CN1332918C - Method for preparing ultra high-purity alcohol compound - Google Patents
Method for preparing ultra high-purity alcohol compound Download PDFInfo
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- CN1332918C CN1332918C CNB2006100351361A CN200610035136A CN1332918C CN 1332918 C CN1332918 C CN 1332918C CN B2006100351361 A CNB2006100351361 A CN B2006100351361A CN 200610035136 A CN200610035136 A CN 200610035136A CN 1332918 C CN1332918 C CN 1332918C
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Abstract
The present invention discloses a method for removing micro metallic cations and non-metallic anions from alcohol compounds by adsorption. In the method, active carbon for surface oxidation, which is treated by an oxidizing agent, is used as adsorbent; after an alcohol compound contacts the active carbon for surface oxidation for adsorption, an ultra-pure alcohol compound is obtained, and the alcohol compound is liquid at normal temperature and pressure. The method has the advantages of simple operation, and convenient, safe and clean preparation. Compared with the resin exchanging method, the present invention has equivalent treating effect, and has higher speed and efficiency of purification; the dried active carbon for surface oxidation can not bring water into the alcohol compound.
Description
Technical field
The present invention relates to a kind of method of purification of alcohol compound, especially remove the method for trace metal positively charged ion and metalloid anion in the alcohol compound with absorption method.
Background technology
High-purity alcohol compound is because miscible with water, and boiling point is low, and is volatile, is the extensive clean-out system that uses in the production processes such as unicircuit, wafer, printed circuit plate, precision components.High-purity alcohol compound mainly comprises low carbon chain alcohol such as methyl alcohol, ethanol and Virahol, and global annual requirement has few hundred thousand tonnes of, and also there is tens thousand of tons scale the domestic market.
The purification techniques commonly used of preparation ultra-clean and high pure chemical reagent mainly contains technology such as rectifying, distillation, sub-boiling distillation, isothermal distillation, underpressure distillation, low-temperature distillation, chemical treatment, resins exchange, film processing both at home and abroad at present.U.S. Patent Publication specification sheets US5585527 and US5571387 disclose fractionation and the isolating method of vapor permeable membrane in single container, can be used for separating alcohol for example Virahol and water.US5868906 has introduced a kind of multistage distillation tower that adopts and removed the method that moisture and boiling point are lower than any organic impurity of Virahol from contains the Virahol less than 2000ppm water.US5897750 discloses a kind of method of coming acetone, Virahol and water with extractive distillation.Chinese patent prospectus CN1417183 discloses a kind of ultrapure ethanol process for refining technology.The production equipment that this technological process mainly is made up of topping still, dealdehyder tower, treating tower, eparating methanol tower and recovery tower, realization is the ultrapure ethanol of raw material production with the raw materials for production liquid of the ethanol content 5-30% that biological process or chemical method are produced, and it mainly solves is aldehyde, ester and fusel wet goods problem in the fermenting alcohol.CN1600762 has introduced the method for the high purity methanol of rectification method preparation, and purpose is to be that the refining synthetic methanol of 95.50wt% is highly purified methyl alcohol with purity.Above-mentioned these patents mainly study to as if alcohol compound in the moisture isolation technique, and the separation method of zwitterion is not related to.
Chinese patent prospectus CN1431984 discloses the method that a kind of continuous rectification method is produced high-purity isopropanol.This method is included in from knockout tower and takes out high-purity isopropanol later on the step of high-purity isopropanol by ion exchange resin, and multistage distillation is combined with the anion-cation exchange resin treatment technology, can prepare the Virahol of positively charged ion in the ppb level.Simple multistage rectification method is restricted by capacity limit own, all has many difficulties in the high-purity alcohol compound process of preparation in equipment, technological design and production application, and also there is the too high problem of energy consumption in multistage distillation.With the problem of anion-cation exchange resin adsorption technology combination be that resin after the activated processing exists considerable moisture, alcohol compound can have been introduced high-load moisture after by ion exchange resin.For example adopt the product moisture content of dehydrated alcohol after the gel-type anion-cation exchange resin of drying is not handled of water content 0.05% to reach 5%, product moisture content after handling through 2 hours gel-type anion-cation exchange resin of 80 ℃ of oven dry reaches 2%, product after handling through 2 hours gel-type anion-cation exchange resin of 100 ℃ of oven dry still has 0.5% moisture, and drying along with resin, the exchange effect of resin can descend fast, and production efficiency is produced adverse influence.
Summary of the invention
The objective of the invention is to overcome the above-mentioned defective of multistage rectification and multistage distillation and resin method combined method, a kind of method for preparing ultra high-purity alcohol compound of not introducing moisture is provided.
For achieving the above object, the present invention adopts the surface oxidation gac of crossing through oxidizer treatment as sorbent material, with alcohol compound contact with the surface oxidation gac absorption after obtain ultra high-purity alcohol compound, described alcohol compound be normal temperature and pressure under for the liquid state alcohol compound.
A preferred version of aforesaid method is: alcohol compound is flowed through and is obtained ultra high-purity alcohol compound behind the one or more surface oxidation activated carbon column.
Another preferred version of aforesaid method is: described surface oxidation gac joins in the alcohol compound, stirs, and filters taking-up surface oxidation gac and obtains ultra high-purity alcohol compound.
Above-mentioned surface oxidation gac is in sour environment, and after under normal temperature or the heating condition gac being soaked oxygenant, washing to washings with pure water does not have acid ion, and drying is again 80～250 ℃ of oven dry activation down; Wherein, described oxygenant is: concentrated nitric acid, chromic salt, alcohol compound, peracid salt, hypochlorite, permanganate, the mixture of one or more in perchloric acid or its salt, chloric acid or its salt.
Above-mentioned oven dry activation temperature is preferably 120～200 ℃.
In above-mentioned first preferred version, alcohol compound flow through the surface oxidation activated carbon column flow velocity preferably 2～20ml/ minute/100 the gram gacs, be more preferably 5～10ml/ minute/100 the gram gacs.
In above-mentioned second preferred version, the weight ratio of surface oxidation gac and alcohol compound is preferably 1: 10～and 50.
Among the present invention, alcohol compound contacts absorption with the gac of surface oxidation temperature can preferably 10～75 ℃, be more preferably room temperature between 10～83 ℃.
Above-mentioned alcohol compound can be methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, the trimethyl carbinol, ethylene glycol or propylene glycol.
The gac of surface oxidation is the oxidation carbon-coating that forms one deck band portion negative charge at activated carbon surface, thereby possess absorption cationic ability, simultaneously because the carbonoxide top layer of surface oxidation gac is a covalent linkage, but not ionic linkage, its principle that removes ionic compound is not ion-exchange, wait charge layer but in adsorption process, form one,, also will wait the negatively charged ion of electric charge to remove in the lump in the cationic while of absorption at activated carbon surface:
In the formula: M
+=positively charged ion; X
-=negatively charged ion.So the gac that the present invention adopts surface oxidation can prepare the extremely low ultra high-purity alcohol compound of metal ion content easily as negatively charged ion in the adsorbents adsorb alcohol compound and positively charged ion.Use the sorbent material that lost efficacy in the back can adopt above-mentioned method for oxidation regeneration, reuse.
Present method is simple to operate, easy to prepare, safety, cleaning.Because the gac raw material is easy to get, cheap, chemical property is stable, and purge process is difficult for dissolved, swelling can tolerate differing temps in alcohol compound.Compare with exchange resin method, present method can be carried out under normal temperature or reflux temperature, treatment effect and exchange resin method are suitable, but because gac has higher specific surface, speed, the efficient of purifying are higher than exchange resin method, and dried surface oxidation gac can not introduced new moisture to alcohol compound yet.Owing to adopt magnesium oxide/absorbent charcoal one matter purifying alcohol compound, there is not multiple working procedure complicated in the exchange resin method, equipment combination and operating process are simple more and easy.
The index that high-purity alcohol compound that the present invention makes can reach is as follows:
1. colourity (Apha)≤10
2. pure content 〉=99.9%
3. residue on evaporation≤1.0ppm
4. muriate (Cl
-)≤50ppb
5. nitrate (NO
3 -)≤50ppb
6. phosphoric acid salt (PO
4 3-)≤50ppb
7. vitriol (SO
4 2-)≤50ppb
8. single positively charged ion≤1.0ppb
Embodiment 1
At diameter is that 50mm is about and adds 200 gram surface oxidation gacs in the adsorption column of 600mm, under room temperature (about 24 ℃), slowly add the industrial methanol of 5000mL distillation back content 99.9%, when liquid begins to flow out, collect effluent liquid, the control take-off rate is 5ml/ minute/100 gram gacs.When collection was finished, recirculation was adsorbed once, finally collects refined solution 4855mL, single treatment yield 97.10%.The index analysis result is as follows before and after handling:
| Chemical index | Before the processing | After the processing |
| Colourity (Apha) | - | ≤5 |
| Methyl alcohol | 99.91％ | 99.92％ |
| Moisture | 0.039％ | 0.031％ |
| Residue on evaporation | 25ppm | 0.09ppm |
| Muriate (Cl -) | 34ppm | 47ppb |
| Nitrate (NO 3 -) | 27ppm | 45ppb |
| Phosphoric acid salt (PO 4 3-) | 11ppm | 38ppb |
| Vitriol (SO 4 2-) | 18ppm | 36ppb |
| Sodium ion (Na +) | 0.3ppm | 0.93ppb |
| Potassium ion (K +) | 0.2ppm | 0.95ppb |
| Iron ion (Fe 3+) | 7ppm | 0.84ppb |
Embodiment 2
At diameter is that 50mm is about the gac that adds 200 gram surface oxidations in the adsorption column of 600mm, under room temperature (about 24 ℃), slowly add the industrial alcohol of 5000mL distillation back content more than 99.9%, when liquid begins to flow out, collect effluent liquid, the control take-off rate is 5ml/ minute/100 gram gacs.When collection was finished, recirculation was adsorbed once, finally collects refined solution 4862mL, single treatment yield 97.24%.The index analysis result is as follows before and after handling:
| Chemical index | Before the processing | After the processing |
| Colourity (Apha) | - | ≤5 |
| Ethanol | 99.91％ | 99.91％ |
| Moisture | 0.037％ | 0.035％ |
| Residue on evaporation | 35ppm | 0.08ppm |
| Muriate (Cl -) | 36ppm | 41ppb |
| Nitrate (NO 3 -) | 17ppm | 47ppb |
| Phosphoric acid salt (PO 4 3-) | 21ppm | 36ppb |
| Vitriol (SO 4 2-) | 38ppm | 37ppb |
| Sodium ion (Na +) | 0.2ppm | 0.94ppb |
| Potassium ion (k +) | 0.1ppm | 0.99ppb |
| Iron ion (Fe 3+) | 11ppm | 0.89ppb |
Embodiment 3
At diameter is that 50mm is about the gac that adds 200 gram surface oxidations in the adsorption column of 600mm, under room temperature (about 24 ℃), slowly add the industrial isopropanol of 5000mL distillation back content more than 99.9%, when liquid begins to flow out, collect effluent liquid, the control take-off rate is 5ml/ minute/100 gram gacs.When collection was finished, recirculation was adsorbed once, finally collects refined solution 4865mL, single treatment yield 97.30%.The index analysis result is as follows before and after handling:
| Chemical index | Before the processing | After the processing |
| Colourity (Apha) | - | ≤5 |
| Virahol | 99.94％ | 99.94％ |
| Moisture | 0.036％ | 0.033％ |
| Residue on evaporation | 26ppm | 0.09ppm |
| Muriate (Cl -) | 29ppm | 49ppb |
| Nitrate (NO 3 -) | 25ppm | 43ppb |
| Phosphoric acid salt (PO 4 3-) | 21ppm | 39ppb |
| Vitriol (SO 4 2-) | 13ppm | 33ppb |
| Sodium ion (Na +) | 0.4ppm | 0.92ppb |
| Potassium ion (K +) | 0.3ppm | 0.98ppb |
| Iron ion (Fe 3+) | 8ppm | 0.82ppb |
Claims (9)
1. the preparation method of a ultra high-purity alcohol compound is characterized in that, adopts the surface oxidation gac of crossing through oxidizer treatment as sorbent material, alcohol compound is contacted with the surface oxidation gac obtain ultra high-purity alcohol compound after adsorbing:
Described surface oxidation gac is in sour environment, after gac is immersed in aqueous oxidizing agent solution, washing to washings with pure water does not have acid ion, dry, again 80～250 ℃ of oven dry activation down, wherein, described oxygenant is: concentrated nitric acid, chromic salt, hydrogen peroxide, peracid salt, hypochlorite, permanganate, the mixture of one or more of perchloric acid or its salt, chloric acid or its salt;
Described alcohol compound is to be liquid alcohol compound under the normal temperature and pressure.
2. according to the preparation method of the described ultra high-purity alcohol compound of claim 1, it is characterized in that described alcohol compound is flowed through and obtained alcohol compound behind the one or more surface oxidation activated carbon column.
3. according to the preparation method of the described ultra high-purity alcohol compound of claim 1, it is characterized in that described surface oxidation gac joins in the alcohol compound, stir, filter taking-up surface oxidation gac and obtain ultra high-purity alcohol compound.
4. according to the preparation method of the described ultra high-purity alcohol compound of claim 1, it is characterized in that described oven dry activation temperature is 120～200 ℃.
5. according to the preparation method of the described ultra high-purity alcohol compound of claim 2, it is characterized in that the flow through flow velocity of surface oxidation activated carbon column of described alcohol compound is 2～20ml/ minute/100 gram gacs.
6. according to the preparation method of the described ultra high-purity alcohol compound of claim 5, it is characterized in that the flow through flow velocity of surface oxidation activated carbon column of described alcohol compound is 5～10ml/ minute/100 gram gacs.
7. according to the preparation method of the described ultra high-purity alcohol compound of claim 3, it is characterized in that the weight ratio of described surface oxidation gac and alcohol compound is 1: 10～50.
8. according to the preparation method of the described ultra high-purity alcohol compound of claim 1, it is characterized in that described alcohol compound contacts 10～83 ℃ of the temperature of absorption with the gac of surface oxidation.
9. according to the preparation method of the described ultra high-purity alcohol compound of claim 1, it is characterized in that described alcohol compound is methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, the trimethyl carbinol, ethylene glycol or propylene glycol.
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| CNB2006100351361A CN1332918C (en) | 2006-04-24 | 2006-04-24 | Method for preparing ultra high-purity alcohol compound |
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| CNB2006100351361A CN1332918C (en) | 2006-04-24 | 2006-04-24 | Method for preparing ultra high-purity alcohol compound |
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| CN1332918C true CN1332918C (en) | 2007-08-22 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060663A (en) * | 2009-11-18 | 2011-05-18 | 天津市康科德科技有限公司 | Method for preparing chromatographic pure isopropanol |
| CN102649710A (en) * | 2011-02-25 | 2012-08-29 | 苏州宝泽堂医药科技有限公司 | Preparation method for conduritol A |
| CN104744212B (en) * | 2013-12-31 | 2018-01-16 | 上海星可高纯溶剂有限公司 | The method of purification of solvent gradient methanol |
| CN104744213A (en) * | 2013-12-31 | 2015-07-01 | 上海星可高纯溶剂有限公司 | Method for purifying chromatographic grade isopropanol |
| CN105085179B (en) * | 2014-05-16 | 2018-01-16 | 上海星可高纯溶剂有限公司 | The method of purification of liquid chromatography mass combined instrument methanol |
| CN105085184B (en) * | 2014-05-16 | 2018-09-18 | 上海星可高纯溶剂有限公司 | The method of purification of liquid chromatograph-mass spectrometer isopropanol |
| CN105085178B (en) * | 2014-05-16 | 2018-03-06 | 上海星可高纯溶剂有限公司 | The method of purification of hplc grade methanol |
| CN105085180B (en) * | 2014-05-16 | 2018-04-24 | 上海星可高纯溶剂有限公司 | The method of purification of chromatographic grade ethanol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5868906A (en) * | 1995-05-15 | 1999-02-09 | Athens Corporation | Dehydration and purification of isopropyl alcohol to an ultradry and ultrapure level |
| CN1189436C (en) * | 2000-06-02 | 2005-02-16 | 埃克森美孚化学专利公司 | Process for producing ultra-high purity isopropanol |
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2006
- 2006-04-24 CN CNB2006100351361A patent/CN1332918C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5868906A (en) * | 1995-05-15 | 1999-02-09 | Athens Corporation | Dehydration and purification of isopropyl alcohol to an ultradry and ultrapure level |
| CN1189436C (en) * | 2000-06-02 | 2005-02-16 | 埃克森美孚化学专利公司 | Process for producing ultra-high purity isopropanol |
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Address after: Guangdong city of Shantou province Chaoshan Road West Long Street No. 1-3 zip code: 515064 Co-patentee after: Xilong Chemical Plant, Shantou City Patentee after: XILONG CHEMICAL Co.,Ltd. Address before: Guangdong city of Shantou province Chaoshan Road West Long Street No. 1-3 zip code: 515064 Co-patentee before: Xilong Chemical Plant, Shantou City Patentee before: Guangdong Xilong chemical Limited by Share Ltd. Address after: Guangdong city of Shantou province Chaoshan Road West Long Street No. 1-3 zip code: 515064 Co-patentee after: Xilong Chemical Plant, Shantou City Patentee after: Guangdong Xilong chemical Limited by Share Ltd. Address before: Guangdong city of Shantou province Chaoshan Road West Long Street 2 ZIP Code: 515000 Co-patentee before: Xilong Chemical Plant, Shantou City Patentee before: Guangdong Xilong Chemical Co.,Ltd. |
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Effective date of registration: 20091113 Address after: Guangdong city of Shantou province Chaoshan Road West Long Street No. 1-3 zip code: 515064 Patentee after: XILONG CHEMICAL Co.,Ltd. Address before: Guangdong city of Shantou province Chaoshan Road West Long Street No. 1-3 zip code: 515064 Co-patentee before: Xilong Chemical Plant, Shantou City Patentee before: XILONG CHEMICAL Co.,Ltd. |
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Effective date of registration: 20151225 Address after: 528100 Guangdong Province, Foshan City Sanshui Industrial Park District Tang Hing Road No. 29 Patentee after: FOSHAN XILONG CHEMICAL CO.,LTD. Address before: 515064 Guangdong city of Shantou province Chaoshan Road West Long Street No. 1-3 Patentee before: XILONG CHEMICAL Co.,Ltd. |