CN106748652B - Method for removing trace metal impurities in industrial-grade isopropanol - Google Patents
Method for removing trace metal impurities in industrial-grade isopropanol Download PDFInfo
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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Abstract
The invention discloses a method for removing trace metal impurities in industrial-grade isopropanol, and aims to provide a method for removing trace metal impurities, which has the advantages of low removal cost, simple operation and easy control of metal impurity ions; the method comprises the steps of adopting natural fibers subjected to chemical modification treatment as an adsorbent for trace metal ions in isopropanol, and then carrying out ion exchange on feed liquid through a cation exchange column under the pressure of 0.2-1.0Mpa and the flow rate of 60-150l/h to obtain the isopropanol with the content of metal impurity ions being less than 0.1 ppb; belongs to the technical field of organic reagent purification.
Description
Technical Field
The invention relates to a method for removing trace metal impurities in industrial-grade isopropanol, in particular to control of metal ions in electronic-grade isopropanol, and belongs to the technical field of organic reagent purification.
Background
In modern society, with the rapid development of large-scale integrated circuits, higher and higher requirements are also put on various base materials, wherein the purity of chemical reagents directly affects the quality and yield of integrated circuits. The ultra-clean high-purity reagent is mainly used for cleaning and etching the surfaces of chips and silicon wafers, and the purity and cleanliness of the ultra-clean high-purity reagent have great influence on the yield, electrical property and reliability of integrated circuits. Ultra-clean high-purity isopropyl alcohol has been widely used in cleaning, drying, etc. of semiconductor and large-scale integrated circuit processing as an important microelectronic chemical. In the semiconductor industry, the size of semiconductor devices is continuously reduced, the density of elements in chips is continuously increased, the distance between elements is smaller and smaller, even to the nanometer level, and a very small amount of micro-trace impurities in the production process can cause specific defects of the semiconductor devices, thereby affecting the qualification rate of the chips. Accordingly, the International society for Semiconductor Equipment and Materials (SEMI) has established international standards for the specification of ultra-clean, high purity reagents in which the electronic grade isopropanol contains less than 0.1ppb of metal ions.
Chinese patent CN 103613486A discloses a preparation method of ultrapure isopropanol, wherein the removal of metal impurity ions is realized by adding a metal ion complexing agent, namely ethylene diamine tetraacetic acid disodium salt to form a chelate with charges, separating and removing anions and cations with charges through an electrophoresis tank, and then removing the metal impurity ions in the isopropanol through cation exchange resin exchange. The method has the disadvantages of complicated operation, high equipment requirement and incapability of stably controlling the product quality.
Chinese patent CN100398502C also discloses a method for preparing ultrapure isopropanol, wherein the removal of metal impurity ions is realized by multi-stage continuous rectification and distillation. However, the method for removing impurities has high cost and is not beneficial to industrial production.
Disclosure of Invention
The invention aims to provide a method for removing metal impurity ions in industrial-grade isopropanol by combining a modified cellulose adsorbent with cation exchange resin, so as to solve the problems of high cost, complex operation and difficult control of the metal impurity ions in the prior art.
The purpose of the invention is realized by the following technical scheme:
a method for removing trace metal impurities in industrial-grade isopropanol sequentially comprises the following steps:
1) adding 0.001-0.004 g of modified cellulose into each liter of industrial grade isopropanol, and uniformly mixing to obtain a pretreatment feed liquid;
2) under the pressure of 0.2-1.0Mpa and the flow rate of 60-150l/h, the pretreated material liquid in the step 1) is subjected to ion exchange by cation exchange resin, and the isopropanol with the metal impurity ion content less than 0.1ppb is obtained.
Further, in the method for removing trace metal impurities from industrial grade isopropanol, the modified cellulose is one of sulfonic styrene fiber, carboxyl styrene fiber and phosphoric styrene fiber in sulfonic polyethylene fiber, carboxyl polyethylene fiber and phosphoric polyethylene fiber.
Furthermore, in the method for removing the trace metal impurities in the industrial grade isopropanol, the cation exchange resin in the cation exchange column is strong-acid large-aperture sulfonic polystyrene cation exchange resin.
Furthermore, in the method for removing the trace metal impurities in the industrial grade isopropanol, the diameter of the modified cellulose adsorbent is 0.25-1.00 mu m, and the specific surface area is 100-500 m2/g。
Therefore, the modified cellulose is used as the adsorbent to adsorb the metal ions in the mixed isopropanol, so that the electronic chemicals with extremely low metal ion content can be obtained, and the spent adsorbent can be regenerated for reuse after use.
Compared with the prior art, the invention has the advantages that:
1. the metal cations in the mixed isopropanol are adsorbed by the modified cellulose adsorbent, and then the content of impurity metal ions can be further reduced after the feed liquid is subjected to exchange separation by cation exchange resin, so that the content of the impurity metal ions in the obtained product can be controlled below 0.1 ppb.
2. The product obtained by the method has low content of impurity metal ions, simple operation and stable quality, meets the requirements of SEMIC12 standard, and is suitable for industrial mass production.
Detailed Description
The invention is further illustrated by the following specific examples, which do not limit the scope of the invention.
It should be noted that the raw materials used in the technical scheme provided by the present invention, except for the specific description, are prepared by conventional means or purchased through commercial channels.
Example 1
0.1g of sulfonated polyethylene fiber was added to 100L of technical grade isopropanol at normal temperature and pressure. Mixing in a mixing processor, flowing the mixed isopropanol solution through a cation exchange column filled with strongly acidic D002 large-aperture sulfonic polystyrene resin under the pressure of 0.2Mpa, controlling the flow rate at 60L/h, collecting a sample by using a sample bottle, and finally respectively measuring the content of metal ions in the sample by adopting a standard mode and a cold flame mode of an inductively coupled plasma mass spectrometer, wherein the obtained results are shown in the table I.
Example 2
0.2g of sulfonated polyethylene fiber was added to 150L of technical grade isopropanol at normal temperature and pressure. Mixing in a mixing processor, flowing the mixed isopropanol solution through a cation exchange column filled with strongly acidic D002 large-aperture sulfonic polystyrene resin under the pressure of 0.3Mpa, controlling the flow rate at 80L/h, collecting a sample by using a sample bottle, and finally respectively measuring the content of metal ions in the sample by adopting a standard mode and a cold flame mode of an inductively coupled plasma mass spectrometer, wherein the obtained results are shown in the table I.
Example 3
0.5g of sulfonated polyethylene fiber was added to 300L of technical grade isopropanol at normal temperature and pressure. Mixing in a mixing processor, flowing the mixed isopropanol solution through a cation exchange column filled with strongly acidic D002 large-aperture sulfonic polystyrene resin under the pressure of 0.5Mpa, controlling the flow rate at 100L/h, collecting a sample by using a sample bottle, and finally respectively measuring the content of metal ions in the sample by adopting a standard mode and a cold flame mode of an inductively coupled plasma mass spectrometer, wherein the obtained results are shown in the table I.
Example 4
0.8g of sulfonated polyethylene fiber was added to 450L of technical grade isopropanol at room temperature and pressure. Mixing in a mixing processor, flowing the mixed isopropanol solution through a cation exchange column filled with strongly acidic D002 large-aperture sulfonic polystyrene resin under the pressure of 0.8Mpa, controlling the flow rate at 120L/h, collecting a sample by using a sample bottle, and finally respectively measuring the content of metal ions in the sample by adopting a standard mode and a cold flame mode of an inductively coupled plasma mass spectrometer, wherein the obtained results are shown in the table I.
Example 5
1.00g of sulfonated polyethylene fiber was added to 500L of technical grade isopropanol at normal temperature and pressure. Mixing in a mixing processor, flowing the mixed isopropanol solution through a cation exchange column filled with strongly acidic D002 large-aperture sulfonic polystyrene resin under the pressure of 1.0Mpa, controlling the flow rate at 150L/h, collecting a sample by using a sample bottle, and finally respectively measuring the content of metal ions in the sample by adopting a standard mode and a cold flame mode of an inductively coupled plasma mass spectrometer, wherein the obtained results are shown in the table I.
Example 6
0.5g of sulfostyrene fiber was added to 300L of technical grade isopropanol at ambient temperature and pressure. Mixing in a mixing processor, flowing the mixed isopropanol solution through a cation exchange column filled with strongly acidic D002 large-aperture sulfonic polystyrene resin under the pressure of 0.5Mpa, controlling the flow rate at 100L/h, collecting a sample by using a sample bottle, and finally respectively measuring the content of metal ions in the sample by adopting a standard mode and a cold flame mode of an inductively coupled plasma mass spectrometer, wherein the obtained results are shown in the table I.
Example 7
0.8g of sulfostyrene fiber was added to 450L of technical grade isopropanol at ambient temperature and pressure. Mixing in a mixing processor, flowing the mixed isopropanol solution through a cation exchange column filled with strongly acidic D002 large-aperture sulfonic polystyrene resin under the pressure of 0.8Mpa, controlling the flow rate at 120L/h, collecting a sample by using a sample bottle, and finally respectively measuring the content of metal ions in the sample by adopting a standard mode and a cold flame mode of an inductively coupled plasma mass spectrometer, wherein the obtained results are shown in the table I.
Example 8
1.00g of sulfostyrene fiber was added to 500L of technical grade isopropanol at normal temperature and pressure. Mixing in a mixing processor, flowing the mixed isopropanol solution through a cation exchange column filled with strongly acidic D002 large-aperture sulfonic polystyrene resin under the pressure of 1.0Mpa, controlling the flow rate at 150L/h, collecting a sample by using a sample bottle, and finally respectively measuring the content of metal ions in the sample by adopting a standard mode and a cold flame mode of an inductively coupled plasma mass spectrometer, wherein the obtained results are shown in the table I.
TABLE 1 high purity isopropyl alcohol metal ion
| Item | Unit of | SEMI C12 Standard | Example 1 | Example 2 | Example 3 | Example 4 |
| Aluminum (Al) | PPb | ﹤0.1 | 0.07 | 0.08 | 0.08 | 0.02 |
| Arsenic (As) | PPb | ﹤0.1 | 0.06 | 0.09 | 0.05 | 0.03 |
| Barium (Ba) | PPb | ﹤0.1 | 0.08 | 0.06 | 0.09 | 0.02 |
| Boron (B) | PPb | ﹤0.1 | 0.05 | 0.05 | 0.04 | 0.02 |
| Calcium (Ca) | PPb | ﹤0.1 | 0.03 | 0.10 | 0.08 | 0.01 |
| Copper (Cu) | PPb | ﹤0.1 | 0.05 | 0.05 | 0.10 | 0.03 |
| Iron (Fe) | PPb | ﹤0.1 | 0.02 | 0.03 | 0.08 | 0.02 |
| Lead (Pb) | PPb | ﹤0.1 | 0.06 | 0.08 | 0.07 | 0.03 |
| Magnesium (Mg) | PPb | ﹤0.1 | 0.06 | 0.07 | 0.09 | 0.04 |
| Manganese (Mn) | PPb | ﹤0.1 | Not detected out | Not detected out | Not detected out | Not detected out |
| Nickel (Ni) | PPb | ﹤0.1 | Not detected out | Not detected out | Not detected out | Not detected out |
| Potassium (K) | PPb | ﹤0.1 | 0.08 | 0.07 | 0.08 | 0.05 |
| Sodium (Na) | PPb | ﹤0.1 | 0.06 | 0.06 | 0.08 | 0.03 |
| Tin (Sn) | PPb | ﹤0.1 | Not detected out | Not detected out | Not detected out | Not detected out |
| Titanium (Ti) | PPb | ﹤0.1 | Not detected out | Not detected out | Not detected out | Not detected out |
| Zinc (Zn) | PPb | ﹤0.1 | 0.05 | 0.07 | 0.06 | 0.03 |
TABLE 1 continuation of the table for highly pure isopropanol metal ions
| Item | Unit of | SEMI C12 Standard | Example 5 | Example 6 | Example 7 | Example 8 |
| Aluminum (Al) | PPb | ﹤0.1 | 0.01 | 0.03 | 0.04 | 0.02 |
| Arsenic (As) | PPb | ﹤0.1 | 0.01 | 0.09 | 0.05 | 0.03 |
| Barium (Ba) | PPb | ﹤0.1 | 0.01 | 0.03 | 0.07 | 0.02 |
| Boron (B) | PPb | ﹤0.1 | 0.01 | 0.05 | 0.04 | 0.02 |
| Calcium (Ca) | PPb | ﹤0.1 | 0.02 | 0.05 | 0.08 | 0.01 |
| Copper (Cu) | PPb | ﹤0.1 | 0.01 | 0.05 | 0.02 | 0.03 |
| Iron (Fe) | PPb | ﹤0.1 | 0.01 | 0.10 | 0.03 | 0.02 |
| Lead (Pb) | PPb | ﹤0.1 | 0.01 | 0.05 | 0.07 | 0.03 |
| Magnesium (Mg) | PPb | ﹤0.1 | 0.02 | 0.07 | 0.04 | 0.04 |
| Manganese (Mn) | PPb | ﹤0.1 | Not detected out | Not detected out | Not detected out | Not detected out |
| Nickel (Ni) | PPb | ﹤0.1 | Not detected out | Not detected out | Not detected out | Not detected out |
| Potassium (K) | PPb | ﹤0.1 | 0.02 | 0.01 | 0.02 | 0.05 |
| Sodium (Na) | PPb | ﹤0.1 | 0.05 | 0.09 | 0.08 | 0.03 |
| Tin (Sn) | PPb | ﹤0.1 | Not detected out | Not detected out | Not detected out | Not detected out |
| Titanium (Ti) | PPb | ﹤0.1 | Not detected out | Not detected out | Not detected out | Not detected out |
| Zinc (Zn) | PPb | ﹤0.1 | 0.02 | 0.07 | 0.06 | 0.03 |
Claims (2)
1. A method for removing trace metal impurities in industrial-grade isopropanol is characterized by sequentially comprising the following steps:
1) adding 0.001-0.004 g of sulfonic polyethylene fiber into each liter of industrial grade isopropanol, and uniformly mixing to obtain pretreatment feed liquid;
2) under the pressure of 0.2-1.0Mpa and the flow rate of 60-150l/h, the pretreated material liquid in the step 1) is subjected to ion exchange by D002 large-aperture sulfonic polystyrene resin to obtain isopropanol with the content of metal impurity ions less than 0.1 ppb.
2. The method for removing trace metal impurities from technical grade isopropanol as claimed in claim 1, wherein: the sulfonic polyethylene fiber has a diameter of 0.25-1.00 μm and a specific surface area of 100-500 m2/g。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1431984A (en) * | 2000-06-02 | 2003-07-23 | 埃克森美孚化学专利公司 | Process for producing ultra-high purity isopropanol |
| CN102452897A (en) * | 2010-12-06 | 2012-05-16 | 江苏达诺尔半导体超纯科技有限公司 | Production process of ultra-high-purity isopropanol |
| CN102898275A (en) * | 2012-11-05 | 2013-01-30 | 苏州晶瑞化学有限公司 | Preparation method for high-purity isopropyl alcohol |
| CN103613486A (en) * | 2013-12-02 | 2014-03-05 | 上海化学试剂研究所有限公司 | Preparation method of ultrapure isopropanol |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1431984A (en) * | 2000-06-02 | 2003-07-23 | 埃克森美孚化学专利公司 | Process for producing ultra-high purity isopropanol |
| CN102452897A (en) * | 2010-12-06 | 2012-05-16 | 江苏达诺尔半导体超纯科技有限公司 | Production process of ultra-high-purity isopropanol |
| CN102898275A (en) * | 2012-11-05 | 2013-01-30 | 苏州晶瑞化学有限公司 | Preparation method for high-purity isopropyl alcohol |
| CN103613486A (en) * | 2013-12-02 | 2014-03-05 | 上海化学试剂研究所有限公司 | Preparation method of ultrapure isopropanol |
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