CN109482136A - A kind of adsorbent and preparation method thereof - Google Patents
A kind of adsorbent and preparation method thereof Download PDFInfo
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- CN109482136A CN109482136A CN201811606991.2A CN201811606991A CN109482136A CN 109482136 A CN109482136 A CN 109482136A CN 201811606991 A CN201811606991 A CN 201811606991A CN 109482136 A CN109482136 A CN 109482136A
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
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- B01D53/34—Chemical or biological purification of waste gases
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- B01D53/34—Chemical or biological purification of waste gases
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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Abstract
The present invention relates to a kind of adsorbents and preparation method thereof, specifically, being related to a kind of adsorbent and preparation method thereof for micro-molecular gas absorption.The adsorbent includes physical absorbent and chemosorbent, and chemosorbent is attached on physical absorbent.The present invention uses conventional VOCs treatment physical absorbent for carrier, by adhering to the chemosorbents such as magnesium chloride, calcium chloride, copper sulphate on physical absorbent, its working principle is close with Typical physical adsorbent, technical compatibility is good, there is efficient adsorption capacity to the low carbon numbers small molecule such as methanol, ethyl alcohol, to greatly improve the treatment effect of organic exhaust gas, and sorbent preparation method simple economy, it is suitable for large-scale industrialization promotion and application.
Description
Technical field
The present invention relates to a kind of adsorbents, specifically, being related to a kind of adsorbent for micro-molecular gas absorption.
The invention further relates to a kind of preparation methods of adsorbent, specifically, being related to a kind of for micro-molecular gas absorption
Adsorbent preparation method.
Background technique
Adsorption and purification technology is a kind of traditional VOCs processing method, has low energy consumption, technical maturity, removal rate high, net
Change advantage thorough, easy to spread, there is good environment and economic benefit.The disadvantage is that equipment is huge, process is complicated, and adsorbent needs
It regenerates, and adsorbent is easily poisoned.In recent years, since environmental requirement is increasingly strict, adsorption technology is rapidly developed,
There is new absorbing process and equipment；Simultaneously adsorbent improvement, the application range of adsorption technology has also been enlarged, make absorption at
For the prefered method of organic gas processing technique.
The adsorbent applied to organic gas processing is mainly the porous material such as active carbon, molecular sieve, aluminium oxide, silica gel at present
Material, aperture is generally between 0.6-200nm.But it is limited by material aperture and chemical composition, existing material is only applicable to locate
Some larger-size molecules are managed, such as esters, ketone, benzene homologues, for methanol, this kind of small organic molecule adsorption efficiency of ethyl alcohol
Lowly.And the processing capacity and treatment effeciency of the schemes such as photocatalysis, low-temperature plasma, biodegrade are difficult to reach requirement, and
And there is also the problems of investment, energy consumption and compatibility for parallel multiple technologies simultaneously, the especially usual accounting of this micromolecular is little,
But the influence to purification efficiency is more prominent.
Therefore, there is an urgent need to a kind of efficient, economic, easy adsorbents, to solve problem above.
Summary of the invention
That the object of the present invention is to provide the small organic molecules such as a kind of pair of methanol, ethyl alcohol adsorption effects is good, structure is simple and
Adsorbent being readily produced and preparation method thereof, solve in the prior art it is bad to above-mentioned small organic molecule treatment effect with
And the problem of economy and poor compatibility.
To achieve the above object, the present invention provides the following technical scheme that
A kind of adsorbent, including physical absorbent and chemosorbent, chemosorbent are attached on physical absorbent.
The chemosorbent can be attached to inner surface and/or the outer surface of physical absorbent.
The weight ratio of the physical absorbent is about 5-95%, and the weight ratio of chemosorbent is about 5-95%.
Further, the weight ratio of the physical absorbent is preferably 70-90%, and the weight ratio of the chemosorbent is excellent
It is selected as 10-30%.
The ratio of above-described physical absorbent and chemosorbent, the generally ratio with low carbon number organic matter in exhaust gas
It is consistent.In the present invention, in the case where being based on the conventional organic matter, a small amount of low carbon number organic matter wherein contained is handled,
The adsorbent can give full play to the feature of physical absorbent and chemosorbent respectively.If physical absorbent ratio is excessively high, phase
Answering the ratio of ground chemosorbent will reduce, and decline it to the treatment effect of low carbon number organic matter；And physical absorbent ratio
Example is too low, and correspondingly the ratio of chemosorbent just will increase, and declines it to the treatment effect of conventional organic exhaust gas.Another party
Face, chemosorbent will play one's part to the full, be by a part of surface area of physical absorbent, if physical absorbent surface
It is chemisorbed agent completely to occupy, the treatment effect of conventional organic exhaust gas can be also remarkably decreased.
The physical absorbent can be one or more of molecular sieve, silica gel, active carbon or aluminium oxide；The chemistry
Adsorbent can be one or more of magnesium chloride, calcium chloride or copper sulphate.
The present invention also provides a kind of preparation methods of adsorbent, include the following steps:
(1) physical absorbent and chemosorbent are mixed to form mixture with solid phase or solid-liquid phase；That is, physics
Adsorbent and chemosorbent may each be solid-state and mix, and be also possible to that physical absorbent is solid-state and chemosorbent is liquid
State mixes.
Further, the solid phase or solid-phase physical adsorbent in solid-liquid phase or solid state chemistry adsorbent partial size about exist
Between 100nm-10 μm.
(2) mixture can be formed in the form of squeezing, being granulated etc., or mixture can also be carried in honeycomb class
It is formed on body.
Further, it is described it is molding during can be added binder.The binder can be organic binder and/
Or inorganic binder.
The binder can be silica solution and/or Aluminum sol etc..
(3) molding is dried at about 60-150 DEG C.The drying can be through microwave, infrared or hot
The forms such as wind are dry.
Further, the drying temperature is preferably 80-120 DEG C.
(4) molding after the drying after about 400-600 DEG C removing impurities to get.The impurity generally has
Machine object.
Further, the molding preferably removes organic matter at about 450-550 DEG C.
The organic matter generally refers to some organic binders, the auxiliary agent introduced in the molding preparation process, and one
As be polymer, decomposition temperature is at 300 DEG C or so.Therefore when temperature is too low, the processing time can extend, and be not easy thoroughly to go
It removes；And temperature is excessively high, then energy consumption increases, then can bring unnecessary loss.
Adsorbent of the invention uses conventional VOCs treatment physical absorbent for carrier, by inhaling in physics
The chemosorbents such as attached dose of upper attachment magnesium chloride, calcium chloride, copper sulphate, working principle is close with Typical physical adsorbent, skill
Art good compatibility has efficient adsorption capacity to the low carbon numbers small molecule such as methanol, ethyl alcohol, to greatly improve organic exhaust gas
Treatment effect compensates for the deficiencies in the prior art.Sorbent preparation method simple economy of the invention is suitable for large-scale industry
Change promotion and application.
Detailed description of the invention
Fig. 1 is a kind of microstructure schematic diagram of adsorbent of the invention.
Description of symbols in figure: 1- chemosorbent, 2- physical absorbent.
Specific embodiment
Below by comparative example and embodiment, the technical scheme of the present invention will be explained in further detail, but is not limited to this
The content of embodiment.
Comparative example 1
With the NaY molecular sieve (diameter 4mm is spherical) that silica alumina ratio (molar ratio) is 6:1, layer height 15cm is filled, with 2m/s wind
Speed purging concentration is 200mg/m3Ethyl alcohol, 25 DEG C of temperature, humidity 60%RH, detection filled layer Export Ethanol concentration is 20mg/m3When
Time be 4min.
Embodiment 1
A kind of adsorbent, as shown in Figure 1, the NaY molecular sieve and calcium chloride that are 6:1 including silica alumina ratio (molar ratio), described
NaY molecular sieve is physical absorbent 2, and the calcium chloride is chemosorbent 1, and calcium chloride is attached in NaY molecular sieve, i.e., chemical
Adsorbent 1 is attached on physical absorbent 2, can be attached to inner surface and/or the outer surface of physical absorbent 2.
The weight ratio of the NaY molecular sieve is about 85%, and the weight ratio of calcium chloride is about 15%.
The present embodiment also provides the preparation method of above-mentioned adsorbent, includes the following steps:
(1) NaY molecular sieve by partial size about between 100nm-10 μm, which is placed in calcium chloride solution, stirs, after filtering
Mixture is obtained, wherein the weight of calcium chloride accounts for the 15% of total weight of the mixture；
(2) a small amount of silica sol binder is added in the mixture, the ball that diameter is about 4mm is formed by granulating and forming
Shape particle；
(3) spheric granules is subjected to microwave drying at 105 DEG C；
(4) spheric granules after the drying is removed after organic matter at about 500 DEG C to get compound adsorbent.
Make filled layer with above-mentioned adsorbent, height 15cm is 200mg/m with 2m/s wind speed purging concentration3Ethyl alcohol, temperature 25
DEG C, humidity 60%RH, detection filled layer Export Ethanol concentration is 20mg/m3When time be 6min.
Embodiment 2
A kind of adsorbent, the NaY molecular sieve and calcium chloride for being 6:1 including silica alumina ratio (molar ratio), calcium chloride are attached to NaY
On molecular sieve.
The weight ratio of the NaY molecular sieve is about 80%, and the weight ratio of calcium chloride is about 20%.
The present embodiment also provides the preparation method of above-mentioned adsorbent, includes the following steps:
(1) NaY molecular sieve by partial size about between 100nm-10 μm, which is placed in calcium chloride solution, stirs, after filtering
Mixture is obtained, wherein the weight of calcium chloride accounts for the 20% of total weight of the mixture；
(2) a small amount of silica sol binder is added in the mixture, the ball that diameter is about 4mm is formed by granulating and forming
Shape particle；
(3) spheric granules is subjected to infra-red drying at 105 DEG C；
(4) spheric granules after the drying is removed after organic matter at about 500 DEG C to get compound adsorbent.
Make filled layer with above-mentioned adsorbent, height 15cm is 200mg/m with 2m/s wind speed purging concentration3Ethyl alcohol, temperature 25
DEG C, humidity 60%RH, detection filled layer Export Ethanol concentration is 20mg/m3When time be 8min.
Embodiment 3
A kind of adsorbent, including silica gel and magnesium chloride, magnesium chloride are attached on silica gel.
The weight ratio of the silica gel is about 70%, and the weight ratio of magnesium chloride is about 30%.
The present embodiment also provides the preparation method of above-mentioned adsorbent, includes the following steps:
(1) silica gel particle by partial size about between 100nm-10 μm is mixed with magnesium chloride granules, wherein the weight of magnesium chloride
Amount accounts for the 20% of total weight of the mixture；
(2) by the mixture extrusion forming；
(3) molding is subjected to heated-air drying at 150 DEG C；
(4) molding after the drying is removed after organic matter at about 400 DEG C to get compound adsorbent.
Make filled layer with above-mentioned adsorbent, height 15cm is 200mg/m with 2m/s wind speed purging concentration3Ethyl alcohol, temperature 25
DEG C, humidity 60%RH, detection filled layer Export Ethanol concentration is 20mg/m3When time be 5min.
Embodiment 4
A kind of adsorbent, active carbon and chemosorbent copper sulphate including pore-size distribution in 10-50nm, copper sulphate attachment
In on silica gel.
The weight ratio of the active carbon is about 90%, and the weight ratio of copper sulphate is about 10%.
The present embodiment also provides the preparation method of above-mentioned adsorbent, includes the following steps:
(1) the above-mentioned active carbon particle by partial size about between 100nm-10 μm is mixed with copper sulfate particle, wherein sulfuric acid
The weight of copper accounts for the 10% of total weight of the mixture；
(2) a small amount of aluminium sol adhesive, extrusion forming are added in the mixture；
(3) molding is subjected to infra-red drying at 60 DEG C；
(4) molding after the drying is removed after organic matter at about 600 DEG C to get compound adsorbent.
Make filled layer with above-mentioned adsorbent, height 15cm is 200mg/m with 2m/s wind speed purging concentration3Ethyl alcohol, temperature 25
DEG C, humidity 60%RH, detection filled layer Export Ethanol concentration is 20mg/m3When time be 5min.
Embodiment 5
A kind of adsorbent, active carbon and chemosorbent calcium chloride including pore-size distribution in 10-50nm, calcium chloride attachment
In on active carbon.
The weight ratio of the active carbon is about 5%, and the weight ratio of calcium chloride is about 95%.
The present embodiment also provides the preparation method of above-mentioned adsorbent, includes the following steps:
(1) the above-mentioned active carbon by partial size about between 100nm-10 μm is mixed with calcium chloride granules, wherein calcium chloride weight
Amount accounts for the 95% of total weight of the mixture；
(2) by extrusion forming after a small amount of silica sol binder of mixture addition；
(3) molding is subjected to heated-air drying at 105 DEG C；
(4) molding after the drying is removed after organic matter at about 450 DEG C to get compound adsorbent.
Make filled layer with above-mentioned adsorbent, height 15cm is 200mg/m with 2m/s wind speed purging concentration3Ethyl alcohol, temperature 25
DEG C, humidity 60%RH, detection filled layer Export Ethanol concentration is 20mg/m3When time be 4.5min.
Embodiment 6
A kind of adsorbent, including aluminium oxide and chemosorbent calcium chloride, calcium chloride are attached on aluminium oxide.
The weight ratio of the aluminium oxide is about 95%, and the weight ratio of calcium chloride is about 5%.
The present embodiment also provides the preparation method of above-mentioned adsorbent, includes the following steps:
(1) alumina particle by partial size about between 100nm-10 μm is mixed with calcium chloride granules, wherein calcium chloride weight
Amount accounts for the 5% of total weight of the mixture；
(2) it is molded on ceramic honey comb after a small amount of silica sol binder being added in the mixture；
(3) molding is subjected to heated-air drying at 80 DEG C；
(4) molding after the drying is removed after organic matter at about 550 DEG C to get compound adsorbent.
Make filled layer with above-mentioned compound adsorbent, height 15cm is 200mg/m with 2m/s wind speed purging concentration3Ethyl alcohol,
25 DEG C of temperature, humidity 60%RH, detection filled layer Export Ethanol concentration is 20mg/m3When time be 6min.
Embodiment 7
A kind of adsorbent, the NaY molecular sieve and calcium chloride for being 6:1 including silica alumina ratio (molar ratio), calcium chloride are attached to NaY
On molecular sieve.
The weight ratio of the NaY molecular sieve is about 80%, and the weight ratio of calcium chloride is about 20%.
The present embodiment also provides the preparation method of above-mentioned adsorbent, includes the following steps:
(1) NaY molecular sieve by partial size about between 100nm-10 μm, which is placed in calcium chloride solution, stirs, after filtering
Mixture is obtained, wherein the weight of calcium chloride accounts for the 20% of total weight of the mixture；
(2) a small amount of silica sol binder is added in the mixture, the ball that diameter is about 4mm is formed by granulating and forming
Shape particle；
(3) spheric granules is subjected to microwave drying at 120 DEG C；
(4) spheric granules after the drying is removed after organic matter at about 520 DEG C to get compound adsorbent.
Make filled layer with above-mentioned adsorbent, height 15cm is 200mg/m with 2m/s wind speed purging concentration3Ethyl alcohol, temperature 25
DEG C, humidity 60%RH, detection filled layer Export Ethanol concentration is 20mg/m3When time be 7min.
Embodiment 8
A kind of adsorbent, mixture and chemosorbent calcium chloride including physical absorbent silica gel and aluminium oxide, chlorine
Change calcium to be attached on the mixture of physical absorbent silica gel and aluminium oxide.
The weight ratio of the mixture of the silica gel and aluminium oxide is about 80%, and the weight ratio of calcium chloride is about 20%.
The present embodiment also provides the preparation method of above-mentioned adsorbent, includes the following steps:
(1) compound particles and calcium chloride granules of the silica gel and aluminium oxide by partial size about between 100nm-10 μm
New mixture is formed, wherein the weight of calcium chloride accounts for the 20% of new total weight of the mixture；
(2) hybrid adhesive of a small amount of silica solution and Aluminum sol is added in the new mixture, passes through granulating and forming
Form the spheric granules that diameter is about 4mm；
(3) spheric granules is subjected to microwave drying at 120 DEG C；
(4) spheric granules after the drying is removed after organic matter at about 520 DEG C to get compound adsorbent.
Make filled layer with above-mentioned adsorbent, height 15cm is 200mg/m with 2m/s wind speed purging concentration3Ethyl alcohol, temperature 25
DEG C, humidity 60%RH, detection filled layer Export Ethanol concentration is 20mg/m3When time be 6.5min.
Embodiment 9
A kind of adsorbent, including the mixture of physical absorbent silica gel and chemosorbent calcium chloride and magnesium chloride, chlorine
The mixture for changing calcium and magnesium chloride is attached on physical absorbent silica gel.
The weight ratio of the silica gel is about 80%, and the weight ratio of the mixture of calcium chloride and magnesium chloride is about 20%.
The present embodiment also provides the preparation method of above-mentioned adsorbent, includes the following steps:
(1) compound particles of the silica gel particle by partial size about between 100nm-10 μm and calcium chloride and magnesium chloride
New mixture is formed, wherein the weight of the mixture of calcium chloride and magnesium chloride accounts for the 20% of new total weight of the mixture；
(2) a small amount of silica sol binder is added in the new mixture, forming diameter by granulating and forming is about 4mm
Spheric granules；
(3) spheric granules is subjected to microwave drying at 105 DEG C；
(4) spheric granules after the drying is removed after organic matter at about 520 DEG C to get compound adsorbent.
Make filled layer with above-mentioned adsorbent, height 15cm is 200mg/m with 2m/s wind speed purging concentration3Ethyl alcohol, temperature 25
DEG C, humidity 60%RH, detection filled layer Export Ethanol concentration is 20mg/m3When time be 6min.
Claims (10)
1. a kind of adsorbent, which is characterized in that including physical absorbent and chemosorbent, chemosorbent is attached to physics suction
On attached dose.
2. adsorbent according to claim 1, it is characterised in that the weight ratio of the physical absorbent is 5-95%, chemistry
The weight ratio of adsorbent is 5-95%.
3. adsorbent according to claim 2, it is characterised in that the weight ratio of the physical absorbent is 70-90%, institute
The weight ratio for stating chemosorbent is 10-30%.
4. adsorbent according to claim 1 to 3, it is characterised in that the physical absorbent be molecular sieve, silica gel,
One or more of active carbon or aluminium oxide；The chemosorbent be one of magnesium chloride, calcium chloride or copper sulphate or
It is several.
5. a kind of preparation method of adsorbent described in claim 1-4, it is characterised in that include the following steps:
(1) physical absorbent and chemosorbent are mixed to form mixture with solid phase or solid-liquid phase；
(2) mixture is to squeeze, be granulated or form on honeycomb class carrier；
(3) molding is dried at 60-150 DEG C；
(4) molding after the drying removed at 400-600 DEG C after organic matter to get.
6. the preparation method of adsorbent according to claim 5, it is characterised in that in step (1), the solid phase or solid-liquid
Solid-phase physical adsorbent or solid state chemistry adsorbent partial size in phase is between 100nm-10 μm.
7. the preparation method of adsorbent according to claim 5, it is characterised in that in step (2), the molding process
Middle addition binder.
8. the preparation method of adsorbent according to claim 7, it is characterised in that the binder is silica solution and/or aluminium
Colloidal sol.
9. the preparation method of adsorbent according to claim 5, it is characterised in that in step (3), the drying temperature is
80-120℃。
10. the preparation method of adsorbent according to claim 5, it is characterised in that in step (4), after the drying at
Type object removes organic matter at 450-550 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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Application publication date: 20190319 |