CN112441567A - Production process of electronic-grade sulfuric acid and low-temperature evaporation, purification and absorption device for production - Google Patents
Production process of electronic-grade sulfuric acid and low-temperature evaporation, purification and absorption device for production Download PDFInfo
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- CN112441567A CN112441567A CN202110000679.4A CN202110000679A CN112441567A CN 112441567 A CN112441567 A CN 112441567A CN 202110000679 A CN202110000679 A CN 202110000679A CN 112441567 A CN112441567 A CN 112441567A
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- sulfuric acid
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 102
- 238000001704 evaporation Methods 0.000 title claims abstract description 78
- 230000008020 evaporation Effects 0.000 title claims abstract description 78
- 238000000746 purification Methods 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 144
- 239000007788 liquid Substances 0.000 claims abstract description 114
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- 238000007872 degassing Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 82
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 21
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 238000009826 distribution Methods 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 230000001154 acute effect Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 239000012263 liquid product Substances 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 238000009835 boiling Methods 0.000 abstract description 5
- 229910021642 ultra pure water Inorganic materials 0.000 abstract description 4
- 239000012498 ultrapure water Substances 0.000 abstract description 4
- 238000010792 warming Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000004821 distillation Methods 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000428 dust Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- 239000011028 pyrite Substances 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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Classifications
-
- 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
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/775—Liquid phase contacting processes or wet catalysis processes
-
- 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
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/80—Apparatus
- C01B17/806—Absorbers; Heat exchangers
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a production process of electronic-grade sulfuric acid and a low-temperature evaporation, purification and absorption device for production. The device comprises an evaporation and purification device and an absorption device which are combined, and the production method of the electronic-grade sulfuric acid by using the device comprises normal-temperature absorption and conversion, negative-pressure low-temperature evaporation, low-temperature absorption and warming degassing, wherein the negative-pressure low-temperature evaporation utilizes the evaporation and purification device and uses low-temperature hot water for heating, so that sulfur trioxide gas is evaporated without boiling; the low-temperature absorption utilizes an absorption device to absorb sulfur trioxide gas at low temperature by using ultrapure water or ultrapure sulfuric acid, and utilizes the impact force of absorption liquid and the absorption of sulfur trioxide to form negative pressure in an evaporation purification device so as to reduce the boiling point of liquid sulfur trioxide. The production method and the production device can ensure the safety of operation while obtaining high-quality electronic-grade sulfuric acid and ensuring the yield and the efficiency.
Description
Technical Field
The invention relates to a device and a process for producing sulfuric acid, in particular to a production process of electronic-grade sulfuric acid and a low-temperature evaporation purification absorption device for production, and belongs to the technical field of production processes and equipment of electronic-grade chemicals.
Background
The electronic grade sulfuric acid, also called ultra-pure sulfuric acid, belongs to ultra-clean high-purity reagent, is a wet electronic chemical with the largest industrial dosage, is mainly used for cleaning, photoetching, corrosion and the like of silicon wafers, corrosion and cleaning of printed circuit boards and the like, and can effectively remove particle impurities, inorganic residues, carbon deposits and the like on the wafers and the printed circuit boards.
The preparation process of the electronic-grade sulfuric acid mainly comprises a rectification method and a gas absorption method. The rectification method is a distillation method for separating liquid mixture with high purity by utilizing reflux, and particularly comprises the steps of adding industrial-grade sulfuric acid into a quartz rectification tower for rectification after strong oxidation treatment, filtering by a microporous membrane to form electronic-grade sulfuric acid, and subpackaging; the distillation method has the advantages of high energy consumption, high cost, difficulty in removing impurities, harm to human bodies due to generated waste gas and acid mist, environmental protection and suitability for small-scale production. The gas absorption method is to directly absorb the purified sulfur trioxide by ultrapure water or ultrapure sulfuric acid, wherein the purification of the sulfur trioxide is the key of reaching the standard of the product; the gas absorption method is suitable for large-scale industrial production, has high impurity removal rate, stable product quality and low energy consumption, and can fully meet the requirements of the semiconductor industry.
The preparation process of electronic grade sulfuric acid in the prior art is shown in figure 1, and the process is as follows: carrying out fluidized bed roasting on sulfurous substances such as pyrite, sulfur and the like in a fluidized bed roaster, wherein the generated furnace gas mainly contains sulfur dioxide, oxygen, nitrogen, water vapor, compounds such as arsenic, selenium and the like, mine dust and the like; the furnace gas is subjected to dry dust removal, wet purification and drying treatment in sequence to form furnace gas mainly containing sulfur dioxide, oxygen and nitrogen; the furnace gas enters a contact chamber and is subjected to catalytic oxidation to sulfur dioxide gas in the contact chamber under the action of a catalyst to form sulfur trioxide gas, and the gas discharged from the contact chamber mainly comprises sulfur trioxide, nitrogen and residual unreacted oxygen and sulfur dioxide; and (3) absorbing sulfur trioxide in the gas by using sulfuric acid with the mass fraction of 98.3% as an absorbent, drying nitrogen, unreacted oxygen and a small amount of sulfur dioxide led out from the upper part of the absorption tower, introducing the dried nitrogen, unreacted oxygen and a small amount of sulfur dioxide into the contact chamber, performing secondary conversion oxidation, and then introducing the gas into the absorption tower for absorption. After absorbing sulfur trioxide gas, 98.3% of sulfuric acid forms industrial liquid sulfur trioxide, fuming sulfuric acid and sulfuric acid products, a kettle-type evaporator is adopted for industrial liquid sulfur trioxide in the products, steam is selected as a medium for distillation and purification, and then the sulfur trioxide after distillation and purification is sequentially absorbed at normal temperature and degassed at normal temperature, and then the electronic-grade sulfuric acid product is obtained through filtration.
In the preparation process in the prior art, steam is adopted for distillation and purification in the distillation and purification stage, and the absorption stage is normal-temperature absorption, so that the operation temperature is high, and the safety is low; meanwhile, in the prior art, a normal-temperature degassing mode is adopted in the degassing stage, so that gas contained in the liquid is difficult to effectively remove.
In addition, the currently existing apparatus for the evaporative purification of sulfur trioxide is a kettle-type evaporator, which uses steam as the evaporation medium. When the kettle-type evaporator is adopted, the sulfur trioxide liquid to be treated is heated in a centralized manner, the heating efficiency is low, the treatment capacity of the sulfur trioxide liquid is generally large, and once an accident occurs, the danger is very high; meanwhile, steam is used as an evaporation medium, the temperature of the steam is high, the sulfur trioxide liquid can be boiled in the evaporation process, the safety is poor, and the energy consumption is high when the steam is used.
Disclosure of Invention
In order to solve the technical problems, the invention provides a production process of electronic-grade sulfuric acid and a low-temperature evaporation purification absorption device for production, wherein the device can realize low-temperature evaporation and low-temperature absorption, the production process utilizes the device to carry out low-temperature evaporation purification and low-temperature absorption on industrial-grade liquid sulfur trioxide, and the device is used for heating and degassing, so that the high-quality electronic-grade sulfuric acid can be obtained, the yield and the efficiency are ensured, and the operation safety is ensured.
The technical scheme of the invention is as follows:
the invention discloses a low-temperature evaporation purification absorption device for producing electronic-grade sulfuric acid, which comprises an evaporation purification device and an absorption device, wherein the evaporation purification device and the absorption device
The evaporation and purification device comprises a straight-end tank body, an upper tank cover and a lower tank cover, wherein the upper tank cover and the lower tank cover are hermetically covered at two ends of the straight-end tank body;
an upper pipe plate and a lower pipe plate are fixedly arranged at the upper end and the lower end of the circumferential inner side wall of the straight-end tank body in a sealing mode along the radial cross section respectively, a plurality of first heat exchange pipes and second heat exchange pipes which are uniformly distributed and have two open ends are fixedly inserted in the upper pipe plate and the lower pipe plate in a through sealing mode, and the upper end and the lower end of each of the first heat exchange pipe and the second heat exchange pipe correspondingly penetrate through the upper pipe plate and the lower pipe plate respectively, so that heating zones are formed between the circumferential inner side wall of the upper pipe plate and the lower pipe plate and between the;
a hot water inlet pipe for supplying hot water into a heating area is arranged above the lower tube plate beside the bottom end of the straight-end tank body, and a hot water outlet pipe for supplying hot water to flow out is arranged below the upper tube plate beside the top end of the straight-end tank body; a solution inlet pipe and a solution outlet pipe which are relatively distributed and used for the inflow and outflow of the liquid to be distilled are arranged above the upper tube plate and positioned beside the top end of the straight-end tank body, and the solution inlet pipe is communicated with the first heat exchange pipe and the second heat exchange pipe through a liquid distribution disc;
the absorption device comprises an absorption chamber, the upper end of the absorption chamber is fixedly provided with an absorption liquid inlet pipe which is communicated with the absorption chamber and is used for absorbing liquid to enter the absorption chamber, the side of the absorption liquid inlet pipe is provided with an absorbed gas inlet pipe which is communicated with the absorption liquid inlet pipe, and the absorbed gas inlet pipe is communicated with a gas outlet pipe of the evaporation purification device.
The further technical scheme is as follows: a snakelike heat exchange tube for hot water to flow is fixedly inserted in the lower tank cover along the radial surface of the lower tank cover, and a fluid inlet and a fluid outlet of the snakelike heat exchange tube are both positioned on the outer side of the circumferential side wall of the lower tank cover; the outer wall fixing sleeve of the S-shaped heat exchange tube is provided with a plurality of heat-conducting plates distributed at intervals, and the heat-conducting plates are all located in the lower tank cover.
The further technical scheme is as follows: the central axes of the first heat exchange tubes and the second heat exchange tubes are parallel to the central axis of the straight-end tank body; and on the radial section, a plurality of first heat exchange tubes are uniformly distributed at intervals on the radial section of the straight-end tank body, and a plurality of second heat exchange tubes are uniformly distributed at intervals on the periphery and the center of the radial section of the straight-end tank body.
The further technical scheme is as follows: the heating area is internally fixedly connected with two baffle plates which are staggered along the radial section of the straight-end tank body at intervals, and the first heat exchange tube and the second heat exchange tube both penetrate through the baffle plates.
The further technical scheme is as follows: the top side of the straight-end tank body is located below the upper tube plate and is provided with an emergency stop air inlet pipe for air to enter, and the bottom side of the straight-end tank body is located above the lower tube plate and is provided with an emergency stop hot water outlet pipe for hot water to flow out.
The further technical scheme is as follows: a L-shaped liquid inlet baffle is fixedly arranged on the inner side wall of the straight end tank body at the pipe orifice of the solution inlet pipe; and a first liquid level meter pipe is positioned on the liquid outlet pipe at the bottom of the lower tank cover, and a second liquid level meter pipe is positioned at the side of the top of the lower tank cover.
The further technical scheme is as follows: an acute included angle is formed between the central axis of the absorbed gas inlet pipe and the central axis of the absorption liquid inlet pipe along the gas inlet direction and the liquid inlet direction, and the acute included angle is 30-45 ℃; and the diameter of the absorption liquid inlet pipe is larger than that of the absorbed gas inlet pipe.
The invention also discloses a process for producing electronic-grade sulfuric acid by using the device, which comprises the following steps:
step S1, introducing the furnace gas from the contact chamber into a first absorption tower to be absorbed by concentrated sulfuric acid with the mass percentage concentration of 98-99%, wherein sulfur trioxide gas contained in the furnace gas is completely absorbed by the concentrated sulfuric acid to obtain fuming sulfuric acid, and the mass percentage concentration of the sulfuric acid in the fuming sulfuric acid is 50-70%; then adding 10-31 wt% of aqueous hydrogen peroxide solution into the fuming sulfuric acid to oxidize a small amount of sulfur dioxide dissolved in the fuming sulfuric acid into sulfur trioxide, wherein the amount of the aqueous hydrogen peroxide solution is 0.01-0.2 wt% of the fuming sulfuric acid; the gas flowing out of the top of the first absorption tower is dried again and then is introduced into the contact chamber for secondary conversion and oxidation, and then enters the first absorption tower to be absorbed by concentrated sulfuric acid to realize tail gas cyclic absorption;
step S2, adding the liquid product obtained in the step S1 into an evaporation and purification device of a low-temperature evaporation and purification absorption device for negative-pressure low-temperature evaporation independently or together with purchased industrial-grade liquid sulfur trioxide, and flowing out sulfur trioxide gas from the top of the evaporation and purification device after the negative-pressure low-temperature evaporation;
step S3, introducing the sulfur trioxide gas obtained after the treatment of the step S2 into a second absorption tower, and performing low-temperature absorption at 40-55 ℃ by using ultra-pure sulfuric acid with the mass percentage concentration of 98% as mother acid to obtain sulfuric acid liquid; then adding 10-31 wt% aqueous hydrogen peroxide solution into the obtained sulfuric acid liquid to oxidize a small amount of sulfur dioxide dissolved in the ultra-pure sulfuric acid as mother acid into sulfur trioxide, wherein the amount of the aqueous hydrogen peroxide solution is 0.01-0.2% of the total mass of fuming sulfuric acid;
step S4, heating and degassing the sulfuric acid obtained by the treatment of the step S3 to remove insoluble gases contained in the liquid, wherein the temperature for heating and degassing is 40-65 ℃;
and step S5, filtering the liquid obtained by the treatment of the step S4 by adopting a membrane filter with the aperture of the filter membrane of 0.05-0.1 μm to obtain electronic-grade sulfuric acid.
The further technical scheme is as follows: the blending mass ratio of the liquid product obtained in the step S1 and the outsourced industrial grade liquid sulfur trioxide in the step S2 is (3-5): 1.
The further technical scheme is as follows: in the step S2, the temperature of hot water entering a heating area in the evaporation and purification device is 40-45 ℃, and the temperature of hot water flowing out of the heating area of the evaporation and purification device is 25-30 ℃; and in the step S2, the negative pressure in the first heat exchange tube and the second heat exchange tube in the evaporation and purification device is 0.01-0.08 MPa.
The beneficial technical effects of the invention are as follows:
1. in the device, the sulfur trioxide liquid to be treated is introduced into the first heat exchange tube and the second heat exchange tube by adopting the evaporation purification device, low-temperature hot water is passed through the heating zone, the hot water is utilized to carry out heat exchange with the liquid in the first heat exchange tube and the second heat exchange tube to carry out low-temperature evaporation, the sulfur trioxide gas is evaporated under the condition of ensuring that the liquid is not boiled, the storage amount of the sulfur trioxide liquid in the device is small in the treatment process, and the risk is low; meanwhile, as the number of the tubes of the first heat exchange tube and the second heat exchange tube used in the device is larger, the evaporation area is still larger under the condition of small total storage amount of sulfur trioxide liquid, so that the evaporation efficiency and the yield are still higher;
2. the device adopts the combination of a low-temperature absorption device and an evaporation purification device, an absorbed gas inlet pipe is communicated with a gas outlet pipe, and the impact force of ultrapure water or ultrapure sulfuric acid and the absorption of the ultrapure water or ultrapure sulfuric acid on sulfur trioxide are utilized to form negative pressure in the absorbed gas inlet pipe, so that negative pressure is formed in a first heat exchange pipe and a second heat exchange pipe which are communicated with the gas outlet pipe in the evaporation purification device, the boiling point of sulfur trioxide liquid is reduced, and negative pressure distillation is formed in the evaporation purification device;
3. in the production process, a small amount of sulfur dioxide dissolved in fuming sulfuric acid is oxidized by using hydrogen peroxide before an evaporation and purification stage, so that the sulfur dioxide is converted into sulfur trioxide; meanwhile, gas flowing out of the first absorption tower flows back to the contact chamber for secondary conversion, so that sulfur dioxide in tail gas can be fully utilized, and the utilization rate of the tail gas is improved;
4. the invention adopts a heating degassing mode to degas the sulfuric acid in a degassing stage to remove insoluble gas contained in the liquid, and compared with a common normal-temperature degassing mode in the prior art, the invention has better degassing effect.
Drawings
FIG. 1 is a flow diagram of a prior art electronic sulfuric acid preparation process;
FIG. 2 is a flow chart of the electronic sulfuric acid preparation process of the present invention;
FIG. 3 is a schematic view of the overall structure of the low-temperature evaporation purification absorption apparatus according to the present invention;
FIG. 4 is a schematic diagram of an evaporation purification apparatus according to the present invention;
FIG. 5 is a schematic top view of the evaporation purification apparatus of the present invention;
FIG. 6 is a schematic structural view of a serpentine heat exchange tube of the present invention;
FIG. 7 is a schematic view of the distribution of the first and second heat exchange tubes of the present invention;
Detailed Description
In order to make the technical means of the present invention clearer and to make the technical means of the present invention capable of being implemented according to the content of the specification, the following detailed description of the embodiments of the present invention is made with reference to the accompanying drawings and examples, which are provided for illustrating the present invention and are not intended to limit the scope of the present invention.
The following embodiments describe in detail a low-temperature evaporation purification absorption apparatus, which includes an evaporation purification apparatus 1 and an absorption apparatus 2. In this embodiment, a low-temperature evaporation purification absorption apparatus for a low-temperature evaporation purification process of sulfur trioxide and a low-temperature absorption process of sulfur trioxide by ultrapure sulfuric acid is taken as an example for description.
The evaporation purification apparatus 1 of this embodiment comprises a straight-end tank body 11 having both ends open, and an upper tank cover 12 and a lower tank cover 13 which are hermetically covered at both ends of the straight-end tank body so that the straight-end tank body, the upper tank cover and the lower tank cover form an integral body. The outer wall a week fixedly connected with of straight end jar body 11 has the ear seat of four equidistance interval arrangements, carries out the handling and the installation is fixed to the device through the ear seat. The top end of the upper tank cover 12 is provided with a gas outlet pipe 121 for the outflow of the evaporated gas, and the bottom end of the lower tank cover is provided with a liquid outlet pipe 131 for the outflow of the evaporated liquid.
An upper tube plate 16 and a lower tube plate 17 are respectively and fixedly arranged at the upper end and the lower end of the circumferential inner side wall of the straight-end tank body 11 along the radial section in a sealing way. A plurality of first heat exchange tubes 18 and second heat exchange tubes 19 which are uniformly distributed and have two open ends are fixedly inserted into the upper tube plate and the lower tube plate in a through type sealing manner, and the upper end and the lower end of each of the first heat exchange tube and the second heat exchange tube are respectively and correspondingly penetrated through the upper tube plate and the lower tube plate, so that a heating area is formed between the circumferential inner side walls of the upper tube plate, the lower tube plate and the straight-end tank body and the outer peripheral walls of the first heat exchange tube and the second heat. The two ends of the first heat exchange tube and the two heat exchange tubes are of an open structure, the peripheral side wall at the upper end of each heat exchange tube is fixedly connected with the upper tube plate in a sealing mode, the peripheral side wall at the lower end of each heat exchange tube is fixedly connected with the lower tube plate in a sealing mode, and the two ends of each heat exchange tube penetrate through the two tube plates, so that the openings at the two ends of each heat exchange tube are positioned.
The central axes of the first heat exchange tube 18 and the second heat exchange tube 19 are all arranged in parallel with the central axis of the straight-end tank body 11. And on the radial section, a plurality of first heat exchange tubes are uniformly distributed at intervals on the radial section of the straight-end tank body 11, and a plurality of second heat exchange tubes 19 are uniformly distributed at intervals on the periphery and at the center of the radial section of the straight-end tank body 11, as shown in fig. 7. In this embodiment, the number of the first heat exchange tubes is set to be 114, and the number of the second heat exchange tubes is set to be 7. The internal straight end jar of body of interval fixedly connected with in foretell zone of heating is baffling board 14 along the radial cross-section staggered arrangement of the straight end jar of body 11, and first heat exchange tube 18 and second heat exchange tube 19 all run through baffling board 14, and the primary function of this baffling board is to carrying out the vortex to the hot water that is located the zone of heating for hot water temperature is more even, and the material of baffling board is the stainless steel, is difficult for taking place the corrosion, and life is higher.
A hot water inlet pipe 111 for supplying hot water into a heating area is arranged at the position above the lower tube plate and beside the bottom end of the straight-end tank body 11, and a hot water outlet pipe 112 for supplying hot water is arranged at the position below the upper tube plate and beside the top end of the straight-end tank body. A solution inlet pipe 113 and a solution outlet pipe 114 which are relatively distributed and used for allowing liquid to be distilled to flow in and out are arranged above the upper tube plate at the side of the top end of the straight-end tank body 11, the solution inlet pipe 113 is communicated with the first heat exchange tube and the second heat exchange tube through a solution distribution disc, and the solution distribution disc is mainly used for distributing liquid entering the heating area through the solution inlet pipe to parts in the first heat exchange tube and the second heat exchange tube, and is a conventional technical scheme in the field and is not repeated in the application. In addition, a plate-like liquid inlet baffle 110 is fixed on the inner side wall of the straight end tank 11 at the mouth of the solution inlet pipe 113, and the baffle mainly functions to make the liquid entering the straight end tank flow into the liquid distribution plate smoothly, thereby preventing the liquid from splashing to other parts.
In this embodiment, a serpentine heat exchange tube 15 for flowing hot water is fixedly inserted on the lower tank cover 13 of the evaporation and purification device 1 along the radial surface of the lower tank cover, and a fluid inlet and a fluid outlet of the serpentine heat exchange tube are both positioned outside the circumferential side wall of the lower tank cover. The fixed cover of outer wall of snakelike heat exchange tube 15 is equipped with the heat-conducting plate 151 of a plurality of interval distribution, and a plurality of heat-conducting plate 151 all is located cover 13 down, and above-mentioned heat-conducting plate 151 can increase snakelike heat exchange tube 15's heat transfer area, improves heat exchange efficiency. Above-mentioned snakelike heat exchange tube 15 and outside circulation hot water source intercommunication, snakelike heat exchange tube can keep warm to the liquid that drips in the cover down, further improves distillation efficiency.
In this embodiment, an emergency stop air inlet pipe 115 for air to enter is disposed below the upper tube plate 16 beside the top end of the straight-end tank 11, and an emergency stop hot water outlet pipe 116 for hot water to flow out is disposed above the lower tube plate 17 beside the bottom end of the straight-end tank 11. The functions of the emergency stop air inlet pipe 115 and the emergency stop hot water outlet pipe 116 are as follows: when emergency happens, air is injected into the heating area of the straight-end tank body 11 through the emergency stop air inlet pipe 115, hot water in the heating area is rapidly discharged through the emergency stop hot water outlet pipe 116, and meanwhile, the air cools the first heat exchange pipe and the second heat exchange pipe, so that rapid distillation stop can be realized, and the safety of the device is greatly improved.
In this embodiment, a first liquid level meter tube 132 is positioned on the liquid outlet tube 131 at the bottom of the lower tank cover 13, and a second liquid level meter tube 133 is positioned at the top side of the lower tank cover 13. The first liquid level meter pipe is mainly used for detecting the lowest liquid level of liquid stored in the lower tank cover, the second liquid level meter pipe is mainly used for detecting the highest liquid level of the liquid stored in the lower tank cover, and when the liquid level in the lower tank cover reaches the highest liquid level, the liquid outlet pipe 131 is opened to allow the liquid to flow out; when the liquid level in the lower tank cover is at the lowest point, the liquid outlet pipe 131 is closed. In addition, a reinforcing bar is fixedly connected between the bottom surface of the lower tank cover 13 and the first gauge pipe 132 for auxiliary support of the first gauge pipe.
In this embodiment, the liquid to be distilled is liquid sulfur trioxide, and the treatment process in the device is as follows: after the sulfur trioxide liquid to be treated enters the liquid distribution disc positioned at the top of the straight-end tank body from the solution inlet pipe, the sulfur trioxide liquid flows into the first heat exchange pipe and the second heat exchange pipe through the liquid distribution disc, redundant sulfur trioxide liquid to be treated overflows through the solution outlet pipe, and the sulfur trioxide liquid to be treated entering the first heat exchange pipe and the second heat exchange pipe is uniformly distributed on the inner side of the pipe wall of the heat exchange pipe and slowly flows downwards along the inner side of the pipe wall to form a liquid film. Advance the pipe through hot water and let in 40 ℃ hot water in the heating zone to the internal portion of straight end jar, then flow out (this outflow hot water is about 30 ℃ of water) through the hot water exit tube and carry out hot water circulation, the hot water is to first, the pending sulfur trioxide liquid in two heat transfer pipes carries out low temperature slow heating, pending sulfur trioxide liquid carries out the cryogenic distillation when flowing in the heat transfer pipe, do not tell under the condition of boiling at sulfur trioxide liquid, sulfur trioxide gas evaporation comes out, this generated sulfur trioxide gas is discharged through gaseous exit tube, remaining sulfur trioxide liquid then drips to the lower cover in, then discharge through the liquid exit tube. The sulfur trioxide liquid to be treated flows through the inner walls of the first heat exchange tube and the second heat exchange tube for distillation, so that the sulfur trioxide liquid reserves in the first heat exchange tube and the second heat exchange tube are small, and the danger is low; meanwhile, because the number of the tubes of the first heat exchange tube and the second heat exchange tube used in the device is larger, the evaporation area is still larger under the condition of small total storage amount of sulfur trioxide liquid, so that the evaporation efficiency and the yield of the device are still not reduced.
The absorption device 2 comprises an absorption chamber 21, the upper end of the absorption chamber is fixedly provided with an absorption liquid inlet pipe 22 communicated with the absorption chamber for the absorption liquid to enter the absorption chamber, the side of the absorption liquid inlet pipe is provided with an absorbed gas inlet pipe 23 communicated with the absorption liquid inlet pipe, and the absorbed gas inlet pipe 23 is communicated with a gas outlet pipe 121 of the evaporation purification device 1. Wherein, an acute included angle is formed between the central axis of the absorbed gas inlet pipe 23 and the central axis of the absorbed liquid inlet pipe 22 along the gas inlet direction and the liquid inlet direction, and the acute included angle is 30-45 ℃. Further, the diameter of the absorption liquid inlet pipe 22 is larger than that of the gas to be absorbed inlet pipe 23.
In this embodiment, the absorbed gas is sulfur trioxide gas flowing out of a gas outlet pipe of the evaporation and purification apparatus, and the absorption liquid is ultrapure sulfuric acid for absorbing sulfur trioxide. When using, the pipe 22 gets into the absorption room is advanced to super pure sulfuric acid and a large amount of self-absorption liquid fast and, in this process by the absorption gas sulfur trioxide through by the absorption gas when advancing the pipe 23 and get into the absorption room, because super pure sulfuric acid can form the negative pressure intraductally when the intraductal flow of absorption liquid advances, super pure sulfuric acid absorbs sulfur trioxide in step simultaneously, thereby make and advance the intraductal negative pressure that also forms of absorbed gas who manages the intercommunication with absorption liquid, and then make in the evaporation purification device with the first of gas outlet pipe intercommunication, also form the negative pressure in the two heat transfer pipes, thereby the boiling point of sulfur trioxide liquid has been reduced, form the negative pressure distillation in the evaporation purification device, further improved distillation efficiency.
The production process of the electronic-grade sulfuric acid by adopting the device comprises the following steps:
the preparation process of sulfur trioxide for producing electronic-grade sulfuric acid is consistent with the prior art, and the specific process comprises the following steps: carrying out fluidized bed roasting on sulfurous substances such as pyrite, sulfur and the like in a fluidized bed roaster, wherein the generated furnace gas mainly contains sulfur dioxide, oxygen, nitrogen, water vapor, compounds such as arsenic, selenium and the like, mine dust and the like; the furnace gas is subjected to dry dust removal, wet purification and drying treatment in sequence to form furnace gas mainly containing sulfur dioxide, oxygen and nitrogen; the furnace gas enters the contact chamber and is catalytically oxidized into sulfur trioxide gas by the action of a catalyst, and the gas coming out of the contact chamber mainly comprises sulfur trioxide, nitrogen and residual unreacted oxygen and sulfur dioxide.
The process for purifying sulfur trioxide and preparing electronic grade sulfuric acid from the purified sulfur trioxide is as follows:
step S1, introducing furnace gas from the contact chamber into a first absorption tower to be absorbed by concentrated sulfuric acid, wherein sulfur trioxide gas contained in the furnace gas is completely absorbed by the concentrated sulfuric acid to obtain fuming sulfuric acid, and then adding aqueous hydrogen peroxide into the fuming sulfuric acid to oxidize a small amount of sulfur dioxide dissolved in the fuming sulfuric acid into sulfur trioxide; the gas flowing out of the top of the first absorption tower is dried again and then is introduced into the contact chamber for secondary conversion and oxidation, and then enters the first absorption tower to be absorbed by concentrated sulfuric acid to realize tail gas cyclic absorption;
step S2, adding the liquid product obtained in the step S1 into an evaporation and purification device of a low-temperature evaporation and purification absorption device for negative-pressure low-temperature evaporation independently or together with purchased industrial-grade liquid sulfur trioxide, and flowing out sulfur trioxide gas from the top of the evaporation and purification device after the negative-pressure low-temperature evaporation;
step S3, introducing the sulfur trioxide gas obtained by the treatment of the step S2 into a second absorption tower, and performing low-temperature absorption by using ultra-pure sulfuric acid with the mass percentage concentration of 98% as mother acid to obtain sulfuric acid liquid; adding an aqueous hydrogen peroxide solution to the obtained sulfuric acid liquid to oxidize a small amount of sulfur dioxide dissolved in ultrapure sulfuric acid as a mother acid to sulfur trioxide;
step S4, heating and degassing the sulfuric acid obtained by the treatment of the step S3 to remove insoluble gases contained in the liquid;
and S5, filtering the liquid obtained by the treatment in the S4 to obtain electronic-grade sulfuric acid.
Preferably, the mass percentage concentration of the concentrated sulfuric acid for absorption in the step S1 is 98-99%, and the mass percentage concentration of the sulfuric acid for industrial use is 98.3%; and the mass percentage concentration of the sulfuric acid in the formed fuming sulfuric acid is 50-70%.
Preferably, the aqueous hydrogen peroxide solution used in step S1 and step S3 has a concentration of 10 to 31% by mass and is used in an amount of 0.01 to 0.2% by mass based on the total mass of oleum.
Preferably, the blending mass ratio of the liquid product obtained in the step S1 and the external industrial grade liquid sulfur trioxide in the step S2 is (3-5): 1.
Preferably, the temperature of the hot water entering the heating zone in the evaporation and purification device in the step S2 is 40-45 ℃, and the hot water is preferably 40 ℃; and the temperature of the hot water flowing out of the heating zone of the evaporation and purification device is 25-30 ℃, and preferably 30 ℃.
Preferably, the negative pressure in the first heat exchange tube and the second heat exchange tube in the evaporation purification device in the step S2 is 0.01-0.08 MPa.
Preferably, the low temperature absorption temperature in step S3 is 40 to 55 ℃.
Preferably, the sulfuric acid treated in step S3 is heated to 40-65 ℃ for degassing in step S4. In a specific operation, the temperature for the temperature-increasing degassing in step S4 is higher than the temperature for the low-temperature absorption in step S3.
Preferably, the filtration in step S5 is performed by using a membrane filter with a membrane pore size of 0.05-0.1 μm.
The concentration of metal ions in the electronic-grade sulfuric acid produced by the production method is lower than 10ppt, the concentration of anions is lower than 15ppb, the concentration of easily-oxidized substances is lower than 1ppm, and the mass percentage concentration of the sulfuric acid is more than 99.5%.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The utility model provides a production electron level is low temperature evaporation purification absorbing device for sulphuric acid which characterized in that: comprises an evaporation and purification device and an absorption device, wherein
The evaporation and purification device comprises a straight-end tank body, an upper tank cover and a lower tank cover, wherein the upper tank cover and the lower tank cover are hermetically covered at two ends of the straight-end tank body;
an upper pipe plate and a lower pipe plate are fixedly arranged at the upper end and the lower end of the circumferential inner side wall of the straight-end tank body in a sealing mode along the radial cross section respectively, a plurality of first heat exchange pipes and second heat exchange pipes which are uniformly distributed and have two open ends are fixedly inserted in the upper pipe plate and the lower pipe plate in a through sealing mode, and the upper end and the lower end of each of the first heat exchange pipe and the second heat exchange pipe correspondingly penetrate through the upper pipe plate and the lower pipe plate respectively, so that heating zones are formed between the circumferential inner side wall of the upper pipe plate and the lower pipe plate and between the;
a hot water inlet pipe for supplying hot water into a heating area is arranged above the lower tube plate beside the bottom end of the straight-end tank body, and a hot water outlet pipe for supplying hot water to flow out is arranged below the upper tube plate beside the top end of the straight-end tank body; a solution inlet pipe and a solution outlet pipe which are relatively distributed and used for the inflow and outflow of the liquid to be distilled are arranged above the upper tube plate and positioned beside the top end of the straight-end tank body, and the solution inlet pipe is communicated with the first heat exchange pipe and the second heat exchange pipe through a liquid distribution disc;
the absorption device comprises an absorption chamber, the upper end of the absorption chamber is fixedly provided with an absorption liquid inlet pipe which is communicated with the absorption chamber and is used for absorbing liquid to enter the absorption chamber, the side of the absorption liquid inlet pipe is provided with an absorbed gas inlet pipe which is communicated with the absorption liquid inlet pipe, and the absorbed gas inlet pipe is communicated with a gas outlet pipe of the evaporation purification device.
2. The cryogenic evaporation purification absorption plant according to claim 1, wherein: a snakelike heat exchange tube for hot water to flow is fixedly inserted in the lower tank cover along the radial surface of the lower tank cover, and a fluid inlet and a fluid outlet of the snakelike heat exchange tube are both positioned on the outer side of the circumferential side wall of the lower tank cover; the outer wall fixing sleeve of the S-shaped heat exchange tube is provided with a plurality of heat-conducting plates distributed at intervals, and the heat-conducting plates are all located in the lower tank cover.
3. The cryogenic evaporation purification absorption plant according to claim 1, wherein: the central axes of the first heat exchange tubes and the second heat exchange tubes are parallel to the central axis of the straight-end tank body; and on the radial section, a plurality of first heat exchange tubes are uniformly distributed at intervals on the radial section of the straight-end tank body, and a plurality of second heat exchange tubes are uniformly distributed at intervals on the periphery and the center of the radial section of the straight-end tank body.
4. The cryogenic evaporation purification absorption plant according to claim 1, wherein: the heating area is internally fixedly connected with two baffle plates which are staggered along the radial section of the straight-end tank body at intervals, and the first heat exchange tube and the second heat exchange tube both penetrate through the baffle plates.
5. The cryogenic evaporation purification absorption plant according to claim 1, wherein: the top side of the straight-end tank body is located below the upper tube plate and is provided with an emergency stop air inlet pipe for air to enter, and the bottom side of the straight-end tank body is located above the lower tube plate and is provided with an emergency stop hot water outlet pipe for hot water to flow out.
6. The cryogenic evaporation purification absorption plant according to claim 1, wherein: a L-shaped liquid inlet baffle is fixedly arranged on the inner side wall of the straight end tank body at the pipe orifice of the solution inlet pipe; and a first liquid level meter pipe is positioned on the liquid outlet pipe at the bottom of the lower tank cover, and a second liquid level meter pipe is positioned at the side of the top of the lower tank cover.
7. The cryogenic evaporation purification absorption plant according to claim 1, wherein: an acute included angle is formed between the central axis of the absorbed gas inlet pipe and the central axis of the absorption liquid inlet pipe along the gas inlet direction and the liquid inlet direction, and the acute included angle is 30-45 ℃; and the diameter of the absorption liquid inlet pipe is larger than that of the absorbed gas inlet pipe.
8. A process for the production of electronic grade sulfuric acid using the apparatus of any of the preceding claims 1 to 7, characterized in that: the method comprises the following steps:
step S1, introducing the furnace gas from the contact chamber into a first absorption tower to be absorbed by concentrated sulfuric acid with the mass percentage concentration of 98-99%, wherein sulfur trioxide gas contained in the furnace gas is completely absorbed by the concentrated sulfuric acid to obtain fuming sulfuric acid, and the mass percentage concentration of the sulfuric acid in the fuming sulfuric acid is 50-70%; then adding 10-31 wt% of aqueous hydrogen peroxide solution into the fuming sulfuric acid to oxidize a small amount of sulfur dioxide dissolved in the fuming sulfuric acid into sulfur trioxide, wherein the amount of the aqueous hydrogen peroxide solution is 0.01-0.2 wt% of the fuming sulfuric acid; the gas flowing out of the top of the first absorption tower is dried again and then is introduced into the contact chamber for secondary conversion and oxidation, and then enters the first absorption tower to be absorbed by concentrated sulfuric acid to realize tail gas cyclic absorption;
step S2, adding the liquid product obtained in the step S1 into an evaporation and purification device of a low-temperature evaporation and purification absorption device for negative-pressure low-temperature evaporation independently or together with purchased industrial-grade liquid sulfur trioxide, and flowing out sulfur trioxide gas from the top of the evaporation and purification device after the negative-pressure low-temperature evaporation;
step S3, introducing the sulfur trioxide gas obtained after the treatment of the step S2 into a second absorption tower, and performing low-temperature absorption at 40-55 ℃ by using ultra-pure sulfuric acid with the mass percentage concentration of 98% as mother acid to obtain sulfuric acid liquid; then adding 10-31 wt% aqueous hydrogen peroxide solution into the obtained sulfuric acid liquid to oxidize a small amount of sulfur dioxide dissolved in the ultra-pure sulfuric acid as mother acid into sulfur trioxide, wherein the amount of the aqueous hydrogen peroxide solution is 0.01-0.2% of the total mass of fuming sulfuric acid;
step S4, heating and degassing the sulfuric acid obtained by the treatment of the step S3 to remove insoluble gases contained in the liquid, wherein the temperature for heating and degassing is 40-65 ℃;
and step S5, filtering the liquid obtained by the treatment of the step S4 by adopting a membrane filter with the aperture of the filter membrane of 0.05-0.1 μm to obtain electronic-grade sulfuric acid.
9. The process for the production of electronic grade sulfuric acid according to claim 8, characterized in that: the blending mass ratio of the liquid product obtained in the step S1 and the outsourced industrial grade liquid sulfur trioxide in the step S2 is (3-5): 1.
10. The process for the production of electronic grade sulfuric acid according to claim 8, characterized in that: in the step S2, the temperature of hot water entering a heating area in the evaporation and purification device is 40-45 ℃, and the temperature of hot water flowing out of the heating area of the evaporation and purification device is 25-30 ℃; and in the step S2, the negative pressure in the first heat exchange tube and the second heat exchange tube in the evaporation and purification device is 0.01-0.08 MPa.
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