CN114590782A - Device and method for directly producing electronic-grade sulfuric acid from pyrite - Google Patents
Device and method for directly producing electronic-grade sulfuric acid from pyrite Download PDFInfo
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- CN114590782A CN114590782A CN202210272983.9A CN202210272983A CN114590782A CN 114590782 A CN114590782 A CN 114590782A CN 202210272983 A CN202210272983 A CN 202210272983A CN 114590782 A CN114590782 A CN 114590782A
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- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
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Abstract
The invention discloses a device and a method for directly producing electronic-grade sulfuric acid from pyrite, and belongs to the technical field of electronic chemical production. The device includes: a roasting device: used for roasting pyrite or sulfur to produce sulfur dioxide furnace gas; purification device connected with roasting device: the device is used for purifying sulfur dioxide furnace gas to obtain pure sulfur dioxide furnace gas; drying device connected with purifier: drying the pure sulfur dioxide furnace gas to obtain dry sulfur dioxide furnace gas; and the sulfur dioxide conversion device is connected with the drying device. In the invention, the device for producing the electronic-grade sulfuric acid is used for roasting pyrite or sulfur to obtain sulfur dioxide furnace gas, then the sulfur dioxide furnace gas is purified, dried and converted to obtain sulfur trioxide gas, and finally the sulfur trioxide is absorbed to obtain the electronic-grade sulfuric acid, so that the energy consumption is low, the safety is high, and the prepared electronic-grade sulfuric acid is purer and can meet the electronic-grade standard.
Description
Technical Field
The invention relates to the technical field of electronic chemical production, in particular to a device and a method for directly producing electronic-grade sulfuric acid from pyrite.
Background
Sulfuric acid of the formula H2SO4The product has a relative molecular mass of 98.08, is colorless and odorless oily liquid, is a high-boiling point and hard-to-volatilize strong acid, is easy to dissolve in water, and can be mixed and dissolved with water in any ratio. Sulfuric acid is one of the important products in the basic chemical industry.
Electronic grade sulfuric acid is widely used in integrated circuit manufacturing process at present for resist stripping, and the most commonly used sulfuric acid concentration is about 98 wt%. Organic contaminants remaining on the substrate and associated equipment can adversely affect normal production, and electronic grade sulfuric acid in combination with hydrogen peroxide or ozone can remove organic contaminants from the substrate surface prior to metal deposition.
The preparation process of the electronic grade sulfuric acid mainly comprises a rectification method and the like. At present, fuming sulfuric acid is adopted to obtain an electronic grade sulfuric acid product with the weight percent of about 98 percent after high-temperature rectification. Because the boiling point of the sulfuric acid is very high, the boiling point of 98 wt% sulfuric acid at normal pressure is 338 ℃, so that the sulfuric acid solution must be heated and distilled in a glass container by using an electric heating wire, and the method is operated at such a high temperature, so that not only certain safety risks exist, but also partial impurities in glass equipment can be dissolved by the sulfuric acid distilled at a high temperature due to the strong corrosivity of the concentrated sulfuric acid, so that the sulfuric acid produced by the method can hardly reach the electronic grade standard which really meets the requirements of integrated circuits.
Disclosure of Invention
In order to solve the problems of the prior art, the invention provides a device and a method for producing electronic-grade sulfuric acid.
In one aspect, an apparatus for producing electronic grade sulfuric acid, the apparatus comprising:
a roasting device: used for roasting pyrite or sulfur to produce sulfur dioxide furnace gas;
a purification device connected to the roasting device: the sulfur dioxide furnace gas is used for purifying the sulfur dioxide furnace gas to obtain pure sulfur dioxide furnace gas;
a drying device connected to the purification device: the sulfur dioxide furnace gas is used for drying the pure sulfur dioxide furnace gas to obtain dry sulfur dioxide furnace gas;
the sulfur dioxide conversion device connected with the drying device: the sulfur dioxide is used for converting sulfur dioxide in the dried sulfur dioxide furnace gas into sulfur trioxide to obtain sulfur trioxide gas;
and a sulfur trioxide absorption device connected with the sulfur dioxide conversion device: used for absorbing the sulfur trioxide gas to obtain the electronic-grade sulfuric acid.
Further, the roasting apparatus includes: a fluidized bed roaster, an air blower and a waste heat boiler; the outlet at the top of the fluidized bed roaster is connected with the inlet of the waste heat boiler, and the air blower is connected with the air inlet at the bottom of the fluidized bed roaster;
the purification device includes: cyclone dust collector, venturi tube, foam tower and electric demister; the outlet of the waste heat boiler is connected with the inlet of the cyclone dust collector, the outlet of the cyclone dust collector is connected with the inlet of the venturi, the outlet of the venturi is connected with the inlet of the foam tower, and the outlet of the foam tower is connected with the inlet of the electric demister;
the drying device includes: a sulfur dioxide blower and a drying tower; an outlet of the electric demister is connected with a gas inlet of the drying tower, and a gas outlet of the drying tower is connected with an inlet of the sulfur dioxide blower;
the sulfur dioxide conversion device comprises: the system comprises a first gas heat exchanger, a second gas heat exchanger, a converter, a third gas heat exchanger and a fourth gas heat exchanger;
the inlet of the first gas heat exchanger is connected with the outlet of the sulfur dioxide blower and the outlet of the third layer of the converter, and the outlet of the first gas heat exchanger is connected with the inlet of the second gas heat exchanger; the inlet of the second gas heat exchanger is also connected with the outlet of the first layer of the converter, and the outlet of the second gas heat exchanger is respectively connected with the inlets of the first layer and the second layer of the converter; an inlet of the third gas heat exchanger is connected with an outlet of the second layer of the converter and an outlet of the fourth gas heat exchanger respectively, an outlet of the third gas heat exchanger is connected with inlets of the third layer and the fourth layer of the converter respectively, and an inlet of the fourth gas heat exchanger is connected with an outlet of the fourth layer of the converter;
the sulfur trioxide absorption device comprises: and a gas inlet of the middle absorption tower is connected with an outlet of the first gas heat exchanger, and a gas outlet of the middle absorption tower is connected with an inlet of the fourth gas heat exchanger.
Further, the sulfur trioxide absorption device further comprises: and a gas inlet of the final absorption tower is connected with an outlet of the fourth gas heat exchanger.
Further, the tops of the intermediate absorption tower and the final absorption tower are provided with fiber demisters.
Further, a first sulfuric acid circulating system is connected to the drying tower;
the first sulfuric acid circulation system includes: a first circulation tank and a first acid cooler;
the drying tower is characterized in that sulfuric acid and a first acid pump are arranged in the first circulating tank, a sulfuric acid outlet of the drying tower is connected with an inlet of the first circulating tank, an outlet of the first acid pump is connected with an inlet of the first acid cooler, and an outlet of the first acid cooler is connected with an inlet of the drying tower.
Further, a second sulfuric acid circulating system is connected to the intermediate absorption tower;
the second sulfuric acid circulation system includes: a second circulation tank and a second acid cooler;
and a sulfuric acid and a second acid pump are arranged in the second circulating tank, a sulfuric acid outlet of the intermediate absorption tower is connected with an inlet of the second circulating tank, an outlet of the second acid pump is connected with an inlet of the second acid cooler, and an outlet of the second acid cooler is connected with an inlet of the intermediate absorption tower.
Further, a third sulfuric acid circulating system is connected to the final absorption tower;
the third sulfuric acid circulation system includes: a third circulation tank and a third acid cooler;
and a sulfuric acid and a third acid pump are arranged in the third circulating tank, a sulfuric acid outlet of the final absorption tower is connected with an inlet of the third circulating tank, an outlet of the third acid pump is connected with an inlet of a third acid cooler, and an outlet of the third acid cooler is connected with an inlet of the final absorption tower.
In another aspect, there is provided a process for producing electronic grade sulfuric acid, the apparatus comprising: the method comprises the following steps:
roasting pyrite or sulfur to obtain sulfur dioxide furnace gas;
purifying the sulfur dioxide furnace gas to obtain the pure sulfur dioxide furnace gas;
drying the pure sulfur dioxide furnace gas to obtain dry sulfur dioxide furnace gas;
carrying out oxidation reaction on the dried sulfur dioxide furnace gas in the presence of a catalyst to obtain sulfur trioxide gas;
and absorbing the sulfur trioxide gas by using sulfuric acid with the concentration of 98 wt% to obtain the electronic-grade sulfuric acid.
Further, the roasting pyrite or sulfur includes:
crushing and conveying the pyrite or the sulfur into a fluidized bed of the fluidized bed roaster, roasting the crushed pyrite or the sulfur and air fed by the air blower at 850-1000 ℃ to generate first furnace gas, conveying the first furnace gas to the waste heat boiler, and cooling the first furnace gas to 320-370 ℃ to obtain sulfur dioxide furnace gas;
the purifying the sulfur dioxide furnace gas comprises: conveying the sulfur dioxide furnace gas to the cyclone dust collector for dust removal to obtain second furnace gas, conveying the second furnace gas to the foam tower through the venturi tube, converting sulfur trioxide contained in the second furnace gas from a sulfuric acid steam form into acid mist, washing and removing solid particles of metal oxides to obtain third furnace gas, conveying the third furnace gas to the electric demister, and removing the residual solid particles and mine dust of the metal oxides under the action of high-voltage static electricity to obtain pure sulfur dioxide furnace gas;
the drying the clean sulfur dioxide furnace gas comprises: conveying the pure sulfur dioxide furnace gas to the drying tower to be dried by sulfuric acid with the concentration of 95 wt% at the temperature below 40 ℃ to obtain the dried sulfur dioxide furnace gas;
conveying the dried sulfur dioxide furnace gas into the first gas heat exchanger through the sulfur dioxide blower, heating the sulfur dioxide furnace gas by the sulfur trioxide gas at the third layer of the converter, then continuously conveying the sulfur dioxide furnace gas into the second gas heat exchanger, heating the sulfur trioxide gas at the first layer of the converter to 400-440 ℃ to obtain fourth furnace gas, conveying the fourth furnace gas to the first layer of the converter through the second gas heat exchanger, carrying out oxidation reaction under the catalytic action of a vanadium catalyst to obtain fifth furnace gas, conveying the fifth furnace gas into the second gas heat exchanger to cool the fifth furnace gas to 430-440 ℃, then conveying the fifth furnace gas into the second layer of the converter, carrying out oxidation reaction under the catalytic action of the vanadium catalyst to obtain sixth furnace gas, conveying the sixth furnace gas to the third gas heat exchanger to cool the sixth furnace gas to 400-410 ℃, then the gas enters a third layer of the converter, oxidation reaction is carried out under the catalysis of a vanadium catalyst to obtain seventh furnace gas, and the seventh furnace gas is conveyed to the first gas heat exchanger to be cooled to 410-420 ℃ to obtain sulfur trioxide gas;
the absorbing the sulfur trioxide gas comprises: and conveying the sulfur trioxide gas to the intermediate absorption tower, and absorbing by using sulfuric acid with the concentration of 98 wt% to obtain the electronic-grade sulfuric acid and eighth furnace gas.
Further, the eighth furnace gas is conveyed to the fourth gas heat exchanger, heated by sulfur trioxide gas on the fourth layer of the converter, conveyed to the third gas heat exchanger, heated to 400-410 ℃ by sulfur trioxide gas on the second layer of the converter to obtain ninth furnace gas, conveyed to the fourth layer of the converter, subjected to oxidation reaction under the catalytic action of a vanadium catalyst, finally converted by sulfur dioxide in the ninth furnace gas to obtain tenth furnace gas, conveyed to the fourth gas heat exchanger to be cooled to 60-80 ℃ to obtain sulfur trioxide gas, conveyed to the final absorption tower, and absorbed by electronic-grade sulfuric acid with the concentration of 98 wt% to obtain the electronic-grade sulfuric acid.
The technical scheme provided by the embodiment of the invention has the following beneficial effects: in the invention, the pyrite or the sulfur is roasted by the device for producing the electronic-grade sulfuric acid to obtain the sulfur dioxide furnace gas, then the sulfur dioxide furnace gas is purified to obtain pure sulfur dioxide furnace gas, the drying is continued to obtain dry sulfur dioxide furnace gas, the conversion is continued to obtain sulfur trioxide gas, and finally the sulfur trioxide is absorbed to obtain the electronic-grade sulfuric acid. In addition, the sulfur dioxide in the sulfur dioxide furnace gas can be converted into sulfur trioxide to the maximum extent through the first gas heat exchanger, the second gas heat exchanger, the converter, the third gas heat exchanger, the fourth gas heat exchanger, the intermediate absorption tower and the final absorption tower, and the electronic-grade sulfuric acid is prepared, so that the resources can be utilized to the maximum extent, and the cost is saved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic connection diagram of an apparatus for producing electronic-grade sulfuric acid according to the present invention.
Reference numerals are as follows: 1-fluidized bed roaster; 2-an air blower; 3-a waste heat boiler; 4-cyclone dust collector; 5-a venturi; 6-a foam tower; 7-an electric demister; 8-a sulfur dioxide blower; 9-a drying tower; 10-a first gas heat exchanger; 11-a second gas heat exchanger; 12-a converter; 13-a third gas heat exchanger; 14-a fourth gas heat exchanger; 15-an intermediate absorber; 16-a final absorber; 17-a first circulation tank; 18-a first acid cooler; 19-a first acid pump; 20-a second circulation tank; 21-a second acid cooler; 22-a second acid pump; 23-a third circulation tank; 24-a third acid cooler; 25-third acid pump.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Referring to fig. 1, an apparatus for producing electronic grade sulfuric acid, comprising: the device comprises a roasting device, a purification device, a drying device, a sulfur dioxide conversion device and a sulfur trioxide absorption device;
the roasting device comprises: the device comprises a fluidized bed roaster 1, an air blower 2 and a waste heat boiler 3, wherein an outlet at the top of the fluidized bed roaster 1 is connected with an inlet of the waste heat boiler 3, and the air blower 2 is connected with an air inlet at the bottom of the fluidized bed roaster 1 and is used for roasting pyrite or sulfur to generate sulfur dioxide furnace gas.
The purification device comprises: the device comprises a cyclone dust collector 4, a venturi 5, a foam tower 6 and an electric demister 7, wherein the venturi 5, the foam tower 6 and the electric demister 7 are all lined with quartz; the outlet of the waste heat boiler 3 is connected with the inlet of the cyclone dust collector 4, the outlet of the cyclone dust collector 4 is connected with the inlet of the venturi 5, the outlet of the venturi 5 is connected with the inlet of the foam tower 6, and the outlet of the foam tower 6 is connected with the inlet of the electric demister 7, so that the waste heat boiler is used for purifying sulfur dioxide furnace gas to obtain pure sulfur dioxide furnace gas.
The drying device includes: a sulfur dioxide blower 8 and a drying tower 9; the outlet of the electric demister 7 is connected with the gas inlet of the drying tower 9, and the gas outlet of the drying tower 9 is connected with the inlet of the sulfur dioxide blower 8, and is used for drying the pure sulfur dioxide furnace gas to obtain the dry sulfur dioxide furnace gas. The drying tower 9 is connected with a first sulfuric acid circulating system; the first sulfuric acid circulation system includes: a first circulation tank 17 and a first acid cooler 18; the first circulation tank 17 is internally provided with sulfuric acid and a first acid pump 19, the sulfuric acid outlet of the drying tower 9 is connected with the inlet of the first circulation tank 17, the outlet of the first acid pump 19 is connected with the inlet of a first acid cooler 18, and the outlet of the first acid cooler 18 is connected with the inlet of the drying tower 9.
The sulfur dioxide conversion device comprises: the system comprises a first gas heat exchanger 10, a second gas heat exchanger 11, a converter 12, a third gas heat exchanger 13 and a fourth gas heat exchanger 14, wherein the converter 12 is internally lined with quartz, the inlet of the first gas heat exchanger 10 is connected with the outlet of a sulfur dioxide blower 8 and the outlet of the third layer of the converter 12, and the outlet of the first gas heat exchanger 10 is connected with the inlet of the second gas heat exchanger 11; the inlet of the second gas heat exchanger 11 is also connected with the outlet of the first layer of the converter 12, and the outlet of the second gas heat exchanger 11 is respectively connected with the inlets of the first layer and the second layer of the converter 12; an inlet of the third gas heat exchanger 13 is respectively connected with an outlet of the second layer of the converter 12 and an outlet of the fourth gas heat exchanger 14, an outlet of the third gas heat exchanger 13 is respectively connected with inlets of the third layer and the fourth layer of the converter 12, and an inlet of the fourth gas heat exchanger 14 is connected with an outlet of the fourth layer of the converter 12; the sulfur dioxide conversion device is used for converting sulfur dioxide in dry sulfur dioxide furnace gas into sulfur trioxide to obtain sulfur trioxide gas.
The sulfur trioxide absorption device comprises: the device comprises an intermediate absorption tower 15 and a final absorption tower 16, wherein polytetrafluoroethylene is lined in both the intermediate absorption tower 15 and the final absorption tower 16, and fiber demisters are arranged at the tops of both the intermediate absorption tower 15 and the final absorption tower 16; be connected with the second sulfuric acid circulation system on the middle absorption tower 15, the second sulfuric acid circulation system includes: a second circulating tank 20 and a second acid cooler 21, wherein the second circulating tank 20 is internally provided with sulfuric acid and a second acid pump 22, the sulfuric acid outlet of the intermediate absorption tower 15 is connected with the inlet of the second circulating tank 20, the outlet of the second acid pump 22 is connected with the inlet of the second acid cooler 21, and the outlet of the second acid cooler 21 is connected with the inlet of the intermediate absorption tower 15. The final absorption tower 16 is connected to a third sulfuric acid circulation system, which includes: a third circulating tank 23 and a third acid cooler 24, wherein sulfuric acid and a third acid pump 25 are arranged in the third circulating tank 23, the sulfuric acid outlet of the final absorption tower 16 is connected with the inlet of the third circulating tank 23, the outlet of the third acid pump 25 is connected with the inlet of the third acid cooler 24, and the outlet of the third acid cooler 24 is connected with the inlet of the final absorption tower 16. The gas inlet of the middle absorption tower 15 is connected with the outlet of the first gas heat exchanger 10, the gas outlet of the middle absorption tower 15 is connected with the inlet of the fourth gas heat exchanger 14, and finally the gas inlet of the absorption tower 16 is connected with the outlet of the fourth gas heat exchanger 14 to absorb sulfur trioxide gas to obtain electronic-grade sulfuric acid.
The method for producing the electronic-grade sulfuric acid by the device for producing the electronic-grade sulfuric acid specifically comprises the following steps:
step (1): conveying crushed and screened pyrite or dried sulfur into a fluidized bed of a fluidized bed roaster 1, roasting the crushed and screened pyrite or dried sulfur and air fed by an air blower 2 at 850-1000 ℃ to generate first furnace gas, discharging slag from the fluidized bed through a slag discharge port at the lower part of the fluidized bed roaster 1, discharging the first furnace gas from the top of the fluidized bed, conveying the first furnace gas to a waste heat boiler 3, cooling the first furnace gas to 320-370 ℃ to obtain sulfur dioxide furnace gas, wherein the waste heat boiler 3 is used for producing superheated steam of 3.82Mpa and 450 ℃, a main steam evaporation tube bundle is arranged in the waste heat boiler 3, a cooling tube arranged in the fluidized bed of the fluidized bed roaster 1 is also used as a part of a thermodynamic system of the waste heat boiler and is connected with a steam pocket of the waste heat boiler 3 to recover part of roasting reaction heat and save energy consumption.
Step (2): conveying sulfur dioxide furnace gas to a cyclone dust collector 4 for dust removal to obtain second furnace gas, and conveying mine dust removed by the cyclone dust collector 4 and slag discharged by the fluidized bed roaster 1 to a slag yard; the second furnace gas is conveyed to a foam tower 6 through a venturi 5, trace sulfur trioxide contained in the second furnace gas is converted into acid mist from a sulfuric acid steam form, oxides of arsenic, selenium and other metals become solid particles, the solid particles are separated from a gas phase to obtain third furnace gas, one part of the solid particles and trace mineral dust remaining in the third furnace gas are washed and removed together, and the other part of the solid particles and the trace mineral dust enter an electric demister 7 along with the third furnace gas and are removed completely under the action of high-voltage static electricity to obtain pure sulfur dioxide furnace gas. The high-dust dilute acid discharged in the step is sent into a sewage treatment system, and is treated by a CN filter and then is pumped back to the system for recycling. The temperature of the purified sulfur dioxide furnace gas is controlled below 40 ℃ so as to ensure the water balance during drying.
And (3): pure sulfur dioxide furnace gas is conveyed into a drying tower 9, sulfuric acid with the concentration of about 95 wt% is circularly sprayed for drying, and dry sulfur dioxide furnace gas is obtained, because a large amount of heat is released in the process of drying the pure sulfur dioxide furnace gas by the sulfuric acid, a first acid cooler 18 is arranged in a first sulfuric acid circulating system of the drying tower, the heat is removed by cooling water, and in order to reduce the corrosion of the gas carrying sulfuric acid mist to equipment, a wire mesh demister is usually arranged at the top of the drying tower 9.
And (4): the pressure is increased through a sulfur dioxide blower 8, the dry sulfur dioxide furnace gas is conveyed to a first gas heat exchanger 10, is heated by sulfur trioxide gas at the third layer of a converter 12, and then is continuously conveyed to a second gas heat exchanger 11, the sulfur trioxide gas at the first layer of the converter 12 is heated to 400-440 ℃ to obtain fourth furnace gas, the fourth furnace gas is conveyed to the first layer of the converter 12 through the second gas heat exchanger 11, partial sulfur dioxide in the fourth furnace gas reacts with oxygen in the gas under the catalytic action of a vanadium catalyst to generate sulfur trioxide and release reaction heat, the temperature of the reacted gas is increased to obtain fifth furnace gas, in order to further convert the unreacted part of sulfur dioxide, the fifth furnace gas is conveyed to the second gas heat exchanger 11 to be cooled to 430-440 ℃, and then enters the second layer of the converter 12, carrying out an oxidation reaction under the catalysis of a vanadium catalyst, continuously converting sulfur dioxide in fifth furnace gas into sulfur trioxide to obtain sixth furnace gas, conveying the sixth furnace gas to a third gas heat exchanger 13, cooling to 400-410 ℃, then entering a third layer of a converter 12, carrying out an oxidation reaction under the catalysis of the vanadium catalyst, continuously converting to convert most of sulfur dioxide into sulfur trioxide to obtain seventh furnace gas, conveying the seventh furnace gas to a first gas heat exchanger 10, cooling to 410-420 ℃ to obtain sulfur trioxide gas in order to achieve higher final conversion rate.
And (5): and conveying the sulfur trioxide gas to an intermediate absorption tower 15, and absorbing the sulfur trioxide gas in the sulfuric acid sulfur trioxide gas with the concentration of 98 wt% to obtain the electronic-grade sulfuric acid, wherein the residual gas is eighth furnace gas.
And (6): conveying the eighth furnace gas from the intermediate absorption tower 15 to a fourth gas heat exchanger 14, heating the eighth furnace gas by sulfur trioxide gas on a fourth layer of a converter 12, conveying the eighth furnace gas to a third gas heat exchanger 13, heating the eighth furnace gas to 400-410 ℃ by sulfur trioxide gas on a second layer of the converter 12 to obtain ninth furnace gas, conveying the ninth furnace gas to the fourth layer of the converter 12, carrying out oxidation reaction under the catalytic action of a vanadium catalyst, finally converting sulfur dioxide in the ninth furnace gas to obtain tenth furnace gas, conveying the tenth furnace gas to the fourth gas heat exchanger 14, cooling to 60-80 ℃ to obtain sulfur trioxide gas, conveying the sulfur trioxide gas to a final absorption tower 16, and carrying out electronic absorption by sulfur trioxide electron with the concentration of 98 wt%, obtaining the electronic grade sulfuric acid.
The intermediate absorption tower 15 and the final absorption tower 16 are respectively provided with a second sulfuric acid circulation system and a third sulfuric acid circulation system, and a second acid cooler 21 and a third acid cooler 24 are respectively arranged in the second sulfuric acid circulation system and the third sulfuric acid circulation system for removing absorption reaction heat, in order to remove sulfuric acid mist entrained in gas, fiber mist eliminators are usually arranged at the tops of the intermediate absorption tower 15 and the final absorption tower 16, acid crossing pipelines are arranged between the second sulfuric acid circulation system, the third sulfuric acid circulation system and the first sulfuric acid circulation system, and concentrated sulfuric acid from the second sulfuric acid circulation system and the third sulfuric acid circulation system is continuously supplemented to the first sulfuric acid circulation system, so that the concentrated sulfuric acid in the first sulfuric acid circulation system keeps a specified concentration. And in order to provide the water required for generating the sulfuric acid by sulfur trioxide, electronic-grade ultrapure water is continuously added into the second sulfuric acid circulating system and the third sulfuric acid circulating system.
And (7): and (4) filtering the electronic-grade sulfuric acid obtained in the step (5) and the step (6) by using an ultrafiltration filter lined with a polytetrafluoroethylene filter, wherein the content of heavy metals in the obtained electronic-grade sulfuric acid is less than 10ppb, and the content of various anions is less than 100 ppb.
It is worth mentioning that in the invention, the device for producing electronic-grade sulfuric acid is used for roasting pyrite or sulfur to obtain sulfur dioxide furnace gas, then the sulfur dioxide furnace gas is purified to obtain pure sulfur dioxide furnace gas, the drying is continuously carried out to obtain dry sulfur dioxide furnace gas, the conversion is continuously carried out to obtain sulfur trioxide gas, and finally the sulfur trioxide is absorbed to obtain the electronic-grade sulfuric acid. In addition, the sulfur dioxide of the sulfur dioxide furnace gas can be converted into sulfur trioxide to the maximum extent through the first gas heat exchanger, the second gas heat exchanger, the converter, the third gas heat exchanger, the fourth gas heat exchanger, the intermediate absorption tower and the final absorption tower, and the electronic-grade sulfuric acid is prepared, so that the resources can be utilized to the maximum extent, and the cost is saved.
The above-mentioned serial numbers of the embodiments of the present invention are only for description, and do not represent the advantages and disadvantages of the embodiments.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. An apparatus for the direct production of electronic grade sulfuric acid from pyrite, the apparatus comprising:
a roasting device: used for roasting pyrite or sulfur to produce sulfur dioxide furnace gas;
a purification device connected to the roasting device: the sulfur dioxide furnace gas is used for purifying the sulfur dioxide furnace gas to obtain pure sulfur dioxide furnace gas;
a drying device connected to the purification device: the drying device is used for drying the pure sulfur dioxide furnace gas to obtain dry sulfur dioxide furnace gas;
the sulfur dioxide conversion device connected with the drying device: the sulfur dioxide is used for converting sulfur dioxide in the dried sulfur dioxide furnace gas into sulfur trioxide to obtain sulfur trioxide gas;
and a sulfur trioxide absorption device connected with the sulfur dioxide conversion device: used for absorbing the sulfur trioxide gas to obtain the electronic-grade sulfuric acid.
2. An apparatus for producing electronic grade sulfuric acid according to claim 1,
the roasting device comprises: a fluidized bed roaster (1), an air blower (2) and a waste heat boiler (3); an outlet at the top of the fluidized bed roaster (1) is connected with an inlet of the waste heat boiler (3), and the air blower (2) is connected with an air inlet at the bottom of the fluidized bed roaster (1);
the purification device comprises: a cyclone dust collector (4), a venturi (5), a foam tower (6) and an electric demister (7); the outlet of the waste heat boiler (3) is connected with the inlet of the cyclone dust collector (4), the outlet of the cyclone dust collector (4) is connected with the inlet of the venturi (5), the outlet of the venturi (5) is connected with the inlet of the foam tower (6), and the outlet of the foam tower (6) is connected with the inlet of the electric demister (7);
the drying device includes: a sulfur dioxide blower (8) and a drying tower (9); the outlet of the electric demister (7) is connected with the gas inlet of the drying tower (9), and the gas outlet of the drying tower (9) is connected with the inlet of the sulfur dioxide blower (8);
the sulfur dioxide conversion device comprises: a first gas heat exchanger (10), a second gas heat exchanger (11), a converter (12), a third gas heat exchanger (13) and a fourth gas heat exchanger (14);
the inlet of the first gas heat exchanger (10) is connected with the outlet of the sulfur dioxide blower (8) and the outlet of the third layer of the converter (12), and the outlet of the first gas heat exchanger (10) is connected with the inlet of the second gas heat exchanger (11); the inlet of the second gas heat exchanger (11) is also connected with the outlet of the first layer of the converter (12), and the outlet of the second gas heat exchanger (11) is respectively connected with the inlets of the first layer and the second layer of the converter (12); the inlet of the third gas heat exchanger (13) is respectively connected with the outlet of the second layer of the converter (12) and the outlet of the fourth gas heat exchanger (14), the outlet of the third gas heat exchanger (13) is respectively connected with the inlets of the third layer and the fourth layer of the converter (12), and the inlet of the fourth gas heat exchanger (14) is connected with the outlet of the fourth layer of the converter (12);
the sulfur trioxide absorption device comprises: the gas inlet of the middle absorption tower (15) is connected with the outlet of the first gas heat exchanger (10), and the gas outlet of the middle absorption tower (15) is connected with the inlet of the fourth gas heat exchanger (14).
3. An apparatus for producing electronic grade sulfuric acid according to claim 2,
the sulfur trioxide absorption device further comprises: a final absorption tower (16), wherein a gas inlet of the final absorption tower (16) is connected with an outlet of the fourth gas heat exchanger (14).
4. A plant for producing electronic grade sulfuric acid according to claim 3, characterized in that the top of the intermediate absorption tower (15) and the top of the final absorption tower (16) are equipped with fiber mist eliminators.
5. An apparatus for producing electronic grade sulfuric acid according to claim 2,
the drying tower (9) is connected with a first sulfuric acid circulating system;
the first sulfuric acid circulation system includes: a first circulation tank (17) and a first acid cooler (18);
sulfuric acid and a first acid pump (19) are arranged in the first circulating tank (17), a sulfuric acid outlet of the drying tower (9) is connected with an inlet of the first circulating tank (17), an outlet of the first acid pump (19) is connected with an inlet of the first acid cooler (18), and an outlet of the first acid cooler (18) is connected with an inlet of the drying tower (9).
6. An apparatus for producing electronic grade sulfuric acid according to claim 2,
the middle absorption tower (15) is connected with a second sulfuric acid circulating system;
the second sulfuric acid circulation system includes: a second circulation tank (20) and a second acid cooler (21);
and sulfuric acid and a second acid pump (22) are arranged in the second circulating tank (20), a sulfuric acid outlet of the intermediate absorption tower (15) is connected with an inlet of the second circulating tank (20), an outlet of the second acid pump (22) is connected with an inlet of the second acid cooler (21), and an outlet of the second acid cooler (21) is connected with an inlet of the intermediate absorption tower (15).
7. An apparatus for producing electronic grade sulfuric acid according to claim 3,
the final absorption tower (16) is connected with a third sulfuric acid circulating system;
the third sulfuric acid circulation system includes: a third circulation tank (23) and a third acid cooler (24);
the third circulation tank (23) is internally provided with sulfuric acid and a third acid pump (25), the sulfuric acid outlet of the final absorption tower (16) is connected with the inlet of the third circulation tank (23), the outlet of the third acid pump (25) is connected with the inlet of a third acid cooler (24), and the outlet of the third acid cooler (24) is connected with the inlet of the final absorption tower (16).
8. A method for producing electronic grade sulfuric acid according to any of claims 1 to 7, characterized in that the method comprises:
roasting pyrite or sulfur to obtain sulfur dioxide furnace gas;
purifying the sulfur dioxide furnace gas to obtain the pure sulfur dioxide furnace gas;
drying the pure sulfur dioxide furnace gas to obtain dry sulfur dioxide furnace gas;
carrying out oxidation reaction on the dried sulfur dioxide furnace gas in the presence of a catalyst to obtain sulfur trioxide gas;
and absorbing the sulfur trioxide gas by using sulfuric acid with the concentration of 98 wt% to obtain the electronic-grade sulfuric acid.
9. The method of claim 8, wherein roasting pyrite or sulfur comprises:
crushing the pyrite or the sulfur, conveying the crushed pyrite or the sulfur into a fluidized bed of the fluidized bed roaster (1), roasting the crushed pyrite or the sulfur and air fed by the air blower (2) at 850-1000 ℃ to generate first furnace gas, conveying the first furnace gas to the waste heat boiler (3), and cooling the first furnace gas to 320-370 ℃ to obtain sulfur dioxide furnace gas;
the purifying the sulfur dioxide furnace gas comprises: conveying the sulfur dioxide furnace gas to the cyclone dust collector (4) for dust removal to obtain second furnace gas, conveying the second furnace gas to the foam tower (6) through the venturi tube (5), converting sulfur trioxide contained in the second furnace gas from a sulfuric acid steam form into acid mist, washing and removing solid particles of metal oxides to obtain third furnace gas, conveying the third furnace gas to the electric demister (7), and removing the residual solid particles of the metal oxides and mine dust under the action of high-voltage static electricity to obtain pure sulfur dioxide furnace gas;
the drying the clean sulfur dioxide furnace gas comprises: conveying the purified sulfur dioxide furnace gas to the drying tower (9) at the temperature below 40 ℃, and drying the purified sulfur dioxide furnace gas by using sulfuric acid with the concentration of 95 wt% to obtain the dried sulfur dioxide furnace gas;
conveying the dried sulfur dioxide furnace gas into the first gas heat exchanger (10) through the sulfur dioxide blower (8), heating the sulfur dioxide furnace gas by sulfur trioxide gas at the third layer of the converter (12), then continuously conveying the sulfur dioxide furnace gas into the second gas heat exchanger (11), heating the sulfur trioxide gas at the first layer of the converter (12) to 400-440 ℃ to obtain fourth furnace gas, conveying the fourth furnace gas to the first layer of the converter (12) through the second gas heat exchanger (11), and performing oxidation reaction under the catalytic action of a vanadium catalyst to obtain fifth furnace gas; conveying the fifth furnace gas into the second gas heat exchanger (11), cooling to 430-440 ℃, then entering a second layer of the converter (12), and carrying out oxidation reaction under the catalytic action of a vanadium catalyst to obtain sixth furnace gas; conveying the sixth furnace gas to the third gas heat exchanger (13), cooling to 400-410 ℃, then entering a third layer of the converter (12), carrying out an oxidation reaction under the catalysis of a vanadium catalyst to obtain seventh furnace gas, conveying the seventh furnace gas to the first gas heat exchanger (10), cooling to 410-420 ℃, and obtaining sulfur trioxide gas;
and conveying the sulfur trioxide gas to the intermediate absorption tower (15), and absorbing with sulfuric acid with the concentration of 98 wt% to obtain the electronic-grade sulfuric acid and eighth furnace gas.
10. The method for producing electronic-grade sulfuric acid according to claim 9, wherein the eighth furnace gas is transported to the fourth gas heat exchanger (14), heated by the sulfur trioxide gas in the fourth layer of the converter (12), and then transported to the third gas heat exchanger (13), heated by the sulfur trioxide gas in the second layer of the converter (12) to 400-410 ℃ to obtain a ninth furnace gas, and transported to the fourth layer of the converter (12), and subjected to an oxidation reaction under the catalysis of a vanadium catalyst to finally convert sulfur dioxide in the ninth furnace gas to obtain a tenth furnace gas, and transported to the fourth gas heat exchanger (14), cooled to 60-80 ℃ to obtain the sulfur trioxide gas, and transported to the final absorption tower (16), and absorbing by using electronic grade sulfuric acid with the concentration of 98 wt% to obtain the electronic grade sulfuric acid.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117205856A (en) * | 2023-09-21 | 2023-12-12 | 福建天甫电子材料有限公司 | Automatic control system for electronic grade sulfuric acid production and method for producing electronic grade sulfuric acid |
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