd. produces with commercially available NaX type zeolite, 8 kilograms (dry basis) down together), with the lithium chloride solution of concentration 5% (the solid lithium chloride reagent preparation of producing by Beijing chemical reagents corporation) exchange 1 hour under 90 ℃ and 20: 1 condition of liquid-solid ratio, repeated exchanged five times, drying is 5 hours under 120 ℃, makes LiX type molecular sieve.With 2 kilograms of (SiO of silicon aluminium microsphere Cracking catalyst
2-Al
2O
3Chang Ling oil-refining chemical factory catalyst plant is produced, its pore volume is 0.36ml/g) grind the back and mix with above-mentioned LiX type molecular sieve, and on small-sized bowling machine, make the bead of 5 millimeters of diameters according to a conventional method, and an amount of spray concentration is rare waterglass of 50g/L in the spin process, the bead of making is behind airing, obtained the adsorbent finished product in 2 hours 600 ℃ of following roastings, recording its bulk density is 0.70g/ml, saturated water adsorptive value 23.6%, surface area 538m
2/ g, pore volume 0.23ml/g, chemical composition sees Table 4, and pore size distribution is similar to the embodiment 1 among Fig. 1, and the ratio that mesopore volume accounts for total pore volume is 24%, and the particle compressive resistance is 66N/mm
2, nitrogen oxygen separation 3.3.
The chemical composition of table 5, embodiment 4 samples:
| Na 2O | ?SiO 2 | ?Al 2O 3 | ?LiO 2 | ?Fe 2O 3 | ?H 2O | ?SiO 2/Al 2O 3(mol) | |
| Embodiment 4 samples | ????2.5 | ????46 | ????36 | ????7.7 | ????0.1 | ????＜1.5 | ????2.3 |
Comparative Examples 2
Prepare with method according to the following of embodiment 4, but replace silicon aluminium microsphere with 2 kilograms of (dry basis) kaolin (production of Suzhou kaolin company), its bulk density of the adsorbent that makes is 0.74g/ml, saturated water adsorptive value 23.1%, surface area 521m
2/ g, pore volume 0.24ml/g, chemical composition sees Table 5, pore size distribution is similar to the Comparative Examples 1 among Fig. 1, wherein mesopore volume account for total pore volume ratio less than 5%, the particle compressive resistance is 77N/mm
2, nitrogen oxygen separation 3.0.
The chemical composition of table 5, Comparative Examples 2 samples:
| Na 2O | ?SiO 2 | ?Al 2O 3 | ?LiO 2 | ?Fe 2O 3 | ?H 2O | ?SiO 2/Al 2O 3(mol) | |
| Comparative Examples 2 samples | ??4.3 | ??41 | ??35 | ??7.5 | ??0.34 | ??＜1.1 | ??2.1 |
Claims (7)
1, a kind of adsorbent that is used for the gas separation, form by A type or X type molecular sieve and inorganic oxide, it is characterized in that in this adsorbent except the contained micropore of aperture of molecular sieve less than 20 dusts, said inorganic oxide has the aperture and is at least 0.3 milliliter/gram greater than the mesopore of 20 dusts and its pore volume, and wherein said aperture is at least 15% greater than the ratio that the pore volume of the mesopore of 20 dusts accounts for the total pore volume of said adsorbent.
2, according to the adsorbent of claim 1, wherein said aperture is 20-40% greater than the ratio that the pore volume of the mesopore of 20 dusts accounts for the total pore volume of said adsorbent.
3, according to the adsorbent of claim 1, wherein said molecular sieve is to be selected from a kind of in the zeolite of the group of being made up of CaA, CaX, LiX, SrX or two or more mixture in them.
4, according to the adsorbent of claim 1, wherein said molecular sieve is CaA or LiX or the combination of the two.
5, according to the adsorbent of claim 1, wherein said inorganic oxide is selected from SiO
2-Al
2O
3, Al
2O
3, SiO
2, or the clay crossed of acid treatment or hydrothermal treatment consists.
6, according to the adsorbent of claim 5, wherein said inorganic oxide is SiO
2-Al
2O
3
7, the described preparation of adsorbent method of claim 1 is characterized in that this method comprises: the molecular sieve that will be selected from CaA, CaX, LiX, SrX or their compound with have the SiO that is selected from that mesopore and its pore volume of aperture greater than 20 dusts is at least 0.3 milliliter/gram
2-Al
2O
3, Al
2O
3, SiO
2, or the inorganic oxide of the clay crossed of acid treatment or hydrothermal treatment consists mix, the ratio of mixing is according to the said molecular sieve of measuring in advance and the pore volume of said inorganic oxide, the aperture of make mixing said inorganic oxide in the gained mixture of back is at least 15% greater than the ratio that the pore volume of the mesopore of 20 dusts accounts for the total pore volume of said mixture, then with the gained mixture according to the conventional method moulding, and with the product after the moulding at 300 ℃～750 ℃ following calcination activation 0.5-8 hours.
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|---|---|---|---|
| CN 00134120 CN1128651C (en) | 2000-12-05 | 2000-12-05 | Adsorbent for gas separation and its preparing process |
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|---|---|---|---|
| CN 00134120 CN1128651C (en) | 2000-12-05 | 2000-12-05 | Adsorbent for gas separation and its preparing process |
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|---|---|
| CN1356155A true CN1356155A (en) | 2002-07-03 |
| CN1128651C CN1128651C (en) | 2003-11-26 |
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|---|---|---|---|
| CN 00134120 Expired - Fee Related CN1128651C (en) | 2000-12-05 | 2000-12-05 | Adsorbent for gas separation and its preparing process |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314589C (en) * | 2004-09-24 | 2007-05-09 | 中国石油化工股份有限公司 | Porous material and its synthesis method |
| CN102160990A (en) * | 2011-03-21 | 2011-08-24 | 天津大学 | Method for preparing lithium oxygen generation adsorbent |
| CN102996978A (en) * | 2011-09-12 | 2013-03-27 | 日立空调·家用电器株式会社 | Vacuum insulation material and equipment made of the same |
| CN107810053A (en) * | 2015-02-02 | 2018-03-16 | 阿肯马法国公司 | Zeolite adsorbents with high external surface area and application thereof |
-
2000
- 2000-12-05 CN CN 00134120 patent/CN1128651C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314589C (en) * | 2004-09-24 | 2007-05-09 | 中国石油化工股份有限公司 | Porous material and its synthesis method |
| CN102160990A (en) * | 2011-03-21 | 2011-08-24 | 天津大学 | Method for preparing lithium oxygen generation adsorbent |
| CN102996978A (en) * | 2011-09-12 | 2013-03-27 | 日立空调·家用电器株式会社 | Vacuum insulation material and equipment made of the same |
| CN102996978B (en) * | 2011-09-12 | 2015-12-09 | 日立空调·家用电器株式会社 | The refrigerator of Vacuum thermal insulating material and use Vacuum thermal insulating material and hot water supply device |
| CN107810053A (en) * | 2015-02-02 | 2018-03-16 | 阿肯马法国公司 | Zeolite adsorbents with high external surface area and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1128651C (en) | 2003-11-26 |
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