CN103638895A - Preparation method of supported acid gas absorbent - Google Patents
Preparation method of supported acid gas absorbent Download PDFInfo
- Publication number
- CN103638895A CN103638895A CN201310580186.8A CN201310580186A CN103638895A CN 103638895 A CN103638895 A CN 103638895A CN 201310580186 A CN201310580186 A CN 201310580186A CN 103638895 A CN103638895 A CN 103638895A
- Authority
- CN
- China
- Prior art keywords
- acid gas
- gas absorbent
- preparation
- support type
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a preparation method of a supported acid gas absorbent. The preparation method comprises following steps: loading of an alkali metal hydroxide, wherein spherical aluminum oxide carrier is added into a water solution of the alkali metal hydroxide for dipping, and an obtained mixture is filtered and dried; in-situ deposition and loading of an alkaline-earth metal salt solution, wherein the modified aluminum oxide is added into an alkaline-earth metal acetate solution for dipping, and an obtained mixed solution is filtered and dried; an obtained product is roasted in a muffle furnace; and phenolphtalein solution is added into the roasted product dropwise so as to obtain the pink acid gas absorbent. According to the preparation method, stepwise loading technology is adopted, porous aluminum oxide is taken as the carrier, the alkali metal hydroxide is loaded with priority, and the alkaline-earth metal salt solution is loaded after drying, and after roasting, selective dipping of phenolphtalein is performed, wherein phenolphtalein is used as an indicator. The supported acid gas absorbent is high in reaction activity, excellent in intensity, low in pulverulent ratio, and is beneficial for preparation of gases with ultra high purity. In addition, the supported acid gas absorbent possesses color rendering properties after phenolphthalein dipping, and when efficacy of the supported acid gas absorbent is lost, the color of the supported acid gas absorbent is changed from pink to colourless.
Description
Technical field
The present invention relates to a kind of preparation method of support type acid gas absorbent, belong to inorganic material and synthesize and Industrial Catalysis technical field.
Background technology
In semiconductor preparation process, the trace acidic gaseous impurity that the carbon dioxide of take is master is having a strong impact on chip performance, therefore extra-high-speed pure gas product requires this class impurity content to be less than 1ppm conventionally.CO in common gas source
2not etc., except the common physical absorbents such as molecular sieve, industrial common chemical absorbent does not mainly comprise alkali metal hydroxide and alkaline earth oxide, as potassium hydroxide, NaOH or soda lime etc. for impurity and water content 1%～1ppm.Hydroxide flake potassium or the NaOH deliquescence that easily absorbs water, heat release is obvious and corrosivity is large, is not suitable for large-scale application.On the other hand, the soda lime that the calcium hydroxide of take is main component is widely used in surgical procedures and submarine, and absorbent is very beneficial for removing the great amount of carbon dioxide existing in moist closed environment, but granule strength is low, easily efflorescence.In high-purity gas preparation process, the efflorescence of soda lime not only causes solid particulate matter content in gas to increase, and the process of efflorescence simultaneously produces huge pressure drop in purification column, has potential safety hazard.
Summary of the invention
The object of the invention is to overcome the deficiency that prior art exists, a kind of preparation method of support type acid gas absorbent is provided.
Object of the present invention is achieved through the following technical solutions:
The preparation method of support type acid gas absorbent, comprises the following steps:
1) supporting of alkali metal hydroxide: ball-aluminium oxide carrier is added to the aqueous solution of alkali metal hydroxide, dipping, filtering drying;
2) in-situ deposition of alkaline-earth metal salt solution and supporting: the aluminium oxide after the modification of step 1) gained is added in Alkaline Earth Metal Acetate solution to dipping, filtering drying;
3) by step 2) products obtained therefrom calcines in Muffle furnace;
4) phenolphthalein test solution is splashed in step 3) products obtained therefrom, finally obtain pink acid gas absorbent.
Further, the preparation method of above-mentioned support type acid gas absorbent, step 1), described ball-aluminium oxide is Woelm Alumina, and particle diameter is 3～8 mm, and specific area is 150～380 m
2g
-1, pore volume is 0.2～0.5 cm
3g
-1.
Further, the preparation method of above-mentioned support type acid gas absorbent, the particle diameter of described ball-aluminium oxide is 3～5 mm, specific area is 250～350 m
2g
-1, pore volume is 0.3～0.45 cm
3g
-1.
Further, the preparation method of above-mentioned support type acid gas absorbent, step 1), described alkali metal hydroxide is lithium hydroxide, NaOH, potassium hydroxide, strontium hydroxide or its mixture.
Further, the preparation method of above-mentioned support type acid gas absorbent, step 2), described Alkaline Earth Metal Acetate solution is calcium acetate, magnesium acetate, barium acetate or its mixture.
Again further, the preparation method of above-mentioned support type acid gas absorbent, step 1) and step 2) in impregnation technology in shaking table, carry out, dip time is 24～48h.
Again further, the preparation method of above-mentioned support type acid gas absorbent, step 3), in Muffle furnace, calcining heat is 500～700 ° of C, and the time is 6～10h, and heating rate is 1～5 ℃ of min
-1.
The substantive distinguishing features that technical solution of the present invention is outstanding and significant progressive being mainly reflected in:
The present invention adopts step load technique, with Woelm Alumina, makes carrier, the hydroxide of preferential carrying alkali metal, and drying and processing back loading alkaline-earth metal salt solution, optionally floods phenolphthalein test solution as indicator after calcining.This acid gas absorbent is optionally removed in inert gas, oxygen and common reducibility gas (hydrogen, CO or NO etc.), alkanes and hydride gas (as silane, ammonia, phosphine and arsine etc.), the carbon dioxide of existence, sulfur dioxide, hydrogen sulfide, hydrogen chloride and a small amount of water etc.This support type acid gas absorbent reactivity is high, intensity large, pulverization rate is extremely low, is conducive to the preparation of extra-high-speed pure gas, and meanwhile, the sample after phenolphthalein dipping has coloring function, and when product failure, absorbent color is become colorless by pink.
The specific embodiment
The present invention be take Woelm Alumina as carrier, and by step load, by NaOH or potassium hydroxide, and calcium oxide supports respectively granule interior, and resulting materials intensity is high, without obviously efflorescence, is applicable to very much the removing of a small amount of sour gas in gas source.In reactive adsorption process, calcium oxide preferentially reacts with water and generates active component calcium hydroxide, and further generates calcium carbonate with carbon dioxide reaction.And NaOH or potassium hydroxide have strengthened the absorption to water in absorbing carbon dioxide, promote the activation of calcium agent adsorbent.Preparation technology is simple, and each active component ratio is adjustable to be applicable to the purifying of different impurities content gas product-derived.
The preparation technology of support type acid gas absorbent is:
1) supporting of alkali metal hydroxide: ball-aluminium oxide carrier is added to the aqueous solution of alkali metal hydroxide, flood 24～48h, filtering drying in shaking table; Wherein, ball-aluminium oxide is Woelm Alumina, and particle diameter is 3～8 mm, and specific area is 150～380 m
2g
-1, pore volume is 0.2～0.5 cm
3g
-1; Preferably, particle diameter 3～5 mm, specific area 250～350 m
2g
-1, pore volume 0.3～0.45 cm
3g
-1.Alkali metal hydroxide is lithium hydroxide, NaOH, potassium hydroxide, strontium hydroxide or its mixture.
2) in-situ deposition of alkaline-earth metal salt solution and supporting: the aluminium oxide after the modification of step 1) gained is added in Alkaline Earth Metal Acetate solution, flood 24～48h in shaking table, filtering drying; Wherein, Alkaline Earth Metal Acetate solution is calcium acetate, magnesium acetate, barium acetate or its mixture.
3) by step 2) products obtained therefrom calcines in Muffle furnace, and calcining heat is 500～700 ° of C, and the time is 6～10h, and heating rate is 1～5 ℃ of min
-1;
4) phenolphthalein test solution is splashed in step 3) products obtained therefrom, finally obtain pink acid gas absorbent.
embodiment 1
25 g NaOH are dissolved in 450 mL deionized waters, and stirring and dissolving, treats that temperature is down to room temperature and adds 450 g ball-aluminium oxides (granular size is 3～5mm, and specific surface is about 300 m
2g
-1), in shaking table, flooding 24h, after particle filtering, in 150 degree baking ovens, dry a few hours are standby.Aluminium oxide after above-mentioned NaOH modification is added in the calcium acetate aqueous solution of 2.5 mol/L (liquor capacity 500 mL), in shaking table, floods 48h, after particle filtering in 150 degree baking ovens dry 8h.Aluminium oxide after above-mentioned modification is calcined in Muffle furnace, and calcination condition is 1.5 ℃ of min
-1be warming up to 600 ° of C, and be incubated 10 h.
Phenolphthalein test solution is splashed in the sample after calcining and is dried in baking oven, obtain pink acid gas absorbent, sample has kept the intensity of original alumina particle.By ICP-OES, record Na in absorbent
2o content is 3.2wt%, and CaO is 10wt%, and this adsorbent can guarantee, in the situation that lower content moisture (<500 ppm) exists, sour gas is had to good assimilation effect.
embodiment 2(the maximum loading test of calcium oxide)
For the purifying of the both sexes gases such as phosphine, arsine, alkali metal oxide support be difficult for too high, therefore compared with high-adsorption-capacity, tested the maximum loading of calcium oxide for keeping.According to the method for embodiment 1, change calcium acetate salting liquid into saturated solution.After calcining, there is crystallization on products obtained therefrom surface, ICP-MS gained Na
2o content is 2wt%, and CaO is 13wt%.The enrichment of surface oxidation calcium easily produces solid particulate matter, pollute source of the gas, so preparation process should be noted activity component load quantity.
embodiment 3
Because calcium oxide is controlled by the content of water in gas to the assimilation effect of carbon dioxide, and NaOH has promoted the activity of calcium oxide to the strong absorption of water, therefore for the source of the gas that contains super low loading moisture (<5 ppm), NaOH ratio needs to increase.In the present embodiment, 80g NaOH is dissolved in 450 mL water, other remains unchanged, Na in products obtained therefrom
2o content is about 6wt%, and CaO is 8wt%, and the competitive Adsorption of NaOH has reduced the rate that supports of calcium oxide.This adsorbent is applicable to moisture lower than the adsorbing and removing of sour gas in 5ppm source of the gas.
comparative example 4
According to the method for embodiment 1, adopt the 5A molecular sieve of big or small 3-5 mm as carrier.25 g NaOH are dissolved in 450 mL deionized waters, stirring and dissolving, treats that temperature is down to room temperature and adds 450 g molecular sieve carriers, floods 24h in shaking table, after particle filtering, in 150 degree baking ovens, be dried a few hours and calcine in Muffle furnace, calcination condition is 1.5 ℃ of min
-1be warming up to 600 ° of C, insulation 10 h.Resulting materials is with after potentiometric titration, and without significant change, it is lower to sour gas adsorption capacity for Preliminary detection.
In preparation technology, adopting Woelm Alumina is carrier, by step load technique, preferentially NaOH or potassium hydroxide is supported in particle duct, floods subsequently the salting liquid of alkaline-earth metal, and then calcining, selectively floods phenolphthalein test solution as indicator.
In sum, the present invention adopts step load technique, with Woelm Alumina, makes carrier, the hydroxide of preferential carrying alkali metal, and drying and processing back loading alkaline-earth metal salt solution, optionally floods phenolphthalein test solution as indicator after calcining.This acid gas absorbent is optionally removed in inert gas, oxygen and common reducibility gas (hydrogen, CO or NO etc.), alkanes and hydride gas (as silane, ammonia, phosphine and arsine etc.), the carbon dioxide of existence, sulfur dioxide, hydrogen sulfide, hydrogen chloride and a small amount of water etc.This support type acid gas absorbent reactivity is high, intensity large, pulverization rate is extremely low, is conducive to the preparation of extra-high-speed pure gas, and meanwhile, the sample after phenolphthalein dipping has coloring function, and when product failure, absorbent color is become colorless by pink.
It is to be understood that: the above is only the preferred embodiment of the present invention; for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (7)
1. the preparation method of support type acid gas absorbent, is characterized in that comprising the following steps:
1) supporting of alkali metal hydroxide: ball-aluminium oxide carrier is added to the aqueous solution of alkali metal hydroxide, dipping, filtering drying;
2) in-situ deposition of alkaline-earth metal salt solution and supporting: the aluminium oxide after the modification of step 1) gained is added in Alkaline Earth Metal Acetate solution to dipping, filtering drying;
3) by step 2) products obtained therefrom calcines in Muffle furnace;
4) phenolphthalein test solution is splashed in step 3) products obtained therefrom, finally obtain pink acid gas absorbent.
2. the preparation method of support type acid gas absorbent according to claim 1, is characterized in that: step 1), and described ball-aluminium oxide is Woelm Alumina, and particle diameter is 3～8 mm, and specific area is 150～380 m
2g
-1, pore volume is 0.2～0.5 cm
3g
-1.
3. the preparation method of support type acid gas absorbent according to claim 2, is characterized in that: the particle diameter of described ball-aluminium oxide is 3～5 mm, and specific area is 250～350 m
2g
-1, pore volume is 0.3～0.45 cm
3g
-1.
4. the preparation method of support type acid gas absorbent according to claim 1, is characterized in that: step 1), described alkali metal hydroxide is lithium hydroxide, NaOH, potassium hydroxide, strontium hydroxide or its mixture.
5. the preparation method of support type acid gas absorbent according to claim 1, is characterized in that: step 2), described Alkaline Earth Metal Acetate solution is calcium acetate, magnesium acetate, barium acetate or its mixture.
6. the preparation method of support type acid gas absorbent according to claim 1, is characterized in that: step 1) and step 2) in impregnation technology in shaking table, carry out, dip time is 24～48h.
7. the preparation method of support type acid gas absorbent according to claim 1, is characterized in that: step 3), and in Muffle furnace, calcining heat is 500～700 ° of C, and the time is 6～10h, and heating rate is 1～5 ℃ of min
-1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310580186.8A CN103638895A (en) | 2013-11-19 | 2013-11-19 | Preparation method of supported acid gas absorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310580186.8A CN103638895A (en) | 2013-11-19 | 2013-11-19 | Preparation method of supported acid gas absorbent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103638895A true CN103638895A (en) | 2014-03-19 |
Family
ID=50244262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310580186.8A Pending CN103638895A (en) | 2013-11-19 | 2013-11-19 | Preparation method of supported acid gas absorbent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103638895A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113318698A (en) * | 2021-06-29 | 2021-08-31 | 西安热工研究院有限公司 | Alkali metal loaded ceramic catalytic filler and preparation method thereof |
| CN116159536A (en) * | 2023-04-25 | 2023-05-26 | 格林斯达(北京)环保科技股份有限公司 | Gas purifying material with indicating performance and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1081398A (en) * | 1992-07-20 | 1994-02-02 | 中国科学院上海冶金研究所 | Effective carbon-dioxide absorbent and preparation method thereof |
| CN1307929A (en) * | 2000-12-25 | 2001-08-15 | 化学工业部天津化工研究设计院 | Preparation process of alumina adsorbant |
| CN101659877A (en) * | 2008-08-29 | 2010-03-03 | 中国石油化工股份有限公司 | Absorbent of H2S contained in hydrocarbon gases and use thereof |
| CN102658023A (en) * | 2012-05-17 | 2012-09-12 | 东南大学 | Carbon dioxide solid absorbent capable of effectively inhibiting active components from losing effect |
| CN102784630A (en) * | 2012-07-25 | 2012-11-21 | 华中科技大学 | Preparation method for calcium-based CO2 sorbent |
-
2013
- 2013-11-19 CN CN201310580186.8A patent/CN103638895A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1081398A (en) * | 1992-07-20 | 1994-02-02 | 中国科学院上海冶金研究所 | Effective carbon-dioxide absorbent and preparation method thereof |
| CN1307929A (en) * | 2000-12-25 | 2001-08-15 | 化学工业部天津化工研究设计院 | Preparation process of alumina adsorbant |
| CN101659877A (en) * | 2008-08-29 | 2010-03-03 | 中国石油化工股份有限公司 | Absorbent of H2S contained in hydrocarbon gases and use thereof |
| CN102658023A (en) * | 2012-05-17 | 2012-09-12 | 东南大学 | Carbon dioxide solid absorbent capable of effectively inhibiting active components from losing effect |
| CN102784630A (en) * | 2012-07-25 | 2012-11-21 | 华中科技大学 | Preparation method for calcium-based CO2 sorbent |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113318698A (en) * | 2021-06-29 | 2021-08-31 | 西安热工研究院有限公司 | Alkali metal loaded ceramic catalytic filler and preparation method thereof |
| CN116159536A (en) * | 2023-04-25 | 2023-05-26 | 格林斯达(北京)环保科技股份有限公司 | Gas purifying material with indicating performance and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hu et al. | Synthesis of highly efficient, structurally improved Li4SiO4 sorbents for high-temperature CO2 capture | |
| Zhou et al. | Molten K2CO3-promoted high-performance Li4SiO4 sorbents at low CO2 concentrations | |
| CA3113375C (en) | Nitrogen oxide absorption slurry and its preparation and use method thereof | |
| WO2019042158A1 (en) | Calcium oxide-based high temperature co2 adsorbent, and preparation method therefor | |
| CN102019166A (en) | Method for preparing modified attapulgite clay adsorbing material | |
| US9108859B2 (en) | Engineered process of manufacturing calcium aluminate carbonates for medium-high temperature CO2 capture | |
| CN112619609B (en) | Adsorbent for synergistically removing sulfur and mercury and preparation method and application thereof | |
| CN103482624A (en) | Preparation method for active carbon with photocatalysis function | |
| TW201829049A (en) | Agent for removing halogen gas, method for producing same, method for removing halogen gas with use of same, and system for removing halogen gas | |
| KR20090033300A (en) | Alkali metal-based solid sorbent for carbon dioxide capture with low temperature regeneration | |
| CN107970877B (en) | Preparation method of modified porous alumina decarbonizer | |
| CN114100576B (en) | Cobalt disulfide/carbon composite material and preparation method and application thereof | |
| KR20130106989A (en) | Continuous oxygen separation method and apparatus using oxygen selective sorbent | |
| KR101502238B1 (en) | Carbon dioxide absorbent and carbon dioxide capture process thereof | |
| CN103638895A (en) | Preparation method of supported acid gas absorbent | |
| CN105903458A (en) | Preparation method and application of calcium-based adsorbent | |
| JP2008505750A (en) | Purification method of nitrogen trifluoride gas using zeolite ion exchanged with alkaline earth metal | |
| US6892473B1 (en) | Process for removing water from ammonia | |
| Yu et al. | Development of a novel Ca/Al carbonates for medium-high temperature CO2 capture | |
| Yanase et al. | CO2 capture and release of Na0. 7MnO2. 05 under water vapor at 25–150° C | |
| CN109482144A (en) | A kind of desulfurization removes the preparation method of carbon adsorbent | |
| KR100803325B1 (en) | Titanium dioxide added alkali-carbonate regenerable sorbent for carbon dioxide removal | |
| Lee et al. | Characteristics of new potassium-based sorbents prepared with nano-titanium oxide for carbon dioxide capture | |
| CN108654555A (en) | A kind of preparation method of the positive silicic acid lithium material of absorbing carbon dioxide at high temperature | |
| CN113318699A (en) | Method for reducing composite molten salt in adsorbent by adding high-activity ions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: QUANJIAO NANDA PHOTOELECTRIC MATERIAL CO., LTD. Free format text: FORMER OWNER: SUZHOU DANBAILI ELECTRONIC MATERIAL CO., LTD. Effective date: 20141209 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 215021 SUZHOU, JIANGSU PROVINCE TO: 239500 CHUZHOU, ANHUI PROVINCE |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20141209 Address after: 239500 Quanjiao, Anhui Province, the town of the town of Tan Tan Industrial Park, the ten Applicant after: QUANJIAO NANDA PHOTOELECTRIC MATERIAL CO., LTD. Address before: 215021 No. 40 Sheng Ping Road, Suzhou Park, Jiangsu, China Applicant before: SUZHOU DANBAILI ELECTRONIC MATERIAL CO., LTD. |
|
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140319 |