CN101362969A - Method for preparing desulfurizer containing nitrogen and carbon aerogel - Google Patents
Method for preparing desulfurizer containing nitrogen and carbon aerogel Download PDFInfo
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- CN101362969A CN101362969A CNA2008102007921A CN200810200792A CN101362969A CN 101362969 A CN101362969 A CN 101362969A CN A2008102007921 A CNA2008102007921 A CN A2008102007921A CN 200810200792 A CN200810200792 A CN 200810200792A CN 101362969 A CN101362969 A CN 101362969A
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Abstract
The invention relates to a preparation method of a nitrogen-containing carbon aerogel desulfurizer, formaldehyde and melamine are taken as polymer precursors and mixed with silica sol according to a certain proportion, then the sol-gel reaction is carried out, and a high nitrogen-containing carbon aerogel can be prepared through the steps of drying, high-temperature carbonization, silicon removal, and the like. The high nitrogen-containing carbon aerogel is carried out the impregnation and the drying by using sodium or potassium alkaline compounds, thereby preparing the desulfurizer. The desulfurizer which is prepared by using the method has great breakthrough sulfur capacity and saturated sulfur capacity. The preparation method has the advantages of simple preparation method, conventional production devices and the ability of being applicable to large-scale production, so that the preparation method can be widely applied in the H2S removing process of exhaust gas of petroleum, natural gas, synthetic gas and sewage treatment plants.
Description
Technical field
The present invention relates to a kind of H
2The preparation of S sweetening agent is specifically related to a kind of preparation method of high nitrogenous carbon aerogel desulfurizing agent.
Background technology
H
2S is a kind of toxic and harmful, mainly results from the various Industrial processes, as combustion gas manufacturing, ammonia synthesizing industry, coal gas gas making.Sewage disposal and petrochemical industry etc.Along with industrial expansion, it is important that cleaning and desulfurization more seems.This process has influence on directly that poisoning of catalyst causes that production efficiency falls sharply, the deterioration of the quality of product and environment.When with coal, oil and natural gas being products such as main material production ammonia, methyl alcohol, methanation coal gas, sulfide in the unstripped gas (mainly is H
2S, COS, CS
2Deng) be the major cause of poisoning of catalyst inactivation; In addition, contain H
2The SO that the fuel gas burning back of S generates
2Be one of gas that forms acid rain.Therefore, effectively from unstripped gas, remove H in the fuel gas
2S occupies very consequence in chemical industry, removing of hydrogen sulfide is the urgent problem that faces now.
Charcoal-aero gel is a kind of nano-meter porous amorphous carbon materials of controllable structure, has characteristics such as abundant hole, successive network structure, higher specific surface area and excellent conducting performance, variable density scope are wide, Adjustable structure.Document (R.W.Pekala, Organic aerogls from the polycondensation of resorcinolwith formaldehyde, Journal of Materials Science, 24 (1989) 3221-3227) and U.S. Pat 4,873,218, US4997,804 to disclose a kind of be the method for feedstock production low density organic aerogel with Resorcinol and formaldehyde, owing to the reason of Resorcinol price has limited its industrialized production.Chinese patent (application number 200610116392.3) provides a kind of preparation method of nitrogenous charcoal-aero gel, but because it need carry out drying under super critical condition, more loaded down with trivial details on the technology, also limited scale operation.
In the synthetic process, there is such problem:, destroyed the aperture structure and the distribution of aerogel, owing to shrink the reduction that causes specific surface area and pore volume because the existence of capillary tension causes gel network to produce structure when dry and carbonization process and caves in.Therefore our synthetic organic and inorganic network utilizes silicon to form skeleton structure and plays a supportive role, and prevents because the network that capillary tension causes subsides, thereby can obtain structural integrity, pore size distribution is narrow and the charcoal-aero gel of high-specific surface area and high pore volume.
At present, the H of research and development
2The S removal methods is of a great variety, and as wet desulphurization and dry desulfurization etc., Chinese patent (ZL9410271.1) discloses a kind of columnar activated carbon and removed H
2The method of S, but efficient is not high; Chinese patent (CN1088387C) discloses a kind of Immesion active carbon absorption H
2The method of S, it penetrates Sulfur capacity, and can to reach 45% (be that the 1g sweetening agent can absorb 0.45gH
2S).This charcoal-aero gel is compared with gac, penetrates Sulfur capacity and is greatly improved, and after optimization process, it penetrates Sulfur capacity can reach 65%, is higher than general activated carbon desulphurization agent far away.
Summary of the invention
The objective of the invention is to be to provide a kind of N of containing carbon aerogel desulfurizing agent.
The object of the present invention is achieved like this, earlier polymer precursor and inorganic silicon body is mixed into solution by a certain percentage, and sol gel reaction takes place down in water-bath, the aging organic and inorganic composite aquogel that obtains; Behind the constant pressure and dry again under protection of inert gas high temperature carbonization just obtain the charcoal composite aerogel.With the sour inorganic template flush away of inciting somebody to action wherein of HF, utilize deionized water with pH value furnishing neutrality, both got charcoal-aero gel after the drying.With the basic cpd of charcoal-aero gel, obtain sweetening agent after the oven dry by a kind of sodium of dipping or potassium.
A kind of preparation method of nitrogenous carbon aerogel desulfurizing agent is characterized in that present method comprises the steps:
(1) be 1:(1～4 in molar ratio with formaldehyde, trimeric cyanamide, silicon sol): (1～3) is mixed into organic precursor, adds water, makes in every 100ml water to contain reactant 40～50g, at 70 ℃ of heating in water bath 10～40min, makes precursor solution;
(2) precursor solution that makes in the step (1) is quickly cooled to 30～40 ℃, and regulates pH value to 1～4.5, again under 60～90 ℃ after sol gel reaction, aging 2～5 days of water-bath obtains the organic-inorganic composite aquogel;
(3) will make hydrogel in the step (2), often press dry dry after, place charring furnace, 700～900 ℃ of high temperature carbonization cracking 5～7 hours under the protection of rare gas element, obtain composite aerogel;
(4) composite aerogel that makes in the step (3) was utilized the HF acid soak 2～3 days, remove silicon wherein, utilize deionized water that it is washed then, with pH value furnishing neutrality, drying obtains charcoal-aero gel under the normal pressure;
(5) charcoal-aero gel that makes in the step (4) is ground the sample dipping basic cpd aqueous solution that back screening particle diameter is 0.3～0.7mm, obtain sweetening agent after the oven dry.
Described silicon sol is SiO
2Grain diameter is commercial grade silicon sol 1# and the silicon sol 2# of 7nm～12nm, wherein, the article number that No. 1, silicon sol: 420794, the article number that No. 2, silicon sol: 42082-4;
Rare gas element is nitrogen or argon gas described in the above-mentioned steps (3);
The basic cpd aqueous solution in the above-mentioned steps (5) is that concentration is 1～10%, NaOH, NaHCO
3, Na
2CO
3, KOH, KHCO
3, K
2CO
3A kind of in the solution; Dipping time is 3-24h, and dipping temperature is 25 ℃, and pressure is a standard atmospheric pressure;
Regulate the pH agents useful for same in the above-mentioned steps (4) and be a kind of of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, its concentration is 0.1mol/L.
Beneficial effect
.... the carbon aerogel desulfurizing agent that adopts method of the present invention to make, have very big Sulfur capacity and the saturated Sulfur capacity of penetrating, its specific surface area is 100～1000m
2/ g, pore volume are 0.1～1.5m
3/ g, density is at 0.20～0.80Cm
3/ g, mean pore size is at 7～70nm.Preparation method of the present invention is simple, conventional production device, and the advantage of suitable scale operation can be widely used in H in oil and gas, synthetic gas and the sewage work's tail gas
2The subtractive process of S.
Embodiment
The present invention is further elaborated below by embodiment and subordinate list.
Embodiment 1
With No. 1, trimeric cyanamide, formaldehyde, silicon sol in molar ratio for 1:3:1.5 is mixed into precursor solution, at 70 ℃ of following water-bath 20min.Be quickly cooled to 30 ℃ again.Utilize 0.1mol/L hydrochloric acid that the pH value is adjusted to 1.Solid content is 40g/100ml.Under 85 ℃, carry out sol gel reaction again, continue to obtain in aging 4 days composite aquogel.Behind the normal pressure under protection of inert gas, 600 ℃ of charing 3h.Be placed on again in the HF acid solution and soak, remove silicon wherein, with deionized water its pH value is transferred to neutrality again, carry out drying under the normal pressure after, obtain charcoal-aero gel.At last charcoal-aero gel and 8% NaOH solution are carried out incipient impregnation, make carbon aerogel desulfurizing agent in 130 ℃ of dry 24h.Its BET specific surface area is 700m
2/ g, pore volume are 1.1cm
3/ g, at normal pressure, temperature is 30 ℃, relative humidity is 90%, H
2S inlet concentration 1000ppm, oxygen content carry out desulfurization performance to characterize under 1% the condition, when breakthrough concentration was 1ppm, test-results showed that the Sulfur capacity that penetrates of sweetening agent is 65%, and saturated Sulfur capacity is 89%.
Embodiment 2
With No. 1, trimeric cyanamide, formaldehyde, silicon sol in molar ratio for 1:3:1.5 is mixed into precursor solution, at 70 ℃ of following water-bath 20min.Be quickly cooled to 30 ℃ again.Utilize 0.1mol/L hydrochloric acid that the pH value is adjusted to 3.Solid content is 40g/100ml.Under 85 ℃, carry out sol gel reaction again, continue to obtain in aging 4 days composite aquogel.Behind the normal pressure under protection of inert gas, 700 ℃ of charing 3h.Be placed on again in the HF acid solution and soak, remove silicon wherein, with deionized water its pH value is transferred to neutrality again, carry out drying under the normal pressure after, obtain charcoal-aero gel.At last with charcoal-aero gel and 6% K
2CO
3Solution carries out incipient impregnation, makes carbon aerogel desulfurizing agent in 130 ℃ of dry 24h.Its BET specific surface area is 580m
2/ g, pore volume are 0.8cm
3/ g, at normal pressure, temperature is 30 ℃, relative humidity is 90%, H
2S inlet concentration 1000ppm, oxygen content carry out desulfurization performance to characterize under 1% the condition, when breakthrough concentration was 1ppm, test-results showed that the Sulfur capacity that penetrates of sweetening agent is 49%, and saturated Sulfur capacity is 73%.
Embodiment 3
With trimeric cyanamide, formaldehyde, silicon sol is for No. 2 to be mixed into precursor solution at 1: 3: 2 in molar ratio, at 70 ℃ of following water-bath 20min.Be quickly cooled to 30 ℃ again.Utilize 0.1mol/L hydrochloric acid that the pH value is adjusted to 1.Solid content is 50g/100ml.Under 85 ℃, carry out sol gel reaction again, continue to obtain in aging 4 days composite aquogel.Behind the normal pressure under protection of inert gas, 600 ℃ of charing 3h.Be placed on again in the HF acid solution and soak, remove silicon wherein, with deionized water its pH value is transferred to neutrality again, carry out drying under the normal pressure after, obtain charcoal-aero gel.At last with charcoal-aero gel and 6% Na
2CO
3Solution carries out incipient impregnation, makes carbon aerogel desulfurizing agent in 130 ℃ of dry 24h.Its BET specific surface area is 680m
2/ g, pore volume are 0.9cm
3/ g, at normal pressure, temperature is 30 ℃, relative humidity is 90%, H
2S inlet concentration 1000ppm, oxygen content carry out desulfurization performance to characterize under 1% the condition, when breakthrough concentration was 1ppm, test-results showed that the Sulfur capacity that penetrates of sweetening agent is 57%, and saturated Sulfur capacity is 80%.
Embodiment 4
With trimeric cyanamide, formaldehyde, silicon sol is for No. 2 to be mixed into precursor solution at 1: 3: 2 in molar ratio, at 70 ℃ of following water-bath 20min.Be quickly cooled to 30 ℃ again.Utilize 0.1mol/L hydrochloric acid that the pH value is adjusted to 3.Solid content is 50g/100ml.Under 85 ℃, carry out sol gel reaction again, continue to obtain in aging 4 days composite aquogel.Behind the normal pressure under protection of inert gas, 700 ℃ of charing 3h.Be placed on again in the HF acid solution and soak, remove silicon wherein, with deionized water its pH value is transferred to neutrality again, carry out drying under the normal pressure after, obtain charcoal-aero gel.At last charcoal-aero gel and 10% KOH solution are carried out incipient impregnation, make carbon aerogel desulfurizing agent in 130 ℃ of dry 24h.Its BET specific surface area is 510m
2/ g, pore volume are 0.6cm
3/ g, at normal pressure, temperature is 30 ℃, relative humidity is 90%, H
2S inlet concentration 1000ppm, oxygen content carry out desulfurization performance to characterize under 1% the condition, when breakthrough concentration was 1ppm, test-results showed that the Sulfur capacity that penetrates of sweetening agent is 44%.Saturated Sulfur capacity is 70%.
Embodiment 5
At normal pressure, temperature is 30 ℃, and relative humidity is 90%, H in the unstripped gas
2S content is 1000ppm, oxygen content is under 1% the condition, the poly-sweetening agent of embodiment 1 charcoal airsetting, common Immesion active carbon, high sulfur capacity maceration active carbon used as dry method desulfurizer (patent No. CN1088387C), U.S. Westvaco gac are carried out performance relatively, the results are shown in Table 1.As can be seen from Table 1, when breakthrough concentration was 1ppm, this asphalt-base globular active carbon sweetening agent penetrated the Sulfur capacity maximum.
Different carbonaceous sweetening agents of table 1 and Sulfur capacity thereof
Claims (3)
1, a kind of preparation method of nitrogenous carbon aerogel desulfurizing agent is characterized in that, present method comprises the steps:
(1) be 1:(1～4 in molar ratio with formaldehyde, trimeric cyanamide, silicon sol): (1～3) is mixed into organic precursor, adds water, makes in every 100ml water to contain reactant 40～50g, at 70 ℃ of heating in water bath 10～40min, makes precursor solution;
(2) precursor solution that makes in the step (1) is quickly cooled to 30～40 ℃, and regulates pH value to 1～4.5, again under 60～90 ℃ after sol gel reaction, aging 2～5 days of water-bath obtains the organic-inorganic composite aquogel;
(3) will make hydrogel in the step (2), often press dry dry after, place charring furnace, 700～900 ℃ of high temperature carbonization cracking 5～7 hours under the protection of rare gas element, obtain composite aerogel;
(4) composite aerogel that makes in the step (3) was utilized the HF acid soak 2～3 days, remove silicon wherein, utilize deionized water that it is washed then, with pH value furnishing neutrality, drying obtains charcoal-aero gel under the normal pressure;
(5) charcoal-aero gel that makes in the step (4) is ground the sample dipping basic cpd aqueous solution that back screening particle diameter is 0.3～0.7mm, obtain sweetening agent after the oven dry;
Wherein, described silicon sol is SiO
2Grain diameter is the silicon sol of 7nm～12nm,
Rare gas element in the described step (3) is nitrogen or argon gas;
The basic cpd aqueous solution in the described step (5) is that concentration is 1～10%, NaOH, NaHCO
3, Na
2CO
3, KOH, KHCO
3, K
2CO
3A kind of in the solution.
2, the preparation method of a kind of nitrogenous carbon aerogel desulfurizing agent as claimed in claim 1 is characterized in that, the temperature of the dipping alkaline compound solution in the described method steps (5) is 25 ℃, and dipping time is 3-24h, and pressure is a standard atmospheric pressure.
3, the preparation method of a kind of nitrogenous carbon aerogel desulfurizing agent as claimed in claim 1 is characterized in that, regulates the pH agents useful for same in the above-mentioned steps (4) and be a kind of of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and its concentration is 0.1mol/L.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102716700A (en) * | 2012-06-18 | 2012-10-10 | 南京工业大学 | Preparation method for high-strength heat-resisting massive C-AlN compound aerogel |
| CN104167296A (en) * | 2014-08-05 | 2014-11-26 | 郑州大学 | Method for preparing nanoelectrode material of super capacitor |
| CN104446330A (en) * | 2014-12-23 | 2015-03-25 | 中物院成都科学技术发展中心 | Preparation method of ultrahigh-specific-surface-area nitrogen-doped carbon aerogel |
| CN108622991A (en) * | 2017-03-17 | 2018-10-09 | 南开大学 | A kind of method of novel nitrating charcoal-aero gel catalysis persulfate degradation of organic waste water |
| CN113289596A (en) * | 2021-06-11 | 2021-08-24 | 苏州岚露新材料科技有限公司 | Preparation of ZrO from organic aerogel loaded Zr compound2Preparation method of/C freon catalyst |
| CN113289618A (en) * | 2021-06-25 | 2021-08-24 | 苏州岚露新材料科技有限公司 | Method for preparing Pt/C catalyst by organic aerogel supported Pt compound |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4873218A (en) * | 1988-05-26 | 1989-10-10 | The United States Department Of Energy | Low density, resorcinol-formaldehyde aerogels |
| CN1136963C (en) * | 2001-08-24 | 2004-02-04 | 中国科学院山西煤炭化学研究所 | Method for synthesis of furfural-phenolic aldehyde based charcoal aerogel |
| CN1219595C (en) * | 2003-06-07 | 2005-09-21 | 大连理工大学 | Method for preparing nano material of gel of charcoal gas |
| CN100430312C (en) * | 2006-09-22 | 2008-11-05 | 华东理工大学 | Charcoal aerogel |
-
2008
- 2008-10-06 CN CN2008102007921A patent/CN101362969B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102716700A (en) * | 2012-06-18 | 2012-10-10 | 南京工业大学 | Preparation method for high-strength heat-resisting massive C-AlN compound aerogel |
| CN104167296A (en) * | 2014-08-05 | 2014-11-26 | 郑州大学 | Method for preparing nanoelectrode material of super capacitor |
| CN104167296B (en) * | 2014-08-05 | 2017-03-29 | 郑州大学 | A kind of preparation method of the nano-electrode material for ultracapacitor |
| CN104446330A (en) * | 2014-12-23 | 2015-03-25 | 中物院成都科学技术发展中心 | Preparation method of ultrahigh-specific-surface-area nitrogen-doped carbon aerogel |
| CN104446330B (en) * | 2014-12-23 | 2016-08-31 | 中物院成都科学技术发展中心 | A kind of preparation method of superhigh specific surface area nitrating carbon aerogels |
| CN108622991A (en) * | 2017-03-17 | 2018-10-09 | 南开大学 | A kind of method of novel nitrating charcoal-aero gel catalysis persulfate degradation of organic waste water |
| CN113289596A (en) * | 2021-06-11 | 2021-08-24 | 苏州岚露新材料科技有限公司 | Preparation of ZrO from organic aerogel loaded Zr compound2Preparation method of/C freon catalyst |
| CN113289618A (en) * | 2021-06-25 | 2021-08-24 | 苏州岚露新材料科技有限公司 | Method for preparing Pt/C catalyst by organic aerogel supported Pt compound |
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