CN103785351B - Silica gel modification desulfurizing agent and its preparation method and application - Google Patents
Silica gel modification desulfurizing agent and its preparation method and application Download PDFInfo
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- CN103785351B CN103785351B CN201410035468.4A CN201410035468A CN103785351B CN 103785351 B CN103785351 B CN 103785351B CN 201410035468 A CN201410035468 A CN 201410035468A CN 103785351 B CN103785351 B CN 103785351B
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Abstract
The invention discloses a kind of silica gel modification desulfurizing agent and its preparation method and application, the preparation method of described silica gel modification desulfurizing agent, comprises the following steps: a) be soaked in polar solvent A by Bio-sil and make it polarize; B) silica gel after dry described polarization; C) dried polarization silica gel is soaked in silane modifier B, modification is carried out to described silica gel, obtain silica gel modification desulfurizing agent.Silica gel modification desulfurizing agent provided by the invention has higher Sulfur capacity and desulfurization depth, during to coke-stove gas depriving hydrogen sulphide, makes Sulfur capacity be 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.
Description
Technical field
The present invention relates to a kind of desulfurizing agent and preparation method thereof, particularly relate to a kind of silica gel modification desulfurizing agent and its preparation method and application.
Background technology
Coke-stove gas is rich in H
2, CH
4, CO industrial gasses, commercial Application is mainly carried hydrogen, directly burning and CCPP and to be generated electricity (Combined Cycle Power Plant; Combined cycle gas-steam turbine) etc., lower procedure all has respective requirement to coke-stove gas quality.Have the hydrogen sulfide of a great deal of in coke-stove gas, 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 substrates is had an effect, and produces considerable influence to lower procedure.Therefore general coke-stove gas utilizes technique, all can have certain requirement to the coke-stove gas sulfur content entering operation, even directly burn, 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 excellent adsorbent, be commonly used for drier with adsorbed water molecule, again because its surface polarity is comparatively strong, can effectively adsorption of hydrogen sulfide, and its surface chemical property can be revised, and is favored especially in recent years.
But the Sulfur capacity of conventional common porous silica gel desulfurization is not high enough, and desulfurization depth is also unsatisfactory, to common porous silica gel carry out modification with improve its Sulfur capacity and desulfurization depth necessary.
US Patent No. 20050282934A1 discloses a kind of surface modification silica gel, and its purposes is as two-component coating adding material.
Chinese patent CN1817442A discloses a kind of hybrid inorganic-organic modified silica-gel, and it produces specific hole by modification, has optionally adsorption capacity to obtain to copper ion.
Chinese patent CN102407099A discloses a kind of silica gel load polyhydroxy efficiently except the preparation method of boron-specific chelating resin, and being carried on, silica gel is polyhydroxy, and purposes prepares chelating resin.
Although above-mentioned patent has all carried out modification to Bio-sil, there is the purposes that it is special, do not improved its Sulfur capacity and desulfurization depth, the desulfurization requirement of hydrogen sulfide in coke oven cannot have been met.
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, carries out modification to common silica gel, improves Sulfur capacity and desulfurization depth.
The present invention solves the problems of the technologies described above the preparation method that the technical scheme adopted is to provide a kind of silica gel modification desulfurizing agent, comprises the following steps: a) be soaked in polar solvent A by Bio-sil and make it polarize; B) silica gel after dry described polarization; C) dried polarization silica gel is soaked in silane modifier B, modification is carried out to described silica gel, 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: be soaked in by Bio-sil in polar solvent A and stir, and keeps temperature 60 ~ 90 DEG C, holds 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, keep temperature 80 ~ 140 DEG C, hold 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 made to be soaked in silane modifier B, stir, keep temperature 65 ~ 90 DEG C, hold time 2.5 ~ 6 hours.
The preparation method of above-mentioned silica gel modification desulfurizing agent, wherein, carry out modifiedly carrying out drying to described silica gel in described step c), dry run is as follows: in drying oven, pass into N
2, N
2purity >99%, takes out modified silica gel, inserts in drying oven, keeps temperature 65 ~ 145 DEG C, holds time 2.5 ~ 4 hours; Silica gel modification desulfurizing agent is obtained after drying.
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, gets silane C, inserts 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
and
in at least one.
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 adopted 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 adopted to be to provide a kind of above-mentioned silica gel modification desulfurizing agent for carrying out desulfurization process to coke-stove gas.
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 common silica gel is carried out polarization process and silane-modified, the silica gel modification desulfurizing agent obtained has higher Sulfur capacity and desulfurization depth, during to coke-stove gas depriving hydrogen sulphide, make Sulfur capacity be increased to more than 15% by the highest 10%, 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 porous silica gel and the embodiment of the present invention.
Detailed description of the invention
Below in conjunction with drawings and Examples, the invention will be further described.
Concrete preparation method and the application of silica gel modification desulfurizing agent provided by the invention are as follows:
Embodiment 1
Common porous silica gel is soaked in polar solvent acetone, puts it in thermostat, stir, keep temperature 70 C, maintain 3 hours; N is passed in drying oven
2, N
2purity >99%, takes out the silica gel after polarization, puts into drying oven, keeps temperature 80 DEG C, maintains 2.5 hours; Dried polarization silica gel is put into modification device, makes it be soaked in silane modifier B
In, stir, keep temperature 90 DEG C, hold time 4 hours; N is passed in drying oven
2, N
2purity >99%, takes out modified silica gel, inserts in drying oven, keeps temperature 100 DEG C, holds time 3 hours, obtain 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
and
in at least one.
Be used for carrying out desulfurization process to coke-stove gas by the modified silica-gel desulfurizing agent that above-mentioned steps is obtained.Coke-stove gas index is as follows:
Hydrogen sulfide 500mg/Nm
3
Temperature 40 DEG C
Pressure 15KPa(gauge pressure)
Carry out Temp .-changing adsorption lock out operation to coke-stove gas, modified silica-gel shows excellent desulfurization performance, and purification after cure hydrogen content is 0.07mg/Nm
3, Sulfur capacity 16%.
Embodiment 2
Common porous silica gel is soaked in pyridine, puts it in thermostat, stir, keep temperature 60 C, maintain 4 hours; N is passed in drying oven
2, N
2purity >99%, takes out the silica gel after polarization, puts into drying oven, keeps temperature 90 DEG C, maintains 2.5 hours; Dried polarization silica gel is put into modification device, makes it be soaked in silane modifier
In, stir, keep temperature 90 DEG C, hold time 2.5 hours; N is passed in drying oven
2, N
2purity >99%, takes out modified silica gel, inserts in drying oven, keeps temperature 65 DEG C, holds time 4 hours, obtain silane-modified silica gel desulfurizing agent.
Be used for carrying out desulfurization process to coke-stove gas by the modified silica-gel desulfurizing agent that above-mentioned steps is obtained.Coke-stove gas index is as follows:
Hydrogen sulfide 800mg/Nm
3
Temperature 45 C
Pressure 12KPa(gauge pressure)
Carry out Temp .-changing adsorption lock out operation to coke-stove gas, modified silica-gel desulfurizing agent shows excellent desulfurization performance, and purification after cure hydrogen content is 0.05mg/Nm
3, Sulfur capacity 17%.
Embodiment 3
Common porous silica gel is soaked in oxolane, puts it in thermostat, stir, keep temperature 90 DEG C, maintain 6 hours; N is passed in drying oven
2, N
2purity >99%, takes out the silica gel after polarization, puts into drying oven, keeps temperature 140 DEG C, maintains 1 hour; Dried polarization silica gel is put into modification device, makes it be soaked in silane modifier B
In, stir, keep temperature 65 DEG C, hold time 6 hours; N is passed in drying oven
2, N
2purity >99%, takes out modified silica gel, inserts in drying oven, keeps temperature 145 DEG C, holds time 2.5 hours, obtain silane-modified silica gel desulfurizing agent.
Be used for carrying out desulfurization process to coke-stove gas by the modified silica-gel desulfurizing agent that above-mentioned steps is obtained.Coke-stove gas index is as follows:
Hydrogen sulfide 850mg/Nm
3
Temperature 40 DEG C
Pressure 9KPa(gauge pressure)
Carry out Temp .-changing adsorption lock out operation to coke-stove gas, modified silica-gel desulfurizing agent shows excellent desulfurization performance, and purification 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 common silica gel is carried out polarization process and silane-modified, the silica gel modification desulfurizing agent obtained has higher Sulfur capacity and desulfurization depth, during to coke-stove gas depriving hydrogen sulphide, make Sulfur capacity be increased to more than 15% by the highest 10%, 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 porous silica gel and the embodiment of the present invention, in Fig. 1, and 3400cm
-1place is the absworption peak of Si-OH in silica gel, and because Si-OH is combined with silane modifier in modified silica-gel, 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 itself and be not used 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 amendment and perfect, therefore protection scope of the present invention is when being as the criterion of defining with claims.
Claims (9)
1. a preparation method for silica gel modification desulfurizing agent, is characterized in that, comprises the following steps:
A) Bio-sil is soaked in polar solvent A makes it polarize;
B) silica gel after dry described polarization;
C) dried polarization silica gel is soaked in silane modifier B, modification is carried out to described silica gel, obtain silica gel modification desulfurizing agent; 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
in at least one.
2. the preparation method of silica gel modification desulfurizing agent as claimed in claim 1, it is characterized in that, described step a) process is as follows: be soaked in by Bio-sil in polar solvent A and stir, and keeps temperature 60 ~ 90 DEG C, holds 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%, take out step a) in polarization after silica gel, put into drying oven, keep temperature 80 ~ 140 DEG C, hold 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 made to be soaked in silane modifier B, stir, keep temperature 65 ~ 90 DEG C, 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, described step c) in carry out modifiedly carrying out drying to described silica gel, dry run is as follows: in drying oven, pass into N
2, N
2purity >99%, takes out modified silica gel, inserts in drying oven, keeps temperature 65 ~ 145 DEG C, holds time 2.5 ~ 4 hours; Silica gel modification desulfurizing agent is obtained after drying.
6. the preparation method of silica gel modification desulfurizing agent as claimed in claim 1 or 2, it is characterized in that, described polar solvent A is at least one in oxolane, toluene, acetone and pyridine.
7. the preparation method of silica gel modification desulfurizing agent as claimed in claim 1, it is characterized in that, described silane modifier B structural formula is
8. a silica gel modification desulfurizing agent, is characterized in that, is produced by the preparation method described in any one of claim 1-7.
9. silica gel modification desulfurizing agent as claimed in claim 8 is used for carrying out desulfurization process to coke-stove gas.
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| CN110452742B8 (en) * | 2019-09-04 | 2020-08-04 | 江苏峰业科技环保集团股份有限公司 | High-efficiency desulfurization method |
| CN110452743B (en) * | 2019-09-04 | 2020-06-05 | 西安凯尔文石化助剂制造有限公司 | High-efficiency desulfurizing agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2655800B2 (en) * | 1993-06-02 | 1997-09-24 | 工業技術院長 | Gas desulfurizing agent and desulfurization method for hydrogen sulfide-containing gas |
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2014
- 2014-01-24 CN CN201410035468.4A patent/CN103785351B/en active Active
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| CN1887704A (en) * | 2006-07-17 | 2007-01-03 | 天津博纳固体材料科技有限公司 | Surface modified nanometer silica gel ball and its prepn |
| CN101721970A (en) * | 2008-10-22 | 2010-06-09 | 中国科学院大连化学物理研究所 | Method for preparing modification functional groups on external surfaces of pores of mesoporous silica material |
| CN101856606A (en) * | 2010-06-11 | 2010-10-13 | 大连理工大学 | Preparation method of modified silicon gel absorbing agent used for protecting on-vehicle fuel batteries |
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