CN111672346A - Device and process for continuously preparing titanium oxychloride solution - Google Patents
Device and process for continuously preparing titanium oxychloride solution Download PDFInfo
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- CN111672346A CN111672346A CN202010664112.2A CN202010664112A CN111672346A CN 111672346 A CN111672346 A CN 111672346A CN 202010664112 A CN202010664112 A CN 202010664112A CN 111672346 A CN111672346 A CN 111672346A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/30—Injector mixers
- B01F25/31—Injector mixers in conduits or tubes through which the main component flows
- B01F25/312—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
- B01F35/90—Heating or cooling systems
- B01F35/92—Heating or cooling systems for heating the outside of the receptacle, e.g. heated jackets or burners
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
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- C—CHEMISTRY; METALLURGY
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
- B01F35/90—Heating or cooling systems
- B01F2035/98—Cooling
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Abstract
The invention belongs to the field of chemical industry, and particularly relates to a device and a process for continuously preparing a titanium oxychloride solution. The device includes: the device comprises a titanium tetrachloride flowmeter, a Venturi mixer, a pure water flowmeter, a falling film absorber, a hydrochloric acid absorption tower, a U-shaped pipe, a heat exchanger, a liquid preparation circulating pump, a liquid preparation circulating tank, an absorption circulating pump, a tail gas fan, a hydrochloric acid circulating tank and a hydrochloric acid circulating pump. The device and the process can continuously produce and prepare the titanium oxychloride solution with adjustable concentration and adjustable temperature, can remove reaction heat generated by continuous mixing reaction, and avoids bumping caused by a large amount of heat release. Because the whole system of the device operates under the micro negative pressure, the device has no potential safety hazard of gas leakage. The device can continuously suck and convey titanium tetrachloride under negative pressure according to metering, and is safe and reliable.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a device and a process for continuously preparing a titanium oxychloride solution.
Background
Titanium tetrachloride is an important raw material for titanium sponge and titanium-containing compounds. Most titanium tetrachloride is used for producing titanium dioxide and pigments. Titanium tetrachloride is a colorless liquid at room temperature and when exposed to air reacts with water in the air to produce a large amount of white smoke and a mixture of hydrated titanium dioxide and hydrochloric acid droplets. Titanium tetrachloride is hydrolyzed under certain temperature and water quantity to generate titanium oxychloride, and the chemical reaction equation is as follows:
TiCl4+H2O＝TiOCl2+2HCl
titanium tetrachloride is subjected to irreversible hydrolysis reaction at a high temperature and in a water excess state to generate hydrated titanium dioxide, and the side reaction of excessive hydrolysis to generate titanium dioxide is not expected to occur in the preparation of a titanium oxychloride solution. The chemical reaction equation for over-hydrolysis is as follows:
TiCl4+3H2O＝TiO2·H2O+4HCl
in the industries of electronic materials, nano-titanium dioxide, pearlescent effect materials and the like, titanium tetrachloride is often prepared into a titanium oxychloride solution with a certain concentration for the next procedure. The existing titanium oxychloride solution preparation equipment is mostly composed of a reaction kettle, cooling water, an absorption tower and the like. The existing preparation method is generally that metered process water is added into a reaction kettle firstly, metered titanium tetrachloride is slowly added under the condition of stirring, cooling water is introduced into a jacket of the reaction kettle, and tail gas of the reaction kettle is absorbed by an absorption tower. Since the titanyl dichloride solution is not just a simple physical mixing dilution of titanium tetrachloride and water involving complex hydrolysis chemistry, differences in solution concentration, temperature control during formulation can cause different degrees of hydrolysis of titanium tetrachloride. A large amount of chemical reaction heat is released in the preparation process of the titanium tetrachloride, and a large amount of hydrochloric acid mist is generated and escaped. The existing preparation method is mostly operated intermittently, and the concentration gradient changes greatly, so that the temperature in the preparation process is increased, and further local bumping is easily formed; moreover, the existing preparation equipment cannot timely treat the escaped gas, so that gas leakage is easily caused, the environment is further polluted, and the preparation process is interfered.
For example, chinese patent document CN2923668Y discloses a titanium tetrachloride dilution plant. The device consists of a titanium tetrachloride metering tank, a vacuum unit, a mixing nozzle, a titanium tetrachloride preparation tank and a falling film absorption system. The device uses a vacuum unit to intermittently suck titanium liquid into a metering tank and then mixes the titanium liquid with process water which is quantitatively added in advance. The device runs intermittently, and continuous operation cannot be realized. When the preparation is started each time, a small amount of concentrated titanium tetrachloride titanium liquid reacts with a large amount of water, the initial concentration of the prepared solution is low, irreversible excessive hydrolysis reaction is easy to occur, titanium dioxide is generated, the quality is affected, and waste is caused. The device has large solution concentration gradient change in the preparation process, and is not beneficial to quality control.
For another example: chinese patent document CN206676368U discloses a production device of titanium oxychloride solution, which comprises a liquid storage tank, a reaction kettle, a buffer tank and a vacuum pump. The device utilizes a vacuum pump to suck titanium tetrachloride into a reaction kettle, and titanium tetrachloride liquid reacts with water which is added in the reaction kettle in advance. The device is operated intermittently and cannot produce continuously. A small amount of pure titanium tetrachloride solution reacts with a large amount of water each time the preparation is started, the initial concentration of the prepared solution is low, irreversible hydrolysis reaction is easy to occur, a large amount of titanium dioxide is generated, the quality is affected, and waste is caused. The device has large solution concentration gradient change in the preparation process, and is not beneficial to quality control. The device is controlled improperly, hydrochloric acid enters the vacuum pump, and equipment is damaged easily.
For another example: chinese patent document CN102764601A discloses a titanium tetrachloride aqueous solution preparation device and process. The device comprises a jet vacuum pump, a graphite heat exchanger, a titanium tetrachloride mixing tank, an acid mist absorption tower and the like. The device and the process are intermittent operation, and continuous production cannot be realized. The device has no gas escape channel between the jet vacuum pump and the heat exchanger, and the hydrogen chloride gas escaped in the preparation process is brought into the heat exchanger, so that the heat exchange effect is influenced.
In conclusion, the prior device and method for preparing the titanium oxychloride solution have the following problems that firstly, the continuous production cannot be realized; secondly, the risks of excessive hydrolysis side reaction, uneven concentration and local bumping exist; thirdly, the titanium tetrachloride liquid is difficult to measure and transfer; and fourthly, the risk of polluting the environment due to gas leakage exists.
Disclosure of Invention
The first technical problem to be solved by the invention is that the titanium oxychloride solution can not be continuously produced and prepared.
The second technical problem to be solved by the invention is to reduce the problems of excessive hydrolysis side reaction, uneven concentration of the titanium oxychloride solution and bumping caused by incapability of removing a large amount of heat in time in the preparation process.
The third technical problem to be solved by the invention is the problem that the titanium tetrachloride liquid is difficult to meter and transfer.
The fourth technical problem to be solved by the invention is the problem of environmental pollution caused by gas leakage in the process of preparing the titanium oxychloride solution.
The invention aims to provide a device and a process for continuously preparing a titanium oxychloride solution, which not only can continuously generate the titanium oxychloride solution with stable concentration and stable temperature, but also can continuously carry out mixing reaction and remove reaction heat, can continuously recover hydrochloric acid escaping from the reaction, and can also continuously extract titanium tetrachloride according to metering and continuous negative pressure.
The invention is realized by the following technical scheme:
in a first aspect, the present invention provides an apparatus for continuously preparing a titanyl dichloride solution, comprising: the system comprises a titanium tetrachloride flowmeter, a Venturi mixer, a pure water flowmeter, a falling film absorber, a hydrochloric acid absorption tower, a heat exchanger, a liquid preparation circulating pump, a liquid preparation circulating tank and an absorption circulating pump;
wherein the titanium tetrachloride flowmeter is connected with a first suction port of the Venturi mixer; a circulating liquid inlet of the Venturi mixer is connected with an outlet pipe of the liquid preparation circulating pump, and a mixed liquid outlet of the Venturi mixer is connected with an upper pipe side inlet of the heat exchanger; the pure water flowmeter is connected with a second suction inlet of the Venturi mixer; an upper liquid inlet of the falling film absorber is connected with an outlet of an absorption circulating pump through a pipeline, a lower tube pass outlet of the falling film absorber is connected with an inlet of a liquid distribution circulating groove, and an upper tube pass outlet of the falling film absorber is connected with a lower gas inlet pipe of a hydrochloric acid absorption tower; a gas inlet at the lower part of the hydrochloric acid absorption tower is connected with a gas outlet of the falling film absorber through a pipeline; an upper gas outlet of the heat exchanger is connected with a lower tube pass inlet of the falling film absorber, and a lower tube pass outlet of the heat exchanger is connected with an inlet of the liquid distribution circulating tank; an inlet pipe of the liquid preparation circulating pump is connected with an outlet of the liquid preparation circulating tank; an inlet pipe of the absorption circulating pump is connected with an outlet of the liquid distribution circulating tank. The continuous production can be realized by using the Venturi mixer to continuously extract the titanium tetrachloride and the pure water simultaneously; the Venturi mixer is used for mixing a large amount of circulating mother liquor with a small amount of titanium tetrachloride and a small amount of pure water, so that the reaction temperature rise is reduced, and the concentration gradient is reduced.
The titanium tetrachloride flow meter is preferably a mass flow meter, and the pure water flow meter is preferably a vortex shedding flow meter.
The flow rates of titanium tetrachloride and pure water drawn by the venturi mixer are set according to the concentration of the titanyl dichloride solution to be prepared. The flow rate of the suction pipe is regulated by the valve opening and monitored by a flow meter.
The falling film absorber absorbs hydrogen chloride generated by the reaction and returns the circulating mother liquor in the form of hydrochloric acid. The hydrochloric acid can maintain the acidity of the prepared titanium oxychloride solution and inhibit the further occurrence of excessive hydrolysis side reaction. The heat absorbed by the hydrochloric acid in the falling film absorber is taken away by the refrigerant, and the heat exchange function of the falling film absorber can also reduce the temperature of the circulating liquid.
And the liquid distribution circulating pump is used for pumping the circulating mother liquid entering the Venturi mixer and providing power for the vacuum generated by the two suction inlet pipes of the Venturi mixer.
And the liquid preparation circulating tank is used for buffering and storing the prepared titanium oxychloride solution and providing a volume space for circulating and mixing the solution.
The absorption circulating pump is used for pumping the circulating mother liquor conveyed to the falling film absorber; and also used for conveying the prepared titanyl dichloride solution to a required process.
Preferably, in the above apparatus, the venturi mixer comprises a circulating liquid inlet, a nozzle, a convergent section, a divergent section, a mixing chamber, a first suction port, a second suction port and a mixed liquid outlet; the first suction port enters the mixing chamber from the excircle tangential direction of the mixing chamber; the second suction inlet enters the mixing chamber from the tangential direction of the excircle of the mixing chamber; the central lines of the first suction port and the second suction port are parallel to each other in space, the first suction port and the second suction port are positioned at any position of the outer circular surface of the mixing chamber in the axial direction, and preferably, the first suction port and the second suction port are positioned on the same cross section of the mixing chamber; the centerline of the first suction port does not spatially intersect perpendicularly with the centerline of the circulating liquid inlet; the central line of the second suction inlet and the central line of the circulating liquid inlet do not vertically intersect in space.
When the circulating mother liquor is sprayed out through a nozzle (the diameter of the circulating mother liquor is smaller than that of a circulating liquid inlet), the flow rate is increased, the pressure is reduced, certain vacuum is formed in the mixing chamber, and titanium tetrachloride and pure water respectively enter the Venturi mixer from the two suction inlet pipes by virtue of the vacuum. The tangential arrangement of the two suction inlet pipes can reduce the mutual influence when the pressures of the two suction inlet pipes are not balanced, and is more favorable for uniform mixing.
Preferably, in the above apparatus, a gas-liquid separation space is provided in an upper part of a tube side of the heat exchanger. The gas-liquid separation space can avoid gas entering the heat exchanger tube pass to influence heat exchange.
Preferably, in the above device, the device further comprises a U-shaped tube; the U-shaped pipe is arranged between the lower pipe pass outlet of the heat exchanger and the inlet of the liquid distribution circulation tank; preferably, the bottom of the U-shaped pipe is provided with a drain pipe and a valve. The bottom of the U-shaped pipe is provided with a drain pipe and a valve, so that the drain can be conveniently maintained.
Preferably, in the above apparatus, the coolant carries away the reaction heat from the coolant in the shell side of the heat exchanger. The temperature of the prepared titanium oxychloride solution can be adjusted by adjusting the flow and the temperature of the refrigerant.
Preferably, in the above apparatus, the height of the U-shaped tube is 50% to 90%, preferably 80%, of the tube side height of the heat exchanger. The U-tubes within the above height range ensure that the liquid on the heat exchanger tube side fills the tubes.
Preferably, in the above apparatus, the apparatus further comprises: a tail gas fan, a hydrochloric acid circulating tank and a hydrochloric acid circulating pump; the upper gas outlet of the hydrochloric acid absorption tower is connected with an inlet of a tail gas fan through a pipeline, the upper liquid inlet of the hydrochloric acid absorption tower is connected with an outlet pipe of a hydrochloric acid circulating pump through a pipeline, and the lower liquid outlet of the hydrochloric acid absorption tower is connected with an inlet of a hydrochloric acid circulating tank through a pipeline; the outlet of the tail gas fan is connected with a tail gas treatment system; the outlet of the hydrochloric acid circulating tank is connected with the inlet of a hydrochloric acid circulating pump; and a pure water inlet is formed in the hydrochloric acid circulating tank.
The hydrochloric acid absorption tower is used for absorbing hydrogen chloride gas which is not completely absorbed by the falling film absorber, producing byproduct hydrochloric acid and improving economic benefit.
A small amount of tail gas enters a tail gas treatment system through a tail gas fan to be treated and discharged after being qualified. The tail gas fan is arranged at the tail end of a gas phase pipeline of the whole device, so that the whole device can maintain micro negative pressure, and the risk of environmental pollution caused by hydrogen chloride gas leakage at each sealing point in the device is reduced.
And the hydrochloric acid circulating tank is used for buffering and storing the byproduct hydrochloric acid and providing a volume space for circularly mixing the hydrochloric acid. The hydrochloric acid circulating tank is provided with a pure water adding port, and the pure water is added to adjust the concentration of the hydrochloric acid and maintain the capability of the hydrochloric acid circulating liquid for absorbing hydrogen chloride.
The hydrochloric acid circulating pump is used for pumping the hydrochloric acid circulating liquid; and also for transporting by-product hydrochloric acid to a desired process.
In a second aspect, the invention provides a process for continuously preparing a titanium oxychloride solution, which comprises the following steps: the titanium tetrachloride flowmeter is extracted into the Venturi mixer from the first suction port, meanwhile, pure water is extracted into the Venturi mixer from the second suction port through the pure water flowmeter, meanwhile, circulating mother liquor is conveyed into the Venturi mixer by the liquor preparation circulating pump, the extracted titanium tetrachloride and the pure water are fully mixed with a large amount of circulating mother liquor, the produced titanium oxychloride solution is conveyed into the liquor preparation circulating tank by the liquor preparation circulating pump, heat generated by mixing reaction is taken away by a refrigerant in the heat exchanger, hydrogen chloride gas generated by the reaction is conveyed into the falling film absorber through the absorption circulating pump to be absorbed, then the hydrogen chloride gas returns to the circulating mother liquor in the liquor preparation circulating tank in the form of hydrochloric acid, and the rest hydrogen chloride gas is washed and absorbed through the hydrochloric acid absorption tower to obtain a byproduct hydrochloric acid.
The hydrogen chloride absorbed by the falling film absorber returns to the circulating mother liquor in the form of hydrochloric acid, so that excessive hydrolysis of the titanyl dichloride solution can be inhibited.
Preferably, in the above process, titanium tetrachloride is pumped into the venturi mixer from the outside of the mixing chamber in a tangential direction of a circle through a titanium tetrachloride flow meter from a first suction port, and pure water is pumped into the venturi mixer from the outside of the mixing chamber in a tangential direction of a circle through a pure water flow meter from a second suction port, wherein the flow direction of the titanium tetrachloride and the flow direction of the circulating mother liquor form a spiral mixing, and the flow direction of the pure water and the flow direction of the circulating mother liquor form a spiral mixing. The tangential entry is to reduce interference between the two intake ducts when the pressures are not balanced, and to provide more uniform helical mixing.
The flow rate of the circulating liquid inlet pipe of the Venturi mixer is several times to ten times of the flow rate of the extracted titanium tetrachloride and pure water. The large amount of circulating mother liquor can reduce the concentration gradient change of the prepared titanium oxychloride solution, and simultaneously, the large amount of circulating mother liquor can be used as a heat carrier to reduce the temperature rise of a reaction system, thereby bringing heat into a heat exchanger.
Preferably, in the above process, the hydrogen chloride gas generated by the reaction is separated from the liquid in the gas-liquid separation space at the upper part of the tube side of the heat exchanger, the separated hydrogen chloride gas enters the falling film absorber through the gas phase pipeline, and the liquid enters the tube side of the heat exchanger.
Preferably, in the above process, the refrigerant is one or more of circulating cooling water, frozen brine and glycol mixed aqueous solution.
When the concentration of the prepared titanyl dichloride solution is more than or equal to 4mol/L, the refrigerant is preferably circulating cooling water; when the concentration of the prepared titanyl dichloride solution is lower than 4mol/L, the refrigerant is preferably a low-temperature ethylene glycol mixed aqueous solution at the temperature of minus 10 ℃ to minus 30 ℃.
Preferably, when the concentration of the prepared titanium oxychloride solution is more than or equal to 4mol/L, controlling the temperature of the prepared titanium oxychloride solution to be lower than 50 ℃; preferably, when the concentration of the prepared titanyl dichloride solution is equal to 2mol/L, the temperature of the prepared titanyl dichloride solution is controlled to be lower than 18 ℃.
Preferably, in the above process, the byproduct hydrochloric acid is conveyed into the hydrochloric acid circulation tank by the hydrochloric acid circulation pump, and a small amount of tail gas enters the tail gas treatment system for treatment by the tail gas fan.
The technical scheme of the invention has the following advantages:
the device and the process for preparing the titanium oxychloride solution can continuously produce the titanium oxychloride solution with adjustable concentration and adjustable temperature, can remove reaction heat generated by continuous mixing reaction, avoid bumping caused by a large amount of heat release, and inhibit the generation of excessive hydrolysis side reaction. Because the whole system operates under the micro negative pressure, the potential safety hazard of gas leakage is avoided. The device and the process can pump and convey the titanium tetrachloride according to the metering continuous negative pressure, and are safe and reliable.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the present disclosure taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a schematic structural view of an apparatus for continuously preparing a titanyl dichloride solution in example 1 of the present invention; the system comprises a titanium tetrachloride flow meter 1, a venturi mixer 2, a pure water flow meter 3, a falling film absorber 4, a hydrochloric acid absorption tower 5, a tail gas fan 6, a heat exchanger 7, a U-shaped pipe 8, a liquid preparation circulating pump 9, a liquid preparation circulating tank 10, an absorption circulating pump 11, a hydrochloric acid circulating tank 12 and a hydrochloric acid circulating pump 13, wherein the tail gas fan 7 is connected with a heat exchanger;
FIG. 2 is a schematic structural view of a venturi mixer in example 1 of the present invention; wherein, 14-circulating liquid inlet, 15-mixing chamber, 16-nozzle, 17-contraction section, 18-diffusion section, 19-mixed liquid outlet, 20-first suction inlet, 21-second suction inlet.
Detailed Description
Example 1
As shown in FIG. 1, the apparatus for continuously preparing a titanyl dichloride solution in the present embodiment comprises: the device comprises a titanium tetrachloride flowmeter 1, a Venturi mixer 2, a pure water flowmeter 3, a falling film absorber 4, a hydrochloric acid absorption tower 5, a tail gas fan 6, a heat exchanger 7, a U-shaped pipe 8, a liquid preparation circulating pump 9, a liquid preparation circulating tank 10, an absorption circulating pump 11, a hydrochloric acid circulating tank 12 and a hydrochloric acid circulating pump 13.
Wherein, the titanium tetrachloride flowmeter 1 is connected with a first suction port 20 of the Venturi mixer 2; a circulating liquid inlet 14 of the Venturi mixer 2 is connected with an outlet pipe of the liquid distribution circulating pump 9, and a mixed liquid outlet 19 of the Venturi mixer 2 is connected with an upper pipe side inlet of the heat exchanger 7; the pure water flow meter 3 is connected with the second suction port 21 of the venturi mixer 2; an upper liquid inlet of the falling film absorber 4 is connected with an outlet of an absorption circulating pump 11 through a pipeline, a lower tube pass outlet of the falling film absorber 4 is connected with an inlet of a liquid distribution circulating groove 10, and an upper tube pass outlet of the falling film absorber 4 is connected with a lower gas inlet pipe of the hydrochloric acid absorption tower 5; a gas inlet at the lower part of the hydrochloric acid absorption tower 5 is connected with a gas outlet of the falling film absorber 4 through a pipeline, a gas outlet at the upper part of the hydrochloric acid absorption tower 5 is connected with an inlet of the tail gas fan 6 through a pipeline, a liquid inlet at the upper part of the hydrochloric acid absorption tower 5 is connected with an outlet pipe of a hydrochloric acid circulating pump 13 through a pipeline, and a liquid outlet at the lower part of the hydrochloric acid absorption tower 5 is connected with an inlet of a hydrochloric acid circulating tank 12 through a pipeline; the outlet of the tail gas fan 6 is connected with a tail gas treatment system; an upper gas outlet of the heat exchanger 7 is connected with a lower tube pass inlet of the falling film absorber 4, a lower tube pass outlet of the heat exchanger 7 is connected with an inlet of the liquid distribution circulating tank 10, and a gas-liquid separation space is arranged at the upper part of a tube pass of the heat exchanger 7; the heat exchanger 7 is a YKch-30 type round block hole type graphite dilution cooler, and the heat exchange area is 30 square meters; the U-shaped pipe 8 is arranged between the outlet of the lower pipe pass of the heat exchanger 7 and the inlet of the liquid distribution circulation tank 10, the height of the U-shaped pipe 8 is 80% of the height of the pipe pass of the heat exchanger 7, and the pipe diameter of the U-shaped pipe 8 is 200 mm; an inlet pipe of the liquid preparation circulating pump 9 is connected with an outlet of the liquid preparation circulating tank 10; an inlet pipe of the absorption circulating pump 11 is connected with an outlet of the liquid distribution circulating tank 10; an outlet of the hydrochloric acid circulating tank 12 is connected with an inlet of a hydrochloric acid circulating pump 13, and the hydrochloric acid circulating tank 12 is provided with a pure water adding port.
As shown in fig. 2, the venturi mixer 2 in this embodiment includes a circulating liquid inlet 14, a mixing chamber 15, a nozzle 16, a convergent section 17, a divergent section 18, a mixed liquid outlet 19, a first suction port 20, and a second suction port 21. Wherein the first suction port 20 enters the mixing chamber 15 from an outer circumferential tangential direction of the mixing chamber 15; the second suction port 21 enters the mixing chamber 15 from the tangential direction of the excircle of the mixing chamber 15; the central lines of the first suction port 20 and the second suction port 21 are parallel to each other in space, the first suction port 20 and the second suction port 21 are located at any position of the outer circular surface of the mixing chamber in the axial direction, and the first suction port 20 and the second suction port 21 are located at the same cross section of the mixing chamber 15; the centerline of the first suction port 20 does not intersect the centerline of the circulating liquid inlet 14 vertically in space; the centerline of the second suction port 21 does not intersect the centerline of the circulating liquid inlet 14 vertically in space. The structural parameter relationship is as follows: the diameter d1 of the circulating liquid inlet 14 is related to the diameter d2 of the nozzle 16 by d1 ≈ 2 × d 2; the diameter d2 of the nozzle 16 is related to the diameter d3 of the convergent section 17 by d2 ≈ d 3; the relationship h of the length h of the constriction 17 to the diameter d3 of the constriction 17 ≈ d 3; the distance h1 between the end of the nozzle 16 and the convergent section 17 is approximately equal to d 2; the relation between the diameter d5 of the first suction port 20 and the diameter d2 of the nozzle 16 is d5 ═ 0.2 to 0.3 × d 2; the diameter d4 of the mixed liquid outlet 19 is related to the diameter d1 of the circulating liquid inlet 14 by d4 ≈ 1.5 × d 1; the included angle of the diffuser section 18 is about 7 °; the included angle of the convergent section is about 25 °. The specific structural parameters are as follows: d 1-65 mm, d 2-30 mm, d 3-30 mm, d 4-100 mm, d 5-15 mm, d 5-15 mm, h-30 mm, h 1-30 mm, the angle of the divergent section 18 is 7 °, and the angle of the convergent section is 25 °. Wherein, the material of the Venturi mixer 2 is titanium alloy TA2 or polytetrafluoroethylene.
The device for continuously preparing the titanyl dichloride solution in the embodiment has the following start sequence:
1) the valve of the first suction port 20 is closed.
2) The valve of the second suction port 21 is closed.
3) The valve of the hydrochloric acid outlet pipe on the outlet branch pipe of the hydrochloric acid circulating pump 13 is closed.
4) The valve of the titanium oxychloride outlet pipe on the outlet branch pipe of the absorption circulating pump 11 is closed.
5) And opening a valve of a refrigerant inlet of the falling film absorber 4. The refrigerant enters the shell side of the falling film absorber.
6) And opening a valve of a refrigerant outlet of the falling film absorber 4. The coolant carries away the heat of reaction from the shell side.
7) The refrigerant inlet valve of the heat exchanger 7 is opened. The refrigerant enters the shell side of the falling film absorber.
8) And opening a refrigerant outlet valve of the heat exchanger 7. The coolant carries away the heat of reaction from the shell side.
9) Adding titanium oxychloride solution with the concentration to be prepared into the solution preparation circulating tank 10 as circulating mother solution. The circulating mother liquor can reduce the concentration change gradient in the preparation process, can also be used as a heat carrier to reduce the temperature rise in the preparation process, and brings heat into a heat exchanger.
10) Pure water is added to the hydrochloric acid circulation tank 12. Pure water is used as an absorbent to absorb hydrogen chloride gas.
11) And preparing the tail gas treatment system for tail gas treatment.
12) And starting the tail gas fan 6 to provide micro negative pressure for the whole system and provide gas phase flowing power.
13) And starting the hydrochloric acid circulating pump 13 and pumping the hydrochloric acid circulating liquid.
14) The absorption circulation pump 11 is started to pump the circulating absorption liquid.
15) And starting the liquid preparation circulating pump 9 and pumping the prepared circulating liquid. The circulating liquid provides power for the negative pressure generated by the suction inlet of the Venturi mixer.
16) The valve of the pure water inlet of the second suction port 21 is opened, the pure water flowmeter 3 is observed, and the valve opening is adjusted to a set flow rate.
17) The valve of the titanium tetrachloride inlet of the first suction port 20 was opened, the titanium tetrachloride flowmeter 1 was observed, and the valve opening was adjusted to a set flow rate.
18) And adjusting the opening degree of a refrigerant inlet valve of the heat exchanger 7 or adjusting the temperature of the refrigerant according to the temperature of the prepared titanium oxychloride solution. And adjusting the opening degree of a refrigerant inlet valve of the falling film absorber 4.
19) The concentration of the titanyl dichloride solution is sampled and detected, and the flow of the titanium tetrachloride or the pure water entering the Venturi mixer 2 is finely adjusted according to the concentration change.
20) Sampling and detecting the concentration of the byproduct hydrochloric acid, and adjusting the flow of the pure water entering the hydrochloric acid circulating tank 12 according to the concentration change.
21) After the system is stabilized, a valve on an outlet branch pipe of the absorption circulating pump 11 can be opened, and qualified titanium oxychloride solution can be continuously produced according to the required amount.
22) After the system is stabilized, a valve on an outlet branch pipe of the hydrochloric acid circulating pump 13 can be opened, and the by-product hydrochloric acid can be continuously produced according to the required amount.
23) And finishing the driving.
The parking sequence is as follows:
1) the valve of the hydrochloric acid outlet pipe on the outlet branch pipe of the hydrochloric acid circulating pump 13 is closed.
2) The valve of the titanium oxychloride outlet pipe on the outlet branch pipe of the absorption circulating pump 11 is closed.
3) The valve of the first suction port 20 was closed and the supply of titanium tetrachloride was stopped.
4) The valve of the second suction port 21 is closed and the supply of pure water is stopped.
5) The pure water inlet valve on the hydrochloric acid circulation tank 12 is closed.
6) And circulating for a period of time.
7) And closing a valve of a refrigerant inlet of the falling film absorber 4.
8) And closing a valve of a refrigerant outlet of the falling film absorber 4.
9) And closing a refrigerant inlet valve of the heat exchanger 7.
10) And closing a refrigerant outlet valve of the heat exchanger 7.
11) The liquid preparation circulating pump 9 is stopped.
12) The absorption circulation pump 11 is stopped.
13) The hydrochloric acid circulation pump 13 is stopped.
14) The tail gas fan 6 is stopped.
15) The parking is completed.
The process for continuously preparing the titanyl dichloride solution with the concentration of 4mol/L in the embodiment comprises the following steps: titanium tetrachloride is pumped into a Venturi mixer 2 from the external tangent direction of a mixing chamber 15 through a first suction port 20 by a titanium tetrachloride flowmeter 1, pure water is pumped into the Venturi mixer 2 from the external tangent direction of the mixing chamber 15 through a second suction port 21 by a pure water flowmeter 3, the flow direction of the titanium tetrachloride and the flow direction of circulating mother liquor form spiral mixing, the flow direction of the pure water and the flow direction of the circulating mother liquor form spiral mixing, the circulating mother liquor is conveyed into the Venturi mixer 2 by a liquid distribution circulating pump 9, the pumped titanium tetrachloride and the pure water are fully mixed with a large amount of circulating mother liquor, heat generated by mixing reaction is taken away by refrigerant circulating cooling water in a heat exchanger 7, the inlet temperature of the refrigerant circulating cooling water is 32 ℃, the outlet temperature is 37 ℃, hydrogen chloride gas generated by the reaction is conveyed into a falling film absorber 4 through an absorption circulating pump 11 to be absorbed, then returning to the circulating mother liquor of the liquid preparation circulating tank 10 in the form of hydrochloric acid, and washing and absorbing the rest hydrogen chloride gas by a hydrochloric acid absorption tower 5 to obtain a byproduct hydrochloric acid.
The hydrogen chloride gas generated by the reaction is separated from the liquid through a gas-liquid separation space at the upper part of the tube pass of the heat exchanger 7, the separated hydrogen chloride gas enters the falling film absorber 4 through a gas phase pipeline, and the liquid enters the tube pass of the heat exchanger 7. The byproduct hydrochloric acid is conveyed into a hydrochloric acid circulating tank 12 by a hydrochloric acid circulating pump 13, and a small amount of tail gas enters a tail gas treatment system for treatment by a tail gas fan 6.
Wherein, the flow rate of the titanium tetrachloride led in from the first suction port 20 of the Venturi mixer 2 is 750L/h, and the flow rate of the pure water led in from the second suction port 21 is 1000L/h. The flow Q of the liquid preparation circulating pump 9 is 50m3H, the lift H is 30 m; flow rate Q of the absorption circulation pump 11 is 50m3H, the lift H is 30 m; the flow Q of the hydrochloric acid circulation pump 13 is 50m3And H, the head H is 30 m.
The device and the process for continuously preparing the titanium oxychloride solution in the embodiment can realize the production and preparation of the titanium oxychloride solution with the concentration of 4mol/L and the temperature of less than or equal to 50 ℃ in the continuous production capacity of 1250L/h.
Comparative example 1
The device is operated by adopting a titanium tetrachloride dilution complete set device as disclosed in CN2923668Y, and comprises a titanium tetrachloride metering tank, a glass viewing cylinder, a mixed type nozzle, a vacuum unit, a titanium tetrachloride preparation tank, a primary falling film absorption tower, an absorption circulation tank, a secondary falling film absorption tower, a pressure stabilizing pipe and a No. 2 circulation pump.
Because the device adopts the vacuum unit to suck the titanium tetrachloride to the metering tank, hydrochloric acid fog can enter the vacuum unit in the titanium tetrachloride transferring mode, and the corrosion damage of the vacuum unit is easily caused.
The device adopts an intermittent operation mode, and the intermittent operation can not avoid the side reaction of excessive hydrolysis caused by the fact that the ratio of water to titanium tetrachloride is far larger than the chemical balance of the titanium oxychloride at the initial preparation stage.
Comparative example 2
The operation is carried out by adopting a titanium tetrachloride aqueous solution preparation device as disclosed in CN102764601, and the device comprises a jet vacuum pump, an anticorrosive centrifugal pump, a graphite heat exchanger, a titanium tetrachloride mixing tank, an absorption tower, a centrifugal fan and the like.
The apparatus, which uses a jet vacuum pump to suck titanium tetrachloride to mix with a circulating liquid, has a problem of unbalanced suction, and in addition, the apparatus uses an intermittent operation, the concentration of the system solution decreases when pure water is added, and the concentration of the system solution increases when titanium tetrachloride is added. The whole process operation process is a process of concentration fluctuation of the system solution.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. An apparatus for continuously preparing a titanyl dichloride solution, comprising: the device comprises a titanium tetrachloride flowmeter (1), a Venturi mixer (2), a pure water flowmeter (3), a falling film absorber (4), a hydrochloric acid absorption tower (5), a heat exchanger (7), a liquid preparation circulating pump (9), a liquid preparation circulating tank (10) and an absorption circulating pump (11);
wherein the titanium tetrachloride flowmeter (1) is connected with a first suction port (20) of the Venturi mixer (2); a circulating liquid inlet (14) of the Venturi mixer (2) is connected with an outlet pipe of the liquid distribution circulating pump (9), and a mixed liquid outlet (19) of the Venturi mixer (2) is connected with an upper pipe side inlet of the heat exchanger (7); the pure water flowmeter (3) is connected with a second suction inlet (21) of the Venturi mixer (2); an upper liquid inlet of the falling film absorber (4) is connected with an outlet of an absorption circulating pump (11) through a pipeline, a lower tube pass outlet of the falling film absorber (4) is connected with an inlet of a liquid distribution circulating groove (10), and an upper tube pass outlet of the falling film absorber (4) is connected with a lower gas inlet pipe of the hydrochloric acid absorption tower (5); a gas inlet at the lower part of the hydrochloric acid absorption tower (5) is connected with a gas outlet of the falling film absorber (4) through a pipeline; an upper gas outlet of the heat exchanger (7) is connected with a lower tube pass inlet of the falling film absorber (4), and a lower tube pass outlet of the heat exchanger (7) is connected with an inlet of the liquid distribution circulating tank (10); an inlet pipe of the liquid distribution circulating pump (9) is connected with an outlet of the liquid distribution circulating tank (10); an inlet pipe of the absorption circulating pump (11) is connected with an outlet of the liquid distribution circulating tank (10).
2. The device according to claim 1, characterized in that the venturi mixer (2) comprises a circulating liquid inlet (14), a convergent section (17), a nozzle (16), a divergent section (18), a mixing chamber (15), a first suction inlet (20), a second suction inlet (21) and a mixed liquid outlet (19); the first suction port (20) enters the mixing chamber (15) from the direction of the excircle tangent of the mixing chamber (15); the second suction port (21) enters the mixing chamber (15) from the excircle tangential direction of the mixing chamber (15); the central lines of the first suction port (20) and the second suction port (21) are parallel to each other in space, the first suction port (20) and the second suction port (21) are positioned at any position of the outer circular surface of the mixing chamber in the axial direction, and preferably, the first suction port (20) and the second suction port (21) are positioned at the same cross section of the mixing chamber (15); the centerline of the first suction port (20) does not intersect the centerline of the circulating liquid inlet (14) vertically in space; the central line of the second suction inlet (21) and the central line of the circulating liquid inlet (14) do not vertically intersect in space.
3. The apparatus according to claim 1 or 2, wherein a gas-liquid separation space is provided in an upper portion of a tube side of the heat exchanger (7).
4. A device according to any one of claims 1-3, characterized in that the device further comprises U-shaped tubes (8), which U-shaped tubes (8) are arranged between the lower tube side outlet of the heat exchanger (7) and the inlet of the liquid distribution circulation tank (10); preferably, the bottom of the U-shaped pipe (8) is provided with a drain pipe and a valve.
5. The device according to claim 4, characterized in that the height of the U-shaped tubes (8) is 50-90%, preferably 80%, of the tube side height of the heat exchanger (7).
6. The apparatus of any one of claims 1-5, further comprising: a tail gas fan (6), a hydrochloric acid circulating tank (12) and a hydrochloric acid circulating pump (13); wherein, the upper gas outlet of the hydrochloric acid absorption tower (5) is connected with the inlet of the tail gas fan (6) through a pipeline, the upper liquid inlet of the hydrochloric acid absorption tower (5) is connected with the outlet pipe of the hydrochloric acid circulating pump (13) through a pipeline, and the lower liquid outlet of the hydrochloric acid absorption tower (5) is connected with the inlet of the hydrochloric acid circulating tank (12) through a pipeline; the outlet of the tail gas fan (6) is connected with a tail gas treatment system; the outlet of the hydrochloric acid circulating tank (12) is connected with the inlet of a hydrochloric acid circulating pump (13); the hydrochloric acid circulating tank (12) is provided with a pure water adding port.
7. A process for continuously preparing a titanium oxychloride solution is characterized by comprising the following steps: the titanium tetrachloride flowmeter (1) is pumped into the Venturi mixer (2) through a first suction port (20), meanwhile, pure water is pumped into the Venturi mixer (2) from a second suction port (21) through the pure water flow meter (3), meanwhile, the circulating mother liquor is conveyed into the Venturi mixer (2) by the liquor-preparing circulating pump (9), the extracted titanium tetrachloride and pure water are fully mixed with a large amount of circulating mother liquor, the produced titanium oxychloride solution is conveyed into a solution preparation circulating tank (10) by a solution preparation circulating pump (9), the heat generated by the mixing reaction is taken away by a refrigerant in the heat exchanger (7), the hydrogen chloride gas generated by the reaction is firstly conveyed to the falling film absorber (4) by the absorption circulating pump (11) to be absorbed, and then returns to the circulating mother liquor of the liquor preparation circulating tank (10) in the form of hydrochloric acid, the rest hydrogen chloride gas is washed and absorbed by a hydrochloric acid absorption tower (5) to obtain a byproduct hydrochloric acid.
8. The process according to claim 7, characterized in that titanium tetrachloride is drawn into the venturi mixer (2) from the direction of the outer circumference of the mixing chamber (15) tangentially through a first suction port (20) by means of a titanium tetrachloride flow meter (1), while pure water is drawn into the venturi mixer (2) from the direction of the outer circumference of the mixing chamber (15) tangentially through a second suction port (21) by means of a pure water flow meter (3), the flow direction of the titanium tetrachloride and the flow direction of the circulating mother liquor forming a helical mixing, the flow direction of the pure water and the flow direction of the circulating mother liquor forming a helical mixing.
9. The process according to claim 7 or 8, characterized in that the hydrogen chloride gas generated by the reaction is separated from the liquid in a gas-liquid separation space at the upper part of the tube side of the heat exchanger (7), the separated hydrogen chloride gas enters the falling film absorber (4) through a gas phase pipeline, and the liquid enters the tube side of the heat exchanger (7).
10. The process according to any one of claims 7 to 9, wherein the refrigerant is one or more of circulating cooling water, frozen brine and glycol mixed aqueous solution; and/or
The byproduct hydrochloric acid is conveyed into a hydrochloric acid circulating tank (12) by a hydrochloric acid circulating pump (13), and a small amount of tail gas enters a tail gas treatment system for treatment by a tail gas fan (6).
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| CN202010664112.2A CN111672346A (en) | 2020-07-10 | 2020-07-10 | Device and process for continuously preparing titanium oxychloride solution |
| PCT/CN2021/070360 WO2022007378A1 (en) | 2020-07-10 | 2021-01-05 | Apparatus and process for continuously preparing titanium oxychloride solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250117A (en) * | 2020-10-16 | 2021-01-22 | 河南佰利联新材料有限公司 | Method for improving quality of waste and side-product titanium oxychloride |
| WO2022007378A1 (en) * | 2020-07-10 | 2022-01-13 | 广西七色珠光材料股份有限公司 | Apparatus and process for continuously preparing titanium oxychloride solution |
| KR102428917B1 (en) * | 2022-02-11 | 2022-08-02 | 김래희 | Improved process for preparing titanium oxychloride |
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| CN115337764A (en) * | 2022-07-29 | 2022-11-15 | 赞宇科技集团股份有限公司 | Alpha-sodium alkenyl sulfonate tail gas falling film absorption and recycling system and treatment process |
| CN115417449A (en) * | 2022-08-16 | 2022-12-02 | 宁波新福钛白粉有限公司 | System and method for utilizing waste heat of tail gas of rotary kiln for titanium dioxide produced by sulfuric acid process |
| CN117563534B (en) * | 2024-01-17 | 2024-04-05 | 河南嘉颖生物科技有限公司 | Continuous flow reaction device and method for high-purity O, O-dialkyl thiophosphoryl chloride |
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| US4634559A (en) * | 1984-02-29 | 1987-01-06 | Aluminum Company Of America | Fluid flow control process |
| CN2923668Y (en) * | 2006-03-31 | 2007-07-18 | 建德市大洋化工有限公司 | Complete apparatus for diluting titanic chloride |
| CN102234117B (en) * | 2010-05-05 | 2015-11-25 | 刘基扬 | A kind of method for hydrolysis of the material containing hydrolyzable halogen atom |
| CN111672346A (en) * | 2020-07-10 | 2020-09-18 | 广西七色珠光材料股份有限公司 | Device and process for continuously preparing titanium oxychloride solution |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022007378A1 (en) * | 2020-07-10 | 2022-01-13 | 广西七色珠光材料股份有限公司 | Apparatus and process for continuously preparing titanium oxychloride solution |
| CN112250117A (en) * | 2020-10-16 | 2021-01-22 | 河南佰利联新材料有限公司 | Method for improving quality of waste and side-product titanium oxychloride |
| KR102428917B1 (en) * | 2022-02-11 | 2022-08-02 | 김래희 | Improved process for preparing titanium oxychloride |
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