CN103785351A - Silica gel modified desulfurizing agent as well as preparation method and application thereof - Google Patents
Silica gel modified desulfurizing agent as well as preparation method and application thereof Download PDFInfo
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- CN103785351A CN103785351A CN201410035468.4A CN201410035468A CN103785351A CN 103785351 A CN103785351 A CN 103785351A CN 201410035468 A CN201410035468 A CN 201410035468A CN 103785351 A CN103785351 A CN 103785351A
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- silica gel
- desulfurizing agent
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- modification
- silane
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Abstract
The invention discloses a silica gel modified desulfurizing agent as well as a preparation method and an application thereof. The method for preparing the silica gel modified desulfurizing agent comprises the following steps: (a) soaking porous silica gel in a polar solvent A, so as to enable the porous silica gel to be polarized; (b) drying the polarized silica gel; and (c) soaking the dried polarized silica gel in a silane modifier B, and modifying the silica gel, so as to obtain the silica gel modified desulfurizing agent. The silica gel modified desulfurizing agent provided in the invention has the relatively high sulfur capacity and desulfurization depth, when hydrogen sulfide is removed from coke oven gas, the sulfur capacity is increased from the highest 10 percent to over 15 percent, the content of the hydrogen sulfide can be reduced to below 0.1mg/Nm<3> due to the highest desulfurization depth. The silica gel modified desulfurizing agent has the excellent desulfurization performance.
Description
Technical field
The present invention relates to a kind of desulfurizing agent and preparation method thereof, relate in particular to a kind of silica gel modification desulfurizing agent and its preparation method and application.
Background technology
Coke-stove gas is to be rich in H
2, CH
4, CO industrial gasses, commercial Application is mainly to carry hydrogen, directly burning and CCPP generating (Combined Cycle Power Plant; Combustion and steam combined cycle) etc., lower procedure all has requirement separately to coke-stove gas quality.In coke-stove gas, have the hydrogen sulfide of a great deal of, hydrogen sulfide is a kind of pollutant, directly discharge meeting atmosphere pollution, and its chemical property is active, has faintly acid and reproducibility, and easy and downstream material is had an effect, and lower procedure is produced to considerable influence.Therefore general coke-stove gas utilizes technique, all can have certain requirement to the coke-stove gas sulfur content that enters operation, even directly burning, hydrogen sulfide also needs pre-desulfurization.
In coke oven gas dry sulfur removal technology, conventional desulfurizing agent has active carbon, iron oxide, zinc oxide and silica gel etc.Bio-sil is due to its pore structure prosperity, and specific area is large, is a kind of good adsorbent, be commonly used for drier with adsorbed water molecule, again because its surface polarity is stronger, adsorption of hydrogen sulfide very effectively, and its surface chemical property can be revised, and is favored especially in recent years.
But the Sulfur capacity of conventional common Bio-sil desulfurization is not high enough, and desulfurization depth is also unsatisfactory, common Bio-sil is carried out to modification necessary to improve its Sulfur capacity and desulfurization depth.
U.S. Pat 20050282934A1 has announced a kind of surface modification silica gel, and its purposes is to add material as two-component coating.
Chinese patent CN1817442A has announced a kind of hybrid inorganic-organic modified silica-gel, and it produces specific hole by modification, to obtain, copper ion is had to optionally adsorption capacity.
Chinese patent CN102407099A has announced a kind of silica gel load polyhydroxy efficiently except the preparation method of boron chelating resin, and being carried on silica gel is polyhydroxy, and purposes is to prepare chelating resin.
Although above-mentioned patent has all been carried out modification to Bio-sil, there is its special purposes, do not improve its Sulfur capacity and desulfurization depth, cannot meet the desulfurization requirement of sulphur in coke oven gas hydrogen.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of silica gel modification desulfurizing agent and its preparation method and application, and common silica gel is carried out to modification, improves Sulfur capacity and desulfurization depth.
The present invention is the preparation method who solves the problems of the technologies described above the technical scheme adopting and be to provide a kind of silica gel modification desulfurizing agent, comprises the following steps: a) Bio-sil is soaked in and in polar solvent A, makes its polarization; B) silica gel after dry described polarization; C) dried polarization silica gel is soaked in silane modifier B, described silica gel is carried out to modification, obtain silica gel modification desulfurizing agent.
The preparation method of above-mentioned silica gel modification desulfurizing agent, wherein, described step a) process is as follows: Bio-sil is soaked in polar solvent A and is stirred, keep 60～90 ℃ of temperature, hold time 3～6 hours.
The preparation method of above-mentioned silica gel modification desulfurizing agent, wherein, described step b) process is as follows: in drying oven, pass into N
2, described N
2purity >99%, takes out the silica gel after polarization in step a), puts into drying oven, keeps 80～140 ℃ of temperature, holds time 1～2.5 hour.
The preparation method of above-mentioned silica gel modification desulfurizing agent, wherein, described step c) process is as follows: dried polarization silica gel is put into modification device, described polarization silica gel is soaked in silane modifier B, stir, keep 65～90 ℃ of temperature, hold time 2.5～6 hours.
The preparation method of above-mentioned silica gel modification desulfurizing agent, wherein, carries out being dried after modification to described silica gel in described step c), and dry run is as follows: in drying oven, pass into N
2, N
2purity >99%, takes out the silica gel after modification, inserts in drying oven, keeps 65～145 ℃ of temperature, holds time 2.5～4 hours; After dry, obtain silica gel modification desulfurizing agent.
The preparation method of above-mentioned silica gel modification desulfurizing agent, wherein, described polar solvent A is at least one in oxolane, toluene, acetone and pyridine.
The preparation method of above-mentioned silica gel modification desulfurizing agent, wherein, described silane modifier B makes according to the following steps: 1) at room temperature, get silane C, insert in organic container; 2) get epoxyalkane D, the volume of described epoxyalkane D is 1.1～1.5 times of silane C volume; 3) described silane C is mixed with epoxyalkane D, stir, keep 15～25 minutes, obtain silane modifier B;
Wherein, silane C is (CH
3cH
2o)
2si (C
6h
5)
2, (CH
3o)
3siCH
2cH
2cH (SH)
2, (CH
3cH
2o)
3siCH
2cH (Cl)
2(CH
3)
3siCH
2cH (CN)
2in at least one; Epoxyalkane D is
The preparation method of above-mentioned silica gel modification desulfurizing agent, wherein, described silane modifier B structural formula is
The present invention solves the problems of the technologies described above another technical scheme adopting to be to provide a kind of silica gel modification desulfurizing agent, is produced by above-mentioned preparation method.
The present invention solves the problems of the technologies described above the third technical scheme adopting to be to provide a kind of above-mentioned silica gel modification desulfurizing agent for coke-stove gas is carried out to desulfurization processing.
The present invention contrasts prior art following beneficial effect: silica gel modification desulfurizing agent provided by the invention and its preparation method and application, by processing and silane-modified that common silica gel is polarized, the silica gel modification desulfurizing agent obtaining has higher Sulfur capacity and desulfurization depth, during to coke-stove gas depriving hydrogen sulphide, Sulfur capacity is increased to more than 15% by the highest 10%, and the minimum hydrogen sulfide content that makes of desulfurization depth is down to 0.1mg/Nm
3below; Therefore, silica gel modification desulfurizing agent provided by the invention has excellent desulfurization performance.
Accompanying drawing explanation
Fig. 1 is the infrared absorption spectroscopy comparison diagram of the silica gel modification desulfurizing agent in common Bio-sil and the embodiment of the present invention.
The specific embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
The concrete preparation method of silica gel modification desulfurizing agent provided by the invention and application are as follows:
Embodiment 1
Common Bio-sil is soaked in polar solvent acetone, puts it in thermostat, stir, keep temperature 70 C, maintain 3 hours; In drying oven, pass into N
2, N
2purity >99%, takes out the silica gel after polarization, puts into drying oven, keeps 80 ℃ of temperature, maintains 2.5 hours; Dried polarization silica gel is put into modification device, make it be soaked in silane modifier B
In, stir, keep 90 ℃ of temperature, hold time 4 hours; In drying oven, pass into N
2, N
2purity >99%, takes out the silica gel after modification, inserts in drying oven, keeps 100 ℃ of temperature, holds time 3 hours, obtains silane-modified silica gel desulfurizing agent.
Described silane modifier is made according to the following steps:
1) at room temperature, get silane C, insert in organic container;
2) get epoxyalkane D, the volume of described epoxyalkane D is 1.1～1.5 times of silane C volume;
3) described silane C is mixed with epoxyalkane D, stir, keep 15～25 minutes, obtain silane modifier B;
Wherein, silane C is (CH
3cH
2o)
2si (C
6h
5)
2, (CH
3o)
3siCH
2cH
2cH (SH)
2, (CH
3cH
2o)
3siCH
2cH (Cl)
2(CH
3)
3siCH
2cH (CN)
2in at least one; Epoxyalkane D is
The modified silica-gel desulfurizing agent making by above-mentioned steps is for carrying out desulfurization processing to coke-stove gas.Coke-stove gas index is as follows:
Hydrogen sulfide 500mg/Nm
3
40 ℃ of temperature
Pressure 15KPa(gauge pressure)
Coke-stove gas is carried out to Temp .-changing adsorption lock out operation, and modified silica-gel shows excellent desulfurization performance, and purifying after cure hydrogen content is 0.07mg/Nm
3, Sulfur capacity 16%.
Embodiment 2
Common Bio-sil is soaked in pyridine, puts it in thermostat, stir, keep temperature 60 C, maintain 4 hours; In drying oven, pass into N
2, N
2purity >99%, takes out the silica gel after polarization, puts into drying oven, keeps 90 ℃ of temperature, maintains 2.5 hours; Dried polarization silica gel is put into modification device, make it be soaked in silane modifier
In, stir, keep 90 ℃ of temperature, hold time 2.5 hours; In drying oven, pass into N
2, N
2purity >99%, takes out the silica gel after modification, inserts in drying oven, keeps 65 ℃ of temperature, holds time 4 hours, obtains silane-modified silica gel desulfurizing agent.
The modified silica-gel desulfurizing agent making by above-mentioned steps is for carrying out desulfurization processing to coke-stove gas.Coke-stove gas index is as follows:
Hydrogen sulfide 800mg/Nm
3
Temperature 45 C
Pressure 12KPa(gauge pressure)
Coke-stove gas is carried out to Temp .-changing adsorption lock out operation, and modified silica-gel desulfurizing agent shows excellent desulfurization performance, and purifying after cure hydrogen content is 0.05mg/Nm
3, Sulfur capacity 17%.
Embodiment 3
Common Bio-sil is soaked in oxolane, puts it in thermostat, stir, keep 90 ℃ of temperature, maintain 6 hours; In drying oven, pass into N
2, N
2purity >99%, takes out the silica gel after polarization, puts into drying oven, keeps 140 ℃ of temperature, maintains 1 hour; Dried polarization silica gel is put into modification device, make it be soaked in silane modifier B
In, stir, keep 65 ℃ of temperature, hold time 6 hours; In drying oven, pass into N
2, N
2purity >99%, takes out the silica gel after modification, inserts in drying oven, keeps 145 ℃ of temperature, holds time 2.5 hours, obtains silane-modified silica gel desulfurizing agent.
The modified silica-gel desulfurizing agent making by above-mentioned steps is for carrying out desulfurization processing to coke-stove gas.Coke-stove gas index is as follows:
Hydrogen sulfide 850mg/Nm
3
40 ℃ of temperature
Pressure 9KPa(gauge pressure)
Coke-stove gas is carried out to Temp .-changing adsorption lock out operation, and modified silica-gel desulfurizing agent shows excellent desulfurization performance, and purifying after cure hydrogen content is 0.08mg/Nm
3, Sulfur capacity 17%.
To sum up, silica gel modification desulfurizing agent provided by the invention and its preparation method and application, by processing and silane-modified that common silica gel is polarized, the silica gel modification desulfurizing agent obtaining has higher Sulfur capacity and desulfurization depth, during to coke-stove gas depriving hydrogen sulphide, Sulfur capacity is increased to more than 15% by the highest 10%, and the minimum hydrogen sulfide content that makes of desulfurization depth is down to 0.1mg/Nm
3below; There is excellent desulfurization performance; Fig. 1 is the infrared absorption spectroscopy comparison diagram of the silica gel modification desulfurizing agent in common Bio-sil and the embodiment of the present invention, in Fig. 1, and 3400cm
-1place is the absworption peak of Si-OH in silica gel, and in modified silica-gel, because Si-OH is combined with silane modifier, this place's absworption peak weakens, 3000cm
-1place is alkane absworption peak, 1300cm
-1place is epoxyalkane absworption peak.
Although the present invention discloses as above with preferred embodiment; so it is not in order to limit the present invention, any those skilled in the art, without departing from the spirit and scope of the present invention; when doing a little modification and perfect, therefore protection scope of the present invention is worked as with being as the criterion that claims were defined.
Claims (10)
1. a preparation method for silica gel modification desulfurizing agent, is characterized in that, comprises the following steps:
A) Bio-sil is soaked in and in polar solvent A, makes its polarization;
B) silica gel after dry described polarization;
C) dried polarization silica gel is soaked in silane modifier B, described silica gel is carried out to modification, obtain silica gel modification desulfurizing agent.
2. the preparation method of silica gel modification desulfurizing agent as claimed in claim 1, is characterized in that, described step a) process is as follows: Bio-sil is soaked in polar solvent A and is stirred, keep 60～90 ℃ of temperature, hold time 3～6 hours.
3. the preparation method of silica gel modification desulfurizing agent as claimed in claim 1, is characterized in that, described step b) process is as follows: in drying oven, pass into N
2, described N
2purity >99%, takes out the silica gel after polarization in step a), puts into drying oven, keeps 80～140 ℃ of temperature, holds time 1～2.5 hour.
4. the preparation method of silica gel modification desulfurizing agent as claimed in claim 1, it is characterized in that, described step c) process is as follows: dried polarization silica gel is put into modification device, described polarization silica gel is soaked in silane modifier B, stir, keep 65～90 ℃ of temperature, hold time 2.5～6 hours.
5. the preparation method of silica gel modification desulfurizing agent as claimed in claim 1, is characterized in that, in described step c), described silica gel is carried out being dried after modification, and dry run is as follows: in drying oven, pass into N
2, N
2purity >99%, takes out the silica gel after modification, inserts in drying oven, keeps 65～145 ℃ of temperature, holds time 2.5～4 hours; After dry, obtain silica gel modification desulfurizing agent.
6. the preparation method of silica gel modification desulfurizing agent as claimed in claim 1 or 2, is characterized in that, described polar solvent A is at least one in oxolane, toluene, acetone and pyridine.
7. the preparation method of the silica gel modification desulfurizing agent as described in claim 1 or 4, is characterized in that, described silane modifier B makes according to the following steps:
1) at room temperature, get silane C, insert in organic container;
2) get epoxyalkane D, the volume of described epoxyalkane D is 1.1～1.5 times of silane C volume;
3) described silane C is mixed with epoxyalkane D, stir, keep 15～25 minutes, obtain silane modifier B;
Wherein, silane C is (CH
3cH
2o)
2si (C
6h
5)
2, (CH
3o)
3siCH
2cH
2cH (SH)
2, (CH
3cH
2o)
3siCH
2cH (Cl)
2(CH
3)
3siCH
2cH (CN)
2in at least one; Epoxyalkane D is
8. the preparation method of silica gel modification desulfurizing agent as claimed in claim 7, is characterized in that, described silane modifier B structural formula is
9. a silica gel modification desulfurizing agent, is characterized in that, is produced by the preparation method described in claim 1-8 any one.
10. silica gel modification desulfurizing agent as claimed in claim 9 is for carrying out desulfurization processing to coke-stove gas.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452743A (en) * | 2019-09-04 | 2019-11-15 | 山东虎力机械有限公司 | A kind of efficient desulfurizing agent |
| CN110452742A (en) * | 2019-09-04 | 2019-11-15 | 山东虎力机械有限公司 | A kind of high-efficiency desulfurization method |
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2014
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452743A (en) * | 2019-09-04 | 2019-11-15 | 山东虎力机械有限公司 | A kind of efficient desulfurizing agent |
| CN110452742A (en) * | 2019-09-04 | 2019-11-15 | 山东虎力机械有限公司 | A kind of high-efficiency desulfurization method |
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| CN103785351B (en) | 2015-08-19 |
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