CN116425124A - Preparation method of electronic grade ultra-clean high-purity acid - Google Patents
Preparation method of electronic grade ultra-clean high-purity acid Download PDFInfo
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- CN116425124A CN116425124A CN202310423156.XA CN202310423156A CN116425124A CN 116425124 A CN116425124 A CN 116425124A CN 202310423156 A CN202310423156 A CN 202310423156A CN 116425124 A CN116425124 A CN 116425124A
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- 239000002253 acid Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000010521 absorption reaction Methods 0.000 claims abstract description 155
- 239000012498 ultrapure water Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 28
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims description 88
- 239000011344 liquid material Substances 0.000 claims description 42
- 238000001914 filtration Methods 0.000 claims description 25
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 8
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 4
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 abstract description 6
- 230000003749 cleanliness Effects 0.000 abstract description 4
- 238000005507 spraying Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 39
- 238000004064 recycling Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 4
- 239000012043 crude product Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1406—Multiple stage absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1481—Removing sulfur dioxide or sulfur trioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/38—Nitric acid
- C01B21/46—Purification; Separation ; Stabilisation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
- C01B7/0718—Purification ; Separation of hydrogen chloride by adsorption
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/195—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/195—Separation; Purification
- C01B7/197—Separation; Purification by adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
- B01D2257/2045—Hydrochloric acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
- B01D2257/2047—Hydrofluoric acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
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Abstract
The invention discloses a preparation method of electronic grade ultra-clean high-purity acid, which is used for preparing ultra-pure acid such as sulfuric acid, nitric acid, hydrochloric acid and hydrofluoric acid by absorbing process gas raw materials with high-purity water, adopting electronic grade gas as raw materials, spraying and absorbing metal ions and particulate matters in the raw material gas step by a multi-stage absorption process, and then preparing products with different grades of G1, G3 and G5 by configuring filters with different grades. The invention avoids the defect of high requirement on equipment materials in the process of producing acid products by a rectification method, and simultaneously avoids the defects of complex flow, large equipment investment and serious product loss in the existing absorption method, thereby obtaining products with different cleanliness, greatly improving the production efficiency and reducing the production cost.
Description
Technical Field
The invention belongs to the field of preparation of electronic-grade wet electronic chemicals, and particularly relates to a preparation method of electronic-grade ultra-clean high-purity acid.
Background
Ultra-clean and High-purity Reagents (Ultra-clean and High-purity Reagents) are internationally and commonly referred to as process chemicals (Process Chemicals), are one of the key basic chemical materials in the process of manufacturing Ultra-large scale integrated circuits, and are mainly used for cleaning and etching chips, and in addition, the Ultra-clean and High-purity Reagents are also used for chip doping and precipitation processes. The purity and cleanliness of the ultra-clean high-purity reagent have very important effects on the yield, electrical performance and reliability of integrated circuits.
The lower the metal impurity content of the ultra-clean high-purity reagent, the smaller the granularity, and the more advanced the wafer processing technology can be applied. Therefore, the core index of the wet electronic chemicals is the purity, and the SEMI standard and the national standard grade the wet electronic chemicals. SEMI standards were established by the international semiconductor equipment and materials industry association (Semiconductor Equipment and Materials International) which classified wet electronic chemicals into five classes G1-G5 as shown in table 1.1. The applicable process of the G1 grade wet electronic chemical is more than 1.2 mu m, the metal impurity is less than or equal to 1000 mu G/L, and the granularity is less than or equal to 1.0 mu m; the G5 grade wet electronic chemical is suitable for the manufacturing process less than 0.09 mu m, the metal impurity is less than or equal to 0.01 mu G/L, and the granularity is smaller.
Common electronic grade ultra-clean high-purity acids include sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, and the like. At present, common purification technologies for preparing electronic grade ultra-clean high-purity acid at home and abroad include technologies of rectification, sub-boiling distillation, gas absorption and the like.
Patent 202210380210.2 discloses a method and system for producing G1-G5 electronic grade sulfuric acid. The method adopts SO 3 Rectifying system for industrial grade SO 3 Rectifying to remove impurities to obtain ultrahigh-purity SO 3 Then SO is carried out 3 The absorption device and the absorption liquid are absorbed in countercurrent or a static mixer to obtain a crude product of the electronic grade sulfuric acid with the concentration of 95-97 percent, and then the crude product is refined and filtered by a rectifying tower to obtain the G1-G5 grade electronic grade sulfuric acid.
Patent 201410259876.8 discloses a method for preparing ultra-clean high-purity nitric acid. The method heats and rectifies industrial nitric acid, and dilutes pure high-purity water into intermediate products; the intermediate product is treated by an ion exchange column and then is rectified and refined, and finally, the ultra-clean high-purity reagent nitric acid is obtained by filtering by a micro-filter.
Patent 201110330097.9 discloses a preparation process of ultra-clean high-purity hydrochloric acid. The method prepares high-purity hydrochloric acid by sequentially passing hydrogen chloride gas through a separator, an adsorption tower and a filter for pretreatment, washing by a specific complexing agent, absorbing by a gas-liquid separator, absorbing by high-purity water and the like.
Patent 201110132548.8 discloses a process for producing ultra-clean high purity hydrochloric acid. The process selects 36-38% hydrochloric acid solution as raw material, and the hydrochloric acid product is obtained by diluting, rectifying to prepare hydrogen chloride gas, absorbing by high-purity water and filtering by a filter.
Patent CN202010896720.6 discloses a production device and a production method of electronic grade hydrofluoric acid. The method comprises the steps of gasifying anhydrous hydrogen fluoride in the raw material industry through an evaporator, conveying the gasified anhydrous hydrogen fluoride to a purification tower, rectifying the gasified anhydrous hydrogen fluoride to obtain high-purity hydrogen fluoride gas, obtaining an electronic-grade hydrofluoric acid crude product through an absorption tower, and obtaining an electronic-grade hydrofluoric acid product through ultra-pure filtration.
Because of the strong corrosiveness of acid chemicals, the distillation process adopted has serious corrosiveness and high equipment requirements, once corrosion occurs, the cleanliness of the product is reduced, and the post-treatment difficulty of the product is greatly increased. The process of absorbing process gas by high-purity water and filtering by a precise filter is singly adopted, and although the product can be obtained, all metal ions and particulate matters in the process gas are absorbed, and the product of G3 grade or above is obtained, and the multi-stage filter is needed to filter layer by layer, so that the investment of the production flow and the filter is greatly increased, and meanwhile, the loss of the product is increased.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of electronic grade ultra-clean high-purity acid, which is used for preparing ultra-pure acid, such as sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid and the like, by absorbing process gas raw materials through high-purity water, adopting electronic grade gas as raw materials, spraying and absorbing metal ions and particulate matters in the raw material gas step by step through a multi-stage absorption process, and then preparing products of different grades of G, G and G5 by configuring filters of different grades.
The preparation method of the electronic grade ultra-clean high-purity acid comprises the following steps:
the electronic grade gas from the front end process and the high purity water from the tank area respectively enter a first-stage absorption unit, the primary clean gas generated after the treatment of the first-stage absorption unit enters a second-stage absorption unit, a part of the G1 liquid material generated by the first-stage absorption unit is circulated and returned to the first-stage absorption unit, and a part of the G1 liquid material is treated by a G1 filtering unit to obtain a G1 grade product;
the primary clean gas from the primary absorption unit and the high-purity water from the tank area enter the secondary absorption unit, the secondary clean gas processed by the secondary absorption unit enters the tertiary absorption unit, a part of the G3 liquid material produced by the secondary absorption unit is circulated and returned to the secondary absorption unit, and a part of the G3 liquid material is processed by the G3 filtering unit to obtain a G3-grade product;
and (3) the secondary clean gas from the secondary absorption unit and the high-purity water from the tank area enter the tertiary absorption unit, tail gas generated after treatment by the tertiary absorption unit enters the rear end, a part of G5 liquid material generated by the tertiary absorption unit is circulated and returned to the tertiary absorption unit, and a part of the G5 liquid material is treated by the G5 filtering unit to obtain a G5-grade product.
Preferably, the operating pressure of the primary absorption unit is 0.5-1 MPa, and the operating temperature is 40-150 ℃.
Preferably, the molar ratio of the high-purity water to the electron gas in the primary absorption unit is 1-3.5:1, and the molar ratio of the high-purity water to the clean gas in the secondary absorption unit to the secondary absorption unit is 1-3.5:1.
Preferably, the primary absorption unit absorbs 5% -10% of the total amount of the raw gas, the secondary absorption unit absorbs 5% -15% of the total amount of the raw gas, and the tertiary absorption unit absorbs 75% -90% of the total amount of the raw gas.
Preferably, the mass ratio of the circulating quantity of the liquid return circulation of the respective products of the primary absorption unit, the secondary absorption unit and the tertiary absorption unit to the high-purity water is 1-5:1.
Preferably, the operating pressure of the secondary absorption unit is 0.3-0.8 MPa, and the operating temperature is 40-100 ℃.
Preferably, the operating pressure of the three-stage absorption unit is 0.15-0.5 MPa, and the operating temperature is 40-100 ℃.
According to the preparation method of the electronic grade ultra-clean high-purity acid, electronic grade gas is used as a raw material, metal ions and particulate matters in the raw material gas are sprayed and absorbed step by step through a multi-stage absorption process, and then different grades of filters are arranged to obtain products with different grades of G1, G3 and G5 at one time; the defect that the acid products produced by the rectification method have high requirements on equipment materials is avoided; the defects of complex flow, large equipment investment and serious product loss of the existing absorption method are avoided, the production efficiency is greatly improved, and the production cost is reduced.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of electronic grade ultra-clean high-purity acid according to an embodiment of the invention.
Detailed Description
The embodiment of the invention provides a preparation method of electronic grade ultra-clean high-purity acid, aiming at ultra-pure acid such as sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid and the like prepared by absorbing process gas raw materials by high-purity water, adopting electronic grade gas as raw materials, spraying and absorbing metal ions and particulate matters in the raw material gas step by a multi-stage absorption process, and then preparing products with different grades of G1, G3 and G5 by configuring filters with different grades.
As shown in fig. 1, the preparation method of the electronic grade ultra-clean high-purity acid in the embodiment of the invention is realized by adopting the following steps:
the electronic grade gas from the front end process and the high purity water from the tank area enter the first grade absorption unit respectively. The operating pressure of the primary absorption unit is 0.5-1 MPa, the operating temperature is 40-150 ℃, the mol ratio of the high-purity water to the electronic gas is 1-3.5:1, and the raw gas absorbed by the primary absorption unit accounts for 5-10% of the total amount of the raw gas. The primary clean gas produced after the treatment of the primary absorption unit enters the secondary absorption unit, a part of the produced liquid material is circulated and returned to the primary absorption unit, the mass ratio of the circulation quantity to the high-purity water is 1-5:1, and a part of the liquid material is treated by the G1 filtration unit to obtain a G1-grade product.
Primary clean gas from the primary absorption unit and high purity water from the tank farm enter the secondary absorption unit. The operating pressure of the secondary absorption unit is 0.3-0.8 MPa, the operating temperature is 40-100 ℃, the mol ratio of the high-purity water to the electronic gas is 1-3.5:1, and the raw gas absorbed by the secondary absorption unit accounts for 5-15% of the total amount of the raw gas. And (3) introducing the secondary clean gas processed by the secondary absorption unit into the tertiary absorption unit, wherein a part of the produced liquid material is circulated and returned to the secondary absorption unit, the mass ratio of the circulation amount to the high-purity water is 1-5:1, and a part of the produced liquid material is processed by the G3 filtration unit to obtain a G3-grade product.
The secondary clean gas from the secondary absorption unit and the high purity water from the tank farm enter the tertiary absorption unit. The operating pressure of the three-stage absorption unit is 0.15-0.5 MPa, the operating temperature is 40-100 ℃, the mol ratio of the high-purity water to the electronic gas is 1-3.5:1, and the raw gas absorbed by the three-stage absorption unit accounts for 75-90% of the total amount of the raw gas. And (3) enabling the tail gas generated after the treatment of the three-stage absorption unit to enter the rear end, recycling part of the generated liquid material to the three-stage absorption unit, wherein the mass ratio of the recycling amount to the high-purity water is 1-5:1, and the part of the liquid material is treated by the G5 filtration unit to obtain a G5-stage product.
The electron-grade gas includes sulfur trioxide, nitrogen dioxide, hydrogen chloride, hydrogen fluoride gas.
Example 1
The invention will be further described with reference to fig. 1 and the detailed description.
Electronic grade SO from front-end process 3 And high purity water from the tank farm are separately fed to a primary absorption unit wherein SO 3 The feeding rate is 80kg/hr, the high purity water feeding rate is 1.8kg/hr, the operating pressure of the primary absorption unit is 0.5MPa, the operating temperature is 150 ℃, primary clean gas produced after treatment by the primary absorption unit enters the secondary absorption unit, a part of produced liquid material is circulated and returned to the primary absorption unit, the circulation amount is 1.8kg/hr, and a part of the produced liquid material is treated by the G1 filtering unit to obtain a G1 grade product.
Primary clean gas from the primary absorption unit and high purity water from the tank farm enter the secondary absorption unit. Wherein the primary clean gas feed rate is 72kg/hr, the high purity water feed rate is 2.7kg/hr, the secondary absorption unit operating pressure is 0.3MPa, and the operating temperature is 100deg.C. And (3) introducing the secondary clean gas processed by the secondary absorption unit into the tertiary absorption unit, wherein a part of the produced liquid material is circulated back to the secondary absorption unit, the circulation volume is 2.7kg/hr, and a part of the liquid material is processed by the G3 filtration unit to obtain a G3-grade product.
The secondary clean gas from the secondary absorption unit and the high purity water from the tank farm enter the tertiary absorption unit. Wherein the secondary clean gas feed rate is 60kg/hr, the high purity water feed rate is 13.5kg/hr, the secondary absorption unit operating pressure is 0.15, and the operating temperature is 100 ℃. And (3) enabling the tail gas processed by the three-stage absorption unit to enter the rear end, recycling a part of the produced liquid material to the three-stage absorption unit, wherein the recycling amount is 13.5kg/hr, and a part of the liquid material is processed by the G5 filtering unit to obtain a G5-grade product.
Said electronic grade SO 3 The sulfuric acid products with different grades of G1, G3 and G5 can be obtained at one time after being treated by three stages of absorption units, SO 3 The effective utilization rate is more than or equal to 95 percent.
Example 2
Electronic grade NO from front end process 2 And high purity water from the tank farm are separately fed to a primary absorption unit wherein NO 2 The feeding rate is 46kg/hr, the high purity water feeding rate is 1.35kg/hr, the operating pressure of the primary absorption unit is 0.6MPa, the operating temperature is 100 ℃, primary clean gas produced after treatment by the primary absorption unit enters the secondary absorption unit, a part of produced liquid material is circulated and returned to the primary absorption unit, the circulation amount is 1.35kg/hr, and a part of the produced liquid material is treated by the G1 filtering unit to obtain a G1 grade product.
Primary clean gas from the primary absorption unit and high purity water from the tank farm enter the secondary absorption unit. Wherein the primary clean gas feed rate is 43.7kg/hr, the high purity water feed rate is 2.7kg/hr, the secondary absorption unit operating pressure is 0.3MPa, and the operating temperature is 60 ℃. And (3) introducing the secondary clean gas processed by the secondary absorption unit into the tertiary absorption unit, wherein a part of the produced liquid material is circulated back to the secondary absorption unit, the circulation volume is 2.7kg/hr, and a part of the liquid material is processed by the G3 filtration unit to obtain a G3-grade product.
The secondary clean gas from the secondary absorption unit and the high purity water from the tank farm enter the tertiary absorption unit. Wherein the feed rate of the secondary clean gas is 39.1kg/hr, the feed rate of the high purity water is 23kg/hr, the operating pressure of the secondary absorption unit is 0.15, and the operating temperature is 40 ℃. And (3) enabling the tail gas processed by the three-stage absorption unit to enter the rear end, recycling a part of the produced liquid material to the three-stage absorption unit, wherein the recycling amount is 23kg/hr, and a part of the liquid material is processed by the G5 filtering unit to obtain a G5-stage product.
Said electronic grade NO 2 The nitric acid products with different grades of G1, G3 and G5 can be obtained at one time after being treated by three stages of absorption units, and NO 2 The effective utilization rate is more than or equal to 95 percent.
Example 3
The electronic grade HCl from the front end process and the high purity water from the tank area respectively enter a first-stage absorption unit, wherein the HCl feeding rate is 36.5kg/hr, the high purity water feeding rate is 1.8kg/hr, the operating pressure of the first-stage absorption unit is 1MPa, the operating temperature is 40 ℃, the primary clean gas produced after being treated by the first-stage absorption unit enters a second-stage absorption unit, a part of the produced liquid material is circulated back to the first-stage absorption unit, the circulation amount is 1.8kg/hr, and a part of the produced liquid material is treated by a G1 filtering unit to obtain a G1-grade product.
Primary clean gas from the primary absorption unit and high purity water from the tank farm enter the secondary absorption unit. Wherein the primary clean gas feed rate is 32.85kg/hr, the high purity water feed rate is 1.8kg/hr, the secondary absorption unit operating pressure is 0.8MPa, and the operating temperature is 40 ℃. And (3) introducing the secondary clean gas processed by the secondary absorption unit into the tertiary absorption unit, wherein a part of the produced liquid material is circulated back to the secondary absorption unit, the circulation volume is 1.8kg/hr, and a part of the liquid material is processed by the G3 filtration unit to obtain a G3-grade product.
The secondary clean gas from the secondary absorption unit and the high purity water from the tank farm enter the tertiary absorption unit. Wherein the feed rate of the secondary clean gas is 29.2kg/hr, the feed rate of the high purity water is 14.4kg/hr, the operating pressure of the secondary absorption unit is 0.5, and the operating temperature is 40 ℃. And (3) enabling the tail gas processed by the three-stage absorption unit to enter the rear end, recycling a part of the produced liquid material to the three-stage absorption unit, wherein the recycling amount is 14.4kg/hr, and a part of the liquid material is processed by the G5 filtering unit to obtain a G5-grade product.
The electronic grade HCl is treated by three-stage absorption units, so that hydrochloric acid products with different grades of G1, G3 and G5 can be obtained at one time, and the effective utilization rate of HCl is more than or equal to 95%.
Example 4
The electronic grade HF from the front end process and the high purity water from the tank area enter a first grade absorption unit respectively, wherein the HF feeding rate is 20kg/hr, the high purity water feeding rate is 0.9kg/hr, the operating pressure of the first grade absorption unit is 0.5MPa, the operating temperature is 80 ℃, the primary clean gas produced after being treated by the first grade absorption unit enters a second grade absorption unit, a part of the produced liquid material is circulated to the first grade absorption unit, the circulation amount is 0.9kg/hr, and a part of the produced liquid material is treated by a G1 filtering unit to obtain a G1 grade product.
Primary clean gas from the primary absorption unit and high purity water from the tank farm enter the secondary absorption unit. Wherein the primary clean gas feed rate is 19kg/hr, the high purity water feed rate is 0.9kg/hr, the secondary absorption unit operating pressure is 0.3MPa, and the operating temperature is 60 ℃. And (3) introducing the secondary clean gas processed by the secondary absorption unit into the tertiary absorption unit, wherein a part of the produced liquid material is circulated back to the secondary absorption unit, the circulation volume is 0.9kg/hr, and a part of the liquid material is processed by the G3 filtration unit to obtain a G3-grade product.
The secondary clean gas from the secondary absorption unit and the high purity water from the tank farm enter the tertiary absorption unit. Wherein the secondary clean gas feed rate is 18kg/hr, the high purity water feed rate is 16.2kg/hr, the secondary absorption unit operating pressure is 0.15, and the operating temperature is 40 ℃. And (3) enabling the tail gas processed by the three-stage absorption unit to enter the rear end, recycling a part of the produced liquid material to the three-stage absorption unit, recycling 16.2kg/hr, and processing a part of the liquid material by the G5 filtering unit to obtain a G5-stage product.
The electronic grade HF is treated by three-stage absorption units, so that hydrofluoric acid products with different grades of G1, G3 and G5 can be obtained at one time, and the effective utilization rate of the HF is more than or equal to 95%.
According to the preparation method, electronic grade gas is used as a raw material, metal ions and particulate matters in the raw material gas are sprayed and absorbed step by step through a multi-stage absorption process, and then different grades of filters are arranged to obtain G, G and G5 products at different grades at one time, so that the defect that acid products produced by a rectification method have high requirements on equipment materials is avoided, and meanwhile, the defects of complex flow, large equipment investment and serious product loss of the existing absorption method are avoided, so that products with different cleanliness are obtained, the production efficiency is greatly improved, and the production cost is reduced.
Claims (8)
1. The preparation method of the electronic grade ultra-clean high-purity acid is characterized by comprising the following steps of:
the electronic grade gas from the front end process and the high purity water from the tank area respectively enter a first-stage absorption unit, the primary clean gas generated after the treatment of the first-stage absorption unit enters a second-stage absorption unit, a part of the G1 liquid material generated by the first-stage absorption unit is circulated and returned to the first-stage absorption unit, and a part of the G1 liquid material is treated by a G1 filtering unit to obtain a G1 grade product;
the primary clean gas from the primary absorption unit and the high-purity water from the tank area enter the secondary absorption unit, the secondary clean gas processed by the secondary absorption unit enters the tertiary absorption unit, a part of the G3 liquid material produced by the secondary absorption unit is circulated and returned to the secondary absorption unit, and a part of the G3 liquid material is processed by the G3 filtering unit to obtain a G3-grade product;
and (3) the secondary clean gas from the secondary absorption unit and the high-purity water from the tank area enter the tertiary absorption unit, tail gas generated after treatment by the tertiary absorption unit enters the rear end, a part of G5 liquid material generated by the tertiary absorption unit is circulated and returned to the tertiary absorption unit, and a part of the G5 liquid material is treated by the G5 filtering unit to obtain a G5-grade product.
2. The method for preparing an electronic grade ultra-clean high purity acid according to claim 1, wherein the operating pressure of the primary absorption unit is 0.5 to 1MPa and the operating temperature is 40 to 150 ℃.
3. The method for producing an electronic grade ultra-clean high purity acid according to claim 1, wherein the molar ratio of the high purity water to the electron gas in the primary absorption unit is 1 to 3.5:1, and the molar ratio of the high purity water to the clean gas in the secondary absorption unit to the secondary absorption unit is 1 to 3.5:1, respectively.
4. The method for preparing the electronic grade ultra-clean high-purity acid according to claim 1, wherein the raw gas absorbed by the primary absorption unit accounts for 5% -10% of the total amount of the raw gas, the raw gas absorbed by the secondary absorption unit accounts for 5% -15% of the total amount of the raw gas, and the raw gas absorbed by the tertiary absorption unit accounts for 75% -90% of the total amount of the raw gas.
5. The method for producing ultra-clean high-purity acid according to claim 1, wherein the mass ratio of the circulating amount of the liquid return circulation of each product of the primary absorption unit, the secondary absorption unit, and the tertiary absorption unit to the high-purity water is 1 to 5:1.
6. The method for preparing the electronic grade ultra-clean high-purity acid according to claim 1, wherein the operating pressure of the secondary absorption unit is 0.3-0.8 MPa and the operating temperature is 40-100 ℃.
7. The method for preparing the electronic grade ultra-clean high-purity acid according to claim 1, wherein the operating pressure of the three-stage absorption unit is 0.15-0.5 MPa, and the operating temperature is 40-100 ℃.
8. The method for preparing the electronic grade ultra-clean high purity acid according to claim 1, wherein the electronic grade gas comprises sulfur trioxide, nitrogen dioxide, hydrogen chloride, hydrogen fluoride gas.
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