CN101804325A - Preparation method of modified activated carbon adsorption desulfurizing agent - Google Patents
Preparation method of modified activated carbon adsorption desulfurizing agent Download PDFInfo
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Abstract
The invention relates to a preparation method of a modified activated carbon adsorption desulfurizing agent. Cocoa nut activated charcoal serves as a carrier; oxidant, such as concentrated nitric acid, concentrated sulfuric acid or ammonium sulphate and the like, is added for modification; active components, such as copper, silver, nipple, cerium and the like are loaded; the metallic oxide content of active components accounts for 1-20 wt% of activated carbon; the mixture is dried to obtain desulfurizing agent. Compared with the prior art, the preparation method has the characteristics of large sulfur adsorption capacity, high desulfurization precision, convenient reproduction and the like, and can be widely applied to producing ultra clean fuel oil in the petrochemical industry field.
Description
Technical field
The present invention relates to a kind of preparation method of desulfurizing agent, especially relate to a kind of preparation method of modified activated carbon adsorption desulfurizing agent.
Background technology
Along with the environmental regulation increasingly stringent, world's fuel oil III class and IV class standard have all reached 30ppm and 5～10ppm to the restriction of vapour, diesel oil sulfur content.By 2010, the sulfur content of European gasoline, diesel oil also all will be reduced to 10ppm.Therefore, the fuel oil degree of depth and the ultra-deep desulfurization technology of exploitation high-efficiency and economic reach the fuel oil quality standard of hanging down sulfuration and not having sulfuration as early as possible and have great importance.
After deliberation, China's gasoline has 80% from FCC gasoline, and the organic compounds containing sulfur in the gasoline about 85% derives from FCC gasoline, and the sulfide in the FCC gasoline is thiophenic sulfur and derivative thereof more than 90%; Thiophene-type sulfide accounts for total sulfur more than 80% in the diesel oil, and benzothiophene (BT) and dibenzothiophenes (DBT) account for more than 70% of thiophene-based again.Therefore, thiophene-type sulfide removes the most important thing that becomes desulfurizing oil.So the thiophene-based organic sulfur compound that present domestic and international research person mainly removes with difficulty is the sulfide in the model fuel oil, study the rule of adsorption desulfurize
In numerous deep desulfurization of fuel oil technology, the absorption method deep desulfurization of fuel oil is considered to a kind of ultra-deep desulfurization technology with strong competitiveness and wide market prospects because of the operating condition of its mitigation, lower desulphurization cost with to the advantages such as special selectivity of complicated sulfur-containing compound.Because active carbon has flourishing pore structure, high-specific surface area; Contain (or can affix) multiple functional group on the carbon surface; Has catalytic activity; Stable performance can be used under different temperatures and acid-base value; Can recycling utilization etc. advantage and be widely used as the adsorbent of adsorption desulfurize.So research has great importance with the adsorbent of active carbon as the fuel oil adsorption desulfurize.
U.S. Pat 5,454,933 disclose a kind of method of distillate adsorption desulfurize, it is by the difficult sulfide that removes of solid absorbent absorption with the intermediate oil of hydrodesulfurization, used adsorbent adopts coal or other materials process carbonization and oxidation processes and obtains, but adsorbent is lower to the adsorption capacity of sulfide, only is 0.12g sulfide/g adsorbent.
Chinese patent 200710041059.5 discloses a kind of spherical activated charcoal with high-specific surface area and preparation method thereof.The particle diameter of this spherical activated charcoal is 0.01mm-2mm, and specific area is greater than 500m
2/ g (1430-2359m
2/ g), pore volume is greater than 0.3cm
3/ g; Wherein the aperture less than the specific area in 2nm hole greater than 350m
2/ g, the aperture greater than the pore volume in 2nm hole greater than 0.15cm
3/ g.
Chinese patent 02109886.7 discloses a kind of fractional oil desulfurizing acticarbon and preparation method thereof, this fractional oil desulfurizing acticarbon, and the specific area that records this adsorbent with nitrogen adsorption method is 800-1500m
2/ g, total pore volume is 0.2-1.5ml/g, and the 2-50nm mesopore volume is 0.1-0.8ml/g, and this adsorbent 2-5nm hole pore volume accounts for total mesopore volume 65%, hole surface was more than or equal to 30% during surface area accounted for, and this adsorbent is the 0.24-0.30g/g adsorbent to the adsorption capacity of sulfide.
Summary of the invention
Purpose of the present invention is exactly that a kind of preparation method with higher desulfuration performance, simple to operate, security performance good, selectivity is high, desulfurization depth is high, absorption property is strong modified activated carbon adsorption desulfurizing agent is provided in order to overcome the defective that above-mentioned prior art exists.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of modified activated carbon adsorption desulfurizing agent, it is characterized in that this method may further comprise the steps: after placing oxidizing agent solution to carry out oxidation modification active carbon, place metal salt solution again, carrying transition metal on active carbon promptly gets desulfurizing agent after the oven dry.
This method specifically may further comprise the steps:
(1) magnesium oxide/absorbent charcoal: active carbon is added in the oxidizing agent solution, and the control temperature is 30-60 ℃, vibration 5-12h, spend deionised water, suction filtration then after, 100-150 ℃ of down oven dry, obtain the oxidation modification active carbon;
(2) equi-volume impregnating carried metal component: with oxidation modification active carbon incipient impregnation in the nitrate solution of transition metal, place 5-24h under the room temperature, carrying transition metal on active carbon, the weight of the metal oxide that control load forms accounts for the 1-20wt% of active carbon total amount, then load there is the active carbon of transition metal oxide to place 100-150 ℃ of oven dry 10-15h down, in 250-450 ℃ of roasting 2-4h, promptly obtain desulfurizing agent again.
Active carbon in the described step (1) is a 20-60 order cocoanut active charcoal, the parameter of this active carbon: moisture 5-8wt%, content of ashes 3-6wt%, bulk density 450-600g/L, specific area 600-1100m
2/ g, intensity 95%-99%, iodine sorption value 900-1100mg/g, carbon tetrachloride adsorptive value 50%-70%.
Oxidizing agent solution in the described step (1) comprises hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, chloroazotic acid, ammonium persulfate or hydrogen peroxide.
The concentration of described hydrochloric acid is 30-37wt%, the concentration of described nitric acid is 30-65wt%, the concentration of described sulfuric acid is 90-98wt%, described concentration of phosphoric acid is 83-90wt%, concentration in the described ammonium persulfate vitriolization is 0.8-1.2mol/L, and the concentration of described hydrogen peroxide is 28-35wt%.
The preferred 50-65wt% of the concentration of described nitric acid.
Transition metal in the described step (2) comprises one or more in copper, silver, nickel, zinc or the cerium.
The desulfurizing agent of the present invention's preparation has selectivity height, desulfurization depth height, absorption property is strong and the big characteristics of absorption Sulfur capacity, under normal temperature and normal pressure, the sulfur content in the fuel oil is reduced to 10ppm from a hundreds of ppm, reach the 5 stage sulfur content standards (10ppm) that Europe will be implemented clean fuel oil V standard (10ppm) and China of enforcement in 2013 in 2010, the absorption Sulfur capacity of this material is bigger than the Sulfur capacity of existing desulfurizing agent simultaneously, be particularly suitable for preparing the fuel oil of the low content of European standard, the double goal that is expected to realize the deep desulfuration of fuel oil and keeps oil property.
Compared with prior art, the present invention has the following advantages:
(1) desulfurizing agent of the present invention to big molecule thiophene-type sulfide, as dibenzothiophenes, has better removal performance under normal temperature condition, can remove the sulfide in the fuel oil more completely;
(2) desulfurizing agent of the present invention carries out under the normal temperature conditions of non-hydrogen, operates simplyr, and condition is more preferential, and security is better;
(3) desulfurizing agent of the present invention in use can not produce sulphur-bearing waste solution and contaminated environment;
The specific embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1
The desulfurizing agent preparation
The activated carbon adsorption desulfurizing agent of modification, oxidant are that concentration is the nitric acid of 65wt%, and active component is the Cu element, and the content of CuO accounts for 5% of active carbon weight.The preparation method is: with particle diameter is that 40 purpose cocoanut active charcoals are put into conical flask, adds the nitric acid of 65wt% then, leaves standstill oxidation 12h under the room temperature, with deionized water fully wash, suction filtration, at 110 ℃ of following dry 12h, obtain the active carbon of oxidation modification.With the active carbon incipient impregnation of oxidation modification in Cu (NO
3)
2In the solution, the content of CuO accounts for 5% of active carbon weight, places 24h under the room temperature, dry 12h under 110 ℃ of temperature then, and at last 350 ℃ of following roastings, roasting time is 3h, promptly gets desulfurizing agent.
The desulfurization performance test
In the conical flask of 25ml, add the 0.4g catalyst, add the normal octane simulation oil product (containing sulphur concentration is 500 μ g/g) that 15ml is furnished with thiophene, the sealing of jumping a queue.Conical flask is placed in the oscillator of constant temperature (30 ℃) reaction and filters after 3 hours, and filtrate is done the analysis of sulfur content.Just the same to simulation desulfurizing oil performance test of benzothiophene and dibenzothiophenes and thiophene, result of the test sees Table 1.
Embodiment 2
The oxidant that the desulfurizing agent preparation is selected for use is the sulfuric acid of concentration 98wt%, handles 12h with sulfuric acid oxidation under the room temperature, and all the other preparation processes and desulfurization performance test are according to embodiment 1, and result of the test sees Table 1.
Embodiment 3
It is the phosphoric acid of concentration 85wt% that oxidant is selected in the desulfurizing agent preparation for use, and with phosphoric acid oxidation processes 12h, all the other preparation processes and desulfurization performance test are according to embodiment 1 under the room temperature, and result of the test sees Table 1.
Embodiment 4
It is chloroazotic acid that oxidant is selected in the desulfurizing agent preparation for use, and with chloroazotic acid oxidation processes 12h, all the other preparation processes and desulfurization performance test are according to embodiment 1 under the room temperature, and result of the test sees Table 1.
Embodiment 5
It is ammonium persulfate that oxidant is selected in the desulfurizing agent preparation for use, and ammonium persulfate vitriolization concentration is 1mol/L, and with ammonium persulfate solution oxidation processes 12h, all the other preparation processes and desulfurization performance test are according to embodiment 1 under the room temperature, and result of the test sees Table 1.
Embodiment 6
It is the hydrogen peroxide of concentration 30wt% that oxidant is selected in the desulfurizing agent preparation for use, handles 12h with hydrogen peroxide oxidation under the room temperature, and all the other preparation processes and desulfurization performance test are according to embodiment 1, and result of the test sees Table 1.
Table 1
| Embodiment | Thiophene adsorbance (mg/g) | Benzothiophene adsorbance (mg/g) | Dibenzothiophenes adsorbance (mg/g) |
| Embodiment 1 | ??4.32 | ??7.03 | ??13.47 |
| Embodiment 2 | ??3.29 | ??5.82 | ??10.75 |
| Embodiment 3 | ??3.46 | ??5.88 | ??10.22 |
| Embodiment 4 | ??3.11 | ??5.13 | ??9.46 |
| Embodiment 5 | ??3.96 | ??6.11 | ??11.08 |
| Embodiment | Thiophene adsorbance (mg/g) | Benzothiophene adsorbance (mg/g) | Dibenzothiophenes adsorbance (mg/g) |
| Embodiment 6 | ??4.05 | ??5.72 | ??11.21 |
Embodiment 7
It is the Ag element that desulfurizing agent prepares selected active component, with the active carbon incipient impregnation of oxidation modification in AgNO
3In the solution, Ag
2O content accounts for 5% of active carbon total amount, and all the other preparation processes and desulfurization performance test are according to embodiment 1, and result of the test sees Table 2.
Embodiment 8
It is the Ni element that desulfurizing agent prepares selected active component, with the active carbon incipient impregnation of oxidation modification in Ni (NO
3)
2In the solution, NiO content accounts for 5% of active carbon total amount, and all the other preparation processes and desulfurization performance test are according to embodiment 1, and result of the test sees Table 2.
Embodiment 9
It is the Ce element that desulfurizing agent prepares selected active component, with the active carbon incipient impregnation of oxidation modification in Ce (NO
3)
3In the solution, Ce
2O
3Content accounts for 5% of active carbon total amount, and all the other preparation processes and desulfurization performance test are according to embodiment 1, and result of the test sees Table 2.
Embodiment 10
It is Cu and Ag element that desulfurizing agent prepares selected active component, with the active carbon incipient impregnation of oxidation modification in Cu (NO
3)
2And AgNO
3In the mixed solution, CuO and Ag
2O content respectively accounts for 2.5% of active carbon total amount, and residue preparation process and desulfurization performance test are according to embodiment 1, and result of the test sees Table 2.
Embodiment 11
It is Cu and Ni element that desulfurizing agent prepares selected active component, with the active carbon incipient impregnation of oxidation modification in Cu (NO
3)
2And Ni (NO
3)
2In the mixed solution, CuO and NiO content respectively account for 2.5% of active carbon total amount, and residue preparation process and desulfurization performance test are according to embodiment 1, and result of the test sees Table 2.
Embodiment 12
It is Cu and Ce element that desulfurizing agent prepares selected active component, with the active carbon incipient impregnation of oxidation modification in Cu (NO
3)
2And Ce (NO
3)
3In the mixed solution, CuO and Ce
2O
3Content respectively accounts for 2.5% of active carbon total amount, and residue preparation process and desulfurization performance test are according to embodiment 1, and result of the test sees Table 2.
Table 2
| Embodiment | Thiophene | Benzothiophene | Dibenzothiophenes |
| Adsorbance (mg/g) | Adsorbance (mg/g) | Adsorbance (mg/g) | |
| Embodiment 7 | ??5.22 | ??8.14 | ??14.55 |
| Embodiment 8 | ??4.35 | ??6.43 | ??11.86 |
| Embodiment 9 | ??4.48 | ??6.75 | ??12.07 |
| Embodiment 10 | ??5.37 | ??8.07 | ??14.09 |
| Embodiment 11 | ??4.96 | ??7.42 | ??13.02 |
| Embodiment 12 | ??5.08 | ??7.83 | ??13.39 |
Embodiment 13
A kind of preparation method of modified activated carbon adsorption desulfurizing agent, this method specifically may further comprise the steps:
(1) magnesium oxide/absorbent charcoal: active carbon is added in the hydrochloric acid that concentration is 30wt%, the control temperature is 30 ℃, vibration 12h, spend deionised water, suction filtration then after, 100 ℃ of down oven dry, obtain the oxidation modification active carbon, wherein active carbon is 20 purpose cocoanut active charcoals, the parameter of this active carbon: moisture 5wt%, content of ashes 3wt%, bulk density 450g/L, specific area 600m
2/ g, intensity 95%, iodine sorption value 900mg/g, carbon tetrachloride adsorptive value 50%;
(2) equi-volume impregnating carried metal component: with the active carbon incipient impregnation of oxidation modification in the solution of copper nitrate, place 5h under the room temperature, load copper on active carbon, the weight of the cupric oxide that control load forms accounts for the 1wt% of active carbon total amount, then load there is the active carbon of cupric oxide to place 100 ℃ of oven dry 15h down, in 250 ℃ of roasting 4h, promptly obtain desulfurizing agent again.
Embodiment 14
A kind of preparation method of modified activated carbon adsorption desulfurizing agent, this method specifically may further comprise the steps:
(1) magnesium oxide/absorbent charcoal: active carbon is added in the nitric acid that concentration is 30wt%, the control temperature is 60 ℃, vibration 5h, spend deionised water, suction filtration then after, 150 ℃ of down oven dry, obtain the oxidation modification active carbon, wherein active carbon is 60 purpose cocoanut active charcoals, the parameter of this active carbon: moisture 8wt%, content of ashes 6wt%, bulk density 600g/L, specific area 1100m
2/ g, intensity 99%, iodine sorption value 1100mg/g, carbon tetrachloride adsorptive value 70%;
(2) equi-volume impregnating carried metal component: with the active carbon incipient impregnation of oxidation modification in liquor argenti nitratis ophthalmicus, place 24h under the room temperature, carried metal silver on active carbon, the weight of the silver oxide that control load forms accounts for the 20wt% of active carbon total amount, then load there is the active carbon of silver oxide to place 150 ℃ of oven dry 10h down, in 450 ℃ of roasting 2h, promptly obtain desulfurizing agent again.
Embodiment 15
A kind of preparation method of modified activated carbon adsorption desulfurizing agent, this method specifically may further comprise the steps:
(1) magnesium oxide/absorbent charcoal: active carbon is added in the sulfuric acid that concentration is 90wt%, the control temperature is 40 ℃, vibration 8h, spend deionised water, suction filtration then after, 120 ℃ of down oven dry, obtain the oxidation modification active carbon, wherein active carbon is 40 purpose cocoanut active charcoals, the parameter of this active carbon: moisture 6wt%, content of ashes 5wt%, bulk density 500g/L, specific area 800m
2/ g, intensity 95%, iodine sorption value 1000mg/g, carbon tetrachloride adsorptive value 60%;
(2) equi-volume impregnating carried metal component: with the active carbon incipient impregnation of oxidation modification in the solution of pernitric acid copper, place 12h under the room temperature, load copper on active carbon, the weight of the cupric oxide that control load forms accounts for the 2wt% of active carbon total amount, then load there is the active carbon of cupric oxide to place 120 ℃ of oven dry 12h down, in 300 ℃ of roasting 4h, promptly obtain desulfurizing agent again.
Embodiment 16
It is ammonium persulfate solution that oxidant is selected in the desulfurizing agent preparation for use, and ammonium persulfate vitriolization concentration is 0.8mol/L, and with ammonium persulfate solution oxidation processes 12h, all the other preparation processes prepare desulfurizing agent according to embodiment 15 under the room temperature.
Embodiment 17
It is ammonium persulfate solution that oxidant is selected in the desulfurizing agent preparation for use, and ammonium persulfate vitriolization concentration is 1.2mol/L, and with ammonium persulfate solution oxidation processes 12h, all the other preparation processes prepare desulfurizing agent according to embodiment 15 under the room temperature.
Embodiment 18
It is phosphoric acid that oxidant is selected in the desulfurizing agent preparation for use, and concentration of phosphoric acid is 83wt%, and with phosphoric acid oxidation processes 12h, all the other preparation processes prepare desulfurizing agent according to embodiment 15 under the room temperature.
Embodiment 19
It is hydrogen peroxide that oxidant is selected in the desulfurizing agent preparation for use, and the concentration of hydrogen peroxide is 28wt%, uses hydrogen peroxide oxidation to handle 12h under the room temperature, and all the other preparation processes prepare desulfurizing agent according to embodiment 15.
Embodiment 20
It is hydrochloric acid that oxidant is selected in the desulfurizing agent preparation for use, and the concentration of hydrochloric acid is 37wt%, and with hydrochloric acid oxidation processes 12h, all the other preparation processes prepare desulfurizing agent according to embodiment 15 under the room temperature.
Embodiment 21
It is nitric acid that oxidant is selected in the desulfurizing agent preparation for use, and the concentration of nitric acid is 50wt%, handles 12h with nitric acid oxidation under the room temperature, and all the other preparation processes prepare desulfurizing agent according to embodiment 15.
Embodiment 22
It is phosphoric acid that oxidant is selected in the desulfurizing agent preparation for use, and concentration of phosphoric acid is 90wt%, and with phosphoric acid oxidation processes 12h, all the other preparation processes prepare desulfurizing agent according to embodiment 15 under the room temperature.
Embodiment 23
It is hydrogen peroxide that oxidant is selected in the desulfurizing agent preparation for use, and the concentration of hydrogen peroxide is 35wt%, uses hydrogen peroxide oxidation to handle 12h under the room temperature, and all the other preparation processes prepare desulfurizing agent according to embodiment 15.
Claims (7)
1. the preparation method of a modified activated carbon adsorption desulfurizing agent, it is characterized in that this method may further comprise the steps: after placing oxidizing agent solution to carry out oxidation modification active carbon, place metal salt solution again, carrying transition metal on active carbon promptly gets desulfurizing agent after the oven dry.
2. the preparation method of a kind of modified activated carbon adsorption desulfurizing agent according to claim 1 is characterized in that, this method specifically may further comprise the steps:
(1) magnesium oxide/absorbent charcoal: active carbon is added in the oxidizing agent solution, and the control temperature is 30-60 ℃, vibration 5-12h, spend deionised water, suction filtration then after, 100-150 ℃ of down oven dry, obtain the oxidation modification active carbon;
(2) equi-volume impregnating carried metal component: with oxidation modification active carbon incipient impregnation in the nitrate solution of transition metal, place 5-24h under the room temperature, carrying transition metal on active carbon, the weight of the metal oxide that control load forms accounts for the 1-20wt% of active carbon total amount, then load there is the active carbon of transition metal oxide to place 100-150 ℃ of oven dry 10-15h down, in 250-450 ℃ of roasting 2-4h, promptly obtain desulfurizing agent again.
3. the preparation method of a kind of modified activated carbon adsorption desulfurizing agent according to claim 2, it is characterized in that, active carbon in the described step (1) is a 20-60 order cocoanut active charcoal, the parameter of this active carbon: moisture 5-8wt%, content of ashes 3-6wt%, bulk density 450-600g/L, specific area 600-1100m
2/ g, intensity 95%-99%, iodine sorption value 900-1100mg/g, carbon tetrachloride adsorptive value 50%-70%.
4. the preparation method of a kind of modified activated carbon adsorption desulfurizing agent according to claim 2 is characterized in that, the oxidizing agent solution in the described step (1) comprises hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, chloroazotic acid, ammonium persulfate or hydrogen peroxide.
5. the preparation method of a kind of modified activated carbon adsorption desulfurizing agent according to claim 4, it is characterized in that, the concentration of described hydrochloric acid is 30-37wt%, the concentration of described nitric acid is 30-65wt%, the concentration of described sulfuric acid is 90-98wt%, described concentration of phosphoric acid is 83-90wt%, and the concentration in the described ammonium persulfate vitriolization is 0.8-1.2mol/L, and the concentration of described hydrogen peroxide is 28-35wt%.
6. the preparation method of a kind of modified activated carbon adsorption desulfurizing agent according to claim 5 is characterized in that, the preferred 50-65wt% of the concentration of described nitric acid.
7. the preparation method of a kind of modified activated carbon adsorption desulfurizing agent according to claim 2 is characterized in that, the transition metal in the described step (2) comprises one or more in copper, silver, nickel, zinc or the cerium.
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| CN113522234A (en) * | 2021-06-28 | 2021-10-22 | 中国兵器工业第五九研究所 | Sulfur dioxide adsorption material and preparation method thereof |
| CN114192114A (en) * | 2021-12-28 | 2022-03-18 | 山东亮剑环保新材料有限公司 | Preparation method of metal ion modified activated carbon desulfurizer |
| CN115212843A (en) * | 2022-07-19 | 2022-10-21 | 安徽省农业科学院植物保护与农产品质量安全研究所 | Preparation method and application of doped modified activated carbon loaded with metal oxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003022426A1 (en) * | 2001-09-07 | 2003-03-20 | Phillips Petroleum Company | Desulfurization and sorbent for same |
| CN1952049A (en) * | 2006-11-16 | 2007-04-25 | 中国海洋大学 | Modified active carbon FCC absorbent and desulfurizer for gasoline and diesel oil and its preparation method |
-
2010
- 2010-04-22 CN CN 201010153493 patent/CN101804325A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003022426A1 (en) * | 2001-09-07 | 2003-03-20 | Phillips Petroleum Company | Desulfurization and sorbent for same |
| CN1952049A (en) * | 2006-11-16 | 2007-04-25 | 中国海洋大学 | Modified active carbon FCC absorbent and desulfurizer for gasoline and diesel oil and its preparation method |
Non-Patent Citations (3)
| Title |
|---|
| 《中国优秀硕士学位论文全文数据库 工程科技I辑》 20080315 王振永 活性炭基脱硫剂FCC汽油吸附脱硫性能评价及物化性质表征 第55,62页 4，5 , 第3期 * |
| 《中国优秀硕士学位论文全文数据库 工程科技I辑》 20080315 王振永 活性炭基脱硫剂FCC汽油吸附脱硫性能评价及物化性质表征 第55,62页 4，5 , 第3期 2 * |
| 《石油与天然气化工》 20061231 王振永等 活性炭基脱硫剂吸附脱除汽油中含硫化合物的研究 第2，440-443页 1-6 第35卷, 第6期 * |
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