CN114804036B - Method and system for producing G1-G5 electronic-grade sulfuric acid - Google Patents

Method and system for producing G1-G5 electronic-grade sulfuric acid Download PDF

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CN114804036B
CN114804036B CN202210380210.2A CN202210380210A CN114804036B CN 114804036 B CN114804036 B CN 114804036B CN 202210380210 A CN202210380210 A CN 202210380210A CN 114804036 B CN114804036 B CN 114804036B
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sulfuric acid
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rectifying tower
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CN114804036A (en
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张扬
谢佳华
侯文贵
王健
高云山
徐梦
杨盼
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Nanjing Jiahua Technology Co ltd
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Nanjing Jiahua Engineering Technology Co ltd
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/90—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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Abstract

The invention discloses a method for producing G1-G5 electronic-grade sulfuric acid, which comprises the following steps: by SO 3 Rectification system for industryClass SO 3 Rectifying and removing impurities to obtain ultra-high purity SO 3 (ii) a Ultra-high purity SO 3 Into SO 3 An absorption apparatus, countercurrent absorption or static mixing with the absorption liquid to obtain crude electronic grade sulfuric acid with a sulfuric acid concentration of 95-97% by weight; the electronic-grade sulfuric acid crude product is filtered by a G1-grade filter to obtain G1-grade electronic-grade sulfuric acid, or enters a rectification lightness-removing device to be rectified and lightness-removing to obtain high-purity electronic-grade sulfuric acid; the high-purity electronic-grade sulfuric acid is filtered by a G2-grade or G3-grade filter to obtain G2-grade or G3-grade electronic-grade sulfuric acid, or enters a rectification and de-weighting device to be rectified and de-weighted to obtain ultra-high-purity electronic-grade sulfuric acid, and a G4-grade or G5-grade filter is adopted to obtain G4-grade or G5-grade electronic-grade sulfuric acid. The method has the advantages of low investment, low energy consumption and little environmental pollution, and can prepare the electronic-grade sulfuric acid with high efficiency and high product flexibility.

Description

Method and system for producing G1-G5 electronic-grade sulfuric acid
Technical Field
The invention belongs to the field of electronic grade chemical production, and relates to a method and a system for producing G1-G5 electronic grade sulfuric acid, which belongs to the field of electronic grade chemical production and is refined into electronic grade sulfuric acid production.
Background
Sulfuric acid of the formula H 2 SO 4 Anhydrous sulfuric acid is a colorless oily liquid. Sulfuric acid is one of the most active strong inorganic binary acids. It is an important industrial raw material, and can be used in the industries of fertilizer, explosive, pigment, detergent, storage battery, metal smelting, dye and the like.
Electronic-grade sulfuric acid, also known as high-purity sulfuric acid and ultrapure sulfuric acid, belongs to an ultra-clean high-purity reagent, and is an indispensable key basic chemical reagent in the development process of microelectronic technology. The electronic-grade sulfuric acid is widely applied to the assembly and processing processes of semiconductors and very large scale integrated circuits, is mainly used for cleaning and etching silicon wafers, and can effectively remove impurity particles, inorganic residues and carbon deposits on the wafers.
In recent years, with the rise of the semiconductor industry in China, the nationality rate is continuously improved, the perfection of the layout of upstream and downstream industrial chains is urgently needed, and the demand of electronic-grade sulfuric acid is rapidly increased.
The electronic grade sulfuric acid is divided according to the ultra-clean high-purity reagent SEMI international standard grade, and can be divided into five categories of G1, G2, G3, G4 and G5, wherein G1 belongs to low-grade products, G2 belongs to medium-grade and low-grade products, G3 belongs to medium-grade and high-grade products, and G4 and G5 belong to high-grade products.
In recent years, although the domestic electronic-grade sulfuric acid capacity is rapidly expanded, the problem of insufficient yield still exists in a short period due to short production time, the existing capacity mainly comprises the low-grade, medium-grade and medium-grade G1, G2 and G3 grade capacities, the G4 and G5 high-grade products are low in capacity, and particularly, domestic G5 grade product production enterprises are few and mainly depend on imports. The demand standard of the downstream semiconductor market for electronic-grade sulfuric acid products in the future will be continuously improved, the gap of the G5-grade electronic-grade sulfuric acid market is larger, the added value of the products is higher, and the development prospect is good.
Chinese patent CN 103407972A proposes a production method of electronic-grade sulfuric acid, and only liquid SO can be used as raw material 3 The limitation is large; evaporating liquid SO 3 Changing to gaseous state for absorption reaction, purchased SO 3 Containing N 2 、O 2 、HF、SO 2 The light components must be accompanied by gaseous SO 3 Enters an ultrapure water absorption system together, SO that the generated electronic-grade sulfuric acid contains SO 2 、N 2 、O 2 And the like; although subsequently degassed with compressed air, the SO dissolved in the sulfuric acid cannot be completely removed 2 、SO 3 At the same time, the sulfuric acid can be dissolved more N 2 、O 2 Resulting in a lower grade final electronic grade sulfuric acid product. Moreover, the method needs to consume high-purity compressed air, and has high production cost.
Chinese patent CN 112320768A proposes a production method of electronic-grade sulfuric acid, which uses concentrated sulfuric acid to absorb gas-phase SO 3 Generating oleum, and oxidizing SO in oleum with hydrogen peroxide 2 Is SO 3 Then distilling off SO 3 A gas. The process needs to consume high-purity reagents, and in order to ensure the purity of electronic-grade sulfuric acid products, hydrogen peroxide used in the process needs to be also electronic grade, so that the production cost is high. And O is generated in the oxidation process of hydrogen peroxide 2 With gaseous SO 3 The mixture enters the next working procedure and is dissolved in the product, and the O can not be completely removed by a simple degassing method 2 Affecting the final product grade.
Disclosure of Invention
The invention aims to provide a method for producing electronic-grade sulfuric acid, which has the advantages of low investment, low energy consumption, less environmental pollution, high efficiency, wide adaptability and high product flexibility.
The purpose of the invention is realized by the following technical scheme:
a process for producing G1-G5 electronic grade sulfuric acid comprising the steps of:
step (1), rectification and impurity removal: by SO 3 Rectification system for industrial grade SO 3 Rectifying and removing impurities to obtain ultra-high purity SO with purity of more than or equal to 99.999 percent by weight 3 ；
Step (2), ultrapure water absorption: ultra-high purity SO 3 Into SO 3 An absorption device which performs countercurrent absorption or static mixing with the absorption liquid to obtain an electronic grade sulfuric acid crude product with the sulfuric acid concentration of 95-97 percent by weight;
removing particles from the electronic-grade sulfuric acid crude product through a G1-grade filter to obtain G1-grade electronic-grade sulfuric acid;
or the electronic-grade sulfuric acid crude product enters a rectification lightness-removing device to be rectified and lightness-removed to remove a small amount of light component impurities, so that high-purity electronic-grade sulfuric acid is obtained;
removing particles from the high-purity electronic-grade sulfuric acid by a G2-grade filter or a G3-grade filter to obtain G2-grade or G3-grade electronic-grade sulfuric acid; or the high-purity electronic-grade sulfuric acid enters a rectification and de-weight device to be rectified and de-weight to obtain ultra-high-purity electronic-grade sulfuric acid, and a G4-grade filter or a G5-grade filter is adopted to remove particles to obtain G4-grade or G5-grade electronic-grade sulfuric acid.
In step (1), industrial grade SO 3 Is industrial grade liquid SO 3 Oleum, technical grade gaseous SO 3 . Industrial grade SO 3 Containing N 2 、O 2 、SO 2 Light component impurities such as HF, H 2 O、H 2 SO 4 And (4) waiting for heavy component impurities.
When industrial grade SO 3 Is industrial grade liquid SO 3 The rectification impurity removal is specifically as follows: industrial grade SO 3 First from SO 3 The heat generated by the absorption device is preheated to 20-50 ℃, and then enters the first rectifying tower 1, the gas phase at the top of the first rectifying tower 1 is pressurized by a compressor and then is sent to a second rectifying tower reboiler 5 to be used as a heat source for heat exchange, and then enters the second rectifying tower condenser 6 to be condensed, the gas phase is sent to a tail gas treatment device, and the liquid phase obtained by condensation flows back to the first rectifying tower 1; pumping the materials at the bottom of the first rectifying tower 1 into a second rectifying tower 4, pressurizing the gas phase at the top of the first rectifying tower 1 by a compressor, feeding the gas phase into a reboiler 2 of the first rectifying tower as a heat source for heat exchange, and condensing the gas phase in a condenser 3 of the first rectifying tower, wherein the gas phase is ultrahigh-purity SO 3 To SO 3 And in the absorption device, the liquid phase obtained by condensation flows back to the second rectifying tower 4.
The number of plates of the first rectifying tower 1 is 10-40, preferably 15-30; the operation temperature is 30-100 ℃, and preferably 40-70 ℃; the operation pressure is 0.05 to 0.5MPa, preferably 0.1 to 0.3MPa; the reflux ratio is 0.2 to 15, preferably 0.5 to 8.
The gas phase at the top of the first rectifying tower 1 is pressurized by a compressor to the pressure of 0.4 to 2MPa, preferably 0.6 to 1.5MPa.
The number of plates of the second rectifying tower 4 is 10-50, preferably 20-35; the operation temperature is 20-120 ℃, and preferably 40-80 ℃; the operation pressure is 0.05 to 0.5MPa, preferably 0.1 to 0.3MPa; the reflux ratio is 2 to 80, preferably 5 to 60.
The gas phase at the top of the second rectifying tower 4 is pressurized to the pressure of 0.5 to 1.5MPa, preferably 0.6 to 1.0MPa by a compressor.
When industrial grade SO 3 Is industrial grade gaseous SO 3 Or when fuming sulfuric acid, the rectification impurity removal is specifically as follows: SO in oleum is evaporated by an evaporator 3 Then enters a rectifying tower 1 or industrial grade gaseous SO 3 Directly entering a first rectifying tower 1, pressurizing a gas phase at the top of the first rectifying tower 1 through a compressor, sending the gas phase to a second rectifying tower reboiler 5 to be used as a heat source for heat exchange, then entering a second rectifying tower condenser 6 for condensation, refluxing a liquid phase obtained by condensation to the top of the first rectifying tower 1, sending a gas phase subjected to condensation treatment to a second rectifying tower 4, and sending a material at the bottom of the first rectifying tower 1 as a heavy component to be treated; the gas phase at the top of the second rectifying tower 4 is pressurized by a compressor and then sent to a first rectifying tower reboiler 2 to be used as a heat source for heat exchange, then enters a first rectifying tower condenser 3 for condensation, the gas phase after condensation treatment is sent to a tail gas treatment device, the liquid phase obtained by condensation flows back to the second rectifying tower 4, and high-purity gas phase SO is extracted from the lower lateral line of the second rectifying tower 4 3 Or high-purity liquid phase SO is extracted from the tower bottom of the second rectifying tower 4 3 (ii) a High purity gaseous SO 3 And/or high purity liquid phase SO 3 Is sent to SO 3 An absorption device.
The number of plates of the first rectifying tower 1 is 10-40, preferably 15-30; the operation temperature is 35-110 ℃, preferably 45-75 ℃; the operation pressure is 0.05 to 0.5MPa, preferably 0.1 to 0.3MPa; the reflux ratio is 0.1 to 10, preferably 0.2 to 5.
The gas phase at the top of the first rectifying tower 1 is pressurized by a compressor to the pressure of 0.5 to 1.5MPa, preferably 0.6 to 1.0MPa.
The number of plates of the second rectifying tower 4 is 10-50, preferably 20-35; the operation temperature is 25-110 ℃, preferably 50-90 ℃; the operation pressure is 0.05 to 0.5MPa, preferably 0.1 to 0.3MPa; the reflux ratio is 1 to 100, preferably 10 to 80.
The gas phase at the top of the second rectifying tower 2 is pressurized by a compressor to the pressure of 0.4-2 MPa, preferably 0.6-1.5 MPa.
In the step (2), the absorption liquid is ultrapure water or ultrahigh-purity SO 3 And superPure water in SO 3 The sulfuric acid solution formed in the device is absorbed.
The ultrapure water is EW-I level ultrapure water.
SO 3 The absorption device comprises 1-9 SO connected in series in sequence 3 The absorption tower preferably comprises 2 to 5 SO connected in series 3 Absorption column of each SO 3 The absorption tower is equipped with a cooler in which the cooling water or SO to be introduced is cooled 3 Industrial grade liquid SO of rectification system 3 Removing reaction heat, heating cooling water and using the heated cooling water in SO in the system 3 Heat tracing prevention SO for pipelines and equipment 3 And (5) solidifying.
The operating temperature of each absorption tower is 10-60 ℃, preferably 20-50 ℃, and the operating pressure is 0.05-0.5 MPa, preferably 0.1-0.3 MPa.
Ultra-high purity SO 3 Is gaseous SO 3 From SO 3 Introducing gaseous SO to the bottom of the absorption tower 3 From SO 3 Spraying absorption liquid and gaseous SO on the top of the absorption tower 3 Absorbing with absorption liquid in counter current to generate sulfuric acid solution, SO 3 The sulfuric acid solution in the tower kettle of the absorption tower is circulated to SO outside the tower 3 Continuously spraying with ultrahigh-purity SO from the top of the absorption tower 3 Counter-current absorption and cooling water or SO to be introduced into the cooler while circulating outside the tower 3 Industrial grade liquid SO of rectifying device 3 Heat exchange is carried out to remove reaction heat; when SO 3 When the sulfuric acid concentration in the tower kettle of the absorption tower reaches 95-97 percent by weight, the crude electronic-grade sulfuric acid is extracted.
It is further preferred when said SO 3 When the number of the absorption towers is at least 2, the first stage SO 3 Continuously introducing gaseous SO to the bottom of the absorption tower 3 From last stage SO 3 Ultrapure water is continuously introduced into the absorption tower from SO 3 Spraying ultrapure water or sulfuric acid solution and gaseous SO on the top of the absorption tower 3 And ultra pure water or sulfuric acid solution are absorbed in a counter-current way to generate sulfuric acid solution, each SO 3 Part of tower bottom liquid of the absorption tower is circulated and refluxed to SO outside the absorption tower 3 Absorption tower and cooling water or SO in cooler 3 Industrial grade liquid SO of rectification system 3 Heat exchange is carried out to remove reaction heat, and the rest part is conveyed to the previous stage SO 3 The absorption tower is used as absorption liquid; when first stage SO 3 The sulfuric acid concentration in the tower kettle of the absorption tower reaches 95-97 percent by weight, and an electronic grade sulfuric acid crude product is obtained; from last stage SO 3 And discharging the residual gas phase components from the top of the absorption tower and entering a tail gas treatment device.
Ultra-high purity SO 3 Is liquid SO 3 Very high purity SO 3 Fully mixed with ultrapure water in a static mixer 28, and cooled by a cooler 29 to remove reaction heat, thus obtaining the electronic grade sulfuric acid crude product.
In the step (3), the rectification lightness-removing treatment comprises the following steps: preheating the electronic-grade sulfuric acid crude product, then feeding the electronic-grade sulfuric acid crude product into a sulfuric acid lightness-removing tower 19, condensing materials at the top of the sulfuric acid lightness-removing tower, then feeding a gas phase into a vacuum system, refluxing a liquid phase to the sulfuric acid lightness-removing tower 19 from the top of the sulfuric acid lightness-removing tower, extracting high-purity electronic-grade sulfuric acid from a measurement line of the sulfuric acid lightness-removing tower 19, and filtering the high-purity electronic-grade sulfuric acid by a G2 or G3 grade filter to obtain G2 or G3 grade electronic sulfuric acid; the tower bottom material of the sulfuric acid lightness-removing tower 19 exchanges heat with the electronic grade sulfuric acid crude product to be fed into the sulfuric acid lightness-removing tower 19, and the electronic grade sulfuric acid crude product is fed into a rectification weight-removing device for weight-removing treatment.
Preferably, the crude electronic-grade sulfuric acid is preheated to 50-120 ℃ by the material in the tower kettle of the sulfuric acid lightness-removing tower, and preferably 70-100 ℃.
The number of the plates of the sulfuric acid lightness-removing tower 19 is 10-40, preferably 10-30; the operation temperature at the top of the tower is 30-90 ℃, and preferably 40-70 ℃; the operation temperature of the tower kettle is 150-310 ℃, and preferably 200-260 ℃; the operating pressure is 0.005-0.1 MPa, preferably 0.01-0.1 MPa; the reflux ratio is 0.1 to 2, preferably 0.2 to 1.
The rectification and de-weight treatment comprises the following steps: high-purity electronic-grade sulfuric acid (namely, material in a tower kettle of a sulfuric acid lightness-removing tower) enters a sulfuric acid weight-removing tower 23 after being preheated, material at the top of the sulfuric acid weight-removing tower is condensed, a gas phase enters a vacuum system, a certain reflux ratio is controlled, a part of liquid phase reflows to the sulfuric acid weight-removing tower from the top of the tower, the rest part is extracted, G4-grade or G5-grade electronic-grade sulfuric acid is obtained through a G4-grade or G5-grade filter, and heavy component in the tower kettle of the sulfuric acid weight-removing tower is used for preheating the high-purity electronic-grade sulfuric acid to be entered into the sulfuric acid weight-removing tower.
The plate number of the sulfuric acid de-weighting tower 23 is 15-50, preferably 20-35; the operation temperature at the top of the tower is 100-220 ℃, and the preferable temperature is 150-190 ℃; the operation temperature of the tower kettle is 150-250 ℃, and preferably 180-220 ℃; the operating pressure is 0.0001 to 0.1MPa, preferably 0.001 to 0.05MPa; the reflux ratio is 0.2 to 20, preferably 0.5 to 15.
The sulfuric acid concentration of the electronic-grade sulfuric acid crude product is 95-97 wt%, and the content of metal impurities is 0.2-0.3 ppm.
The sulfuric acid concentration in the high-purity electronic grade sulfuric acid is 95-97 wt%, and the content of metal impurities is 0.1-1 ppb.
The sulfuric acid concentration in the ultra-high-purity electronic grade sulfuric acid is 95-97 wt%, and the content of metal impurities is 0.01-0.1 ppb.
The sulfuric acid concentration in the ultra-high purity electronic grade sulfuric acid is 95-97 wt%, and the content of metal impurities is 0.01-0.1 ppb.
It is another object of the present invention to provide a system for producing G1-G5 electronic grade sulfuric acid comprising: SO (SO) 3 Rectification system for industrial grade SO 3 Rectifying and removing impurities; SO (SO) 3 Absorption apparatus of SO 3 Absorbing and reacting with ultrapure water or sulfuric acid solution to generate an electronic grade sulfuric acid crude product; the rectification light-weight removal device and the rectification heavy-weight removal device are used for purifying the electronic-grade sulfuric acid crude product; and the ultrafiltration device is used for removing electronic-grade sulfuric acid particles.
The system for producing the G1-G5 electronic-grade sulfuric acid also comprises a tail gas treatment device, and the tail gas treatment device is used for treating tail gas.
When industrial grade SO 3 Is industrial grade liquid SO 3 When said SO is 3 The rectifying system comprises a rectifying tower 1 and a rectifying tower 4, wherein a feed inlet of the rectifying tower 1 is connected with a raw material conveying pipeline, and the raw material conveying pipeline is connected with SO 3 First SO in the absorber 3 The cooler of the absorption tower is connected with SO 3 Absorption of heat generated by the apparatus to industrial grade liquid SO 3 Preheating is carried out; a rectifying column reboiler 2 is equipped with at the bottom of rectifying column 1 tower, and the discharge gate is connected with No. two rectifying column 4 feed inlets at the bottom of rectifying column 1 tower, and No. two rectifying column reboilers 5 that No. 1 top gas outlet of rectifying column was equipped with at the bottom of first compressor 7 and No. two rectifying column 4 towers are evenA heat source is provided for a second rectifying tower reboiler, the second rectifying tower reboiler 5 is connected with a second rectifying tower condenser 6, the gas outlet of the second rectifying tower condenser 6 is connected with a tail gas treatment device, noncondensable gas is conveyed to the tail gas treatment device for treatment, and the liquid outlet of the second rectifying tower condenser 6 is connected with the reflux inlet at the upper part of the first rectifying tower 1; no. two rectifying column 4 tower bottoms are equipped with the heavy ends discharge gate, no. two rectifying column 4 top gas outlets are connected through second compressor 8 and rectifying column reboiler 2 and provide the heat source for a rectifying column reboiler, a rectifying column reboiler 2 is connected with rectifying column condenser 3, the liquid outlet and the 4 upper portion inlet of No. two rectifying column of rectifying column condenser 3 are connected, the gas outlet and the SO of rectifying column condenser 3 3 The air inlet of the absorption device is connected.
When industrial grade SO 3 Is industrial grade gaseous SO 3 When said SO is 3 The rectifying system comprises a first rectifying tower 1 and a second rectifying tower 4, wherein a feed inlet of the first rectifying tower 1 is connected with a raw material conveying pipeline, a first rectifying tower reboiler 2 is arranged at the bottom of the first rectifying tower 1, a heavy component discharge port is arranged at the bottom of the first rectifying tower 1, a gas outlet at the top of the first rectifying tower 1 is connected with a second rectifying tower reboiler 5 arranged at the bottom of the second rectifying tower 4 through a first compressor 7 to provide a heat source for the second rectifying tower reboiler, the second rectifying tower reboiler 5 is connected with a second rectifying tower condenser 6, a gas outlet of the second rectifying tower condenser 6 is connected with a gas inlet of the second rectifying tower 4, and a liquid outlet of the second rectifying tower condenser 6 is connected with a reflux port at the upper part of the first rectifying tower 1; an air outlet at the top of the second rectifying tower 4 is connected with a first rectifying tower reboiler 2 through a second compressor 8 to provide a heat source for the first rectifying tower reboiler, the first rectifying tower reboiler 2 is connected with a first rectifying tower condenser 3, a liquid outlet of the first rectifying tower condenser 3 is connected with a liquid inlet at the upper part of the second rectifying tower 4, and an air outlet of the first rectifying tower condenser 3 is connected with a tail gas treatment device to send noncondensable gas to the tail gas treatment device for treatment; no. two rectifying column 4 tower bottom liquid outlet, side line gas outlet and SO 3 The absorption device is connected.
When industrial grade SO 3 In the case of oleum, gaseous SO of technical grade is suitable 3 SO of (A) 3 Rectification systemA fuming sulfuric acid evaporator 30 is added on the system, the gas outlet of the fuming sulfuric acid evaporator 30 is connected with the feed inlet of the first rectifying tower 1, the fuming sulfuric acid evaporator 30 is provided with a jacket, the inlet of the jacket is connected with the gas outlet at the top of the sulfuric acid de-weighting tower 23 in the rectifying de-weighting device, the gas phase at the top of the sulfuric acid de-weighting tower is used as a heat source, and the outlet of the jacket is connected with the condenser 25 at the top of the sulfuric acid de-weighting tower in the rectifying de-weighting device. In particular, the SO 3 The rectification system comprises a fuming sulfuric acid evaporator 30, a first rectification tower 1 and a second rectification tower 4, wherein an air outlet of the fuming sulfuric acid evaporator 30 is connected with a feed inlet of the first rectification tower 1; the tower bottom of the first rectifying tower 1 is provided with a first rectifying tower reboiler 2, the tower bottom of the first rectifying tower 1 is provided with a heavy component discharge port, a gas outlet at the tower top of the first rectifying tower 1 is connected with a second rectifying tower reboiler 5 arranged at the tower bottom of the second rectifying tower 4 through a first compressor 7 to provide a heat source for the second rectifying tower reboiler, the second rectifying tower reboiler 5 is connected with a second rectifying tower condenser 6, a gas outlet of the second rectifying tower condenser 6 is connected with a gas inlet of the second rectifying tower 4, and a liquid outlet of the second rectifying tower condenser 6 is connected with a reflux port at the upper part of the first rectifying tower 1; an air outlet at the top of the second rectifying tower 4 is connected with a first rectifying tower reboiler 2 through a second compressor 8 to provide a heat source for the first rectifying tower reboiler, the first rectifying tower reboiler 2 is connected with a first rectifying tower condenser 3, a liquid outlet of the first rectifying tower condenser 3 is connected with a liquid inlet at the upper part of the second rectifying tower 4, and an air outlet of the first rectifying tower condenser 3 is connected with a tail gas treatment device to send noncondensable gas to the tail gas treatment device for treatment; no. two rectifying column 4 tower bottom liquid outlet and side line gas outlet and SO 3 The absorption device is connected.
The first compressor 7 and the second compressor 8 are both heat pumps.
The rectification lightness-removing device comprises a sulphuric acid lightness-removing tower 19, a sulphuric acid lightness-removing tower reboiler 20, a sulphuric acid lightness-removing tower top condenser 21 and a sulphuric acid lightness-removing tower reflux tank 22; the feed inlet of the sulfuric acid lightness-removing tower 19 is connected with SO through a first feed preheater 16 3 A discharge port of the absorption device; the gas outlet at the top of the sulfuric acid lightness-removing tower 19 is connected with a condenser 21 at the top of the sulfuric acid lightness-removing tower, and the gas outlet of the condenser 21 at the top of the sulfuric acid lightness-removing tower is connected with a tail gas treatment device through a vacuum systemThe liquid outlet of the top condenser 21 of the sulfuric acid lightness-removing tower is connected with the top reflux port of the sulfuric acid lightness-removing tower 19 through the reflux tank 22 of the sulfuric acid lightness-removing tower; a discharge hole at the bottom of the sulfuric acid lightness-removing tower 19 is connected with a heat supply medium inlet of a first feed preheater 16, and a heat supply medium outlet of the first feed preheater 16 is connected with a feed inlet of the rectification and de-weighting device through a second feed preheater 18; the side draw outlet of the sulfuric acid lightness-removing tower 19 is connected with a G2 or G3 stage filter 17.
The rectification and de-weighting device comprises a sulfuric acid de-weighting tower 23, a sulfuric acid de-weighting tower reboiler 24, a sulfuric acid de-weighting tower top condenser 25 and a sulfuric acid de-weighting tower reflux tank 26; the feed inlet of the sulfuric acid heavy component removal tower 23 is connected with the discharge outlet at the bottom of the sulfuric acid light component removal tower 19 through a second feed preheater; the gas outlet at the top of the sulfuric acid heavy-duty tower 23 is connected with a condenser 25 at the top of the sulfuric acid heavy-duty tower, the gas outlet of the condenser 25 at the top of the sulfuric acid heavy-duty tower is connected with a vacuum system, the liquid outlet of the condenser 25 at the top of the sulfuric acid heavy-duty tower is connected with a reflux tank 26 of the sulfuric acid heavy-duty tower, and the liquid outlet of the reflux tank 26 of the sulfuric acid heavy-duty tower is respectively provided with a connecting pipeline and a product extraction pipeline which are connected with the top reflux port of the sulfuric acid heavy-duty tower 23.
The invention has the following beneficial effects:
(1) The starting materials of the invention may be selected from liquid phase SO 3 Gas phase SO 3 And fuming sulfuric acid, etc., and are widely available.
(2) The method has higher economic benefit and industrial value, the product grade of the electronic grade sulfuric acid is flexibly adjustable from G1 to G5, and a corresponding production plan is made according to the real-time market condition, so that the maximum economic benefit is ensured.
(3)、SO 3 The freezing point of the (C) is 16.8 ℃, the (SO) is easy to solidify and block pipelines in autumn and winter 3 The invention fully utilizes self heat release and is used for liquid phase SO 3 Preheating of feed and SO 3 Heat tracing prevention of SO for associated piping and equipment 3 Solidification is realized, and additional energy consumption is not needed;
SO 3 the rectification system and the sulfuric acid rectification device are both in thermal coupling design, and SO 3 Ultrapure water or sulfuric acid solution in an absorption apparatus andhigh purity gaseous SO 3 Countercurrent absorption of exothermic heat for neutralization of SO 3 The liquid phase feeding is subjected to coupling heat exchange, so that the energy consumption of the device is reduced; further reducing energy consumption; the fuming sulfuric acid evaporator adopts the gas phase discharged material at the top of the sulfuric acid de-weighting tower as a heat source, and simultaneously reduces the consumption of heat and cold;
SO 3 the rectification system can adopt a double-tower heat pump rectification technology, so that the overall energy consumption of the device is saved; energy conservation is not considered, thermal coupling is not adopted, and the same purity effect can be obtained by direct rectification;
SO 3 the rectification system adopts a heat pump rectification design, and saves a large amount of energy consumption compared with the traditional rectification system.
Drawings
FIG. 1 is a liquid SO 3 Or fuming sulfuric acid as raw material.
FIG. 2 is in gaseous SO 3 Is a flow schematic diagram of the production of electronic grade sulfuric acid from raw materials.
1-first rectifying tower, 2-first rectifying tower reboiler, 3-first rectifying tower condenser, 4-second rectifying tower, 5-second rectifying tower reboiler, 6-second rectifying tower condenser, 7-first compressor, 8-second compressor, 9-first cooler, 10-second cooler, 11-third cooler, 12-first SO 3 Absorption column, 13-second SO 3 Absorption column, 14-third SO 3 The system comprises an absorption tower, a 15-G1 or G2 stage filter, a 16-first feeding preheater, a 17-G3 or G4 stage filter, a 18-second feeding preheater, a 19-sulfuric acid lightness-removing tower, a 20-sulfuric acid lightness-removing tower reboiler, a 21-sulfuric acid lightness-removing tower top condenser, a 22-sulfuric acid lightness-removing tower reflux tank, a 23-sulfuric acid lightness-removing tower, a 24-sulfuric acid lightness-removing tower reboiler, a 25-sulfuric acid lightness-removing tower top condenser, a 26-sulfuric acid lightness-removing tower reflux tank, a 27-G5 stage filter, a 28-static mixer, a 29-fourth cooler and a 30-fuming sulfuric acid evaporator.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the accompanying drawings and examples.
Example 1
As shown in FIG. 1, a liquid SO 3 Producing electricity from raw materialsA system for sub-grade sulfuric acid, comprising: SO (SO) 3 Rectification system for industrial grade SO 3 Rectifying and removing impurities; SO (SO) 3 Absorption apparatus of SO 3 Absorbing and reacting with ultrapure water or sulfuric acid solution to generate an electronic grade sulfuric acid crude product; the rectification light-removing device and the rectification heavy-removing device are used for purifying the electronic-grade sulfuric acid crude product; the ultrafiltration device is used for removing electronic-grade sulfuric acid particles; and the tail gas treatment device is used for treating the tail gas.
Said SO 3 The rectifying system comprises a first rectifying tower 1 and a second rectifying tower 4, wherein a feed inlet of the first rectifying tower 1 is connected with a raw material conveying pipeline, a first rectifying tower reboiler 2 is arranged at the bottom of the first rectifying tower 1, a discharge outlet at the bottom of the first rectifying tower 1 is connected with a feed inlet of the second rectifying tower 4, a gas outlet at the top of the first rectifying tower 1 is connected with a second rectifying tower reboiler 5 arranged at the bottom of the second rectifying tower 4 through a first compressor 7 to provide a heat source for the second rectifying tower reboiler, the second rectifying tower reboiler 5 is connected with a second rectifying tower condenser 6, a gas outlet of the second rectifying tower condenser 6 is connected with a tail gas treatment device to convey non-condensable gas to the tail gas treatment device for treatment, and a liquid outlet of the second rectifying tower condenser 6 is connected with a reflux port at the upper part of the first rectifying tower 1; no. two rectifying column 4 tower bottoms are equipped with the heavy ends discharge gate, no. two rectifying column 4 top gas outlets are connected through second compressor 8 and rectifying column reboiler 2 and provide the heat source for a rectifying column reboiler, a rectifying column reboiler 2 is connected with rectifying column condenser 3, the liquid outlet and the 4 upper portion inlet of No. two rectifying column of rectifying column condenser 3 are connected, the gas outlet and the SO of rectifying column condenser 3 3 The gas inlet of the absorption device is connected with ultrahigh-purity SO obtained by rectification and impurity removal 3 Is sent to SO 3 An absorption device.
The first compressor 7 and the second compressor 8 are both heat pumps.
SO 3 The absorption device comprises a first SO 3 Absorption tower 12, second SO 3 Absorption tower 13, third SO 3 Absorption column 14, first SO 3 Absorption tower 12, second SO 3 Absorption tower 13, third SO 3 The absorption tower 14 is provided with a first cooler 9, a second cooler 10, and a third coolerThree coolers 11, the first cooler 9 is connected with the raw material conveying pipeline through SO 3 Heat generated by the absorber is preheated to enter the SO 3 Industrial grade liquid SO of rectification system 3 (ii) a First SO 3 The air inlet of the absorption tower 12 is connected with the air outlet of the first rectifying tower condenser 3, and the former SO 3 The gas outlet at the top of the absorption tower and the next SO 3 Inlet connection of absorption tower, third SO 3 The gas outlet at the top of the absorption tower 14 is connected with a tail gas treatment device; second SO 3 Absorption tower 13, third SO 3 The liquid outlets at the bottom of the absorption tower 14 are respectively provided with two pipelines, and one pipeline returns the SO through the respective coolers 3 The top of the absorption tower, the other pipeline and the former SO 3 The liquid inlet of the absorption tower is connected, and ultrapure water or sulfuric acid solution is input into the upper stage SO 3 The absorption tower is used as absorption liquid; first SO 3 The outlet at the bottom of the absorption tower 12 is provided with two lines, one of which returns SO via the first cooler 9 3 The other pipeline is connected with a feed inlet of a sulfuric acid lightness-removing tower 19 of the rectification lightness-removing device through a first feed preheater 16 at the top of the absorption tower; the first SO 3 The tower bottom liquid outlet of the absorption tower 12 is also connected with a G1 stage filter 15; the cooling water inlets of the second cooler 10 and the third cooler 11 are connected with a cooling water pipeline, the cooling water outlets of the coolers are connected with a circulating pipeline to use hot water for SO in the system 3 Pipes and apparatus (including SO) 3 A feeding buffer tank, a first rectifying tower 1 and a second rectifying tower 4 for conveying SO 3 Pump, etc.) to prevent SO 3 And (5) solidifying.
The rectification lightness-removing device comprises a sulfuric acid lightness-removing tower 19, a sulfuric acid lightness-removing tower reboiler 20, a sulfuric acid lightness-removing tower top condenser 21 and a sulfuric acid lightness-removing tower reflux tank 22; the feed inlet of the sulfuric acid lightness-removing tower 19 is connected with SO through a first feed preheater 16 3 First SO of absorption plant 3 The liquid outlet at the bottom of the absorption tower 12 is connected; the gas outlet at the top of the sulfuric acid lightness-removing tower 19 is connected with a condenser 21 at the top of the sulfuric acid lightness-removing tower, the gas outlet of the condenser 21 at the top of the sulfuric acid lightness-removing tower is connected with a vacuum system, and the liquid outlet of the condenser 21 at the top of the sulfuric acid lightness-removing tower passes through a reflux tank 22 of the sulfuric acid lightness-removing tower and a reflux port at the top of the sulfuric acid lightness-removing tower 19Connecting; a side draw outlet of the sulfuric acid lightness-removing tower 19 is connected with a G2 or G3 grade filter 17; the discharge port at the bottom of the sulfuric acid lightness-removing tower 19 is connected with the hot side inlet of the first feed preheater 16 and is used for preheating the electronic-grade sulfuric acid crude product to be fed into the sulfuric acid lightness-removing tower 19, the hot side outlet of the first feed preheater 16 is connected with the cold side inlet of the second feed preheater 18, and the cold side outlet of the second feed preheater 18 is connected with the feed port of the rectification and weight removal device.
The rectification and de-weighting device comprises a sulfuric acid de-weighting tower 23, a sulfuric acid de-weighting tower reboiler 24, a sulfuric acid de-weighting tower top condenser 25 and a sulfuric acid de-weighting tower reflux tank 26; the feed inlet of the sulfuric acid heavy component removal tower 23 is connected with the tower bottom discharge port of the sulfuric acid light component removal tower 19 through a second feed preheater 18; the gas outlet of the top of the sulfuric acid de-weighting tower 23 is connected with a condenser 25 at the top of the sulfuric acid de-weighting tower, the gas outlet of the condenser 25 at the top of the sulfuric acid de-weighting tower is connected with a vacuum system, the liquid outlet of the condenser 25 at the top of the sulfuric acid de-weighting tower is connected with a reflux tank 26 of the sulfuric acid de-weighting tower, the liquid outlet of the reflux tank 26 of the sulfuric acid de-weighting tower is respectively provided with a reflux pipeline and a product extraction pipeline which are connected with a reflux port at the top of the sulfuric acid de-weighting tower 23, and the product extraction pipeline is connected with a G4 or G5 grade filter 27; the discharge port at the bottom of the sulfuric acid de-weighting tower 23 is connected with the hot side inlet of the second feed preheater 18 for preheating the high-purity electronic-grade sulfuric acid to be fed into the sulfuric acid de-weighting tower 23.
99.55% by weight of liquid SO 3 As raw material, liquid SO 3 Also contains SO 2 0.2％、H 2 SO 4 0.25％、H 2 O 0.0001％、O 2 0.0002％、N 2 0.0003% and HF 0.0002%. The method for producing the G1-G5 electronic-grade sulfuric acid based on the system of the embodiment comprises the following steps:
step (1), industrial grade SO 3 Deep impurity removal: liquid SO 3 From SO via a first cooler 9 3 Preheating the heat generated by the absorption device to 35 ℃, entering a first rectifying tower 1 (the number of tower plates is 24, the operating temperature is 52 ℃, the operating pressure is 0.15MPa, the reflux ratio is 1.2), compressing the gas phase at the top of the first rectifying tower to 0.9MPa by a heat pump, sending the gas phase to a second rectifying tower reboiler 5 as a heat source, then entering a second rectifying tower condenser 6 for condensation, and sending the gas phase to a tail gas treatmentThe device is used for refluxing a liquid phase obtained by condensation to the first rectifying tower 1, and the reflux ratio is controlled to be 1.2; pumping the tower bottom material of the first rectifying tower 1 into a second rectifying tower 4 (the number of tower plates is 25, the operating temperature is 61 ℃, the operating pressure is 0.18MPa, the reflux ratio is 10), compressing the gas phase at the top of the second rectifying tower to 0.8MPa through a heat pump, sending the gas phase to a reboiler 2 of the first rectifying tower to be used as a heat source, then entering a condenser 3 of the first rectifying tower for condensation, wherein the gas phase is ultra-high purity SO 3 (purity 99.9999% by weight), to SO 3 And in the absorption device, the liquid phase obtained by condensation flows back to the second rectifying tower 4.
Step (2), ultrapure water absorption: mixing ultra-high purity SO 3 Continuously fed to the first SO 3 Absorption column 12, from third SO 3 EW-I level ultrapure water is continuously introduced into the absorption tower 14, and each SO is controlled 3 The operation temperature of the absorption tower is 40 ℃, and the operation pressure is 0.15MPa; SO (SO) 3 Spraying ultrapure water or sulfuric acid solution and gaseous SO on the top of the absorption tower 3 Absorbing with ultrapure water or sulfuric acid solution in countercurrent to generate sulfuric acid solution, collecting the generated sulfuric acid solution in a tower kettle, and collecting each SO 3 The tower bottom liquid of the absorption tower is circulated and refluxed to SO by the outside of the pump tower 3 The absorption tower is cooled in a cooler by cooling water (a second cooler 10 and a third cooler 11) or SO 3 Industrial grade liquid SO of rectification system 3 (first cooler 9) to remove the heat of reaction, and the rest is sent to the upper stage SO 3 The absorption tower is used as absorption liquid; detecting the first SO 3 The concentration of sulfuric acid in the tower kettle of the absorption tower 12 reaches 95.8 percent by weight, the content of metal impurities is 0.1 to 0.3ppm, and a crude product of electronic grade sulfuric acid is collected; from the third SO 3 Discharging residual gas phase components from the top of the absorption tower 14, and feeding the residual gas phase components into a tail gas treatment device;
the electronic grade sulfuric acid crude product passes through a G1 grade filter (a microfiltration membrane with the pore diameter of 0.5 mu m is filled inside the electronic grade sulfuric acid crude product), and the number of particles (the particle diameter is less than or equal to 1 mu m) is reduced to 19 particles/mL, so that G1 electronic grade sulfuric acid is obtained;
step (3), sulfuric acid lightness removal: from the first SO 3 The crude electronic-grade sulfuric acid product in the absorption tower 12 is preheated to 80 ℃ by high-purity electronic-grade sulfuric acid extracted from a discharge port at the bottom of the sulfuric acid lightness-removing tower, and is sent to the sulfuric acid lightness-removing tower 19 (the number of tower plates is 30, the operation temperature at the top of the tower is 65 ℃, and the operation at the bottom of the tower is carried outThe temperature is 235 ℃, the operating pressure is 0.05MPa, the reflux ratio is 0.5), the gas phase at the top of the tower is condensed, then the gas phase is connected with a vacuum system and then sent to a tail gas treatment device, the liquid phase reflows to a sulfuric acid lightness-removing tower 19 from the top of the tower, high-purity electronic-grade sulfuric acid (the sulfuric acid concentration is 96.2 wt%, and the content of metal impurities is less than or equal to 10 ppb) is taken out by measuring line at the 24 th plate of the sulfuric acid lightness-removing tower, the high-purity electronic-grade sulfuric acid is filtered by a G2 grade filter (a microfiltration membrane and a nanofiltration membrane with the inner part filled with the pore diameter of 0.1 mu m and the pore diameter of 0.5 nm), and the number of particles (the particle diameter is less than or equal to 0.5 mu m) is reduced to 13 particles/mL, so as to obtain the G2 electronic-grade sulfuric acid; or high-purity electronic-grade sulfuric acid (the concentration of the sulfuric acid is 95.9 percent by weight, and the content of metal impurities is less than or equal to 1 ppb) is extracted at the 6 th plate of the sulfuric acid lightness-removing tower through a side line, and the number of particles (the particle size is less than or equal to 0.5 mu m) is reduced to 3/mL through a G3-grade filter (a nanofiltration membrane with the pore diameter of 0.5nm and a nanofiltration membrane with the pore diameter of 0.2nm are filled inside the filter), so that the G3 electronic-grade sulfuric acid is obtained;
step (4), removing the weight of the high-purity sulfuric acid: preheating the tower bottom heavy components of a sulfuric acid lightness-removing tower 19, pumping the preheated tower bottom heavy components into a sulfuric acid weight-removing tower 23 (the number of tower plates is 25, the operation temperature of the tower top is 180 ℃, the operation temperature of the tower bottom is 211 ℃, and the operation pressure is 0.002 MPa), condensing the tower top materials of the sulfuric acid weight-removing tower, connecting a gas phase with a vacuum system, and sending the condensed gas phase to a tail gas treatment device, wherein the reflux ratio is controlled to be 1.5, and the liquid phase is ultra-pure sulfuric acid with the sulfuric acid concentration of 96.7 wt% and the metal impurity content of less than or equal to 0.1 ppb; controlling the reflux ratio to be 10, wherein the liquid phase is ultra-pure sulfuric acid with the sulfuric acid concentration of 96.9 percent and the metal impurity content of less than or equal to 0.01 ppb; the tower kettle is sulfuric acid containing heavy components (mainly metal impurities) and is used for preheating sulfuric acid light component removal tower kettle materials to enter a sulfuric acid heavy component removal tower;
96.7 wt% ultra-high-purity sulfuric acid with the metal impurity content less than or equal to 0.1ppb is extracted from the top of the sulfuric acid de-weighting tower 23, and the particle size index of the particles is controlled to be less than or equal to 0.2 mu m through a G4 grade microfiltration device (a nanofiltration membrane with the pore diameter of 0.5nm and a nanofiltration membrane with the pore diameter of 0.2nm are filled inside the ultra-high-purity sulfuric acid), so as to obtain G4 electronic grade sulfuric acid; controlling higher reflux ratio, extracting 96.9 wt% ultra-high purity sulfuric acid with metal impurity content less than or equal to 0.01ppb from the top of the de-weighting tower, and performing G5 grade ultrafiltration device (with nanofiltration membrane with pore diameter of 0.2nm filled inside) to obtain G5 electronic grade sulfuric acid.
Example 2
As shown in FIG. 2, a process of using gaseous SO 3 As raw materialsA system for producing electronic grade sulfuric acid comprising: SO (SO) 3 Rectification system for industrial grade SO 3 Rectifying and removing impurities; SO (SO) 3 Absorption apparatus of SO 3 Absorbing and reacting with ultrapure water or sulfuric acid solution to generate an electronic grade sulfuric acid crude product; the rectification light-removing device and the rectification heavy-removing device are used for purifying the electronic-grade sulfuric acid crude product; the ultrafiltration device is used for removing electronic-grade sulfuric acid particles; and the tail gas treatment device is used for treating the tail gas.
Said SO 3 The rectifying system comprises a first rectifying tower 1 and a second rectifying tower 4, wherein a feed inlet of the first rectifying tower 1 is connected with a raw material conveying pipeline, a first rectifying tower reboiler 2 is arranged at the bottom of the first rectifying tower 1, a heavy component discharge port is arranged at the bottom of the first rectifying tower 1, a gas outlet at the top of the first rectifying tower 1 is connected with a second rectifying tower reboiler 5 arranged at the bottom of the second rectifying tower 4 through a first compressor 7 to provide a heat source for the second rectifying tower reboiler, the second rectifying tower reboiler 5 is connected with a second rectifying tower condenser 6, a gas outlet of the second rectifying tower condenser 6 is connected with a gas inlet of the second rectifying tower 4, and a liquid outlet of the second rectifying tower condenser 6 is connected with a reflux port at the upper part of the first rectifying tower 1; an air outlet at the top of the second rectifying tower 4 is connected with a first rectifying tower reboiler 2 through a second compressor 8 to provide a heat source for the first rectifying tower reboiler, the first rectifying tower reboiler 2 is connected with a first rectifying tower condenser 3, a liquid outlet of the first rectifying tower condenser 3 is connected with a liquid inlet at the upper part of the second rectifying tower 4, and an air outlet of the first rectifying tower condenser 3 is connected with a tail gas treatment device to convey non-condensed gas to the tail gas treatment device for treatment; no. two rectifying column 4 tower bottom liquid outlet, side line gas outlet and SO 3 The absorption device is connected.
The first compressor 7 and the second compressor 8 are both heat pumps.
SO 3 The absorption device comprises a first SO 3 Absorption tower 12, second SO 3 Absorption tower 13, third SO 3 Absorber tower 14, static mixer 28, first SO 3 Absorption tower 12, second SO 3 Absorption tower 13, third SO 3 The absorption tower 14 is provided with a first cooler 9, a second cooler 10, a third cooler 11, and a fourth cooler 29, respectively; first, aSO 3 The gas inlet of the absorption tower 12 is connected with the side gas outlet of the second rectifying tower 4, and the former SO 3 The gas outlet at the top of the tower of the absorption tower and the next SO 3 The air inlet of the absorption tower is connected with the third SO 3 The gas outlet at the top of the absorption tower 14 is connected with a tail gas treatment device; second SO 3 Absorption tower 13, third SO 3 The liquid outlets at the bottom of the absorption tower 14 are respectively provided with two pipelines, and one pipeline returns SO through the respectively equipped cooler 3 The top of the absorption tower, the other pipeline and the former SO 3 The liquid inlet of the absorption tower is connected, and ultrapure water or sulfuric acid solution is input into the upper stage SO 3 The absorption tower is used as absorption liquid; first SO 3 The liquid outlet at the bottom of the absorption tower 12 is provided with two pipelines, one pipeline returns SO through the first cooler 9 3 The other pipeline of the tower top of the absorption tower is connected with a feed inlet of a sulfuric acid lightness-removing tower 19 of the rectification lightness-removing device through a first feed preheater 16; the first SO 3 The tower bottom liquid outlet of the absorption tower 12 is also connected with a G1 stage filter 15; a liquid inlet of the static mixer 28 is respectively connected with a liquid outlet at the bottom of the second rectifying tower 4 and an ultrapure water conveying pipeline, and a liquid outlet of the static mixer 28 is connected with the G1-grade filter 15 through a fourth cooler 29; the cooling water inlets of the 4 coolers are connected with a cooling water pipeline, and the cooling water outlets of the coolers are connected with a circulating pipeline to use hot water for SO in the system 3 Heat tracing prevention SO for pipelines and equipment 3 And (5) solidifying.
The rectification lightness-removing device comprises a sulfuric acid lightness-removing tower 19, a sulfuric acid lightness-removing tower reboiler 20, a sulfuric acid lightness-removing tower top condenser 21 and a sulfuric acid lightness-removing tower reflux tank 22; the feed inlet of the sulfuric acid lightness-removing tower 19 is connected with SO through a first feed preheater 16 3 First SO of absorption plant 3 The liquid outlet at the bottom of the absorption tower 12 is connected; the gas outlet at the top of the sulfuric acid lightness-removing tower 19 is connected with a condenser 21 at the top of the sulfuric acid lightness-removing tower, the gas outlet of the condenser 21 at the top of the sulfuric acid lightness-removing tower is connected with a vacuum system, and the liquid outlet of the condenser 21 at the top of the sulfuric acid lightness-removing tower is connected with the top reflux port of the sulfuric acid lightness-removing tower 19 through a reflux tank 22 of the sulfuric acid lightness-removing tower; a side draw outlet of the sulfuric acid lightness-removing tower 19 is connected with a G2 or G3 grade filter 17; the discharge hole at the bottom of the sulfuric acid lightness-removing tower 19 and the first feeding material are preheatedThe hot side inlet of the device 16 is connected with an electronic grade sulfuric acid crude product to be fed into a sulfuric acid lightness-removing tower 19, the hot side outlet of the first feed preheater 16 is connected with the cold side inlet of the second feed preheater 18, and the cold side outlet of the second feed preheater 18 is connected with the feed inlet of the rectification and de-weighting device.
The rectification and de-weighting device comprises a sulfuric acid de-weighting tower 23, a sulfuric acid de-weighting tower reboiler 24, a sulfuric acid de-weighting tower top condenser 25 and a sulfuric acid de-weighting tower reflux tank 26; the feed inlet of the sulfuric acid heavy component removal tower 23 is connected with the discharge outlet at the bottom of the sulfuric acid light component removal tower 19 through a second feed preheater 18; the gas outlet of the top of the sulfuric acid de-weighting tower 23 is connected with a condenser 25 at the top of the sulfuric acid de-weighting tower, the gas outlet of the condenser 25 at the top of the sulfuric acid de-weighting tower is connected with a vacuum system, the liquid outlet of the condenser 25 at the top of the sulfuric acid de-weighting tower is connected with a reflux tank 26 of the sulfuric acid de-weighting tower, the liquid outlet of the reflux tank 26 of the sulfuric acid de-weighting tower is respectively provided with a reflux pipeline and a product extraction pipeline which are connected with a reflux port at the top of the sulfuric acid de-weighting tower 23, and the product extraction pipeline is connected with a G4 or G5 grade filter 27; and a tower bottom discharge port of the sulfuric acid de-weighting tower 23 is connected with a hot side inlet of the second feeding preheater 18 and used for preheating high-purity electronic-grade sulfuric acid to enter the sulfuric acid de-weighting tower 23.
99.37% by weight of gaseous SO 3 As raw material, gaseous SO 3 Also contains SO 2 0.48％、H 2 SO 4 0.15％、H 2 O 0.0002％、O 2 0.00015％、N 2 0.00045% and HF 0.0008%. The method for producing the G1-G5 electronic-grade sulfuric acid based on the system of the embodiment comprises the following steps:
step (1), industrial grade SO 3 Deep impurity removal: gaseous SO 3 Entering a first rectifying tower 1 (the number of tower plates is 20, the operating temperature is 66 ℃, the operating pressure is 0.17MPa, and the reflux ratio is 0.8), compressing the gas phase at the top of the first rectifying tower 1 to 0.75MPa through a heat pump, sending the gas phase into a second rectifying tower reboiler 5 to be used as a heat source for heat exchange, then entering a second rectifying tower condenser 6 for condensation, refluxing the condensed liquid phase to the top of the first rectifying tower 1, and sending the condensed gas phase to a second rectifying tower 4 (the number of tower plates is 28, the operating temperature is 58 ℃, the operating pressure is 0.14MPa, and the reflux ratio is 30); the gas phase at the top of the second rectifying tower 4 passes through the heat pump pressureCondensing to 0.65MPa, sending to a reboiler 2 of a first rectifying tower for heat exchange as a heat source, then entering a condenser 3 of the first rectifying tower for condensation, sending the gas phase subjected to condensation treatment to a tail gas treatment device, refluxing the liquid phase obtained by condensation to a second rectifying tower 4, and collecting high-purity gas phase SO from the lower lateral line of the second rectifying tower 4 3 (99.9995% by weight), high purity gaseous SO 3 Is sent to SO 3 An absorption device;
step (2), ultrapure water absorption: introducing high-purity gas phase SO 3 Continuously fed to the first SO 3 Absorption column 12, from third SO 3 EW-I level ultrapure water is continuously introduced into the absorption tower 14, and each SO is controlled 3 The operation temperature of the absorption tower is 45 ℃, and the operation pressure is 0.13MPa; SO (SO) 3 Spraying ultrapure water or sulfuric acid solution and gaseous SO on the top of the absorption tower 3 Absorbing with ultrapure water or sulfuric acid solution in countercurrent to generate sulfuric acid solution, collecting the generated sulfuric acid solution in a tower kettle, and collecting each SO 3 The tower bottom liquid of the absorption tower is partially circulated and refluxed to SO by a pump tower 3 The absorption tower is cooled in a cooler by cooling water (a second cooler 10 and a third cooler 11) or SO 3 Industrial grade liquid SO of rectification system 3 (first cooler 9) to remove the heat of reaction, and the rest is sent to the upper stage SO 3 The absorption tower is used as absorption liquid; detecting the first SO 3 The sulfuric acid concentration in the tower kettle of the absorption tower 12 reaches 96.1 percent by weight, the content of metal impurities is 0.1 to 0.3ppm, and an electronic grade sulfuric acid crude product is obtained; from the third SO 3 Discharging the residual gas phase component from the top of the absorption tower 14, and feeding the residual gas phase component into a tail gas treatment device;
the electronic grade sulfuric acid crude product passes through a G1 grade filter (a microfiltration membrane with the pore diameter of 0.5 mu m is filled inside the electronic grade sulfuric acid crude product), and the number of particles (the particle diameter is less than or equal to 1 mu m) is reduced to 21 particles/mL, so that G1 electronic grade sulfuric acid is obtained;
step (3), sulfuric acid lightness removal: from the first SO 3 The crude electronic-grade sulfuric acid product of the absorption tower 12 is preheated to 65 ℃ from high-purity electronic-grade sulfuric acid extracted from a discharge port at the bottom of a light sulfuric acid removal tower, is sent into a light sulfuric acid removal tower 19 (the number of tower plates is 26, the operation temperature at the top of the tower is 67 ℃, the operation temperature at the bottom of the tower is 245 ℃, the operation pressure is 0.06MPa, the reflux ratio is 0.8), the gas phase at the top of the tower is condensed, is connected with a vacuum system and then is sent to a tail gas treatment device, and the liquid phase reflows to a tail gas treatment device from the top of the towerA sulfuric acid lightness removing tower 19, which is used for extracting high-purity electronic-grade sulfuric acid (the sulfuric acid concentration is 96.4 percent by weight, and the content of metal impurities is less than or equal to 10 ppb) at a measuring line at a 20 th plate of the sulfuric acid lightness removing tower, filtering the high-purity electronic-grade sulfuric acid by a G2-grade filter (a microfiltration membrane with the pore diameter of 0.1 mu m and a nanofiltration membrane with the particle diameter of 0.5nm are filled inside the high-purity electronic-grade sulfuric acid), and reducing the number of particles (the particle diameter is less than or equal to 0.5 mu m) to 16 particles/mL to obtain the G2 electronic-grade sulfuric acid; or high-purity electronic-grade sulfuric acid (the concentration of the sulfuric acid is 96.3 percent by weight, and the content of metal impurities is less than or equal to 1 ppb) is extracted at the 6 th plate of the sulfuric acid lightness-removing tower through a side line, and the number of particles (the particle size is less than or equal to 0.5 mu m) is reduced to 3/mL through a G3-grade filter (a nanofiltration membrane with the pore diameter of 0.5nm and a nanofiltration membrane with the pore diameter of 0.2nm are filled inside the filter), so that the G3 electronic-grade sulfuric acid is obtained;
step (4), removing the weight of the high-purity sulfuric acid: preheating the tower bottom materials of a 19-tower bottom of a sulfuric acid lightness-removing tower by using heavy components of a 23-tower bottom of the sulfuric acid lightness-removing tower, then pumping the preheated materials into a 23-tower top of the sulfuric acid lightness-removing tower (the number of tower plates is 28, the operation temperature of the tower top is 188 ℃, the operation temperature of the tower bottom is 216 ℃, and the operation pressure is 0.005 MPa), condensing the tower top materials of the sulfuric acid lightness-removing tower, connecting a gas phase with a vacuum system, and then sending the condensed materials to a tail gas treatment device, wherein the reflux ratio is controlled to be 2.2, and a liquid phase is ultra-pure sulfuric acid with the sulfuric acid concentration of 96.6 wt% and the metal impurity content of less than or equal to 0.1 ppb; controlling the reflux ratio to be 12.5, wherein the liquid phase is ultra-pure sulfuric acid with the sulfuric acid concentration of 96.8 percent and the metal impurity content of less than or equal to 0.01 ppb; the tower kettle is sulfuric acid containing heavy components (mainly metal impurities) and is used for preheating sulfuric acid lightness-removing tower kettle materials to enter a sulfuric acid weight-removing tower;
96.6 wt% of ultra-high purity sulfuric acid with the metal impurity content less than or equal to 0.1ppb is extracted from the top of the sulfuric acid de-weighting tower 23, and the particle size index of the particles is controlled to be less than or equal to 0.2 mu m by a G4 grade microfiltration device (the inside of which is filled with a nanofiltration membrane with the pore diameter of 0.5nm and a nanofiltration membrane with the pore diameter of 0.2 nm), so as to obtain G4 electronic grade sulfuric acid; controlling higher reflux ratio, extracting 96.8 wt% ultra-high-purity sulfuric acid with metal impurity content less than or equal to 0.01ppb from the top of the de-weighting tower, and performing G5 grade ultrafiltration device (with nanofiltration membrane with pore diameter of 0.2nm filled inside) to obtain G5 electronic grade sulfuric acid.
Example 3
In 99.12% by weight of gaseous SO 3 As raw material, gaseous SO 3 Also contains SO 2 0.55％、H 2 SO 4 0.33％、H 2 O0.0004％、O 2 0.0003％、N 2 0.0007％0.0012 percent of HF. The method for producing the G1-G5 electronic grade sulfuric acid based on the system of the embodiment 2 comprises the following steps:
step (1), industrial grade SO 3 Deep impurity removal: gaseous SO 3 Entering a first rectifying tower 1 (the number of tower plates is 22, the operating temperature is 73 ℃, the operating pressure is 0.175MPa, and the reflux ratio is 2), compressing a gas phase at the top of the first rectifying tower 1 to 1.1MPa through a heat pump, sending the gas phase into a second rectifying tower reboiler 5 to be used as a heat source for heat exchange, then entering a second rectifying tower condenser 6 for condensation, refluxing a liquid phase obtained by condensation to the top of the first rectifying tower 1, and sending the gas phase after condensation treatment to a second rectifying tower 4 (the number of tower plates is 24, the operating temperature is 65 ℃, the operating pressure is 0.16MPa, and the reflux ratio is 30); the gas phase at the top of the second rectifying tower 4 is compressed to 0.95MPa through a heat pump, and is sent to a first rectifying tower reboiler 2 to be used as a heat source for heat exchange, and then enters a first rectifying tower condenser 3 for condensation, the gas phase after condensation treatment is sent to a tail gas treatment device, the liquid phase obtained by condensation flows back to the second rectifying tower 4, and high-purity liquid phase SO is extracted from the tower kettle of the second rectifying tower 4 3 (99.9999% by weight), high purity liquid phase SO 3 To SO 3 An absorption device.
Step (2), ultrapure water absorption: mixing high-purity liquid phase SO 3 The raw material and EW-I level ultrapure water are fed into a static mixer 28 according to the mass ratio of 3.5 to react to generate an electronic level sulfuric acid crude product (the sulfuric acid concentration is 95.3 wt%, and the metal impurity content is 0.1-0.3 ppm), and the reaction heat is removed through a fourth cooler 29, and the temperature of a sulfuric acid outlet is controlled to be 45 ℃;
the electronic grade sulfuric acid crude product passes through a G1 grade filter (a microfiltration membrane with the pore diameter of 0.5 mu m is filled inside the electronic grade sulfuric acid crude product), and the number of particles (the particle diameter is less than or equal to 1 mu m) is reduced to 13 particles/mL, so that G1 electronic grade sulfuric acid is obtained;
step (3), removing light of crude sulfuric acid: from the first SO 3 The crude product of the electronic-grade sulfuric acid in the absorption tower 12 is preheated to 77 ℃ from high-purity electronic-grade sulfuric acid extracted from a discharge port at the bottom of the sulfuric acid lightness-removing tower, sent to the sulfuric acid lightness-removing tower 19 (the number of tower plates is 30, the operation temperature at the top of the tower is 68 ℃, the operation temperature at the bottom of the tower is 255 ℃, the operation pressure is 0.075MPa, and the reflux ratio is 0.5), the gas phase at the top of the tower is condensed, then sent to a tail gas treatment device after being connected with a vacuum system, and the liquid phase reflows to the sulfuric acid lightness-removing tower 19 from the top of the tower, and then sent to the sulfuric acid lightness-removing tower 19 in the sulfuric acid lightness-removing processExtracting high-purity electronic-grade sulfuric acid (the concentration of the sulfuric acid is 95.7 percent by weight, and the content of metal impurities is less than or equal to 10 ppb) from a 25 th plate measuring line of the light tower, filtering the high-purity electronic-grade sulfuric acid by using a G2-grade filter (a microfiltration membrane with the pore diameter of 0.1 mu m and a nanofiltration membrane with the particle diameter of 0.5nm are filled inside the high-purity electronic-grade sulfuric acid), and reducing the number of particles (the particle diameter is less than or equal to 0.5 mu m) to 11 particles/mL to obtain G2 electronic-grade sulfuric acid; or high-purity electronic-grade sulfuric acid (the concentration of the sulfuric acid is 96.0 percent by weight, and the content of metal impurities is less than or equal to 1 ppb) is extracted at the lateral line of the 5 th plate of the sulfuric acid lightness-removing tower, and the number of particles (the particle size is less than or equal to 0.5 mu m) is reduced to 1/mL through a G3-grade filter (a nanofiltration membrane with the pore diameter of 0.5nm and a nanofiltration membrane with the pore diameter of 0.2nm are filled inside the filter), so that the G3 electronic-grade sulfuric acid is obtained;
step (4), removing the weight of the high-purity sulfuric acid: preheating the tower bottom materials of a 19-tower sulfuric acid lightness-removing tower by using the tower bottom heavy components of a 23-tower sulfuric acid lightness-removing tower, pumping the preheated tower bottom materials into a 23-tower sulfuric acid lightness-removing tower (the number of tower plates is 24, the operation temperature of the tower top is 185 ℃, the operation temperature of the tower bottom is 213 ℃, and the operation pressure is 0.004 MPa), condensing the tower top materials of the sulfuric acid lightness-removing tower, connecting a gas phase with a vacuum system, and then delivering the condensed gas phase to a tail gas treatment device, wherein the reflux ratio is controlled to be 3.5, and the liquid phase is ultra-pure sulfuric acid with the sulfuric acid concentration of 96.3 percent by weight and the metal impurity content of less than or equal to 0.1 ppb; controlling the reflux ratio of 14, wherein the liquid phase is ultra-pure sulfuric acid with the sulfuric acid concentration of 96.6 percent and the metal impurity content of less than or equal to 0.01 ppb; the tower kettle is sulfuric acid containing heavy components (mainly metal impurities) and is used for preheating the material to enter the sulfuric acid light component removal tower kettle of the sulfuric acid heavy component removal tower;
96.3 wt% ultra-high-purity sulfuric acid with the metal impurity content less than or equal to 0.1ppb is extracted from the top of the sulfuric acid de-weighting tower 23, and the particle size index of the particles is controlled to be less than or equal to 0.2 mu m through a G4 grade microfiltration device (a nanofiltration membrane with the pore diameter of 0.5nm and a nanofiltration membrane with the pore diameter of 0.2nm are filled inside the ultra-high-purity sulfuric acid), so as to obtain G4 electronic grade sulfuric acid; controlling higher reflux ratio, extracting 96.6 wt% ultra-high-purity sulfuric acid with metal impurity content less than or equal to 0.01ppb from the top of the de-weighting tower, and performing G5 grade ultrafiltration device (with nanofiltration membrane with pore diameter of 0.2nm filled inside) to obtain G5 electronic grade sulfuric acid.
Example 4
As shown in fig. 2, a fuming sulfuric acid evaporator 30 is added on the basis of example 2 to obtain a system for producing electronic-grade sulfuric acid by using fuming sulfuric acid as a raw material, an air outlet of the fuming sulfuric acid evaporator 30 is connected with a feed inlet of a first rectifying tower 1, the fuming sulfuric acid evaporator 30 is provided with a jacket, an inlet of the jacket is connected with an air outlet at the top of a sulfuric acid de-weighting tower 23 in a rectification de-weighting device, a gas phase at the top of the sulfuric acid de-weighting tower serves as a heat source, and an outlet of the jacket is connected with a condenser 25 at the top of the sulfuric acid de-weighting tower in the rectification de-weighting device.
With SO 3 The concentration is 20% wt fuming sulfuric acid as raw material (containing SO) 2 0.1％、H 2 O 1.79％、O 2 0.003％、N 2 0.0045% and HF 0.0005%) as raw materials, and based on the method for producing G1-G5 electronic grade sulfuric acid by the system of the present embodiment, the steps are as follows:
step (1), industrial grade SO 3 Deep impurity removal: fuming sulfuric acid enters a fuming sulfuric acid evaporator 30, gas phase materials from the top of a sulfuric acid heavy-removing tower are taken as a heat source and are introduced into a jacket of the fuming sulfuric acid evaporator 30, and evaporated gas phase SO 3 The gas phase at the top of the first rectifying tower 1 is compressed to 0.9MPa through a heat pump, and is sent to a second rectifying tower reboiler 5 to be used as a heat source for heat exchange, and then is sent to a second rectifying tower condenser 6 for condensation, the condensed liquid phase flows back to the top of the first rectifying tower 1, and the condensed gas phase is sent to a second rectifying tower 4 (the number of the tower plates is 22, the operating temperature is 61 ℃, the operating pressure is 0.145MPa, and the reflux ratio is 45); the gas phase at the top of the second rectifying tower 4 is compressed to 0.88MPa by a heat pump, sent to a first rectifying tower reboiler 2 to be used as a heat source for heat exchange, then enters a first rectifying tower condenser 3 for condensation, the gas phase after condensation treatment is sent to a tail gas treatment device, the liquid phase obtained by condensation flows back to the second rectifying tower 4, and high-purity gas phase SO is extracted from the lower part of the second rectifying tower 4 3 (99.9998% by weight), high purity gaseous SO 3 Is sent to SO 3 An absorption device;
step (2), ultrapure water absorption: mixing ultra-high purity SO 3 Continuously delivered to the first SO 3 Absorption column 12, from third SO 3 EW-I level ultrapure water is continuously fed into the absorption tower 14, and each SO is controlled 3 The operation temperature of the absorption tower is 45 ℃, and the operation pressure is 0.13MPa; SO 3 Spraying ultrapure water or sulfuric acid solution and gaseous SO on the top of the absorption tower 3 And ultra pure water or sulfuric acid solution are absorbed in a counter-current way to generate sulfuric acid solutionThe sulfuric acid solution is collected in the tower kettle, and each SO 3 The tower bottom liquid of the absorption tower is partially circulated and refluxed to SO by a pump tower 3 Absorption tower and cooling water (second cooler 10, third cooler 11) or SO in the cooler 3 Industrial grade liquid SO of rectification system 3 (first cooler 9) to remove the heat of reaction, and the rest is sent to the upper stage SO 3 The absorption tower is used as absorption liquid; detecting the first SO 3 The concentration of sulfuric acid in the tower kettle of the absorption tower 12 reaches 95.5 percent by weight, the content of metal impurities is 0.1 to 0.3ppm, and a crude electronic grade sulfuric acid product is collected; from the third SO 3 Discharging the residual gas phase component from the top of the absorption tower 14, and feeding the residual gas phase component into a tail gas treatment device;
the electronic grade sulfuric acid crude product passes through a G1 grade filter (a microfiltration membrane with the pore diameter of 0.5 mu m is filled inside the electronic grade sulfuric acid crude product), and the number of particles (the particle diameter is less than or equal to 1 mu m) is reduced to 14 particles/mL, so that G1 electronic grade sulfuric acid is obtained;
step (3), removing light of crude sulfuric acid: from the first SO 3 The crude product of the electronic-grade sulfuric acid in the absorption tower 12 is preheated to 77 ℃ from the high-purity electronic-grade sulfuric acid extracted from a discharge port at the bottom of the sulfuric acid lightness-removing tower, sent to the sulfuric acid lightness-removing tower 19 (the number of tower plates is 24, the operation temperature at the top of the tower is 63 ℃, the operation temperature at the bottom of the tower is 251 ℃, the operation pressure is 0.08MPa, the reflux ratio is 0.7), the gas phase at the top of the tower is condensed, then sent to a tail gas treatment device after being connected with a vacuum system, the liquid phase reflows to the sulfuric acid lightness-removing tower 19 from the top of the tower, the high-purity electronic-grade sulfuric acid (the sulfuric acid concentration is 96.3 wt, and the content of metal impurities is less than or equal to 10 ppb) is extracted at a measuring line at the 28 th plate of the sulfuric acid lightness-removing tower, and filtered by a G2-grade filter (a microfiltration membrane with the inner diameter of 0.1 μm and a nanofiltration membrane with the particle diameter of 0.5nm are filled inside), the number of particles is reduced to 18/mL, and G2-grade electronic-grade sulfuric acid is obtained; or high-purity electronic-grade sulfuric acid (the concentration of the sulfuric acid is 96.1 percent by weight, and the content of metal impurities is less than or equal to 1 ppb) is extracted at the position of the 8 th plate of the sulfuric acid lightness-removing tower through the lateral line, and the number of particles (the particle size is less than or equal to 0.5 mu m) is reduced to 2/mL through a G3-grade filter (nanofiltration membranes with the pore diameter of 0.5nm and 0.2nm are filled inside the filter), so that the G3 electronic-grade sulfuric acid is obtained;
step (4), removing the weight of the high-purity sulfuric acid: preheating the tower bottom materials of a 19-tower bottom of a sulfuric acid lightness-removing tower by using heavy components of a 23-tower bottom of the sulfuric acid lightness-removing tower, then pumping the preheated materials into a 23-tower top of the sulfuric acid lightness-removing tower (the number of tower plates is 30, the operation temperature of the tower top is 181 ℃, the operation temperature of the tower bottom is 203 ℃, and the operation pressure is 0.002 MPa), condensing the tower top materials of the sulfuric acid lightness-removing tower, connecting a gas phase with a vacuum system, and then sending the condensed materials to a tail gas treatment device, wherein the reflux ratio is controlled to be 3.1, and a liquid phase is ultra-pure sulfuric acid with the sulfuric acid concentration of 96.5 wt% and the metal impurity content of less than or equal to 0.1 ppb; controlling the reflux ratio to be 14, wherein the liquid phase is ultra-pure sulfuric acid with the sulfuric acid concentration of 96.7 percent and the metal impurity content of less than or equal to 0.01 ppb; the tower kettle is sulfuric acid containing heavy components (mainly metal impurities) and is used for preheating sulfuric acid light component removal tower kettle materials to enter a sulfuric acid heavy component removal tower;
96.5-wt% ultra-high-purity sulfuric acid with the metal impurity content of less than or equal to 0.1ppb is extracted from the top of the sulfuric acid de-weighting tower 23, and the particle size index of the particles is controlled to be less than or equal to 0.2 mu m through a G4-level microfiltration device (a nanofiltration membrane with the pore diameter of 0.5nm and a nanofiltration membrane with the pore diameter of 0.2nm are filled inside the ultra-high-purity sulfuric acid), so that G4 electronic-level sulfuric acid is obtained; controlling higher reflux ratio, extracting 96.7 wt% ultra-high-purity sulfuric acid with metal impurity content less than or equal to 0.01ppb from the top of the de-weighting tower, and performing G5 grade ultrafiltration device (with nanofiltration membrane with pore diameter of 0.2nm filled inside) to obtain G5 electronic grade sulfuric acid.
The specific embodiments are merely illustrative and not restrictive, and those skilled in the art can modify the embodiments without inventive contribution as required after reading this specification, but only within the scope of the claims of the present invention.

Claims (13)

1. A method for producing G1-G5 electronic grade sulfuric acid is characterized in that: the method comprises the following steps:
step (1), rectification and impurity removal: by SO 3 Rectification system for industrial grade SO 3 Rectifying and removing impurities to obtain ultra-high purity SO with the purity of more than or equal to 99.999 percent by weight 3 ；
When industrial grade SO 3 Is industrial grade liquid SO 3 In the process, the rectification impurity removal is as follows: industrial grade SO 3 First from SO 3 Preheating the heat generated by the absorption device to 20-50 ℃, then entering a first rectifying tower, pressurizing the gas phase at the top of the first rectifying tower by a compressor, then sending the gas phase into a reboiler of a second rectifying tower for heat exchange, condensing by a condenser, and refluxing the liquid phase obtained by condensation to the first rectifying towerA distillation column; pumping the material at the bottom of the first rectifying tower into a second rectifying tower, pressurizing the gas phase at the top of the second rectifying tower by a compressor, sending the gas phase into a reboiler of the first rectifying tower for heat exchange, and condensing the gas phase by a condenser, wherein the gas phase is ultrahigh-purity SO 3 To SO 3 The absorption device is used for refluxing the liquid phase obtained by condensation to the second rectifying tower;
the number of plates of the first rectifying tower is 10-40; the operation temperature is 30-100 ℃; the operating pressure is 0.05-0.5 MPa; the reflux ratio is 0.2 to 15;
pressurizing the gas phase at the top of the first rectifying tower to the pressure of 0.4-1.5 MPa;
the number of plates of the second rectifying tower is 10-50; the operation temperature is 20-120 ℃; the operating pressure is 0.05-0.5 MPa; the reflux ratio is 2-80;
pressurizing the overhead gas camera of the second rectifying tower to the pressure of 0.5-1.5 MPa;
when industrial grade SO 3 Is industrial grade gaseous SO 3 Or when fuming sulfuric acid, the rectification impurity removal is as follows: SO in oleum is evaporated by an evaporator 3 Then enters a rectifying tower I or industrial grade gaseous SO 3 Directly entering a first rectifying tower, pressurizing a gas phase at the top of the first rectifying tower by a compressor, sending the gas phase into a reboiler of a second rectifying tower for heat exchange, condensing by a condenser, refluxing a liquid phase obtained by condensation to the top of the first rectifying tower, and sending the condensed gas phase to the second rectifying tower; the gas phase at the top of the second rectifying tower is pressurized by a compressor and then sent into a reboiler of the first rectifying tower for heat exchange, then condensed by a condenser, the liquid phase obtained by condensation reflows to the second rectifying tower, and high-purity gas phase SO is extracted from the side line of the second rectifying tower 3 Or high-purity liquid phase SO is extracted from the tower bottom of the second rectifying tower 3 (ii) a High purity gaseous SO 3 And/or high purity liquid phase SO 3 Is sent to SO 3 An absorption device;
the number of plates of the first rectifying tower 1 is 10-40; the operation temperature is 35-110 ℃; the operating pressure is 0.05-0.5 MPa;
pressurizing the gas phase at the top of the first rectifying tower to the pressure of 0.5-1.5 MPa;
the number of plates of the second rectifying tower 4 is 10-50; the operation temperature is 25-110 ℃; the operating pressure is 0.05-0.5 MPa;
pressurizing the gas phase at the top of the second rectifying tower to the pressure of 0.4-2 MPa;
step (2), ultrapure water absorption: ultra-high purity SO 3 Into SO 3 An absorption device which performs countercurrent absorption or static mixing with the absorption liquid to obtain an electronic grade sulfuric acid crude product with the sulfuric acid concentration of 95-97 percent by weight;
SO 3 the absorption device comprises 1-9 SO connected in series in sequence 3 Absorption tower of each SO 3 The absorption tower is equipped with a cooler in which cooling water or SO is fed 3 Industrial grade liquid SO of rectification system 3 Removing reaction heat;
removing particles from the electronic grade sulfuric acid crude product through a G1 grade filter to obtain G1 grade electronic grade sulfuric acid;
or the electronic-grade sulfuric acid crude product enters a rectification lightness-removing device to be subjected to rectification lightness-removing treatment and removal, so that high-purity electronic-grade sulfuric acid is obtained;
removing particles from the high-purity electronic-grade sulfuric acid by a G2-grade filter or a G3-grade filter to obtain G2-grade or G3-grade electronic-grade sulfuric acid; or the high-purity electronic-grade sulfuric acid enters a rectification and de-weighting device to be rectified and de-weighted to obtain the ultra-high-purity electronic-grade sulfuric acid, and the G4-grade filter or the G5-grade filter is adopted to remove particles to obtain the G4-grade or G5-grade electronic-grade sulfuric acid.
2. The process for producing G1-G5 electronic grade sulfuric acid according to claim 1, characterized in that: in step (1), when the industrial grade SO 3 Is industrial grade liquid SO 3 In the process, the number of plates of the first rectifying tower is 15-30; the operation temperature is 40-70 ℃; the operating pressure is 0.1-0.3 MPa; the reflux ratio is 0.5 to 8;
pressurizing the gas phase at the top of the first rectifying tower to the pressure of 0.6-1.0 MPa;
the number of plates of the second rectifying tower is 20-35; the operation temperature is 40-80 ℃; the operating pressure is 0.1-0.3 MPa; the reflux ratio is 5 to 60;
pressurizing the overhead gas camera of the second rectifying tower to the pressure of 0.6-1.0 MPa;
when industrial grade SO 3 Is industrial grade gaseous SO 3 Or when fuming sulfuric acid, rectification No. oneThe number of the plates of the tower 1 is 15-30; the operation temperature is 45-75 ℃; the operating pressure is 0.1-0.3 MPa;
pressurizing the gas phase at the top of the first rectifying tower to the pressure of 0.6-1.0 MPa;
the number of plates of the second rectifying tower 4 is 20-35; the operation temperature is 50-90 ℃; the operating pressure is 0.1-0.3 MPa;
the gas phase at the top of the second rectifying tower is pressurized to the pressure of 0.6 to 1.5MPa.
3. The process for producing G1-G5 electronic grade sulfuric acid according to claim 1, characterized in that: in the step (2), the absorption liquid is ultrapure water or ultrahigh-purity SO 3 With ultra pure water in SO 3 The sulfuric acid solution formed in the device is absorbed.
4. The process for producing G1-G5 electronic grade sulfuric acid according to claim 1, characterized in that: in the step (2), the operation temperature of each absorption tower is 10-60 ℃, and the operation pressure is 0.05-0.5 MPa.
5. The process for producing G1-G5 electronic grade sulfuric acid according to claim 1, characterized in that: in step (2), SO 3 The absorption device comprises 2-5 SO connected in series in sequence 3 An absorption tower.
6. The process for producing G1-G5 electronic grade sulfuric acid according to claim 4, characterized in that: in the step (2), the operation temperature of each absorption tower is 20-50 ℃, and the operation pressure is 0.1-0.3 MPa.
7. The process for producing G1-G5 electronic grade sulfuric acid according to claim 1, 3 or 4, characterized in that: in the step (2), ultra-high purity SO 3 Is gaseous SO 3 From SO 3 Introducing gaseous SO to the bottom of the absorption tower 3 From SO 3 Spraying absorption liquid and gaseous SO from the top of the absorption tower 3 Absorbing with absorption liquid in counter current to generate sulfuric acid solution, SO 3 The sulfuric acid solution in the tower kettle of the absorption tower is circulated to SO outside the tower 3 Continuously spraying and mixing the water and the water on the top of the absorption towerHigh purity SO 3 Counter-current absorption and cooling water or SO to be introduced into the cooler while circulating outside the tower 3 Industrial grade liquid SO of rectification system 3 Heat exchange is carried out to remove reaction heat; when SO 3 The sulfuric acid concentration in the tower kettle of the absorption tower reaches 95-97 percent by weight, and an electronic grade sulfuric acid crude product is obtained;
ultra-high purity SO 3 Is liquid SO 3 Very high purity SO 3 Mixing with ultrapure water in a static mixer, and cooling to obtain the electronic grade sulfuric acid crude product.
8. The process for producing G1-G5 electronic grade sulfuric acid according to claim 1, characterized in that: in the step (3), the rectification lightness-removing treatment comprises the following steps: preheating the electronic-grade sulfuric acid crude product, then feeding the preheated electronic-grade sulfuric acid crude product into a sulfuric acid lightness-removing tower, condensing materials at the top of the sulfuric acid lightness-removing tower, refluxing a liquid phase to the sulfuric acid lightness-removing tower from the top of the sulfuric acid lightness-removing tower, extracting high-purity electronic-grade sulfuric acid from a measuring line of the sulfuric acid lightness-removing tower, exchanging heat with the electronic-grade sulfuric acid crude product to be fed into the sulfuric acid lightness-removing tower, and filtering the electronic-grade sulfuric acid crude product by a G2 or G3 filter to obtain G2 or G3 electronic sulfuric acid; feeding the material in the tower bottom of the light sulfuric acid removal tower into a rectification and de-weighting device for de-weighting treatment;
the number of the plates of the sulfuric acid lightness-removing tower is 10-40; the operation temperature at the top of the tower is 30-90 ℃; the operation temperature of the tower kettle is 150-310 ℃; the operating pressure is 0.005-0.1 MPa; the reflux ratio is 0.1-2.
9. The process for producing G1-G5 electronic grade sulfuric acid according to claim 8, characterized in that: the number of the plates of the sulfuric acid lightness-removing tower is 10-30; the operation temperature at the top of the tower is 40-70 ℃; the operation temperature of the tower kettle is 200-260 ℃; the operation pressure is 0.01-0.1 MPa; the reflux ratio is 0.2 to 1.
10. The process for producing G1-G5 electronic grade sulfuric acid according to claim 1, characterized in that: in the step (3), the rectification and de-weight treatment comprises the following steps: preheating high-purity electronic-grade sulfuric acid, then feeding the preheated high-purity electronic-grade sulfuric acid into a sulfuric acid de-weighting tower, condensing materials at the top of the sulfuric acid de-weighting tower, refluxing a part of liquid phase from the top of the tower to the sulfuric acid de-weighting tower, extracting the rest part of the liquid phase, and passing through a G5-grade filter to obtain G5-grade electronic-grade sulfuric acid, wherein heavy components at the tower kettle of the sulfuric acid de-weighting tower are used for preheating the high-purity electronic-grade sulfuric acid to be fed into the sulfuric acid de-weighting tower;
the number of plates of the sulfuric acid heavy-duty tower is 15-50; the operation temperature at the top of the tower is 100-220 ℃; the operation temperature of the tower kettle is 150-250 ℃; the operating pressure is 0.0001-0.1 MPa; the reflux ratio is 0.2-5.
11. The process for producing G1-G5 electronic grade sulfuric acid according to claim 10, characterized in that: the number of plates of the sulfuric acid heavy-duty tower is 20-35; the operation temperature at the top of the tower is 150-190 ℃; the operation temperature of the tower kettle is 180-220 ℃; the operation pressure is 0.001 to 0.05MPa; the reflux ratio is 0.5 to 2.
12. A system for producing G1-G5 electronic grade sulfuric acid as claimed in claim 1, characterized in that: the method comprises the following steps: SO (SO) 3 Rectification system for industrial grade SO 3 Rectifying and removing impurities; SO 3 Absorption apparatus of SO 3 Absorbing and reacting with ultrapure water or sulfuric acid solution to generate an electronic grade sulfuric acid crude product; the rectification light-removing device and the rectification heavy-removing device are used for purifying the electronic-grade sulfuric acid crude product; the ultrafiltration device is used for removing electronic-grade sulfuric acid particles;
when industrial grade SO 3 Is industrial grade liquid SO 3 When said SO is 3 The rectifying system comprises a rectifying tower I and a rectifying tower II, wherein a feed inlet of the rectifying tower I is connected with a raw material conveying pipeline, and the raw material conveying pipeline is connected with SO 3 First SO in the absorber 3 The cooler of the absorption tower is connected with SO 3 Absorption of heat generated by the apparatus to industrial grade liquid SO 3 Preheating is carried out; the bottom of the first rectifying tower is provided with a first rectifying tower reboiler, the bottom discharge port of the first rectifying tower is connected with the feed inlet of a second rectifying tower, the top gas outlet of the first rectifying tower is connected with the second rectifying tower reboiler arranged at the bottom of the second rectifying tower through a first compressor, the second rectifying tower reboiler is connected with a second rectifying tower condenser, and the liquid outlet of the second rectifying tower condenser is connected with the reflux port of the first rectifying tower; the gas outlet of the second rectifying tower is connected with the first rectifying tower through a gas inletThe second compressor is connected with the first rectifying tower reboiler, the first rectifying tower reboiler is connected with the first rectifying tower condenser, the liquid outlet of the first rectifying tower condenser is connected with the liquid inlet of the second rectifying tower, and the gas outlet of the first rectifying tower condenser is connected with the SO 3 The air inlet of the absorption device is connected;
when industrial grade SO 3 Is industrial grade gaseous SO 3 When said SO is 3 The rectifying system comprises a first rectifying tower and a second rectifying tower, wherein a feeding port of the first rectifying tower is connected with a raw material conveying pipeline, a first rectifying tower reboiler is arranged at the bottom of the first rectifying tower, a heavy component discharging port is arranged at the bottom of the first rectifying tower, a gas outlet of the first rectifying tower is connected with the second rectifying tower reboiler arranged at the bottom of the second rectifying tower through a first compressor, the second rectifying tower reboiler is connected with a second rectifying tower condenser, and a liquid outlet of the second rectifying tower condenser is connected with a reflux port at the upper part of the first rectifying tower; the gas outlet of the second rectifying tower is connected with the first rectifying tower reboiler through a second compressor to provide a heat source for the first rectifying tower reboiler, the first rectifying tower reboiler is connected with the first rectifying tower condenser, and the liquid outlet of the first rectifying tower condenser is connected with the liquid inlet of the second rectifying tower; liquid outlet at bottom of second rectifying tower, side gas outlet and SO 3 The absorption device is connected;
when industrial grade SO 3 In the case of oleum, industrial-grade gaseous SO is suitable 3 SO of (A) 3 The upper part of the rectification system is provided with a fuming sulfuric acid evaporator, the gas outlet of the fuming sulfuric acid evaporator is connected with the feed inlet of the first rectification tower, the fuming sulfuric acid evaporator is provided with a jacket, the inlet of the jacket is connected with the gas outlet at the top of the sulfuric acid de-weighting tower in the rectification de-weighting device, the gas phase at the top of the sulfuric acid de-weighting tower is used as a heat source, and the outlet of the jacket is connected with the condenser at the top of the sulfuric acid de-weighting tower in the rectification de-weighting device.
13. The system of G1-G5 electronic grade sulfuric acid of claim 12, wherein: the rectification lightness-removing device comprises a sulfuric acid lightness-removing tower, a reboiler of the sulfuric acid lightness-removing tower, a condenser at the top of the sulfuric acid lightness-removing tower and a reflux tank of the sulfuric acid lightness-removing tower; the feed inlet of the sulfuric acid lightness-removing tower passes through a first feed preheaterWith SO 3 The discharge port of the absorption device is connected; the top gas outlet of the tower of the sulfuric acid lightness-removing tower is connected with a condenser at the top of the sulfuric acid lightness-removing tower, the gas outlet of the condenser at the top of the sulfuric acid lightness-removing tower is connected with a tail gas treatment device through a vacuum system, and the liquid outlet of the condenser at the top of the sulfuric acid lightness-removing tower is connected with the top reflux port of the sulfuric acid lightness-removing tower through a reflux tank of the sulfuric acid lightness-removing tower; the tower bottom discharge port of the sulfuric acid lightness-removing tower is connected with the heat supply medium inlet of the first feed preheater, and the heat supply medium outlet of the first feed preheater is connected with the feed port of the rectification de-weighting device through the second feed preheater; the side line extraction outlet of the sulfuric acid lightness-removing tower is connected with a G1 or G2 grade filter;
the rectification and de-weighting device comprises a sulfuric acid de-weighting tower, a sulfuric acid de-weighting tower reboiler, a sulfuric acid de-weighting tower top condenser and a sulfuric acid de-weighting tower reflux tank; the feed inlet of the sulfuric acid heavy component removal tower is connected with the discharge outlet at the bottom of the sulfuric acid light component removal tower through a second feed preheater; the gas outlet of the top of the sulfuric acid de-weighting tower is connected with a condenser at the top of the sulfuric acid de-weighting tower, the gas outlet of the condenser at the top of the sulfuric acid de-weighting tower is connected with a vacuum system, the liquid outlet of the condenser at the top of the sulfuric acid de-weighting tower is connected with a reflux tank of the sulfuric acid de-weighting tower, and the liquid outlet of the reflux tank of the sulfuric acid de-weighting tower is respectively provided with a connecting pipeline and a product extraction pipeline which are connected with a tower top reflux port of the sulfuric acid de-weighting tower.
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