CN106219557A - A kind of technique preparing gas-phase silica for raw material low temperature with SILICA FUME/diatomite in powder/albumen stone powder - Google Patents

Abstract

The invention provides a process for preparing fumed silica at low temperature by using microsilica powder/diatomaceous earth powder/opal powder as raw materials. Hydrochloric acid and nitric acid are reacted to produce high value-added product fumed silica. The SiO ₂ content in the product is greater than 99.9%. The specific surface area measured by multi-point BET method is: 350-500m ² /g, reaching The effect of turning waste into treasure; the acid gas produced in the above preparation process is absorbed by the negative pressure water absorption tank, and the corresponding acid liquid can be produced, and the acid liquid can be recycled after being concentrated to a certain concentration. Simultaneously, the present invention also provides a production device used in the above-mentioned process. The components used in the production device are commonly used equipment in chemical plants, and the cost is low, and large-scale industrial production can be realized.

Description

A low-temperature preparation of gas-phase white carbon using microsilica fume/diatomite powder/opal powder as raw materials black craft

technical field

The invention relates to a process method and a device for producing gas-phase white carbon black at low temperature by using microsilica powder/diatomite powder/opal powder, and belongs to the technical field of chemical purification and environmental protection.

Background technique

Micro-silica fume is also called silica fume or condensed silica fume. It is ferroalloy. When smelting ferrosilicon and industrial silicon (metal silicon), a large amount of highly volatile SiO ₂ and Si gases are produced in the submerged thermal electric furnace. The air rapidly oxidizes and condenses and precipitates and is recovered through dust removal and environmental protection equipment. It is a by-product of industrial silicon and ferrosilicon smelting. At present, it is mainly used as cement or concrete admixture, refractory additive, metallurgical pellet binder, chemical product dispersant, etc.; diatomaceous earth belongs to siliceous rock, its main component is silicon dioxide, and SiO2 usually accounts for 80% Above, up to 94%, it is mainly used as a filler in industry; opal is a natural hardened silica gel, containing 5-10% moisture; consulting relevant materials and Chinese patent documents, no use of silica fume or Diatomaceous earth powder or protein powder is the source of raw silicon, and there are related reports on the preparation of fumed silica.

The raw materials for the preparation of white carbon black by gas phase method are generally silicon tetrachloride, oxygen (or air) and hydrogen, which are reacted at high temperature. Its chemical reaction formula is: SiCl ₄ +2H ₂ +O ₂ —>SiO ₂ +4HCl, silicon tetrachloride is gasified at high temperature (flame temperature 1000-1800°C), and a certain amount of hydrogen and oxygen (or air ) at a high temperature of about 1800°C for gas-phase hydrolysis; at this time, the generated gas-phase silica particles are extremely fine, and form aerosols with the gas, which is not easy to capture, so it is first aggregated into larger particles in the aggregator, and then It is collected by a cyclone separator, and then sent to a deacidification furnace, and the fumed silica is purged with nitrogen-containing air until the pH value is 4-6, which is the finished product. At present, most of the enterprises producing fumed silica in our country adopt this method, which is also the production method of fumed silica commonly used in the world. There are also enterprises in my country that use methyltrichlorosilane to produce fumed silica, and have successfully completed industrial production. Today's fumed silica production process not only has a high-temperature process, but also uses very dangerous, flammable and explosive hydrogen and oxygen. The operating environment for workers in the production process is relatively difficult; the safety factor is very demanding. high. After consulting relevant materials and Chinese patent documents, no relevant reports on the production of fumed silica using other raw materials have been found.

If micro-silica powder can be used for secondary processing and combined with the preparation of fumed silica for the preparation of fumed silica products, then the above two thorny technical problems in this field will be solved, and there will be significant progress.

Contents of the invention

The invention provides a production process and device for preparing fumed white carbon black with microsilica powder/diatomaceous earth powder/opal powder as raw materials; it successfully avoids the use of hydrogen in the current fumed white carbon black process and oxygen and high-temperature hydrolysis process, the present invention also provides a new process technology and a production device capable of producing gas-phase white carbon black products at normal temperature and pressure.

The technical scheme adopted to realize the above-mentioned purpose of the present invention is:

A kind of technology that microsilica fume/diatomaceous earth powder/opal powder is low-temperature preparation fumed silica as raw material, comprises the following steps: (1), a kind of in hydrofluoric acid, fluosilicic acid, and nitric acid, hydrochloric acid Mix more than one of them to obtain mixed acid solution;

(2), put the mixed acid solution into the reactor, open the stirring device of the reactor and the exhaust gas absorption device in the reaction system, and put the microsilica powder/diatomaceous earth powder/opal powder into the reactor;

(3) Control the reaction temperature in the reactor to 75-85°C, and the hydrofluoric acid or fluosilicic acid in the mixed acid solution reacts with the silicon dioxide in the microsilica powder/diatomaceous earth powder/opal powder to form tetrafluoroethylene Silicon gas, silicon tetrafluoride gas, acid gas volatilized in the mixed acid solution and water vapor are sent into the cooling tank together;

(4) Control the cooling temperature in the cooling tank to 0-36°C, and the mixed gas reacts in the cooling tank to generate HF, Cl ₂ /NO ₂ , SiO ₂ ·nH ₂ O, in which HF and Cl ₂ /NO ₂ are negatively The pressure is taken out from the cooling tank and absorbed by water to generate reusable hydrofluoric acid, hydrochloric acid/nitric acid, SiO ₂ ·nH ₂ O is condensed and adsorbed on the cooling device in the cooling tank, and the SiO ₂ in the cooling tank is collected nH2O _;

(5) Preheat the collected SiO ₂ ·nH ₂ O in a vacuum heater under negative pressure to remove the residual acid gas HF and Cl ₂ /NO ₂ , and then dry it. After drying, it can be obtained For fumed white carbon black products, the SiO ₂ content in the product is greater than 99.9%, and the specific surface area measured by the multi-point BET method is not less than 350m ² /g.

The mass concentration or volume concentration of said hydrofluoric acid is 2-30%, the mass concentration or volume concentration of fluosilicic acid is 10-30%, the mass concentration or volume concentration of nitric acid is 10-40%, and the mass concentration of hydrochloric acid Or the volume concentration is 10% to 30%.

The present invention also provides a device used in the above process, which includes a hot air feeding system, a chemical reaction system, a cooling system and an exhaust gas absorption system, wherein the hot air feeding system is used to store compressed air and heat the air Afterwards, it is sent into the chemical reaction system; the chemical reaction system is composed of an acid liquid storage tank, a silo and a reactor, and the bottom of the acid liquid storage tank and the silo are connected with the reactor through a pipeline, and a stirring device is arranged in the reactor , the lining of the reaction kettle is made of temperature-resistant, acid-resistant and wear-resistant materials. Above the bottom of the reaction kettle, there is an annular round pipe with vent holes or vent pipes evenly distributed on the round pipe. There are more than one pipes in the reaction kettle. A standpipe connected with an annular circular pipe, the top of the standpipe communicates with the hot air feeding system through a pipe valve on the lid of the reactor; the inner wall of the kettle is installed from top to bottom or bottom to top The helical PTFE capillary tube bundle that is close to the kettle wall, the upper and lower ends of the tube bundle are respectively connected with the cold and hot medium outside the kettle wall through the valves, and the cold and hot medium is passed into the capillary inside the tube bundle to provide the kettle An internal reaction system provides heating or cooling.

The cooling system is composed of a primary cooling kettle and a secondary cooling kettle connected in series; the primary cooling kettle is connected to the reactor, and the lid of the reactor is equipped with a The pipeline of the primary cooling kettle is provided with a cooling device, the bottom of the primary cooling kettle is provided with a discharge valve, and the lid of the primary cooling kettle is provided with a tube that is connected to the secondary cooling kettle and penetrates into the secondary cooling kettle. The pipe in the center of the bottom, the inside of the secondary cooling kettle is provided with a cooling device, the bottom of the secondary cooling kettle is provided with a discharge valve; the lid of the secondary cooling kettle is provided with a pipeline connected to the exhaust gas absorption system , the waste gas absorption system is composed of more than one negative pressure water absorption tank and acid mist absorption device, the top of the negative pressure water absorption tank is provided with a pipe and connected to the induced draft fan in the acid mist absorption device through the pipe.

The hot air feeding system includes an air compressor, an air storage tank, an air heater and pipelines, the air compressor, the air storage tank and the air heater are connected through pipelines, and valves and instruments are also arranged on the pipelines.

Ventilation pipes with a diameter of 10-20 mm and different orientations are evenly distributed on the circular pipe, the distance between adjacent ventilating pipes is 50-150 mm, and the gap between the protruding directions of adjacent ventilating pipes is The angle is 60-120°, and two vertical pipes are arranged in the reactor, and the two vertical pipes are respectively connected to the left and right ends of the circular pipe.

The cooling device of the primary cooling kettle is composed of a rotating shaft and a cooling disc. The rotating shaft is a hollow circular tube wrapped with polytetrafluoroethylene, and the top of the rotating shaft protrudes from the lid of the primary cooling kettle. A top-down cooling water pipe A is arranged inside the rotating shaft. The top of the cooling water pipe A is the water inlet and the water inlet is connected to the cooling water source; cooling discs are evenly distributed on the rotating shaft, and the cooling discs are centered on the rotating shaft. The center of the circle is fixed on the rotating shaft and rotates with the rotating shaft. The cooling disc is a hollow structure. The inside of all cooling discs is provided with cooling water pipes B distributed in a spiral shape, and the cooling in the adjacent cooling discs up and down The water pipe B is connected end to end, the water inlet end of the cooling water pipe B in the bottommost cooling disc is connected with the bottom end of the cooling water pipe A, and the water outlet end of the cooling water pipe B in the topmost cooling disc leads to the hollow circular pipe. The cooling water discharged from the cooling water pipe B overflows from the top of the rotating shaft; vertical ventilation holes are evenly distributed on the cooling disks, and the ventilation holes on the adjacent cooling disks are misaligned.

The diameter of the air holes is 10-20 mm, and the center-to-center distance between adjacent air holes is 20 mm-30 mm.

The lid of the primary cooling kettle is provided with a vacuum gauge and a manhole for easy maintenance, and the lid of the primary cooling kettle is also provided with a compressed air blowing device, which is connected to a compressed gas source .

The cooling device in the secondary cooling kettle is a multi-layer fin structure, the wall of the secondary cooling kettle is provided with a cooling water inlet and a cooling water outlet, and the cooling water inlet is connected with the water inlet of the lowermost fin, The cooling water flows in from the lowermost fin, the fins are in a continuous bending structure, the ends of the adjacent upper and lower fins are connected, and the cooling water outlet is connected with the water outlet of the uppermost fin; The lid of the cooling kettle is equipped with a compressed air blowing device, which is connected to the compressed gas source. The lid of the secondary cooling kettle is equipped with a vacuum gauge, and the lid and bottom of the kettle are equipped with convenient Manhole for maintenance.

There are two negative pressure water absorption tanks, and the two negative pressure water absorption tanks are connected in series or in parallel.

Compared with the prior art, the technical solution provided by the present invention has the following advantages: 1. The present invention uses microsilica powder/diatomaceous earth powder/opal powder and other wastes as raw materials to prepare them into high value-added product gas phase White carbon black, the SiO ₂ content in the prepared product is greater than 99.9%, and its specific surface area measured by the multi-point BET method is not less than 350m ² /g, thus achieving the effect of turning waste into treasure. 2. The preparation process provided by the present invention belongs to a brand-new process idea, which solves the shortcomings of the existing high-temperature process and the use of very dangerous flammable and explosive hydrogen and oxygen in the existing fumed silica preparation process . The production process provided by the invention can be prepared under normal temperature and pressure. 3. After the acid gas produced in the preparation process of the present invention is absorbed by the negative pressure water absorption tank, the corresponding acid liquid can be produced. When the acid liquid is concentrated to a certain concentration, it can be recycled, which can greatly save the production cost. The cost and environmental protection of waste water treatment. 4. The production device provided by the present invention can realize large-scale industrial production, and the parts used are common equipment in chemical plants, and the cost is low.

Description of drawings

Fig. 1 is the overall structural schematic diagram of the preparation device provided by the present invention;

Fig. 2 is the structural representation of cooling disc in the primary cooling tank;

Fig. 3 is the structural representation of fin in the secondary cooling tank;

In the figure: 1-acid liquid storage tank, 2-silo, 3-reaction kettle, 4-stirring device, 5-round pipe, 6-vertical pipe, 7-first-level cooling tank, 8-secondary cooling tank, 9 -Outlet valve, 10-negative pressure water absorption tank, 11-acid mist absorption device, 12-air compressor, 13-air storage tank, 14-air heater, 15-rotating shaft, 16-cooling disc, 17- Cooling water pipe A, 18-air vent, 19-fin.

detailed description

The present invention will be described in detail below in conjunction with the accompanying drawings and specific embodiments, but the protection scope of the present invention is not limited to the following embodiments.

The structure of the preparation device provided in this embodiment is shown in Figure 1. The device includes a hot air feeding system, a chemical reaction system, a cooling system, and a waste gas absorption system, wherein the hot air feeding system is used to store compressed air and The air is heated and sent into the chemical reaction system. The hot air feeding system includes an air compressor 12, an air storage tank 13, an air heater 14 and pipelines, an air compressor 12, an air storage tank 13 and an air heating system. The device 14 is connected by a pipeline, and the pipeline is also provided with valves and instruments.

The chemical reaction system is composed of an acid liquid storage tank 1, a feed bin 2 and a reactor 3, the bottoms of the acid liquid storage tank 1 and the feed bin 2 are connected with the reactor 3 through a pipeline, and the reactor 3 is provided with a stirring device 4 , The inner lining of the reactor is made of temperature-resistant, acid-resistant and wear-resistant materials, specifically silicon carbide, fluorine materials, graphite materials, etc. At about 200 mm above the bottom of the reaction kettle 3, there is an annular circular tube 5 with a diameter of 100-200 mm. The space between adjacent ventilation pipes is 50-150 mm, and the angle between the protruding directions of adjacent ventilation pipes is 60-120°. The reaction kettle is provided with two vertical pipes 6 connected with the circular pipe, and the two vertical pipes 6 are respectively connected to the left and right ends of the circular pipe 5. The pipe valve communicates with the hot air feed system. There are spiral hooks on the wall of the reactor to support the polytetrafluoroethylene capillary bundles used for heating or cooling in the reactor.

The cooling system is composed of a primary cooling kettle 7 and a secondary cooling kettle 8 connected in series; wherein the primary cooling kettle 7 is connected to the reactor 3, and the lid of the reactor 3 is provided with a tube connected to the primary cooling kettle 7 and deep into the The pipeline in the center of the bottom of the primary cooling kettle, the inside of the primary cooling kettle 7 is provided with a cooling device, the cooling device of the primary cooling kettle is composed of a rotating shaft 15 and a cooling disc 16, and the rotating shaft 15 is an outer wrapping The hollow tube of polytetrafluoroethylene, the top of the rotating shaft protrudes from the lid of the primary cooling kettle, and a top-down cooling water pipe A17 is arranged inside the rotating shaft, the top of the cooling water pipe A is the water inlet end and the water inlet The end is connected with the cooling water source; cooling discs 16 are evenly distributed on the rotating shaft 15 . The structure of the cooling disc is shown in Figure 2. The cooling disc 16 is fixed on the rotating shaft with the rotating shaft 15 as the center of the circle, and rotates with the rotating shaft. The cooling disc is a hollow structure, and all cooling discs are provided with There are cooling water pipes B distributed in a spiral shape, and the cooling water pipes B in the upper and lower adjacent cooling discs are connected end to end, and the water inlet end of the cooling water pipe B in the bottom cooling disc is connected with the bottom end of the cooling water pipe A , the water outlet end of the cooling water pipe B in the top cooling disc leads to the hollow tube, and the cooling water discharged in the cooling water pipe B overflows from the top of the rotating shaft. Vertical air holes 18 are evenly distributed on the cooling disks, and the air holes on adjacent cooling disks are misaligned to ensure the cooling effect of the gas. The diameter of the air holes is 10-20 mm, and the center-to-center distance between adjacent air holes is 20 mm-30 mm.

The lid of the primary cooling kettle is provided with a vacuum gauge and a manhole for easy maintenance, and the lid of the primary cooling kettle is also provided with a compressed air blowing device, which is connected to a compressed gas source . The lid of the primary cooling kettle 7 is provided with a pipeline connected to the secondary cooling kettle 8 and deep into the center of the bottom of the secondary cooling kettle 8 . A discharge valve 9 is provided at the bottom of the primary cooling kettle.

The inside of the secondary cooling kettle 8 is provided with a cooling device, the cooling device in the secondary cooling kettle is a multi-layer fin structure, and the wall of the secondary cooling kettle 8 is provided with a cooling water inlet and cooling water The outlet and the cooling water inlet are connected with the water inlet of the lowermost fin, and the cooling water flows in from the lowermost fin. The fin 19 is in a continuous bending structure, as shown in FIG. 3 . The ends of the adjacent upper and lower layers of fins are connected, the cooling water outlet is connected with the water outlet of the uppermost layer of fins, and the cooling water enters from the lowermost layer of fins and flows out from the uppermost layer of fins. The kettle cover of the secondary cooling kettle is provided with a compressed air blowing device, which is connected with a compressed gas source, and is blown with compressed air when discharging. The lid of the secondary cooling kettle is equipped with a vacuum gauge, and the lid and bottom of the kettle are equipped with manholes for easy maintenance. The bottom of the secondary cooling kettle is provided with a discharge valve 9; the lid of the secondary cooling kettle 8 is provided with a pipe connected to the waste gas absorption system.

The waste gas absorption system is composed of two negative pressure water absorption tanks 10 and an acid mist absorption device 11, and the two negative pressure water absorption tanks are connected in series or in parallel. A pipeline is arranged on the top of the negative pressure water absorption tank and is connected with the induced draft fan in the acid mist absorption device through the pipeline. The acid mist absorbed by the secondary water absorption tank is neutralized with the droplets of liquid alkali solution in the acid mist absorption device and then discharged into the air. When the acid liquid in the negative pressure water absorption tank reaches a certain concentration, it is sent to Recycle for the workshop.

The detailed preparation process of the present invention will be described in detail below by taking microsilica produced by a mining company in Hubei as an example. The components of diatomaceous earth powder and opal powder are similar to microsilica, so they can be processed in the same way. After analysis, the total content of Si, SiO and SiO2 in the microsilica powder is 95.4%. The specific production steps are as follows:

(1) Mix one of hydrofluoric acid and fluosilicic acid with more than one of nitric acid and hydrochloric acid to prepare a mixed acid solution. Fluosilicic acid, nitric acid or hydrochloric acid are all industrial grade; or use industrial By-products are available. Preferably, the mass concentration or volume concentration of hydrofluoric acid is 2-30%, the mass concentration or volume concentration of fluosilicic acid is 10-30%, the mass concentration or volume concentration of nitric acid is 10-40%, hydrochloric acid The mass concentration or volume concentration is 10% to 30%.

(2) Put the mixed acid solution into the reaction kettle, turn on the stirring device of the reaction kettle and the exhaust gas absorption device in the reaction system, and slowly put the microsilica powder into the reaction kettle.

(3) If the input mixed acid solution contains hydrofluoric acid, since the reaction process between it and silicon dioxide is an exothermic process, it is necessary to open the cooling water valve outside the reaction kettle to maintain the reaction temperature at 75-85°C. If the mixed acid liquid does not contain hydrofluoric acid but contains fluosilicic acid, it is necessary to open the steam in the jacket of the reactor to heat the reactor slowly. The hydrofluoric acid or fluosilicic acid in the mixed acid solution reacts with the silicon dioxide in the microsilica powder to generate silicon tetrafluoride gas, and a part of the gas dissolves in the water of the reaction system to form fluosilicic acid to continue dissolving the silica in the microsilica powder. Silicon oxide, another part of the overflow silicon tetrafluoride gas and volatilized nitric acid/hydrochloric acid gas and water vapor are sent into the cooling tank together.

(4) Control the cooling temperature in the cooling tank to 0-36°C. The mixed gas reacts in the cooling tank to generate HF, Cl ₂ /NO ₂ , SiO ₂ ·nH ₂ O. The chemical reaction formula is as follows:

SiF ₄ +4HNO ₃ +nH ₂ O＝4HF↑+4NO ₂ ↑+SiO ₂ ·nH ₂ O

SiF ₄ +4HCl+nH ₂ O＝4HF↑+Cl ₂ ↑+SiO ₂ ·nH ₂ O

Among them, HF and Cl ₂ /NO ₂ are taken out by negative pressure from the primary cooling tank and the secondary cooling tank, enter the exhaust gas absorption system and be absorbed by water to generate hydrofluoric acid, hydrochloric acid/nitric acid for repeated use. Acid, hydrochloric acid/nitric acid can be recycled after being concentrated to a certain concentration; this greatly saves the cost in production and the problem of environmental protection wastewater treatment.

And SiO ₂ ·nH ₂ O slowly condenses and adsorbs on the cooling disk in the first-stage cooling tank, condenses on the cooling disk from the beginning, and then slowly and naturally forms crystal clear spherical crystal grains, gathering like fish eggs Together, it is very beautiful. When the cooling disk of the primary cooling kettle gathers to a certain amount, the rotating shaft device is turned on, and the rotating shaft drives the cooling disk to rotate. Under the action of centrifugal force, the material is thrown to the wall of the kettle, and then compressed air It is blown to the bottom of the primary cooling kettle and sent to the drying process through the discharge valve at the bottom; after the materials in the primary cooling kettle are processed, the compressed air valve of the secondary cooling kettle is directly opened to blow the condensed material to the kettle After the bottom, it is sent to the drying process through the discharge valve at the bottom;

(5) Because the material contains moisture, it is acidic, and the volatility of hydrofluoric acid, silicon tetrafluoride, nitric acid or hydrochloric acid gas is extremely strong, so before drying, the collected SiO ₂ ·nH ₂ O Negative pressure preheating is carried out in the vacuum heater to remove the residual acid gas HF and Cl ₂ /NO ₂ , and then dry. After drying, the gas phase silica product can be obtained. The SiO ₂ content in the product is greater than 99.9%. Its specific surface area measured by multi-point BET method is not less than 350m ² /g.

Claims (10)

1. the technique preparing gas-phase silica for raw material low temperature with SILICA FUME/diatomite in powder/albumen stone powder, it is characterised in that Comprise the following steps: (1), one or both in one or both in Fluohydric acid., hexafluosilicic acid, with nitric acid, hydrochloric acid are carried out Mixing, prepares mix acid liquor；

(2), mix acid liquor is put in reactor, the waste gas absorption dress in the agitating device of unlatching reactor and response system Put, SILICA FUME/diatomite in powder/albumen stone powder is put in reactor；

(3), the reaction temperature controlled in reactor be 75～85 DEG C, Fluohydric acid. in mix acid liquor or hexafluosilicic acid and SILICA FUME/ Silicon dioxde reaction in diatomite in powder/albumen stone powder generates silicon tetrafluoride gas, by silicon tetrafluoride gas and mix acid liquor The sour gas and the steam that are volatilized are brought in cooling reactor by negative pressure together；

(4), the chilling temperature controlled in cooling reactor be 0～36 DEG C, mixed gas react in cooling reactor and is generated HF, Cl₂/NO₂、 SiO₂·nH₂O, wherein HF and Cl₂/NO₂Taken out of from cooling reactor by negative pressure, and be only absorbed by the water generation and be available for reusable hydrogen Fluoric acid, hydrochloric acid/nitric acid, SiO₂·nH₂O condenses on absorption chiller in cooling reactor, collects the SiO in cooling reactor₂· nH₂O；

(5), by collected SiO₂·nH₂O carries out negative pressure preheating in vacuum heater, removes the sour gas wherein remained HF and Cl₂/NO₂, it is dried the most again, can be prepared by gas-phase silica product after drying, SiO in product₂Content is more than 99.9%, its multiple spot BET method measurement the specific area is not less than 350m²/g。

The technique that low temperature the most according to claim 1 prepares gas-phase silica, it is characterised in that: the matter of described Fluohydric acid. Amount concentration or volumetric concentration are 2～20%, and the mass concentration of hexafluosilicic acid or volumetric concentration are 10～30%, the mass concentration of nitric acid Or volumetric concentration is 10～40%, the mass concentration of hydrochloric acid or volumetric concentration are 10%～30%.

3. the device prepared for low temperature described in claim 1 in the technique of gas-phase silica, it is characterised in that: described Device includes that hot-air sends into system, chemical reaction system, cooling system and waste gas absorbing system, and wherein hot-air sends into system System for storing compressed air and send into after air is heated chemical reaction system and in；Described chemical reaction system is by acid Liquid storage tank, feed bin and reactor composition, acid solution storage tank is connected with reactor by pipeline with the bottom of feed bin, sets in reactor Being equipped with agitating device, the liner of reactor is heatproof, acidproof, high-abrasive material, bottom reactor above, be provided with an annular Pipe, pipe is evenly distributed with air-vent or permeability cell, be provided with in reactor more than one with annular pipe phase The vertical tube of connection, the top of described vertical tube is sent into system by the pipe valve on the kettle cover of reactor with hot-air and is connected；In still Wall is provided with from top to bottom or from bottom to top is close to still wall and helically wire tetrafluoro bundle of capillary tubes, up and down the two of this tube bank Cold and hot medium outside holding respectively with still wall is connected by its valve, by being passed through cold and hot medium, for still to the capillary tube in restraining Interior response system provides and is heated or cooled.

Cooling system is composed in series by one-level cooling reactor and two grades of cooling reactors；Wherein one-level cooling reactor is connected with reactor, instead The kettle cover answering still is provided with a pipeline being connected and be deep into one-level cooling reactor bottom center with one-level cooling reactor, and one-level cools down Still be internally provided with chiller, the bottom of one-level cooling reactor is provided with outlet valve, and the kettle cover of one-level cooling reactor is provided with One is connected with two grades of cooling reactors and is deep into the pipeline of two grades of cooling reactor bottom center, and the inside of two grades of described cooling reactors sets Being equipped with chiller, the bottom of two grades of cooling reactors is provided with outlet valve；One and waste gas it is provided with on the kettle cover of two grades of cooling reactors The pipeline that absorption system is connected, described waste gas absorbing system is by more than one negative pressure water tourie and acid mist absorbing device Composition, the top of negative pressure water tourie is provided with pipeline and is connected with the air-introduced machine in acid mist absorbing device by pipeline.

Device the most according to claim 3, it is characterised in that: described hot-air send into system include air compressor, Air storage tank, air heater and pipeline, air compressor, air storage tank and air heater are connected by pipeline Connect, pipeline is additionally provided with valve and instrument.

Device the most according to claim 3, it is characterised in that: it is evenly distributed with a diameter of 10～20mm on described pipe And towards different permeability cells, the adjacent spacing between permeability cell is 50～150mm, and the side of stretching out of adjacent permeability cell Angle between to is 60～120 °, is provided with two vertical tubes in reactor, and described two vertical tubes are connected to a left side for pipe Right two ends.

Device the most according to claim 3, it is characterised in that: the chiller of described one-level cooling reactor is by rotating shaft and cooling Disk forms, and described rotating shaft is the hollow circular-tube that an outer wrap has politef, and the top of rotating shaft is by one-level cooling reactor Kettle cover on stretch out, be provided with a top-down cooling water pipe A in rotating shaft, the top of cooling water pipe A is water inlet end and enters Water end (W.E.) is connected with cooling water source；Being evenly distributed with cooling disk in rotating shaft, described cooling disk is installed solid with rotating shaft for the center of circle Being scheduled in rotating shaft, and rotate with rotating shaft, described cooling disk is hollow structure, and the inside of all cooling disks is provided with in dish Cooling water pipe B in the cooling water pipe B of rotation shape distribution, and neighbouring cooling disk joins end to end, the cooling circle of bottommost The water inlet end of the cooling water pipe B in dish is connected with the bottom of cooling water pipe A, the cooling water pipe B in the cooling disk of top Water side lead to hollow circular-tube, in cooling water pipe B discharge cooling water by rotating shaft top overflow；On described cooling disk It is evenly distributed with the passage mutual dislocation on vertical passage, and neighbouring cooling disk.

Device the most according to claim 6, it is characterised in that: a diameter of the 10 of described passage～20mm, adjacent is logical Centre-to-centre spacing between pore is 20mm～30mm.

Device the most according to claim 6, it is characterised in that: the kettle cover of described one-level cooling reactor be provided with vacuum meter and The manhole of easy access, the kettle cover of one-level cooling reactor is additionally provided with compressed air blowning installation, compressed air blowning installation with Compressed gas source is connected.

Device the most according to claim 3, it is characterised in that: the described chiller in two grades of cooling reactors is multilamellar wing Chip architecture, the still wall of two grades of cooling reactors is provided with cooling water inlet and coolant outlet, cooling water inlet and orlop fin Water inlet be connected, cooling water flowed into by undermost fin, described fin is Curved Continuous folded structure, adjacent two-layer up and down The end of fin is connected, and coolant outlet is connected with the outlet of the superiors' fin；Arrange on the kettle cover of two grades of cooling reactors Having compressed air blowning installation, compressed air blowning installation to be connected with compressed gas source, the kettle cover of two grades of cooling reactors is provided with Vacuum meter, and its kettle cover and bottom be designed with the manhole of easy access.

Device the most according to claim 3, it is characterised in that: described negative pressure water tourie is provided with two, bears for two Setting-out tourie is in series or is connected in parallel.