CN103043610B - Method and system for treating silicon tetrachloride by hydrolysis method - Google Patents
Method and system for treating silicon tetrachloride by hydrolysis method Download PDFInfo
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Abstract
The invention provides a method and a system for treating silicon tetrachloride, a by-product of polysilicon production; silicon tetrachloride is converted to anhydrous hydrogen chloride gas by hydrolysis, and white carbon black is generated simultaneously; therefore, the toxic substance of silicon tetrachloride is converted into a product with high value. The anhydrous hydrogen chloride gas can be used for preparing trichlorosilane, a raw material of polysilicon production; therefore, cyclic utilization of the chlorine element in polysilicon production is realized, and the purposes of resource saving and environment friendliness are reached.
Description
Technical field
The present invention relates to the method and system of process for producing anhydrous hydrogen chloride that the silicon tetrachloride as by-product of production of polysilicon is hydrolyzed, the particularly method and system of hydrolysis method processing and utilizing silicon tetrachloride.
Background technology
Polysilicon is semiconductor industry, electronics and information industry, the most basic functional material of solar-energy photo-voltaic cell industry.Along with these industries particularly the developing rapidly of solar photovoltaic industry, greatly have stimulated the market requirement of polysilicon.Method for preparing polysilicon mainly Siemens Method or the improved Siemens of current employing.Wherein, Siemens Method produces the extremely low silicon tetrachloride as by-product of a large amount of utility value.Generally, often produce 1 ton of polysilicon and will produce 8-10 ton liquid silicon tetrachloride.Silicon tetrachloride is a kind of harmful toxic matter with severe corrosive, very easily reacts with water and generates silicon-dioxide and hydrogenchloride, and directly discharge is by serious pollution of ecological environment.Although silicon tetrachloride can be reclaimed Hydrogenation and obtain trichlorosilane by improved Siemens, because transformation efficiency is lower, energy consumption is higher, causes production cost high.Therefore, the important factor being treated as the industry development of restriction polysilicon of so a large amount of silicon tetrachlorides.
The technology of current industrial processing silicon chloride has hydrogenation method and hydrolysis method.
Hydrogenation method is that silicon tetrachloride hydrogenation is generated trichlorosilane, and trichlorosilane for the production of polysilicon, generates silicon tetrachloride as by-product as raw material simultaneously, thus realizes recycling of chlorine element in polysilicon production process.But hydrogenation technique temperature of reaction is high, and energy consumption is high, and cost is high, and trichlorosilane yield is very low.
Hydrolysis method hydrolyzing silicon tetrachloride is generated hydrogenchloride and silicon-dioxide (white carbon black), and chemical equation is: SiCl
4+ 2H
2o=4HCl+SiO
2, this reaction is strong exothermal reaction.Current application hydrolysis method processing silicon chloride main purpose is to obtain the white carbon black with certain commercial exploitation, moisture hydrogenchloride is then as secondary product, being used for making the lower hydrochloric acid of business added value, also having minority technology by hydrogenchloride by being applied after conventional processed.But, because the market demand of white carbon black is very limited, a large amount of silicon tetrachlorides that production of polysilicon produces can not be consumed far away; For the raw materials for production trichlorosilane by preparation of hydrogen chloride polysilicon, this thinking of polysilicon production process is applied to make chlorine element circular, the high-moisture of hydrogenchloride becomes again the technical bottleneck of this route applications of restriction, and thus nobody did the research work of this respect at present.According to the common practise of this area, in the production process of trichlorosilane, the water content of raw material hydrogenchloride for the yield of trichlorosilane and quality influence huge; Hydrogenchloride water content is lower, then the yield of trichlorosilane is higher, and quality is better, and then significantly improves the quality of polysilicon.
About the deep dehydration technology of hydrogenchloride, CN101774543A discloses a kind of method and system preparing anhydrous hydrogen chloride gas.The method makes moisture hydrogen chloride gas enter dehydration tower by the bottom of dehydration tower upwards to flow; Cold hydrogen chloride liquid enters dehydration tower by the top of dehydration tower and flows downward, and carries out heat, mass exchange with the moisture hydrogen chloride gas upwards flowed in dehydration tower; It is 1.0 × 10 that the cold hydrogen chloride liquid wherein flowed downward makes the temperature of the moisture hydrogen chloride gas upwards flowed be reduced in dehydration tower water content under system pressure
-5hydrogen chloride gas dew point below; Then the anhydrous hydrogen chloride gas of discharging from dehydration column overhead is collected.This technology is connected with overhead condenser with refrigerator, for described hydrogen chloride liquid provides required cold.If this technology is applied to processing silicon chloride, then needs a kind of early stage by hydrolyzing silicon tetrachloride, the hydrogen chloride gas produced is carried out to the system process of preliminary hydro-extraction.In addition, this technology adopts refrigerator to obtain cold, and energy consumption is comparatively large, and cost is higher, still leaves some room for improvement.
Based on prior art Problems existing, a kind of hydrolysis method processing silicon chloride is needed to produce the method and system of anhydrous hydrogen chloride.
Summary of the invention
The object of the invention is to provide a kind of hydrolysis method processing silicon chloride to produce the method and system of anhydrous hydrogen chloride.The anhydrous hydrogen chloride that the method generates can be used for producing high-quality trichlorosilane, and then with described trichlorosilane for raw material, the polysilicon of production high-quality, thus the recycle realizing chlorine element in polysilicon production process, both protection of the environment, economize on resources again.
Another object of the present invention is to provide a kind of hydrolysis method processing silicon chloride to produce anhydrous hydrogen chloride, produces the method and system of white carbon black simultaneously.
The technical term mentioned in present specification, implication is as follows:
Anhydrous hydrogen chloride, refers to that water content is lower than 1.0 × 10
-5hydrogenchloride, this hydrogenchloride does not have corrodibility.
The dew point of hydrogen chloride gas, the temperature when hydrogen chloride gas referring to containing a certain amount of steam is cooled to saturated under a certain pressure.Such as when pressure is 0.1-5.0MPa, water content is 1.0 × 10
-5the dew-point temperature of hydrogen chloride gas be-65 to-30 DEG C.
Hydrogenchloride balanced gas, refers under certain temperature and pressure, the hydrogen chloride gas of effusion after hydrogenchloride reaches capacity in solvent; In the system of the present invention, refer under the temperature and pressure of extraction tank, the hydrogen chloride gas of effusion after hydrogenchloride reaches capacity in the slurry of extraction.
For reaching described goal of the invention, the invention provides following technical scheme:
Hydrolysis method processing silicon chloride produces a method for anhydrous hydrogen chloride, comprising:
(1) preparation of hydrogen chloride: the water in silicon tetrachloride and hydrochloric acid soln reacts, obtains slurry that silicon-dioxide and hydrochloric acid soln form and hydrogenchloride unstripped gas; By described slurry extraction;
(2) deep dehydration: described hydrogenchloride unstripped gas is treated or after rectifying preliminary hydro-extraction, enter dehydration tower by the bottom of dehydration tower upwards to flow, and contact with the anhydrous hydrogen chloride liquid countercurrent flowed downward from dehydration column overhead, dehydration column overhead discharges hydrogen chloride gas, the hydrogen chloride liquid after absorbing moisture is discharged at the bottom of dehydration tower tower, wherein, the temperature of the described anhydrous hydrogen chloride liquid flowed downward from dehydration column overhead is 1.0 × 10 lower than water content under dehydration tower internal pressure
-5the dew point of hydrogen chloride gas, and mass flow rate discharge higher than tower top 20% of hydrogen chloride gas mass flow rate; Described from dehydration column overhead discharge be anhydrous hydrogen chloride gas.
According to the preferred embodiment of the present invention, one of described preparation of hydrogen chloride method is:
Water in silicon tetrachloride and hydrochloric acid soln reacts in a kettle., and the slurry that gained silicon-dioxide and hydrochloric acid soln form and the extraction of hydrogenchloride unstripped gas are to separating cucurbitula, and described solution cucurbitula decompression discharges hydrogenchloride unstripped gas.Described hydrogenchloride unstripped gas enters at the bottom of dehydration tower tower and carries out deep dehydration, or first enters at the bottom of rectifying tower and carry out rectifying, obtains the hydrogen chloride gas of preliminary hydro-extraction, then carries out deep dehydration.
Pressure in described solution cucurbitula is preferably negative pressure, thus the hydrogen chloride gas be dissolved in hydrochloric acid soln is fully discharged, and is preferably 5-50KPa, is more preferably 5-12KPa.Pressure in described reactor is preferably malleation, and to make the hydrogenchloride generated be dissolved in solution as much as possible, thus improve the production efficiency of hydrogenchloride, preferably, the pressure in described reactor is 0.1-2.5MPa, is more preferably 0.1-1.0MPa; Temperature in reactor is preferably 35-70 DEG C, is more preferably 45-50 DEG C; Charging concentration of hydrochloric acid solution is preferably 20-33%, is more preferably 23-27%.
Compared with the hydrolyzing silicon tetrachloride reaction method of routine, be malleation in reactor in the method, be conducive to more hydrogen chloride gas to be dissolved in hydrochloric acid soln, separating in cucurbitula is negative pressure, be conducive to hydrogen chloride gas to discharge fully, thus substantially increase the efficiency of preparation of hydrogen chloride; In addition, by controlling many factors, the concentration of the pressure in such as reactor, temperature, charging hydrochloric acid soln, pressure, temperature etc. in cucurbitula can be separated, controls the speed that hydrogenchloride generates and discharges, thus be more conducive to the accurate control of process.
According to the preferred embodiment of the present invention, two of described preparation of hydrogen chloride method is:
Water in silicon tetrachloride and hydrochloric acid soln reacts in a kettle., effusion after the hydrogenchloride generated reaches capacity in hydrochloric acid soln, as hydrogenchloride unstripped gas, described hydrogenchloride unstripped gas enters at the bottom of dehydration tower tower and carries out deep dehydration, or first enter at the bottom of rectifying tower and carry out rectifying, obtain the hydrogen chloride gas of preliminary hydro-extraction, then carry out deep dehydration.
The method is preferably carried out in reactive distillation column.The method can control to react the speed generating hydrogenchloride by the concentration of the temperature in control reactor, charging hydrochloric acid soln.Described charging concentration of hydrochloric acid solution is preferably 20-33%, is more preferably 29-31%; Temperature in reactor is preferably 20-85 DEG C, is more preferably 60-80 DEG C.Preferably, before the slurry that silicon-dioxide and hydrochloric acid soln form is carried out solid-liquid separation, discharge hydrogenchloride balanced gas wherein; The hydrogenchloride balanced gas of described discharge can absorb process, as liquid absorption method, solid absorption method etc., to avoid contaminate environment by ordinary method; According to the preferred embodiment of the present invention, the hydrogen chloride gas of described hydrogenchloride balanced gas and the extraction of rectifying tower top is merged, carry out cooling condensation and gas-liquid separation again, such arrangement both took full advantage of product, avoid contaminate environment, ensure that system internal pressure balances better simultaneously, enhance the security of system.
The method is using the bubbling bed conversion zone of reactive distillation column as reactor, chemical reaction in tower reactor and the sepn process in rectifying section are carried out simultaneously, rectifying make use of the reaction heat that chemical reaction produces, without the need to other heating, thus the effect achieving significant simplified apparatus, save energy, reduce costs.
Water in above-mentioned two kinds of silicon tetrachlorides and hydrochloric acid soln reacts, and generates in the method for hydrogen chloride gas and silicon-dioxide:
Described silicon tetrachloride can participate in reaction in the form of a gas or liquid, and described silicon tetrachloride gas can be that silicon tetrachloride liquid vaporization generates, and also can be the silicon tetrachloride gas that reaction directly generates; For improving reaction efficiency, described reaction can under agitation be carried out;
The temperature that described reactor is conciliate in cucurbitula can be controlled by the water or water vapour passing into suitable temp in reacting kettle jacketing; Temperature in reactor can also be controlled by the temperature controlling charging hydrochloric acid soln, and those skilled in the art can by calculating;
In rectification step before deep dehydration step, the hydrogen chloride gas that reaction generates enters from rectifier bottoms, through rectifying, condensation and gas-liquid separation, gained gas passes into dehydration tower as the unstripped gas preparing anhydrous hydrogen chloride gas and carries out deep dehydration, gained liquid enters rectifying tower as phegma, at the bottom of dehydration tower tower, discharge the hydrogen chloride liquid after absorbing moisture in deep dehydration step also enter rectifying tower as phegma, preferably, the position that described phegma enters rectifying tower is position consistent with described phegma water content to the hydrogen chloride gas body water content of upper flowing in rectifying tower, to obtain better rectification efficiency, those skilled in the art can know described position by calculating,
Massfraction in described slurry shared by silicon-dioxide has material impact to described slurry proper flow in the duct, and according to the preferred embodiment of the present invention, the massfraction in described slurry shared by silicon-dioxide is less than 20%, is preferably less than 10%.
According to the preferred embodiment of the present invention, the slurry that silicon-dioxide forms with hydrochloric acid soln is separated, and one of method obtaining white carbon black is:
By described slurry cooling, filtration, drying, gained silicon-dioxide is white carbon black, and gained concentration of hydrochloric acid solution is adjusted to 20-33%, again for reacting with silicon tetrachloride, thus realizes recycle.Preferably deionized water is used in wherein said washing step.
According to the preferred embodiment of the present invention, the slurry that silicon-dioxide forms with hydrochloric acid soln is separated, and obtain the method for white carbon black two are:
Described slurry is carried out spray drying treatment, and gained solid is white carbon black, and the air of gas containing hydrogen chloride makes hydrochloric acid soln through absorbing, and concentration adjustment, to 20-33%, again for reacting with silicon tetrachloride, thus realizes recycle.Wherein said spray drying temperature adopts 200-600 DEG C, is preferably 300-400 DEG C, thus obtains better drying effect, obtain uniform white carbon black product.
In deep dehydration step, the cold maintained needed for described anhydrous hydrogen chloride fluid temperature is compressed by a part for the anhydrous hydrogen chloride gas of dehydration column overhead being discharged, cooling, throttling expansion refrigeration provides, be specifically as follows: after the anhydrous hydrogen chloride gas of being discharged by dehydration column overhead and the anhydrous hydrogen chloride liquid formed through condensation carry out indirect heat exchange, by compressing at least partially in described anhydrous hydrogen chloride gas, gas after compression forms anhydrous hydrogen chloride liquid through condensation, after this anhydrous hydrogen chloride liquid and the aforementioned hydrogen chloride gas from dehydration column overhead carry out indirect heat exchange, part carries out throttling expansion, cold needed for acquisition.The circulation of this process is carried out, thus continues to obtain institute's chilling requirement.
According to the preferred embodiment of the present invention, before hydrogen chloride gas passes into dehydration tower, first in system, pass into corrosion-free gas, described corrosion-free gas carried out compress, cool, throttling expansion closed-looped refrigeration, being brought down below water content under dehydration tower internal pressure to dehydration column overhead temperature is 1.0 × 10
-5hydrogen chloride gas dew-point temperature after, then pass into reactive distillation method obtain hydrogen chloride gas, start preparation process.Wherein, described corrosion-free gas can be anhydrous hydrogen chloride gas or High Purity Nitrogen, is preferably anhydrous hydrogen chloride gas, and the method that this gas can be provided by CN101774543A obtains, and also can be bought by market and obtain.The mass flow rate of described corrosion-free gas is preferably the 20%-30% of described moisture hydrogen chloride gas mass flow rate.
According to the preferred embodiment of the present invention, the mass flow rate of carrying out the anhydrous hydrogen chloride gas compressed accounts for the 20-30% of the hydrogen chloride gas total mass flow rate of discharging from dehydration column overhead, and remaining 70%-80% is as the extraction of anhydrous hydrogen chloride gas product.
Preferably, the pressure in dehydration tower is 0.1-5.0MPa.
Those skilled in the art can, according to thinking of the present invention, adopt the additive method of this area routine to implement described method.
The present invention also provides hydrolysis method processing silicon chloride to produce the system of anhydrous hydrogen chloride, and described system comprises:
(1) preparation of hydrogen chloride system: at least comprise reactor, reacts wherein for the water in silicon tetrachloride and hydrochloric acid soln, generates hydrogen chloride gas and silicon-dioxide;
(2) deep dehydration system: comprise dehydration tower and refrigeration system, described dehydration tower be used for making hydrogen chloride gas in dehydration tower on flowing, contact with the anhydrous hydrogen chloride liquid countercurrent flowed downward from dehydration column overhead, to prepare anhydrous hydrogen chloride gas; Described refrigeration system is for providing the cold needed for described anhydrous hydrogen chloride liquid.
According to the preferred embodiment of the present invention, described preparation of hydrogen chloride system comprises:
Reactor, reacts wherein for the water in silicon tetrachloride and hydrochloric acid soln, generates hydrogen chloride gas and silicon-dioxide;
Separate cucurbitula, be connected with reactor, for the slurry that silicon-dioxide in reactor and hydrochloric acid soln formed and hydrogen chloride gas extraction, and discharge hydrogen chloride gas;
Rectifying device, for carrying out preliminary hydro-extraction by separating the hydrogen chloride gas discharged in cucurbitula; Described rectifying device comprises rectifying tower, for the rectifying of hydrogen chloride gas; At least one water cooler, for being cooled to liquid state by the hydrogen chloride gas part of rectifying section top extraction; With at least one knockout drum, for cooling through condenser the hydrogen chloride gas and liquid separation that are formed;
Preferably, described system also comprises gas blower, for effectively entering at the bottom of rectifying tower carry out rectifying by separating in cucurbitula the hydrogen chloride gas discharged, or directly enters at the bottom of dehydration tower tower and carries out deep dehydration;
Preferably, described system also comprises white carbon black preparation system, for the slurry of silica solid and hydrochloric acid soln composition is carried out solid-liquid separation, comprising:
Water cooler, for cooling the slurry separating silica solid and hydrochloric acid soln composition in cucurbitula; Filter, for through overcooled slurries filtration, being separated and obtaining white carbon black; Or
Spray-drier, for the slurry of the silica solid and hydrochloric acid soln composition of separating cucurbitula discharge is carried out spraying dry, obtains white carbon black and the warm air containing hydrogen chloride gas; With hydrogen chloride absorption equipment, for absorbing the hydrogen chloride gas in described warm air, obtain hydrochloric acid soln.
Preferably, described system also comprises a hydrochloric acid tank, for storing hydrochloric acid soln.
Preferably, in described reactor, mechanical stirrer is housed.
Preferably, in described solution cucurbitula, mechanical stirrer is housed.
Preferably, described reactor conciliates cucurbitula all with chuck.
Preferably, the condenser in described rectifying device is three grades of graphite cooler condensers; Knockout drum to be arranged between the second stage and third stage condenser and after third stage condenser.
Described hydrogen chloride absorption equipment can be conventional absorption equipment.Preferably, described hydrogen chloride absorption equipment is absorption tower.
According to the present invention another preferred embodiment, described preparation of hydrogen chloride system comprises:
Reactive distillation column, the bubbling bed conversion zone of bottom, as reactor, reacts wherein for the water in silicon tetrachloride gas and hydrochloric acid soln, generates hydrogenchloride and silicon-dioxide; Top is rectifying section, for the rectifying of hydrogenchloride;
Condensation and separating device: at least one condenser, for being cooled to liquid state by the hydrogen chloride gas part of rectifying section top extraction; At least one knockout drum, for cooling through condenser the hydrogen chloride gas and liquid separation that are formed; Described hydrogen chloride gas enters dehydration tower and carries out deep dehydration;
Preferably, described system also comprises white carbon black preparation system, and described white carbon black preparation system comprises:
Extraction tank, for the slurry extraction of the silica solid that will be formed in bubbling bed conversion zone and hydrochloric acid soln composition, and discharges the hydrogenchloride balanced gas in slurry; Water cooler, for cooling the slurry in extraction tank; Filter, for through overcooled slurries filtration, being separated and obtaining white carbon black; Or
Extraction tank, for the slurry extraction of the silica solid that will be formed in bubbling bed conversion zone and hydrochloric acid soln composition, and discharges the hydrogenchloride balanced gas in slurry; Spray-drier, the slurry for the silica solid of being discharged by extraction tank and hydrochloric acid soln composition carries out spraying dry, obtains white carbon black and the warm air containing hydrogen chloride gas; With hydrogen chloride absorption equipment, for absorbing the hydrogen chloride gas in described warm air, obtain hydrochloric acid soln.
Preferably, described system also comprises a hydrochloric acid tank, for storing hydrochloric acid soln.
Preferably, in described bubbling bed conversion zone, mechanical stirrer is housed.
Preferably, described extraction tank top is connected with the hydrogen chloride gas fairlead at rectifying section top through equilibration tube, then is connected to subsequent condensation device, and the hydrogenchloride balanced gas that extraction tank is discharged and the hydrogen chloride gas of rectifying section top extraction merge.Such equipment arrangement both took full advantage of product, avoided environmental pollution, ensure that the pressure equilibrium of system simultaneously better, enhanced the security of system.
Preferably, in described condensation and separating device, condenser is three grades of graphite cooler condensers; Knockout drum to be arranged between the second stage and third stage condenser and after third stage condenser.
Described hydrogen chloride absorption equipment can be conventional absorption equipment.Preferably, described hydrogen chloride absorption equipment is absorption tower.
According to the preferred embodiment of the present invention, the refrigeration system in described deep dehydration system is the condenser being positioned at dehydration column overhead, and the refrigerator be connected with described condenser, for providing the cold in dehydration tower needed for anhydrous hydrogen chloride liquid.
According to the present invention another preferred embodiment, the refrigeration system in described deep dehydration system comprises:
At least one interchanger, the hydrogen chloride gas of discharging for making dehydration column overhead and the hydrogen chloride liquid indirect heat exchange in described interchanger carrying out condenser, be preferably an interchanger;
A compressor, for compressing partial oxidation hydrogen, described compressor is preferably membrane compressor;
At least one condenser, for cooling the hydrogen chloride gas after compressor compression, liquefy, the hydrogen chloride liquid generated is delivered to interchanger, is preferably a condenser;
Throttling valve, is arranged between dehydration column overhead and interchanger, and for making the hydrogen chloride liquid partial throttling swell refrigeration from interchanger, cooling post chlorization hydrogen liquid flows downward from tower top further.
Preferably, described refrigeration system also comprises a surge tank be arranged between described condenser and interchanger, is delivered to interchanger again, with the pressure surge of buffering system for making the hydrogen chloride liquid of condenser after flowing through surge tank.
Preferably, described refrigeration system also comprises a splitter be arranged between interchanger and compressor, for the hydrogen chloride gas from interchanger is divided into two portions, a part is delivered to compressor as recycle gas, and another part is as the extraction of anhydrous chlorides of rase hydrogen production.
Described reactor, solution cucurbitula, rectifying tower, reactive distillation column and extraction tank, adopt the material of hydrochloric acid corrosion resistant.Reactor, parsing tank can be lass lining, enamel or stainless steel lining plastic magnetic agitation still.The composition of tower shell material of rectifying tower selects one or more in the steel of Haas alloy (Hastelloy), plastic-steel matrix material, coating tetrafluoroethylene, tower inner member and the preferred plastics of filler or ceramic; Bubbling bed conversion zone and extraction tank material select one or more in Haas alloy, plastic-steel matrix material, the steel applying tetrafluoroethylene, pottery or plastic material.
Described condenser all adopts graphite material to make.
Described filter, absorption tower, hydrochloric acid tank and hydrochloric acid pump adopt conventional acid-resistant system.
The material of the dehydration tower tower body in described deep dehydration system is selected from one or more in the steel of Haas alloy, plastic-steel matrix material, coating tetrafluoroethylene, tower inner member and the preferred plastics of filler or ceramic;
That runs in interchanger, condenser, compressor, refrigerator and respective line in described deep dehydration system is non-corrosive anhydrous hydrogen chloride, preferably adopts stainless material manufacture.
Single with regard to technical scheme, it is initiative that method design of the present invention and device systems are arranged in processing silicon chloride field, compared with prior art has following technique effect:
(1) the present invention will produce the by product of polysilicon, have the harmful toxic matter hydrolyzing silicon tetrachloride of severe corrosive, obtain simultaneously and there is the anhydrous hydrogen chloride gas of high commercial value and there is the white carbon black of higher commercial value, the silicon tetrachloride process problem of long-standing problem polysilicon industry development is solved with lower cost, turn waste into wealth, killing three birds with one stone.Gained anhydrous hydrogen chloride gas can be used for preparing the high-quality trichlorosilane needed for production of polysilicon, thus realizes the recycle of chlorine element in polysilicon production process, and reach resources conservation and eco-friendly effect, industry meaning is remarkable;
(2) the present invention improves hydrogenchloride deep dehydration technology simultaneously, gas compression merit is utilized to replace the refrigerator of prior art to obtain as the cold needed for the anhydrous hydrogen chloride liquid of phegma, this technical equipment cost is only the 20-30% of refrigerator system, and energy consumption is low, simple to operate, operating safety.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of one of preferred implementation simultaneously preparing anhydrous hydrogen chloride and white carbon black by hydrolyzing silicon tetrachloride.
Fig. 2 is the schematic flow sheet of the preferred implementation two simultaneously being prepared anhydrous hydrogen chloride gas and white carbon black by hydrolyzing silicon tetrachloride.
Fig. 3 is the schematic flow sheet of the preferred implementation three simultaneously being prepared anhydrous hydrogen chloride gas and white carbon black by hydrolyzing silicon tetrachloride.
Embodiment
Further illustrate method and system provided by the present invention below in conjunction with accompanying drawing, but the present invention is not therefore subject to any restriction.
Embodiment 1
Major equipment illustrates:
Reactive distillation column: bubbling bed conversion zone φ 800 × 2000mm; Rectifying section φ 500 × 5000mm, in-built ceramic component;
Dehydration tower: φ 500 × 6000mm, in-built ceramic component;
Heat-exchange equipment: H-100, material is graphite, heat interchanging area 0.6m
2; H-101, material is graphite, heat interchanging area 9.4m
2; H-102, material is graphite, heat interchanging area 2.0m
2; H-103, material is graphite, heat interchanging area 0.7m
2; H-104, material is graphite, heat interchanging area 17.3m
2; H-201, material is stainless steel, heat interchanging area 5.0m
2; H-202, material is stainless steel, heat interchanging area 0.1m
2;
Process description:
As shown in Figure 1, hydrochloric acid soln 16 is pumped in the tower reactor bubbling bed conversion zone of reactive distillation column T-101 by hydrochloric acid pump P-101 from hydrochloric acid tank G-102, silicon tetrachloride liquid 1 is after vaporizer H-100 vaporizes, pass into bubbling bed conversion zone, with the water generation hydrolysis reaction in hydrochloric acid soln, generate hydrogenchloride and silicon-dioxide.This reaction is strong exothermal reaction, overflow from water after the hydrogenchloride solubleness in hydrochloric acid soln generated reaches capacity, upwards rectifying section is entered together with water vapour, with the phegma counter current contact flowed downward in rectifying section, carry out heat, mass exchange, the moisture that boiling point is higher flows downward, the hydrogenchloride that boiling point is lower upwards flows, reach the object of hydrogenchloride and water initial gross separation, then through the hydrogen chloride gas of preliminary hydro-extraction from the extraction of rectifying section top, the hydrogenchloride balanced gas 17 of discharging with extraction tank G-101 merges into hydrogen chloride gas 5, through three grades of graphite cooler condenser H-101, H-102, H-103 condensation and knockout drum F-101, F-102 carries out gas-liquid separation, gained liquid 13 returns rectifying section as hydrogenchloride phegma, gained hydrogen chloride gas 6 enters dehydration tower T-201 from bottom, the anhydrous hydrogen chloride liquid countercurrent flowed downward with dehydration column overhead contacts, then discharge moisture hydrogen chloride liquid 12 at the bottom of dehydration tower tower, this liquid returns the rectifying section of reactive distillation column, as phegma, dehydration column overhead discharges anhydrous hydrogen chloride gas 7, heat up through interchanger H-201 heat exchange, and after shunt through splitter F-201, wherein about 70-80% is as the extraction of product anhydrous hydrogen chloride 3 gas, 20-30% enters molding machine M-201 as refrigerant 9 and is compressed into high pressure gas 10, highly pressurised liquid 11 is condensed into again through condenser H-202 cooling and interchanger H-201, this liquid enters dehydration tower T-201 top through throttling valve J-201 decompression throttling expansion, and the anhydrous hydrogen chloride liquid return liquid as low temperature refluxes.
In the bubbling bed conversion zone of reactive distillation column T-101 bottom, water generation bubbling hydrolysis reaction in silicon tetrachloride gas and hydrochloric acid generates gas chlorination hydrogen and solid silica, major part hydrogenchloride upwards enters rectifying section as gas, small part is then dissolved in the slurry 14 that silicon-dioxide and hydrochloric acid soln form, this slurry 14 enters extraction tank G-101 by the top of bubbling bed conversion zone, the upper gaseous phase of extraction tank is connected with rectifying tower top through equilibration tube, hydrogen chloride gas 5 is become to make the hydrogen chloride gas of hydrogenchloride the balanced gas 17 and rectifying section top extraction of discharging merge, and lower the temperature through condenser H-104 through the slurry 15 of exhaust, then filter through filter L-101, wherein, silica solid washs through deionized water 2, as product 4 extraction, namely can be used as white carbon black product after drying, and filtrate 16 is stored in hydrochloric acid tank G-102 for hydrochloric acid soln, recycle in order to pumping into bubbling bed conversion zone.Concrete flow stream parameters is as shown in table 1.
Table 1 flow stream parameters table
Table 1 flow stream parameters table (Continued)
Embodiment 2
Major equipment illustrates:
Reactive distillation column: stir bubbling bed conversion zone φ 260 × 1500mm; Rectifying section φ 100 × 400mm, in-built ceramic component.
Dehydration tower: φ 500 × 6000mm, in-built ceramic component;
Heat-exchange equipment: H-100, material is graphite, heat interchanging area 0.6m
2; H-101, material is graphite, heat interchanging area 9.4m
2; H-102, material is graphite, heat interchanging area 2.0m
2; H-103, material is graphite, heat interchanging area 0.7m
2; H-104, material is graphite, heat interchanging area 17.3m
2; H-201, material is stainless steel, heat interchanging area 5.0m
2; H-202, material is stainless steel, heat interchanging area 0.1m
2;
Process description:
As shown in Figure 2, by concentration be 35.5% hydrochloric acid soln 15 tower reactor that pumps into reactive distillation column T-101 by hydrochloric acid pump P-101 with the mass flow rate of 60.25kg/hr from hydrochloric acid tank G-102 stir in bubbling bed conversion zone, silicon tetrachloride liquid 1 passes into bubbling bed conversion zone with the mass flow rate of 10kg/hr, with the water generation hydrolysis reaction in hydrochloric acid soln, generate hydrogen chloride gas and silica solid.This reaction is strong exothermal reaction, effusion after the hydrogenchloride solubleness in hydrochloric acid soln generated reaches capacity, upwards enter rectifying section and carry out rectifying together with water vapour, with the hydrogenchloride phegma counter current contact flowed downward in rectifying section, carry out heat, mass exchange, the moisture that boiling point is higher flows downward, and the lower hydrogenchloride of boiling point upwards flows, reach the object of hydrogenchloride and water initial gross separation, then hydrogen chloride gas is from the extraction of rectifying section top, the hydrogenchloride balanced gas of discharging with extraction tank G-101 merges into hydrogen chloride gas 5, through three grades of graphite cooler condenser H-101, H-102, H-103 condensation and knockout drum F-101, F-102 carries out gas-liquid separation, it is 25 DEG C that wherein said three grades of graphite cooling condensation temperature are respectively H-101, H-102 is 0 DEG C, H-103 is-35 DEG C.Gained liquid 13 returns rectifying section as hydrogenchloride phegma, gained enters dehydration tower T-201 through the hydrogen chloride gas 6 of preliminary hydro-extraction from bottom, the anhydrous hydrogen chloride liquid countercurrent flowed downward with dehydration column overhead contacts, then discharge moisture hydrogen chloride liquid 12 at the bottom of dehydration tower tower, this liquid returns the rectifying section of reactive distillation column, as phegma; Dehydration column overhead discharges anhydrous hydrogen chloride gas 7, heat up through interchanger H-201 heat exchange, and after shunt through splitter F-201, wherein about 70-80% is as the extraction of product anhydrous hydrogen chloride 3 gas, 20-30% enters molding machine M-201 as refrigerant 9 and is compressed into high pressure gas 10, highly pressurised liquid 11 is condensed into again through condenser H-202 cooling and interchanger H-201, this liquid enters dehydration tower T-201 top through throttling valve J-201 decompression throttling expansion, and the anhydrous hydrogen chloride liquid return liquid as low temperature refluxes.
Stir in bubbling bed conversion zone in reactive distillation column T-101 tower reactor, water generation bubbling hydrolysis reaction in silicon tetrachloride liquid and hydrochloric acid soln generates gas chlorination hydrogen and solid silica, major part hydrogenchloride upwards enters rectifying section as gas, small part is then dissolved in the slurry 14 that silicon-dioxide and hydrochloric acid forms, this slurry 14 enters extraction tank G-101 by the top of stirring bubbling bed conversion zone, the upper gaseous phase of extraction tank is connected with rectifying tower top through equilibration tube, hydrogen chloride gas 5 is become to make the hydrogen chloride gas of hydrogenchloride the balanced gas 16 and rectifying section top extraction of discharging merge, slurry through being vented is squeezed in spray-drier D-101 directly to contact with warm air through slush pump and is carried out drying, and solid white carbon black 4 encapsulates as precipitated silica product after trap trapping, the mixed tail gas comprising hydrogenchloride, water vapour and air is absorbed with deionized water 2 by absorption tower T-102.Unabsorbed air can be directly emptying, and absorption by Hydrochloric Acid liquid 15 enters in hydrochloric acid tank G-102, recycles in order to pumping into stirring bubbling bed conversion zone.
Table 2 flow stream parameters table
Table 2 flow stream parameters table (Continued)
Embodiment 3
Hydrolytic reaction pot F-101: φ 260 × 1500mm;
Resolve tank F-102: φ 1000 × 3500mm;
Rectifying tower T-101: φ 100 × 4000mm;
Dehydration tower: φ 500 × 6000mm, in-built ceramic component;
Heat-exchange equipment: H-100, material is graphite, heat interchanging area 0.6m
2; H-101, material is graphite, heat interchanging area 9.4m
2; H-102, material is graphite, heat interchanging area 2.0m
2; H-103, material is graphite, heat interchanging area 0.7m
2; H-104, material is graphite, heat interchanging area 17.3m
2; H-201, material is stainless steel, heat interchanging area 5.0m
2; H-202, material is stainless steel, heat interchanging area 0.1m
2;
Process description:
See Fig. 3, be described as follows:
By concentration be 25% hydrochloric acid soln 2 with the mass flow rate of 4900kg/hr from hydrochloric acid tank G-102 by hydrochloric acid pump P-101 squeeze into band stir hydrolytic reaction pot F-101 in, silicon tetrachloride liquid 1 also passes into this stirred autoclave F-101 with the mass flow rate of 1000kg/hr, and with the water generation hydrolysis reaction in hydrochloric acid soln, generate hydrogenchloride and silicon-dioxide.This reaction is strong exothermal reaction, and the hydrogenchloride of generation dissolves and dilute hydrochloric acid is progressively reached capacity in hydrochloric acid soln, and silicon-dioxide forms uniform slurry in this hydrochloric acid soln.Slurry overflow of reducing pressure from hydrolytic reaction pot F-101 enters and separates cucurbitula F-102, be carry out desorb under the condition of negative pressure of 9.73KPa at pressure, the mixed gas 4 of the hydrogen chloride gas formed after desorb and water vapour enters atmospheric distillation tower T-101 by gas blower G-101 and carries out rectifying, with the hydrogenchloride phegma counter current contact flowed downward in rectifying section, carry out heat, mass exchange, the moisture that boiling point is higher flows downward, and the lower hydrogenchloride of boiling point upwards flows, and reaches the object of hydrogenchloride and water initial gross separation.The slurry 14 separated bottom cucurbitula F-102 is squeezed into water cooler H-104 by slush pump P-102 and is cooled, and then enters filter L-101, and as by-product extraction after the further drying of the silica 17 after filtration, the hydrochloric acid 16 of formation enters hydrochloric acid tank G-102.Hydrogen chloride gas 3 is from the extraction of rectifying section top, through three grades of graphite cooler condenser H-101, H-102, H-103 condensations, and carry out gas-liquid separation through knockout drum F-101, F-102 and carry out gas-liquid separation, it is 25 DEG C that the coolant temperature of wherein said three grades of graphite cooling cool condenser is respectively H-101, H-102 is 0 DEG C, and H-103 is-35 DEG C.Gained cooling fluid 13 enters rectifying tower T-101 as hydrogenchloride phegma at suitable feed entrance point, in the rectifying tower of described position on flowing hydrogen chloride gas body water content consistent with described phegma water content, gained is through the hydrogen chloride gas 5 of preliminary hydro-extraction, dehydration tower T-201 is entered from bottom, the anhydrous hydrogen chloride liquid countercurrent flowed downward with dehydration column overhead contacts, then discharge moisture hydrogen chloride liquid 12 at the bottom of dehydration tower tower, this liquid returns the rectifying section of reactive distillation column, as phegma; Dehydration column overhead discharges anhydrous hydrogen chloride gas 6, heat up through interchanger H-201 heat exchange, and after shunt through splitter F-201, wherein about 70-80% is as the extraction of product anhydrous hydrogen chloride 8 gas, 20-30% enters molding machine M-201 as refrigerant 9 and is compressed into high pressure gas 10, highly pressurised liquid 11 is condensed into again through condenser H-202 cooling and interchanger H-201, this liquid enters dehydration tower T-201 top through throttling valve J-201 decompression throttling expansion, and the anhydrous hydrogen chloride liquid return liquid as low temperature refluxes.
The concentrated hydrochloric acid 15 of being discharged by T-101 tower reactor also enters hydrochloric acid tank G-102 as hydrochloric acid soln raw material after a certain amount of deionized water 18 dilutes.Wet basis white carbon black material 17 after filtering enters fluid bed dryer and carries out fluidized drying, and the solid white carbon black after fluidized drying encapsulates as precipitated silica product after trap trapping; The mixed tail gas of hydrogenchloride, water vapour and air is comprised by absorbing by absorption tower after boiling-bed drying.Unabsorbed air can be directly emptying, and certain density absorption by Hydrochloric Acid liquid also enters in hydrochloric acid tank G-102.
Table 3 flow stream parameters table
Table 3 flow stream parameters table (Continued)
Claims (38)
1. hydrolysis method processing silicon chloride produces a method for anhydrous hydrogen chloride, comprising:
(1) preparation of hydrogen chloride: the water in silicon tetrachloride and hydrochloric acid soln reacts, obtains slurry that silicon-dioxide and hydrochloric acid soln form and hydrogenchloride unstripped gas; By described slurry extraction;
(2) deep dehydration: described hydrogenchloride unstripped gas is treated or after rectifying preliminary hydro-extraction, enter dehydration tower by the bottom of dehydration tower upwards to flow, and contact with the anhydrous hydrogen chloride liquid countercurrent flowed downward from dehydration column overhead, dehydration column overhead discharges hydrogen chloride gas, the hydrogen chloride liquid after absorbing moisture is discharged at the bottom of dehydration tower tower, wherein, the temperature of the described anhydrous hydrogen chloride liquid flowed downward from dehydration column overhead is 1.0 × 10 lower than water content under dehydration tower internal pressure
-5the dew point of hydrogen chloride gas, and mass flow rate discharge higher than tower top 20% of hydrogen chloride gas mass flow rate; Described from dehydration column overhead discharge be anhydrous hydrogen chloride gas;
Wherein, in described deep dehydration step, maintain that cold needed for the described anhydrous hydrogen chloride fluid temperature flowed downward from dehydration column overhead is undertaken compressing by a part for the anhydrous hydrogen chloride gas of dehydration column overhead being discharged, cools, throttling expansion is freezed provides.
2. method according to claim 1, it is characterized in that, the method maintaining the cold needed for the described anhydrous hydrogen chloride fluid temperature flowed downward from dehydration column overhead is: after the anhydrous hydrogen chloride gas of being discharged by dehydration column overhead and the anhydrous hydrogen chloride liquid formed through condensation carry out indirect heat exchange, by compressing at least partially in described anhydrous hydrogen chloride gas, gas after compression forms anhydrous hydrogen chloride liquid through condensation, after this anhydrous hydrogen chloride liquid and the aforementioned hydrogen chloride gas from dehydration column overhead carry out indirect heat exchange, part carries out throttling expansion, cold needed for acquisition, the circulation of this process is carried out, thus continues to obtain institute's chilling requirement.
3. method according to claim 2, it is characterized in that, described mass flow rate of carrying out the anhydrous hydrogen chloride gas compressed accounts for the 20-30% of the hydrogen chloride gas total mass flow rate of discharging from dehydration column overhead, and remaining 70%-80% is as the extraction of anhydrous hydrogen chloride gas product.
4. method according to claim 3, is characterized in that, the pressure in described dehydration tower is 0.1-5.0MPa.
5. method according to claim 1, it is characterized in that, described preparation of hydrogen chloride method is: the water in silicon tetrachloride and hydrochloric acid soln reacts in a kettle., the slurry that gained silicon-dioxide and hydrochloric acid soln form and hydrogen chloride gas extraction are to separating cucurbitula, and described solution cucurbitula decompression discharges hydrogenchloride unstripped gas.
6. method according to claim 5, is characterized in that, the pressure in described solution cucurbitula is 5-50KPa.
7. method according to claim 6, is characterized in that, the pressure in described solution cucurbitula is 5-12KPa.
8. method according to claim 6, is characterized in that, the pressure in described reactor is 0.1-2.5MPa.
9. method according to claim 8, is characterized in that, the pressure in described reactor is 0.1-1.0MPa.
10. method according to claim 8, is characterized in that, the temperature in described reactor is 35-70 DEG C.
11. methods according to claim 10, is characterized in that, the temperature in described reactor is 45-50 DEG C.
12. methods according to claim 10, is characterized in that, the charging concentration of hydrochloric acid solution in described reactor is 20-33%.
13. methods according to claim 12, is characterized in that, the charging concentration of hydrochloric acid solution in described reactor is 23-27%.
14. methods according to claim 1, is characterized in that, described preparation of hydrogen chloride method is: the water in silicon tetrachloride and hydrochloric acid soln reacts in a kettle., and effusion after the hydrogenchloride of generation reaches capacity in hydrochloric acid soln, as hydrogenchloride unstripped gas.
15. methods according to claim 14, is characterized in that, the temperature in described reactor is 20-85 DEG C.
16. methods according to claim 15, is characterized in that, the temperature in described reactor is 60-80 DEG C.
17. methods according to claim 15, is characterized in that, the charging concentration of hydrochloric acid solution in described reactor is 20-33%.
18. methods according to claim 17, is characterized in that, the charging concentration of hydrochloric acid solution in described reactor is 29-31%.
19. methods according to any one of claim 1-18, is characterized in that, after the slurry extraction that described silicon-dioxide and hydrochloric acid soln are formed, through cooling, filter, dry, obtain white carbon black.
20. methods according to claim 19, is characterized in that, it is 20-33% that the hydrochloric acid soln after filtration is diluted to concentration through deionized water, for reacting with silicon tetrachloride.
21. methods according to any one of claim 1-18, is characterized in that, are carried out spraying dry, obtain white carbon black after the slurry extraction that described silicon-dioxide and hydrochloric acid soln are formed.
22. methods according to claim 21, is characterized in that, after spraying dry, the absorption of air of gas containing hydrogen chloride makes hydrochloric acid, and being diluted to concentration through deionized water is 20-33%, for reacting with silicon tetrachloride.
23. methods according to claim 21, is characterized in that, described spray drying temperature is 200-600 DEG C.
24. methods according to claim 23, is characterized in that, described spray drying temperature is 300-400 DEG C.
25. 1 kinds of hydrolysis method processing silicon chloride produce the system of anhydrous hydrogen chloride, comprising:
(1) preparation of hydrogen chloride system: at least comprise reactor, reacts wherein for the water in silicon tetrachloride and hydrochloric acid soln; Extraction equipment, for the slurry extraction by the silicon-dioxide of reaction generation and hydrochloric acid soln composition;
(2) deep dehydration system: comprise dehydration tower and refrigeration system, described dehydration tower be used for making hydrogen chloride gas in dehydration tower on flowing, contact with the anhydrous hydrogen chloride liquid countercurrent flowed downward from dehydration column overhead, to prepare anhydrous hydrogen chloride gas; Described refrigeration system is for providing the cold needed for described anhydrous hydrogen chloride liquid; Described refrigeration system comprises:
At least one interchanger, the hydrogen chloride gas of discharging for making dehydration column overhead and the hydrogen chloride liquid indirect heat exchange in described interchanger carrying out condenser;
A compressor, for compressing partial oxidation hydrogen;
At least one condenser, for cooling the hydrogen chloride gas after compressor compression, liquefy, the hydrogen chloride liquid generated is delivered to interchanger;
Throttling valve, is arranged between dehydration column overhead and interchanger, and for making the hydrogen chloride liquid partial throttling swell refrigeration from interchanger, cooling post chlorization hydrogen liquid flows downward from tower top further.
26. systems according to claim 25, is characterized in that, in described refrigeration system, the quantity of described interchanger and condenser is respectively one, and described compressor is membrane compressor.
27. systems according to claim 25, it is characterized in that, described refrigeration system also comprises a surge tank be arranged between described condenser and interchanger, is delivered to interchanger again, with the pressure surge of buffering system for making the hydrogen chloride liquid of condenser after flowing through surge tank.
28. systems according to claim 25, it is characterized in that, described refrigeration system also comprises the splitter be arranged between interchanger and compressor, and for the hydrogen chloride gas from interchanger is divided into two portions, a part is delivered to compressor as recycle gas.
29. systems according to any one of claim 25-28, it is characterized in that, described preparation of hydrogen chloride system comprises:
Reactor, reacts wherein for the water in silicon tetrachloride and hydrochloric acid soln, generates hydrogen chloride gas and silicon-dioxide;
Separate cucurbitula, as extraction equipment, for the slurry that silicon-dioxide in reactor and hydrochloric acid soln formed and hydrogen chloride gas extraction, and discharge hydrogen chloride gas;
Rectifying device, for carrying out preliminary hydro-extraction by separating the hydrogen chloride gas discharged in cucurbitula; Described rectifying device comprises rectifying tower, for the rectifying of hydrogen chloride gas; At least one water cooler, for being cooled to liquid state by the hydrogen chloride gas part of rectifying section top extraction; With at least one knockout drum, for cooling through condenser the hydrogen chloride gas and liquid separation that are formed.
30. systems according to claim 29, is characterized in that, described system also comprises white carbon black preparation system, and described white carbon black preparation system comprises:
Water cooler, for cooling the slurry separating silica solid and hydrochloric acid soln composition in cucurbitula;
Filter, for through overcooled slurries filtration, being separated and obtaining white carbon black.
31. systems according to claim 30, is characterized in that, described white carbon black preparation system also comprises moisture eliminator, for white carbon black is dry.
32. systems according to claim 31, is characterized in that, described moisture eliminator is fluid bed dryer.
33. systems according to claim 29, is characterized in that, described system also comprises white carbon black preparation system, and described white carbon black preparation system comprises:
Spray-drier, for the slurry of the silica solid and hydrochloric acid soln composition of separating cucurbitula discharge is carried out spraying dry, obtains white carbon black and the warm air containing hydrogen chloride gas;
Hydrogen chloride absorption equipment, for absorbing the hydrogen chloride gas in described warm air, obtains hydrochloric acid soln.
34. systems according to claim 33, is characterized in that, described hydrogen chloride absorption equipment is absorption tower.
35. systems according to claim 25, is characterized in that, described preparation of hydrogen chloride system comprises:
Reactive distillation column, the bubbling bed conversion zone of bottom, as reactor, reacts wherein for the water in silicon tetrachloride gas and hydrochloric acid soln, generates hydrogenchloride and silicon-dioxide; Top is rectifying section, for the rectifying of hydrogenchloride;
Condensation and separating device: at least one condenser, for being cooled to liquid state by the hydrogen chloride gas part of rectifying section top extraction; At least one knockout drum, for cooling through condenser the hydrogen chloride gas and liquid separation that are formed.
36. systems according to claim 35, is characterized in that, described system also comprises white carbon black preparation system, and described white carbon black preparation system comprises:
Extraction tank, for the slurry extraction of the silica solid that will be formed in bubbling bed conversion zone and hydrochloric acid soln composition, and discharges the hydrogenchloride balanced gas in slurry;
Water cooler, for cooling the slurry in extraction tank;
Filter, for through overcooled slurries filtration, being separated and obtaining white carbon black.
37. systems according to claim 35, is characterized in that, described system also comprises white carbon black preparation system, and described white carbon black preparation system comprises:
Extraction tank, for the slurry extraction of the silica solid that will be formed in bubbling bed conversion zone and hydrochloric acid soln composition, and discharges the hydrogenchloride balanced gas in slurry;
Spray-drier, the slurry for the silica solid of being discharged by extraction tank and hydrochloric acid soln composition carries out spraying dry, obtains white carbon black and the warm air containing hydrogen chloride gas;
Hydrogen chloride absorption equipment, for absorbing the hydrogen chloride gas in described warm air, obtains hydrochloric acid soln.
38. systems according to claim 36 or 37, it is characterized in that, described extraction tank top is connected with the hydrogen chloride gas fairlead at rectifying section top through equilibration tube, then is connected to subsequent condensation device, for being derived by hydrogenchloride balanced gas wherein.
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