CN112588211B - Titanium dioxide carbonization boiling chlorination simulation reactor and simulation method - Google Patents

Titanium dioxide carbonization boiling chlorination simulation reactor and simulation method Download PDF

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CN112588211B
CN112588211B CN202110063668.0A CN202110063668A CN112588211B CN 112588211 B CN112588211 B CN 112588211B CN 202110063668 A CN202110063668 A CN 202110063668A CN 112588211 B CN112588211 B CN 112588211B
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quartz tube
furnace
heating furnace
titanium dioxide
top cover
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CN112588211A (en
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温良英
陈杨鑫
彭琴
杨帆
白晨光
张生富
尹国亮
王建鑫
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Chongqing University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1836—Heating and cooling the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1809—Controlling processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/02—Halides of titanium
    • C01G23/022—Titanium tetrachloride

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Abstract

The invention relates to a titanium dioxide carbonization boiling chlorination simulation reactor and a simulation method, wherein the reactor comprises a heating furnace and a reactor body; the reactor body comprises a vertical quartz tube, the quartz tube is provided with a bottom end of an expanding opening, a lower sieve plate is transversely arranged in the quartz tube, an inverted funnel-shaped top cover is arranged at the top end of the quartz tube in a matching mode, the top cover is buckled at the top end of the quartz tube through the lower part of the expanding opening of the top cover, the inner cavity of the top cover is vertically communicated, and an upper sieve plate is transversely arranged in the upper part of the top cover; the bottom of the heating furnace is provided with a furnace inlet and is connected with a base through a telescopic rod, and a furnace cover seat matched with the furnace inlet is convexly arranged on the base; the quartz tube is arranged on the furnace cover seat, an air inlet channel is arranged by penetrating through the base and the furnace cover seat, the inner end of the air inlet channel is communicated with the quartz tube, the top of the heating furnace is provided with an exhaust pipe with adjustable vertical height in a penetrating manner, and the inner end of the exhaust pipe is positioned right above the top cover and is matched with the top end of the top cover. The reactor is convenient for simulating the titanium dioxide carbonization boiling chlorination reaction process and acquiring more parameters with reference values.

Description

Titanium dioxide carbonization boiling chlorination simulation reactor and simulation method
Technical Field
The invention belongs to the technical field of solid waste treatment and recovery in metallurgy, and particularly relates to a titanium dioxide carbonization boiling chlorination simulation reactor and a simulation method.
Background
Titanium oxides, especially titanium dioxide (TiO)2) Can not directly react with chlorine gas, and can obviously improve TiO by adding carbon2The chlorination reaction of (1). Based on this, rich in TiO290 percent of high titanium slag is added with petroleum coke (C) and is boiled and chlorinated at high temperature to prepare titanium tetrachloride (TiCl)4) The mainstream process technology of (1). The technological process is a complex multiphase reaction of gas-solid multiphase mutual mixing, and experts and scholars at home and abroad carry out a great deal of research on the reaction, and successively put forward a plurality of viewpoints and conjectures for explaining the macroscopic phenomenon based on thermodynamic analysis, but can not effectively reveal TiO2The complex interaction among multiple substances and the influence rule of each factor on the chlorination reaction rate in the carbon-adding chlorination process cannot well research the reaction process and accumulate technical reference data.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a titanium dioxide carbonization boiling chlorination simulation reactor and a simulation method, which can realize the purpose of simulating the boiling chlorination of TiO2The simulation of the multi-phase mixing effect in the carbonization boiling chlorination process is convenient for researching the TiO2The method for researching the influence of the interaction between the phases of the carbonated chlorinated multi-substance, revealing the action rule influencing the chlorination reaction rate and adjusting and controlling the chlorination reaction process is mainly used for researching the influence of the TiO on the high-temperature boiling chlorination process condition at 850-1050 DEG C2Factors of the chlorination reaction rate and the regulation and control method, in order to understand and master the low-cost and high-efficiency TiCl preparation4And laying a technical foundation.
In order to solve the technical problems, the invention adopts the following technical scheme:
the titanium dioxide carbonization boiling chlorination simulation reactor comprises a heating furnace and a reactor body which can be arranged in the heating furnace; the reactor body comprises a vertical quartz tube, the quartz tube is provided with a flared bottom end, the edge of an opening part of the lower surface of the bottom end is positioned on a horizontal plane so as to be placed stably, and a lower sieve plate is transversely arranged in the quartz tube and used for bearing reactants; the top end of the quartz tube is provided with an inverted funnel-shaped top cover, the top cover is correspondingly buckled at the top end of the quartz tube through the lower part of the flaring of the top cover, the inner cavity of the top cover is vertically communicated so as to facilitate the gas to pass through, and an upper sieve plate is transversely arranged in the upper part of the top cover so as to avoid the outflow of reactants; the bottom of the heating furnace is provided with a furnace inlet; the bottom of the heating furnace is also connected with a base through a telescopic rod of a telescopic mechanism, and the upper surface of the base corresponds to the lower surface of the heating furnace so as to be close to the lower surface of the heating furnace or far away from the heating furnace under the driving of the telescopic rod; a furnace cover seat matched with the furnace inlet is convexly arranged on the base, so that the furnace inlet can be sealed through the furnace cover seat when the base is attached to the lower surface of the heating furnace; the quartz capsule is arranged in on the bell seat, runs through base and bell seat are equipped with inlet channel, and inlet channel's the inner intercommunication quartz capsule, and the top of heating furnace is run through and is equipped with vertical height-adjustable's blast pipe, and the inner of blast pipe is located the top cap directly over, and the inner flaring of blast pipe and adaptation are in order to compress tightly the lock and communicate the top cap when descending in the top of top cap.
Further perfecting the technical scheme, the wall of the heating furnace is provided with a transparent observation window.
Further, the heating furnace is provided with a thermocouple for monitoring the temperature in the furnace.
Further, the lower sieve plate and the upper sieve plate are both 400-mesh quartz sand sintered plates.
Furthermore, the inner wall of the lower part of the top cover flaring and the top end part of the corresponding quartz tube are frosted surfaces so as to improve the sealing performance during buckling connection.
Furthermore, the upper surface of the furnace cover seat is provided with a ring groove which is matched with the edge of the opening part of the lower surface of the bottom end of the quartz tube, and the edge of the opening part of the lower surface of the bottom end of the quartz tube falls into the ring groove.
Furthermore, a certain distance is formed between the lower sieve plate and the lower surface of the bottom end of the quartz tube, and the inner space of the quartz tube below the lower sieve plate is formed into an air inlet preheating uniform distribution area.
Further, the exhaust pipe vertically penetrates through the top of the heating furnace, and the wall of the heating furnace on the outer side wall of the exhaust pipe is of a thread structure matched with each other so that the vertical height can be adjusted through rotation.
The invention also relates to a titanium dioxide carbonization boiling chlorination simulation method, which is carried out based on the titanium dioxide carbonization boiling chlorination simulation reactor; the outer end of the air inlet channel is connected with a tee joint, and the tee joint is also connected with an inert gas source and a chlorine gas source through stop valves respectively; the method comprises the following steps:
1) obtaining a reactor body;
opening the top cover and adding TiO2Respectively weighing the particles and the petroleum coke particles, adding the particles and the petroleum coke particles into a quartz tube, carrying the particles by a lower sieve plate, and fastening a top cover;
2) placing the quartz tube on a furnace cover seat on a base opened through a telescopic rod, and ensuring that the inner end of the air inlet channel is communicated with the quartz tube;
3) heightening the height of the exhaust pipe; then, the base is attached to the lower surface of the heating furnace through the telescopic rod, the furnace cover seat seals the furnace inlet, and the quartz tube is fed into the heating furnace;
4) the height of the exhaust pipe is reduced, and the exhaust pipe is pressed and buckled on the top cover through the inner end of the flaring of the exhaust pipe;
5) heating the heating furnace, and introducing inert gas at the designed gas speed in the heating stage to ensure that TiO in the quartz tube2The mixture of the particles and the petroleum coke particles is fluidized;
6) heating the heating furnace to the temperature required by the reaction and then keeping the temperature; switching the inert gas into chlorine gas, and starting chlorination reaction; when the gas is switched, the stop valve of the inert gas source is gradually closed, and simultaneously, the stop valve of the chlorine gas source is gradually opened to keep the gas speed introduced into the quartz tube unchanged, so that the mixture is prevented from flowing out;
7) after chlorination reaction is carried out according to designed time length, unreacted TiO2Keeping the particles and petroleum coke particles in a quartz tube, cooling, taking out, weighing, recording the weight after reaction, and calculating the weight loss ratio (B-A)/B according to the weight (calculated as A) after reaction and the total weight (calculated as B) respectively weighed in the step 1); the residue after the burning reaction (i.e. unreacted TiO)2Particulate matter and petroleum coke particulate matter) to remove the petroleum coke particulate matter, weighing again and recording the residual weight, and weighing the residual weight (counted as C) and the residual weight in the step 1)Of TiO 22The weight of the pellets (in terms of D) was used to calculate the chlorination ratio (D-C)/D.
Further perfecting the process, in step 1), TiO2The mass ratio of the particles to the petroleum coke particles is 3:1, the particle sizes are respectively 200-mesh and 300-mesh and 120-mesh and 160-mesh, and the particles and the petroleum coke particles are uniformly mixed and then added into a quartz tube;
in the step 5), the designed gas velocity is 0.15-0.25 m/s;
in the step 6), the temperature required by the reaction is 850-1050 ℃; the chlorine gas is evaporated chlorine gas with the concentration of 99 percent;
in step 7), the designed chlorination reaction time is 30 min.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention is different from the conventional integrated fluidization device, the heating furnace and the reactor body are taken as two independent parts, and the lifting is realized through the telescopic rod, so that the implementation of the simulation reaction process is greatly facilitated, the experimental efficiency is improved, and the subsequent disassembly and maintenance are also facilitated.
2. The invention adopts the visual quartz tube, can monitor the fluidization state in the reaction process in real time through the observation window of the heating furnace, and is favorable for controlling the experimental process and adjusting the experimental process in time.
3. The bottom end of the quartz tube is reserved with the air inlet preheating and uniform distribution area, so that the pressure of chlorine entering the quartz tube can be dispersed while the experimental accuracy is improved by preheating the chlorine, and the fluidizing gas is ensured to be more uniform.
4. The exhaust pipe is a flared external threaded pipe, can adapt to quartz pipes with different heights and different inner diameters by adjusting up and down, improves the universality of the heating furnace, ensures the smooth outflow of reaction gas, and is favorable for stable experiment.
Drawings
FIG. 1 is a schematic diagram of a titanium dioxide carbo-boiling chlorination simulation reactor according to an embodiment;
FIG. 2 is a schematic view of a reactor body in an embodiment;
FIG. 3 is a schematic diagram of a simulated reaction process of a titanium dioxide carbo-boiling chlorination simulated reactor according to an embodiment;
the device comprises a machine shell 1, refractory bricks 2, a resistance wire 3, an expansion rod 4, a base 5, an air inlet channel 6, an exhaust pipe 7, a thermocouple 8, a quartz tube 9, a lower sieve plate 10, a bottom end 11, a top cover 12, a furnace inlet 13, a furnace cover seat 14, an upper sieve plate 15 and a heating furnace 100.
Detailed Description
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Referring to fig. 1 to 3, a titanium dioxide carbonization boiling chlorination simulation reactor of an embodiment includes a heating furnace 100 and a reactor body that can be placed in the heating furnace 100; the reactor body comprises a vertical quartz tube 9, the quartz tube 9 is provided with a gradually flared bottom end 11, the edge of the opening part of the lower surface of the bottom end 11 is positioned on a horizontal plane so as to be placed stably, and a lower sieve plate 10 is transversely arranged in the quartz tube 9 and used for bearing reactants; the top end of the quartz tube 9 is provided with an inverted funnel-shaped top cover 12, the lower part of the top cover 12 passing through the flaring thereof is correspondingly buckled with the top end of the quartz tube 9, the inner cavity of the top cover 12 is vertically penetrated so as to facilitate the passing of reaction gas, and the upper part of the top cover 12 is internally and transversely provided with an upper sieve plate 15 to avoid the outflow of reactants; the bottom of the heating furnace 100 is provided with a furnace inlet 13; the bottom of the heating furnace 100 is also connected with a base 5 through a vertical telescopic rod 4 of a telescopic mechanism, and the upper surface of the base 5 corresponds to the lower surface of the heating furnace 100, so that the heating furnace 100 can be closely attached to the lower surface of the heating furnace 100 or far away from the heating furnace 100 under the driving of the telescopic rod 4; a furnace cover seat 14 matched with the furnace inlet 13 is convexly arranged on the base 5, so that the furnace inlet 13 can be sealed by the furnace cover seat 14 when the base 5 is attached to the lower surface of the heating furnace 100; quartz capsule 9 is arranged in on the furnace lid seat 14, run through base 5 and furnace lid seat 14 are equipped with inlet channel 6, inlet channel 6's the inner intercommunication quartz capsule 9 so that let in experimental gas, and the top of heating furnace 100 is run through and is equipped with vertical height-adjustable's blast pipe 7, and the inner of blast pipe 7 is located top cap 12 directly over, and the inner flaring of blast pipe 7 and adaptation are in order to compress tightly lock and communicate top cap 12 (quartz capsule 9) when descending in the top of top cap 12. The telescopic mechanism is in the form of the prior art and can be controlled by an external electric motor. The wall of the furnace 100 is provided with a transparent observation window (not shown) to facilitate real-time monitoring of the fluidization state during the reaction. The heating furnace 100 is provided with a thermocouple 8 for monitoring the temperature in the furnace. It can be understood that the wall of the heating furnace 100 generally comprises a casing 1 and refractory bricks 2 in the casing 1, resistance wires 3 for heating are also arranged in the heating furnace 100, and the furnace cover seat 14 is also made of refractory bricks 2 to ensure the sealing and heat preservation effects. When in use, the furnace cover seat 14 is preferably in a circular truncated cone shape, the shape of the furnace inlet 13 corresponds to that of the circular truncated cone-shaped furnace cover seat 14, and a sealing gasket can be arranged between the furnace inlet 13 and the furnace cover seat 14 or/and between the upper surface of the base 5 and the lower surface of the heating furnace 100.
Wherein, the lower sieve plate 10 and the upper sieve plate 15 are both 400-mesh quartz sand sintered plates.
The inner wall of the lower part of the flaring of the top cover 12 and the top end part of the corresponding quartz tube 9 are frosted surfaces so as to improve the sealing property during buckling connection; the inner wall of the flared inner end of the exhaust pipe 7 and the top end part of the corresponding top cover 12 are frosted surfaces.
Wherein, the annular at the oral area border of adaptation in quartz capsule 9 bottom lower surface is seted up to the upper surface of furnace lid seat 14, and the oral area border of the bottom lower surface of quartz capsule 9 falls in the annular, can improve quartz capsule 9's stability and can play and place spacing effect. It will be appreciated that the inner end of the inlet passage 6 is located centrally of the annular groove.
Wherein, the lower sieve plate 10 has certain distance to the lower surface of the bottom end of the quartz tube 9, and the inner space of the quartz tube 9 below the lower sieve plate 10 forms an air inlet preheating uniform distribution area. Taking the example that the quartz tube 9 is arranged on the furnace cover seat 14, the inner end of the gas inlet channel 6 is preferably at a distance of two centimeters from the lower sieve plate 10 (namely a gas inlet preheating and uniform distribution area) so as to preheat and uniformly distribute the introduced gas.
Wherein, the exhaust pipe 7 vertically runs through the top of the heating furnace 100, and the wall of the heating furnace 100 on the outer side wall of the exhaust pipe 7 is in a thread structure matched with each other so as to adjust the vertical height through rotation. It will be appreciated that the inner end of the exhaust tube 7 is a conical flare, and the centre of rotation of the screw arrangement, the axis of the conical flare, the axis of the top cap 12, the axis of the quartz tube 9, and the inlet passage 6 are all coaxial. In practice, the inner diameter and height of the quartz tube 9 are designed according to the relevant height-diameter ratio.
The invention also provides a titanium dioxide carbonization boiling chlorination simulation method, which is carried out based on the titanium dioxide carbonization boiling chlorination simulation reactor; the outer end of the gas inlet channel 6 is connected with a tee joint, the tee joint is also connected with an inert gas source and a chlorine gas source through stop valves respectively, and the outer end of the exhaust pipe 7 is connected with alkali liquor through a pipeline; the method comprises the following steps:
1) obtaining a reactor body;
opening the top cover 12 and adding TiO2Adding particles and petroleum coke particles into a quartz tube 9, carrying the particles by a lower sieve plate 10, and fastening a top cover 12;
2) placing the quartz tube 9 on a furnace cover seat 14 on the base 5 opened by the telescopic rod 4 to ensure that the inner end of the air inlet channel 6 is communicated with the quartz tube 9;
3) the height of the exhaust pipe 7 is adjusted to be high; then, the base 5 is attached to the lower surface of the heating furnace 100 through the telescopic rod 4, the furnace cover seat 14 seals the furnace inlet 13, and the quartz tube 9 is sent into the heating furnace 100;
4) the height of the exhaust pipe 7 is reduced, and the inner end of the flaring of the exhaust pipe 7 is pressed and buckled on the top cover 12, so that the bottom end of the quartz tube 9 is hermetically connected with the furnace cover seat 14, the top end of the quartz tube 9 is hermetically connected with the top cover 12, and the top end of the top cover 12 is hermetically connected with the exhaust pipe 7;
5) heating the furnace 100, introducing inert gas at the designed gas speed in the heating stage to ensure that TiO is filled in the quartz tube 92The mixture of the particles and the petroleum coke particles is fluidized;
6) the heating furnace 100 is heated to the temperature required by the reaction and then is kept; switching the inert gas into chlorine gas, and starting chlorination reaction; when the gas is switched, the stop valve of the inert gas source is gradually closed, and simultaneously, the stop valve of the chlorine gas source is gradually opened to keep the gas speed introduced into the quartz tube 9 unchanged, so that the mixed material is prevented from flowing out; chlorine gas can be preheated in the gas inlet preheating and uniform distribution area and uniformly distributed by the lower sieve plate 10 and then enters the reaction space of the quartz tube 9, and the upper sieve plate 15 can protectEvidence of TiO2The petroleum coke particles do not flow out (overflow) in the process of introducing chlorine to simulate boiling chlorination reaction. In practice, nitrogen or argon is used as the inert gas.
7) After chlorination reaction is carried out according to designed time length, unreacted TiO2Keeping the particles and petroleum coke particles in the quartz tube 9, cooling, taking out, weighing and calculating the weight loss rate; calculating the chlorination rate after firing; understandably, TiO in step 1)2The particles and the petroleum coke particles need to be respectively weighed and the weight is recorded, so that the weight loss rate and the chlorination rate can be calculated by subsequent comparison. TiCl generated during the chlorination reaction4、CO、CO2The reaction temperature is all absorbed by alkali liquor discharged from the exhaust pipe 7 in a gas form, the boiling fluidization state in the quartz tube 9 can be observed in real time through an observation window in the chlorination reaction process, and whether the heating furnace 100 reaches and maintains the preset temperature of 850-1050 ℃ can be monitored through the thermocouple 8.
Wherein, in the step 1), TiO2The mass ratio of the particles to the petroleum coke particles is 3:1, the particle sizes are respectively 200-mesh and 300-mesh and 120-mesh and 160-mesh, and the particles and the petroleum coke particles are uniformly mixed and then added into a quartz tube 9;
in the step 5), the designed gas velocity is 0.15-0.25 m/s;
in the step 6), the temperature required by the reaction is 850-1050 ℃; the chlorine gas is evaporated chlorine gas with the concentration of 99 percent;
in the step 7), the design time is 30 min.
Example one
TiO with the particle size of 200-300 meshes and the purity of 99 percent2The particles and petroleum coke particles with the particle size of 120-160 meshes and the C content of 99 percent are uniformly mixed and placed in a quartz tube 9, the quartz tube 9 is sent into a heating furnace 100 through a telescopic rod 4, and the height of an exhaust pipe 7 is adjusted to enable the top end of a top cover 12 to be connected and sealed with the exhaust pipe 7. The furnace temperature is adjusted to 900 ℃, a nitrogen gas source is introduced into the gas inlet channel 6 in the temperature rising stage, the apparent gas velocity is adjusted to be 0.15m/s, and the mixture in the quartz tube 9 is boiled and fluidized. And switching the nitrogen gas to chlorine gas when the temperature is increased to 900 ℃, keeping the gas speed unchanged, and reacting for 30 min. TiCl produced by the reaction4、CO、CO2The gas is discharged from the exhaust pipe 7 to be absorbed by alkali liquor, and the unreacted TiO is2The petroleum coke and the petroleum coke are left in a quartz tube 9, are taken out and weighed after being cooled, and the weight loss rate of the petroleum coke and the chlorination rate of the petroleum coke after being burned can be calculated and are shown in table 1.
Example two
TiO with the particle size of 200-300 meshes and the purity of 99 percent2The particles and petroleum coke particles with the particle size of 120-160 meshes and the C content of 99 percent are uniformly mixed and placed in a quartz tube 9, the quartz tube 9 is sent into a heating furnace 100 through an expansion link 4, and the height of an exhaust pipe 7 is adjusted to enable the top end of a top cover 12 to be connected and sealed with the exhaust pipe 7. The furnace temperature is adjusted to 900 ℃, a nitrogen gas source is introduced into the gas inlet channel 6 in the temperature rising stage, the apparent gas velocity is adjusted to be 0.20m/s, and the mixture in the quartz tube 9 is boiled and fluidized. And switching the nitrogen gas to chlorine gas when the temperature is increased to 900 ℃, keeping the gas speed unchanged, and reacting for 30 min. TiCl produced by the reaction4、CO、CO2The gas is discharged from the exhaust pipe 7 to be absorbed by alkali liquor, and the unreacted TiO is2The petroleum coke and the petroleum coke are left in a quartz tube 9, are taken out and weighed after being cooled, and the weight loss rate of the petroleum coke and the chlorination rate of the petroleum coke after being burned can be calculated and are shown in table 1.
EXAMPLE III
TiO with the particle size of 200-300 meshes and the purity of 99 percent2The particles and petroleum coke particles with the particle size of 120-160 meshes and the C content of 99 percent are uniformly mixed and placed in a quartz tube 9, the quartz tube 9 is sent into a heating furnace 100 through a telescopic rod 4, and the height of an exhaust pipe 7 is adjusted to enable the top end of a top cover 12 to be connected and sealed with the exhaust pipe 7. The furnace temperature is adjusted to 900 ℃, a nitrogen gas source is introduced into the gas inlet channel 6 in the temperature rising stage, the apparent gas velocity is adjusted to be 0.25m/s, and the mixture in the quartz tube 9 is boiled and fluidized. And switching the nitrogen gas to chlorine gas when the temperature is increased to 900 ℃, keeping the gas speed unchanged, and reacting for 30 min. TiCl produced by the reaction4、CO、CO2The gas is discharged from the exhaust pipe 7 to be absorbed by alkali liquor, and the unreacted TiO is2The petroleum coke and the petroleum coke are left in a quartz tube 9, are taken out and weighed after being cooled, and the weight loss rate of the petroleum coke and the chlorination rate of the petroleum coke after being burned can be calculated and are shown in table 1.
TABLE 1
Percent weight loss Percentage of chlorination%
Example one 81.03 90.43
Example two 82.82 93.27
EXAMPLE III 86.60 98.49
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.

Claims (10)

1. The titanium dioxide carbonization boiling chlorination simulation reactor comprises a heating furnace and a reactor body which can be arranged in the heating furnace; the method is characterized in that: the reactor body comprises a vertical quartz tube, the quartz tube is provided with a flared bottom end, the edge of an opening part of the lower surface of the bottom end is positioned on a horizontal plane so as to be placed stably, and a lower sieve plate is transversely arranged in the quartz tube and used for bearing reactants; the top end of the quartz tube is provided with an inverted funnel-shaped top cover, the top cover is correspondingly buckled at the top end of the quartz tube through the lower part of the flaring of the top cover, the inner cavity of the top cover is vertically communicated so as to facilitate the gas to pass through, and an upper sieve plate is transversely arranged in the upper part of the top cover so as to avoid the outflow of reactants;
the bottom of the heating furnace is provided with a furnace inlet; the bottom of the heating furnace is also connected with a base through a telescopic rod of a telescopic mechanism, and the upper surface of the base corresponds to the lower surface of the heating furnace so as to be close to the lower surface of the heating furnace or far away from the heating furnace under the driving of the telescopic rod; a furnace cover seat matched with the furnace inlet is convexly arranged on the base, so that the furnace inlet can be sealed through the furnace cover seat when the base is attached to the lower surface of the heating furnace;
the quartz capsule is arranged in on the bell seat, run through base and bell seat are equipped with inlet channel, and inlet channel's the inner intercommunication quartz capsule, and the top of heating furnace is run through and is equipped with vertical height-adjustable's blast pipe, and the inner of blast pipe is located the top cap directly over, and the inner flaring of blast pipe and adaptation are in order can compress tightly lock and intercommunication top cap when descending in the top of top cap.
2. The titanium dioxide carbo-boiling chlorination simulated reactor as claimed in claim 1, wherein: the wall of the heating furnace is provided with a transparent observation window.
3. The titanium dioxide carbo-boiling chlorination simulated reactor as claimed in claim 1, wherein: the heating furnace is provided with a thermocouple for monitoring the temperature in the furnace.
4. The titanium dioxide carbo-boiling chlorination simulated reactor as claimed in claim 1, wherein: the lower sieve plate and the upper sieve plate are both 400-mesh quartz sand sintered plates.
5. The titanium dioxide carbo-boiling chlorination simulated reactor as claimed in claim 1, wherein: the inner wall of the lower part of the top cover flaring and the top end part of the corresponding quartz tube are frosted surfaces so as to improve the sealing performance during buckling connection.
6. The titanium dioxide carbo-boiling chlorination simulated reactor as claimed in claim 1, wherein: the upper surface of the furnace cover seat is provided with an annular groove which is matched with the edge of the opening part of the lower surface of the bottom end of the quartz tube, and the edge of the opening part of the lower surface of the bottom end of the quartz tube falls into the annular groove.
7. The titanium dioxide carbo-boiling chlorination simulated reactor as claimed in claim 1, wherein: the lower sieve plate has a certain distance to the lower surface of the bottom end of the quartz tube, and the inner space of the quartz tube below the lower sieve plate forms an air inlet preheating uniform distribution area.
8. The titanium dioxide carbo-boiling chlorination simulated reactor as claimed in claim 1, wherein: the exhaust pipe vertically penetrates through the top of the heating furnace, and the wall of the heating furnace on the outer side wall of the exhaust pipe is of a thread structure matched with each other so that the vertical height can be adjusted through rotation.
9. A titanium dioxide carbo-boiling chlorination simulation method, which is carried out based on the titanium dioxide carbo-boiling chlorination simulation reactor of any one of claims 1 to 8; the outer end of the air inlet channel is connected with a tee joint, and the tee joint is also connected with an inert gas source and a chlorine gas source through stop valves respectively; the method comprises the following steps:
1) obtaining a reactor body;
opening the top cover and adding TiO2Adding the particles and petroleum coke particles into a quartz tube, carrying the particles by a lower sieve plate, and buckling a top cover;
2) placing the quartz tube on a furnace cover seat on a base opened through a telescopic rod, and ensuring that the inner end of the air inlet channel is communicated with the quartz tube;
3) heightening the height of the exhaust pipe; then the base is attached to the lower surface of the heating furnace through the telescopic rod, the furnace cover seat closes the inlet of the heating furnace, and the quartz tube is sent into the heating furnace;
4) the height of the exhaust pipe is reduced, and the exhaust pipe is pressed and buckled on the top cover through the inner end of the flaring of the exhaust pipe;
5) heating the heating furnace, and introducing inert gas at the designed gas speed in the heating stage to ensure that TiO in the quartz tube2The mixture of the particles and the petroleum coke particles is fluidized;
6) heating the heating furnace to the temperature required by the reaction and then keeping the temperature; switching the inert gas into chlorine gas, and starting chlorination reaction; when the gas is switched, the stop valve of the inert gas source is gradually closed, and simultaneously, the stop valve of the chlorine gas source is gradually opened to keep the gas speed introduced into the quartz tube unchanged, so that the mixture is prevented from flowing out;
7) after chlorination reaction is carried out according to designed time length, unreacted TiO2Keeping the particles and petroleum coke particles in a quartz tube, cooling, taking out, weighing and calculating the weight loss rate; calculating the chlorination rate after ignition.
10. The titanium dioxide carbonation boiling chlorination simulation method according to claim 9, wherein: in step 1), TiO2The mass ratio of the particles to the petroleum coke particles is 3:1, the particle sizes are respectively 200-mesh and 300-mesh and 120-mesh and 160-mesh, and the particles and the petroleum coke particles are uniformly mixed and then added into a quartz tube;
in the step 5), the designed gas velocity is 0.15-0.25 m/s;
in the step 6), the temperature required by the reaction is 850-1050 ℃; the chlorine gas is evaporated chlorine gas with the concentration of 99 percent;
in step 7), the designed chlorination reaction time is 30 min.
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