High-purity electronic-grade short-carbon-chain sugar alcohol as well as purification method and application thereof

Abstract

The invention provides high-purity electronic-grade short-carbon-chain sugar alcohol as well as a purification method and application thereof, and the purification method of the high-purity electronic-grade short-carbon-chain sugar alcohol comprises the following steps: dissolving an industrial-grade short-carbon-chain sugar alcohol solid raw material to obtain an industrial-grade short-carbon-chain sugar alcohol solution, carrying out multi-stage filtration on the industrial-grade short-carbon-chain sugar alcohol solution to remove particles, and drying to obtain the high-purity electronic-grade short-carbon-chain sugar alcohol. Reserving the filtrate; under the condition of 10-40 DEG C, the filtrate is purified through composite exchange resin, metal ions are removed, and an electronic-grade short-carbon-chain sugar alcohol solution is obtained; and drying the electronic-grade short-carbon-chain sugar alcohol solution to obtain the high-purity electronic-grade short-carbon-chain sugar alcohol. The high-purity electronic-grade short-carbon-chain sugar alcohol prepared by the method has the advantages of high purity and low metal ion impurity content, reduces or avoids the influence of metal ion impurities on materials or devices, and can meet the requirements of semiconductor technology, aerospace and photoelectric industry.

Description

Technical Field

[0001] The present invention relates to a purification technology for sugar alcohol substances, and in particular to a high-purity electronic-grade short-chain sugar alcohol, a purification method and application thereof. Background Art

[0002] In the field of semiconductor technology, wet chemicals are key liquid chemicals used in processes such as cleaning, etching, and polishing during the manufacturing process. They have a direct impact on device performance, yield, and reliability, and therefore play a vital role in semiconductor manufacturing. With the rapid development of the semiconductor industry, the market size and technical level of wet chemicals are also constantly improving.

[0003] Sugar alcohols, due to their unique chemical properties, such as hygroscopicity, chelation, and stability, are widely used in wet electronic chemicals. They are primarily used as corrosion inhibitors, chelating agents, wetting agents, and stabilizers. Their environmental and safety characteristics further consolidate their important position in wet electronic chemicals.

[0004] Integrated circuit processing technology places increasingly higher demands on the cleanliness of wet electronic chemicals. Metal ion impurities can severely damage the electrical properties, device reliability, and manufacturing yield of semiconductor materials. Therefore, control of metal ion impurities during semiconductor manufacturing is extremely stringent, typically requiring levels of ppt (parts per trillion). As semiconductor process nodes continue to shrink (e.g., from 28nm to 5nm or even lower), the impact of metal ion impurities becomes increasingly significant. Currently, the metal ion impurity content of industrial-grade and food-grade short-chain sugar alcohols sold on the market is typically at the ppm (parts per million) level, far below the standards for electronic-grade raw materials and unable to meet the requirements of semiconductor processing.

[0005] Therefore, there is an urgent need for a method for obtaining high-purity electronic-grade short-chain sugar alcohols by purification and impurity removal to meet the needs of the semiconductor technology field. Summary of the Invention

[0006] The purpose of the present invention is to provide a method for purifying high-purity electronic-grade short-chain sugar alcohols, addressing the problem that industrial-grade and food-grade short-chain sugar alcohols have high metal ion impurity contents, fail to meet electronic-grade raw material standards, and are unable to satisfy semiconductor process requirements. The high-purity electronic-grade short-chain sugar alcohols prepared by the method have the advantages of high purity and low metal ion impurity content, reduce or avoid the influence of metal ion impurities on materials or devices, and can meet the requirements of semiconductor technology, aerospace, and optoelectronic industries.

[0007] It should be noted that, in the present invention, unless otherwise specified, the specific meaning of "including" in relation to composition limitations and descriptions includes both open-ended "including", "comprising", etc. and similar meanings, as well as closed-ended "composed of", "composed of", etc. and similar meanings.

[0008] To achieve the above object, the technical solution adopted by the present invention is: a method for purifying high-purity electronic-grade short-chain sugar alcohols, comprising the following steps:

[0009] Step 1: adding an industrial-grade short-chain sugar alcohol solid raw material to a solvent to dissolve it to obtain an industrial-grade short-chain sugar alcohol solution, filtering the industrial-grade short-chain sugar alcohol solution through multiple stages, and retaining the filtrate;

[0010] Step 2: Purify the filtrate through a composite exchange resin at 10-40° C. to remove metal ions and obtain an electronic-grade short-chain sugar alcohol solution;

[0011] Step 3: Drying the electronic-grade short-chain sugar alcohol solution to obtain high-purity electronic-grade short-chain sugar alcohol.

[0012] Furthermore, the content of short-chain sugar alcohol in the industrial-grade short-chain sugar alcohol solid raw material is greater than or equal to 95 wt %, and the content of metal ion impurities is below 10 ppm.

[0013] Furthermore, the industrial-grade short-chain sugar alcohol solid raw material has a short-chain sugar alcohol content of 95-98 wt %, and a metal ion impurity content of 1-10 ppm.

[0014] Furthermore, the short-chain sugar alcohol is a sugar alcohol substance with a carbon chain of less than or equal to 6.

[0015] Furthermore, the short-chain sugar alcohol is a tetra-carbon sugar alcohol, a pentose sugar alcohol or a hexose sugar alcohol.

[0016] Furthermore, the tetrasugar alcohol is erythritol or threitol.

[0017] Furthermore, the pentose alcohol is any one of xylitol, arabitol, and ribitol.

[0018] Furthermore, the hexose alcohol is any one of sorbitol, mannitol, galactitol, and iditol.

[0019] Furthermore, the dissolving temperature in step 1 is 50-85°C.

[0020] Furthermore, the solvent in step 1 is ultrapure water.

[0021] Furthermore, the mass ratio of the industrial-grade short-chain sugar alcohol solid raw material to the solvent in step 1 is 10-50:100.

[0022] Furthermore, the multi-stage filtration in step 1 removes particles with a particle size of 10 nm-0.5 μm.

[0023] Furthermore, the multi-stage filtration in step 1 is three-stage filtration.

[0024] Furthermore, in the three-stage filtration, the filtration accuracy of the first-stage filtration is 0.5-1 μm, the filtration accuracy of the second-stage filtration is 0.1-0.3 μm, and the filtration accuracy of the third-stage filtration is 10-30 nm.

[0025] Furthermore, the filtrate in step 2 is passed through the composite exchange resin at a speed of 1-20 BV / h.

[0026] Furthermore, the metal ions in step 2 are one or more of sodium ions, magnesium ions, aluminum ions, potassium ions, calcium ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions, copper ions, zinc ions and lead ions.

[0027] Furthermore, the composite exchange resin in step 2 is formed by mixing a cation exchange resin and an additive.

[0028] Furthermore, the composite exchange resin in step 2 is prepared by the following method:

[0029] S1. Pretreatment of cation exchange resin: Activate the cation exchange resin with hydrochloric acid, then rinse with pure water until the pH of the inlet and outlet water reaches 6-7;

[0030] S2. Evenly mix the cation exchange resin treated in S1 with the additive at 30-60° C., and then fill the ion exchange column with the cation exchange resin to obtain a composite exchange resin.

[0031] Furthermore, the mass concentration of the hydrochloric acid is 3-15%.

[0032] Furthermore, the mass concentration of the hydrochloric acid is preferably 7%.

[0033] Furthermore, the volume ratio of the hydrochloric acid to the cation exchange resin is 1:1-5:1.

[0034] Furthermore, the volume ratio of the hydrochloric acid to the cation exchange resin is preferably 1:1.

[0035] Furthermore, the volume ratio of the additive to the cation exchange resin is 1:10-1:100.

[0036] Furthermore, the volume ratio of the additive to the cation exchange resin is preferably 1:50.

[0037] Furthermore, the additive is one or more of 2-mercapto-3-pyridinecarboxylic acid, 6-mercaptopyridine-3-carboxylic acid and D-cysteine.

[0038] Furthermore, the additive is preferably 2-mercapto-3-pyridinecarboxylic acid.

[0039] Furthermore, the cation exchange resin is a styrene resin containing a sulfonic acid functional group.

[0040] Furthermore, the cation exchange resin is a polystyrene-divinylbenzene cross-linked resin with sulfonic acid groups.

[0041] Furthermore, the cation exchange resin can be commercially available, such as one or more of C100 resin, C120 resin, C150 resin, cation exchange resin 001×7, cation exchange resin 001×8 cation exchange resin and D001 resin.

[0042] Furthermore, the cation exchange resin is preferably D001 resin.

[0043] Furthermore, the amount of cation exchange resin filled in S2 is 1 / 3-2 / 3 of the volume of the ion exchange column, which can be 1 / 3, 1 / 2 or 2 / 3.

[0044] Furthermore, S2 mixes the cation exchange resin treated by S1 and the additives at 50°C.

[0045] Furthermore, the drying temperature in step 3 is 60-100° C., and the drying time is 1-3 hours.

[0046] Furthermore, the drying temperature in step 3 is preferably 90°C.

[0047] Furthermore, the drying time in step 3 is preferably 2 hours.

[0048] Another object of the present invention is to disclose a high-purity electronic-grade short-chain sugar alcohol purified by the above purification method, wherein the purity of the high-purity electronic-grade short-chain sugar alcohol is greater than or equal to 99wt% and the (total) metal ion impurity content is less than 100ppb.

[0049] Another object of the present invention is to disclose the application of a high-purity electronic-grade short-chain sugar alcohol in the field of wet electronic chemicals, especially in the fields of corrosion inhibitors, chelating agents, wetting agents and stabilizers.

[0050] The high-purity electronic-grade short-chain sugar alcohol of the present invention, its purification method and application have the following advantages compared with the prior art:

[0051] 1) The present invention mixes additives into the cation exchange resin. The carboxyl and thiol groups in the additives have the ability to chelate metal ions. They can combine with high-valent metal ion impurities that cannot be effectively removed by the ion exchange resin to form stable water-soluble chelates, which facilitates the effective removal of metal ion impurities in the solution. At the same time, since the short-chain sugar alcohol aqueous solution has a certain viscosity, it will significantly reduce the flow rate of the solution in the ion adsorption column, affecting the purification efficiency. The present invention selects a combination of additives containing hydrophilic groups and cation exchange resins, which can significantly reduce the surface tension of the short-chain sugar alcohol aqueous solution, improve wettability and permeability, increase the specific surface area of ​​the short-chain sugar alcohol aqueous solution in contact with the composite exchange resin, improve the ion exchange ability of the composite exchange resin, and reduce the effect of the viscosity of the short-chain sugar alcohol aqueous solution on the flow rate.

[0052] 2) The present invention reduces particles larger than 10 nm through multi-stage filtration, and the obtained high-purity electronic-grade short-chain sugar alcohol can meet the requirements of semiconductor cleaning processes.

[0053] The high-purity electronic-grade short-chain sugar alcohol of the present invention has good application prospects and large-scale promotion potential in the field of wet electronic chemicals. DETAILED DESCRIPTION

[0054] The present invention will be further described below with reference to the following examples. The following description of the technical features is based on representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:

[0055] Unless otherwise stated, the units used in this specification are international standard units, and the numerical values ​​and numerical ranges appearing in the present invention should be understood to include the inevitable systematic errors in industrial production.

[0056] In this specification, the numerical range expressed using "a numerical value A to a numerical value B" means a range including the endpoints A and B.

[0057] In this specification, the numerical range expressed using "above" or "below" means a numerical range including the number.

[0058] In this specification, the use of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.

[0059] In this specification, the use of "optional" or "optional" indicates that certain substances, components, execution steps, application conditions and other factors are used or not used.

[0060] In this specification, when "normal temperature" or "room temperature" is used, the temperature may be 15-25°C.

[0061] In this manual, the reagents or instruments used without indicating the manufacturer are all conventional products that can be obtained through commercial purchase.

[0062] Example 1

[0063] This embodiment discloses a method for purifying high-purity electronic-grade mannitol, comprising the following steps:

[0064] Step 1: dissolving 40 parts by mass of industrial-grade mannitol raw material (the purity of the raw material is 97.55%) in 100 parts by mass of ultrapure water to obtain an industrial-grade mannitol solution, and passing the industrial-grade mannitol solution sequentially through: a microfiltration membrane made of polypropylene (PP) with a pore size of 0.5 μm for primary filtration to remove large suspended particles, colloids and microorganisms, and protect subsequent precision filter elements; a polyvinylidene fluoride (PVDF) ultrafiltration membrane with a pore size of 0.1 μm for secondary filtration to remove nano-particles, colloids and macromolecular organic matter; a polytetrafluoroethylene (PTFE) folded membrane with a pore size of 10 nm for tertiary filtration to ensure that most particles larger than 10 nm are effectively removed and the filtrate is retained;

[0065] Step 2: Purify the filtrate obtained in step 1 at a rate of 5 BV / h through composite exchange resin 1 at 25° C. to remove metal ions and obtain an electronic grade mannitol solution;

[0066] Step 3: Dry the electronic-grade mannitol solution at 90° C. for 2 h to obtain high-purity electronic-grade mannitol.

[0067] Example 2

[0068] This embodiment discloses a method for purifying high-purity electronic-grade galactitol, comprising the following steps:

[0069] Step 1: dissolving 10 parts by mass of industrial-grade galactitol raw material (the purity of the raw material is 95.92%) in 100 parts by mass of ultrapure water to obtain an industrial-grade galactitol solution, and passing the industrial-grade galactitol solution sequentially through: a microfiltration membrane made of polypropylene (PP) with a pore size of 0.5 μm for primary filtration to remove large suspended particles, colloids and microorganisms, and protect subsequent precision filter elements; a polyvinylidene fluoride (PVDF) ultrafiltration membrane with a pore size of 0.1 μm for secondary filtration to remove nano-particles, colloids and macromolecular organic matter; and a polytetrafluoroethylene (PTFE) folded membrane with a pore size of 10 nm for tertiary filtration to ensure that most particles larger than 10 nm are effectively removed and the filtrate is retained;

[0070] Step 2: Purify the filtrate obtained in step 1 by passing it through composite exchange resin 2 at a flow rate of 5 BV / h at 25° C. to remove metal ions and obtain an electronic grade galactitol solution;

[0071] Step 3: Dry the electronic-grade galactitol solution at 90° C. for 2 h to obtain high-purity electronic-grade galactitol.

[0072] Example 3

[0073] This embodiment discloses a method for purifying high-purity electronic-grade iditol, comprising the following steps:

[0074] Step 1: Dissolve 50 parts by mass of industrial-grade iditol raw material (the purity of the raw material is 96.48%) in 100 parts by mass of ultrapure water to obtain an industrial-grade iditol solution, and pass the industrial-grade iditol solution through: a microfiltration membrane made of polypropylene (PP) with a pore size of 0.5 μm for primary filtration to remove large suspended particles, colloids and microorganisms, and protect subsequent precision filter elements; a polyvinylidene fluoride (PVDF) ultrafiltration membrane with a pore size of 0.1 μm for secondary filtration to remove nanoparticles, colloids and macromolecular organic matter; and a polytetrafluoroethylene (PTFE) folded membrane with a pore size of 10 nm for tertiary filtration to ensure that most particles larger than 10 nm are effectively removed and the filtrate is retained;

[0075] Step 2: Purify the filtrate obtained in step 1 through composite exchange resin 3 at a flow rate of 5 BV / h at 25° C. to remove metal ions and obtain an electronic grade iditol solution;

[0076] Step 3: Dry the electronic grade iditol solution at 90° C. for 2 h to obtain high-purity electronic grade iditol.

[0077] Example 4

[0078] This embodiment discloses a method for purifying high-purity electronic-grade sorbitol, comprising the following steps:

[0079] Step 1: 45 parts by mass of industrial-grade sorbitol raw material (the purity of the raw material is 97.24%) is dissolved in 100 parts by mass of ultrapure water to obtain an industrial-grade sorbitol solution, and the industrial-grade sorbitol solution is sequentially passed through: a microfiltration membrane made of polypropylene (PP) with a pore size of 0.5 μm for primary filtration to remove large suspended particles, colloids and microorganisms, and protect subsequent precision filter elements; a polyvinylidene fluoride (PVDF) ultrafiltration membrane with a pore size of 0.1 μm for secondary filtration to remove nano-particles, colloids and macromolecular organic matter; a polytetrafluoroethylene (PTFE) folded membrane with a pore size of 10 nm for tertiary filtration to ensure that most particles larger than 10 nm are effectively removed and the filtrate is retained;

[0080] Step 2: Purify the filtrate obtained in step 1 by passing it through a composite exchange resin 4 at a rate of 5 BV / h at 25° C. to remove metal ions and obtain an electronic grade sorbitol solution;

[0081] Step 3: Dry the electronic-grade mannitol solution at 90° C. for 2 h to obtain high-purity electronic-grade sorbitol.

[0082] Example 5

[0083] This embodiment discloses a method for purifying high-purity electronic-grade erythritol, comprising the following steps:

[0084] Step 1: 30 parts by mass of industrial-grade erythritol raw material (the purity of the raw material is 96.32%) is dissolved in 100 parts by mass of ultrapure water to obtain an industrial-grade erythritol solution, and the industrial-grade erythritol solution is sequentially passed through: a microfiltration membrane of polypropylene (PP) with a pore size of 0.5 μm for primary filtration to remove large suspended particles, colloids and microorganisms, and protect subsequent precision filter elements; a polyvinylidene fluoride (PVDF) ultrafiltration membrane with a pore size of 0.1 μm for secondary filtration to remove nano-particles, colloids and macromolecular organic matter; a polytetrafluoroethylene (PTFE) folded membrane with a pore size of 10 nm for tertiary filtration to ensure that most particles larger than 10 nm are effectively removed and the filtrate is retained;

[0085] Step 2: Purify the filtrate obtained in step 1 by passing it through a composite exchange resin 4 at a rate of 5 BV / h at 25° C. to remove metal ions and obtain an electronic grade erythritol solution;

[0086] Step 3: Dry the electronic-grade mannitol solution at 90° C. for 2 h to obtain high-purity electronic-grade erythritol.

[0087] Example 6

[0088] This embodiment discloses a method for purifying high-purity electronic-grade arabitol, comprising the following steps:

[0089] Step 1: 15 parts by mass of industrial-grade arabitol raw material (the purity of the raw material is 95.50%) is dissolved in 100 parts by mass of ultrapure water to obtain an industrial-grade erythritol solution, and the industrial-grade arabitol solution is sequentially passed through: a microfiltration membrane made of polypropylene (PP) with a pore size of 0.5 μm for primary filtration to remove large suspended particles, colloids and microorganisms, and protect the subsequent precision filter element; a polyvinylidene fluoride (PVDF) ultrafiltration membrane with a pore size of 0.1 μm for secondary filtration to remove nano-particles, colloids and large molecular organic matter; and a polytetrafluoroethylene (PTFE) folded membrane with a pore size of 10 nm for tertiary filtration to ensure that most particles larger than 10 nm are effectively removed and the filtrate is retained;

[0090] Step 2: Purify the filtrate obtained in step 1 at a rate of 5 BV / h through composite exchange resin 4 at 25° C. to remove metal ions and obtain an electronic grade arabitol solution;

[0091] Step 3: Dry the electronic-grade mannitol solution at 90° C. for 2 h to obtain high-purity electronic-grade arabitol.

[0092] Comparative Example 1

[0093] This comparative example discloses a method for purifying high-purity electronic-grade mannitol, comprising the following steps:

[0094] Step 1: dissolving 40 parts by mass of industrial-grade mannitol raw material (the purity of the raw material is 97.55%) in 100 parts by mass of ultrapure water to obtain an industrial-grade mannitol solution, and passing the industrial-grade mannitol solution sequentially through: a microfiltration membrane made of polypropylene (PP) with a pore size of 0.5 μm for primary filtration to remove large suspended particles, colloids and microorganisms, and protect subsequent precision filter elements; a polyvinylidene fluoride (PVDF) ultrafiltration membrane with a pore size of 0.1 μm for secondary filtration to remove nano-particles, colloids and macromolecular organic matter; and a polytetrafluoroethylene (PTFE) folded membrane with a pore size of 10 nm for tertiary filtration to ensure that most particles larger than 10 nm are effectively removed and the filtrate is retained;

[0095] Step 2: Purify the filtrate obtained in step 1 by passing it through a cation exchange resin D001 at a flow rate of 5 BV / h at 25° C. to remove metal ions and obtain an electronic grade mannitol solution;

[0096] Step 3: Dry the electronic-grade mannitol solution at 90° C. for 2 h to obtain high-purity electronic-grade mannitol.

[0097] Comparative Example 2

[0098] This comparative example discloses a method for purifying high-purity electronic-grade mannitol, comprising the following steps:

[0099] Step 1: dissolving 40 parts by mass of industrial-grade mannitol raw material (the purity of the raw material is 97.55%) in 100 parts by mass of ultrapure water to obtain an industrial-grade mannitol solution, and passing the industrial-grade mannitol solution sequentially through: a microfiltration membrane made of polypropylene (PP) with a pore size of 0.5 μm for primary filtration to remove large suspended particles, colloids and microorganisms, and protect subsequent precision filter elements; a polyvinylidene fluoride (PVDF) ultrafiltration membrane with a pore size of 0.1 μm for secondary filtration to remove nano-particles, colloids and macromolecular organic matter; and a polytetrafluoroethylene (PTFE) folded membrane with a pore size of 10 nm for tertiary filtration to ensure that most particles larger than 10 nm are effectively removed and the filtrate is retained;

[0100] Step 2: Purify the filtrate obtained in step 1 by passing it through a composite exchange resin 5 at a flow rate of 5 BV / h at 25° C. to remove metal ions and obtain an electronic grade mannitol solution;

[0101] Step 3: Dry the electronic-grade mannitol solution at 90° C. for 2 h to obtain high-purity electronic-grade mannitol.

[0102] Comparative Example 3

[0103] This comparative example discloses a method for purifying high-purity electronic-grade mannitol, comprising the following steps:

[0104] Step 1: dissolving 40 parts by mass of industrial-grade mannitol raw material (the purity of the raw material is 97.55%) in 100 parts by mass of ultrapure water to obtain an industrial-grade mannitol solution, and passing the industrial-grade mannitol solution sequentially through: a microfiltration membrane made of polypropylene (PP) with a pore size of 0.5 μm for primary filtration to remove large suspended particles, colloids and microorganisms, and protect subsequent precision filter elements; a polyvinylidene fluoride (PVDF) ultrafiltration membrane with a pore size of 0.1 μm for secondary filtration to remove nano-particles, colloids and macromolecular organic matter; and a polytetrafluoroethylene (PTFE) folded membrane with a pore size of 10 nm for tertiary filtration to ensure that most particles larger than 10 nm are effectively removed and the filtrate is retained;

[0105] Step 2: Purify the filtrate obtained in step 1 through a composite ion exchange resin 6 at a flow rate of 5 BV / h at 25° C. to remove metal ions and obtain an electronic grade mannitol solution;

[0106] Step 3: Dry the electronic-grade mannitol solution at 90° C. for 2 h to obtain high-purity electronic-grade mannitol.

[0107] Comparative Example 4

[0108] This comparative example discloses a method for purifying high-purity electronic-grade mannitol, comprising the following steps:

[0109] Step 1: dissolving 40 parts by mass of industrial-grade mannitol raw material (the purity of the raw material is 97.55%) in 100 parts by mass of ultrapure water to obtain an industrial-grade mannitol solution, and passing the industrial-grade mannitol solution sequentially through: a microfiltration membrane made of polypropylene (PP) with a pore size of 0.5 μm for primary filtration to remove large suspended particles, colloids and microorganisms, and protect subsequent precision filter elements; a polyvinylidene fluoride (PVDF) ultrafiltration membrane with a pore size of 0.1 μm for secondary filtration to remove nano-particles, colloids and macromolecular organic matter; and a polytetrafluoroethylene (PTFE) folded membrane with a pore size of 10 nm for tertiary filtration to ensure that most particles larger than 10 nm are effectively removed and the filtrate is retained;

[0110] Step 2: Add 1 part by mass of 2-mercapto-3-pyridinecarboxylic acid to the filtrate and mix well. Then, at 25° C., pass the mixture through an ion exchange column filled with 50 parts by mass of cation exchange resin D001 at a rate of 5 BV / h to purify the mixture to remove metal ions and obtain an electronic grade mannitol solution.

[0111] Step 3: Dry the electronic-grade mannitol solution at 90° C. for 2 h to obtain high-purity electronic-grade mannitol.

[0112] The preparation methods of the composite exchange resins 1-6 described in Examples 1-6 and Comparative Examples 1-4 are as follows:

[0113] S1: Pretreatment of cation exchange resin: Activate the cation exchange resin with 7% hydrochloric acid (the volume ratio of hydrochloric acid to cation exchange resin is 1:1), and then rinse the cation exchange resin with pure water until the pH of the inlet and outlet water reaches 6;

[0114] S2: At 50°C, mix the cation exchange resin treated in S1 and the additives uniformly. The mixture is then loaded into an ion exchange column to form a composite exchange resin. The resin loading is 1 / 2 the volume of the ion exchange column. The raw materials and proportions for preparing the composite exchange resin are shown in Table 1.

[0115] Table 1 Composition and ratio of composite exchange resin

[0116]

[0117] The cation exchange resin is a polystyrene-divinylbenzene cross-linked skeleton with sulfonic acid groups. This resin has a high degree of cross-linking and is suitable for ion exchange. The cation exchange resin can be prepared in-house or purchased commercially.

[0118] The short-chain sugar alcohols of Examples 1-6 and Comparative Examples 1-4 were tested, and the test methods and results are as follows:

[0119] ICP-MS was used to test the content of short-chain sugar alcohols and metal ion content before and after purification by ion exchange resin, as shown in Table 2.

[0120] Table 2 Mannitol content and metal ion content in mannitol before and after purification

[0121]

[0122]

[0123] Table 3 Contents of galactitol / iditol / sorbitol and metal ion content before and after purification

[0124]

[0125]

[0126] From the experimental results, it can be seen that the high-purity electronic-grade mannitol prepared in Example 1 of the present invention has a purity of 99.99%, the metal ion contents of Na, Mg, Ni, Cu, Zn, Pb, Al, K, Ca, Cr, Mn, and Co are all less than 1 ppb, and the Fe metal ion content is less than 5 ppb. The high-purity electronic-grade short-chain sugar alcohols prepared in Examples 2-6 have a purity greater than 99%, the metal ion contents of Na, Mg, Ni, Cu, Zn, and Pb are all less than 1 ppb, and the Fe metal ion content is less than 5 ppb; the total metal ion content of Examples 1-6 is less than 100 ppb, which shows that the high-purity electronic-grade short-chain sugar alcohols in Examples 1-6 meet the high-purity electronic-grade raw material standards.

[0127] Comparative Example 1 is a purification method using only cationic resin, and the other conditions are the same as those of Example 1. The total metal ion impurity content is greater than 100 ppb, which does not meet the electronic grade raw material standard;

[0128] Comparative Example 2 is to add other functional agents and cationic resin for purification, and the other conditions are the same as those in Example 1. The total metal ion impurity content is greater than 100 ppb, which does not meet the electronic grade raw material standard;

[0129] Comparative Example 3 uses a combination of cation exchange resin D113 and additive 2-mercapto-3-pyridinecarboxylic acid. Since D113 has a carboxylic acid functional group and does not contain a sulfonic acid functional group, the cation exchange resin does not effectively remove Na, Fe, Cu, Mg, Ca, K, and Al metal ions. The total metal ion impurity content in mannitol is greater than 100 ppb, which does not meet the electronic grade raw material standard.

[0130] In Comparative Example 4, 2-mercapto-3-pyridinecarboxylic acid was directly added to the filtrate obtained in step 1 instead of mixing the 2-mercapto-3-pyridinecarboxylic acid into the cation exchange resin, resulting in a total metal ion impurity content in mannitol greater than 100 ppb, which did not meet the electronic grade raw material standards.

[0131] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for purifying high-purity electronic-grade short-chain sugar alcohols, characterized in that: The following steps are involved: Step 1: adding an industrial-grade short-chain sugar alcohol solid raw material to a solvent to dissolve it to obtain an industrial-grade short-chain sugar alcohol solution, filtering the industrial-grade short-chain sugar alcohol solution through multiple stages, and retaining the filtrate; Step 2: Purify the filtrate through a composite exchange resin at 10-40° C. to remove metal ions and obtain an electronic-grade short-chain sugar alcohol solution; Step 3: Drying the electronic-grade short-chain sugar alcohol solution to obtain high-purity electronic-grade short-chain sugar alcohol.

2. The method for purifying high-purity electronic-grade short-chain sugar alcohol according to claim 1, wherein The dissolving temperature in step 1 is 50-85°C; And / or, the mass ratio of the industrial-grade short-chain sugar alcohol solid raw material to the solvent is 10-50:100; And / or, the multi-stage filtration removes particles with a particle size of 10 nm-0.5 μm.

3. The method for purifying high-purity electronic-grade short-chain sugar alcohol according to claim 1, wherein The metal ions in step 2 are one or more of sodium ions, magnesium ions, aluminum ions, potassium ions, calcium ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions, copper ions, zinc ions and lead ions.

4. The method for purifying high-purity electronic-grade short-chain sugar alcohol according to claim 1, wherein The composite exchange resin in step 2 is prepared by the following method: S1. Pretreatment of cation exchange resin: Activate the cation exchange resin with hydrochloric acid, then rinse with pure water until the pH of the inlet and outlet water reaches 6-7; S2. Evenly mix the cation exchange resin treated in S1 with the additive at 30-60° C., and then fill the ion exchange column with the cation exchange resin to obtain a composite exchange resin.

5. The method for purifying high-purity electronic-grade short-chain sugar alcohol according to claim 4, wherein: The volume ratio of the hydrochloric acid to the cation exchange resin is 1:1-5:

1.

6. The method for purifying high-purity electronic-grade short-chain sugar alcohol according to claim 4, wherein: The volume ratio of the additive to the cation exchange resin is 1:10-100; and / or, the additive is one or more of 2-mercapto-3-pyridinecarboxylic acid, 6-mercaptopyridine-3-carboxylic acid, and D-cysteine; And / or, the cation exchange resin is a styrene resin having a sulfonic acid group.

7. The method for purifying high-purity electronic-grade short-chain sugar alcohol according to claim 1, wherein: The drying temperature in step 3 is 60-100° C., and the drying time is 1-3 hours.

8. A high-purity electronic-grade short-chain sugar alcohol, characterized in that: The product is purified by the purification method according to any one of claims 1 to 7.

9. The high-purity electronic-grade short-chain sugar alcohol according to claim 8, characterized in that The purity of the high-purity electronic-grade short-chain sugar alcohol is greater than or equal to 99wt%, and the total metal ion impurity content is below 100ppb.

10. Use of the high-purity electronic-grade short-chain sugar alcohol according to claim 8 or 9 in the field of wet electronic chemicals.

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