CN114534643B - Titanium tetrachloride production system and method - Google Patents
Titanium tetrachloride production system and method Download PDFInfo
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- CN114534643B CN114534643B CN202210256450.1A CN202210256450A CN114534643B CN 114534643 B CN114534643 B CN 114534643B CN 202210256450 A CN202210256450 A CN 202210256450A CN 114534643 B CN114534643 B CN 114534643B
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Abstract
The invention relates to the technical field of titanium tetrachloride production, in particular to a titanium tetrachloride production system and a titanium tetrachloride production method. The system comprises a slag coke powder conveying device, a chlorination device and a titanium tetrachloride collecting device; the slag coke powder conveying device comprises a slag coke powder bin, a high-pressure lock hopper and a high-pressure feeding tank, wherein the bottom of the high-pressure feeding tank is provided with a fluidizing coil pipe; the chlorination device comprises a waste heat boiler, a waste heat boiler circulating pump, a dust filter, a chlorine compressor and a chlorination furnace; a bottom spray combined nozzle is arranged at a top feed inlet of the chlorination furnace, a slag breaker is arranged at a bottom discharge outlet of the chlorination furnace, and a water-cooled coil pipe is arranged in an interlayer of a gasification chamber of the chlorination furnace; the titanium tetrachloride collecting device comprises a slag lock hopper, a Venturi tube, a washing tower, a crude titanium tetrachloride collecting tank and a cooler, so that the titanium tetrachloride production method does not have bed collapse and blockage, has low requirements on the impurity content of raw materials, but has quick reaction, and improves the conversion rate of titanium-rich materials or high-titanium slag by more than 5 percent compared with a boiling method.
Description
Technical Field
The invention relates to the technical field of titanium tetrachloride production, in particular to a titanium tetrachloride production system and a titanium tetrachloride production method.
Background
The existing methods for producing titanium tetrachloride mainly comprise a boiling method and a molten salt method, and although the molten salt method has low requirements on raw materials, the operation environment is severe, the energy consumption of the device is high, and the large-scale production is difficult, so the method belongs to the lagging elimination process.
The boiling method is friendly to the operating environment and relatively low in energy consumption, but has the following problems:
firstly, the boiling method has extremely strict requirements on the content of impurities in titanium-rich ore or high-titanium slag, and especially has strict requirements on the content of CaO and MgO, wherein the domestic YS/T298 standard requires that the content of CaO is less than 0.1wt%, the content of MgO is less than 1.45wt%, and the content of CaO and MgO is not more than 1.5wt%, because CaCl2 (boiling point 1900 ℃, melting point 731 ℃) and MgCl2 (boiling point 1412 ℃, melting point 714 ℃) are generated after the reaction of CaO and MgO and chlorine gas and are in a liquid state in the boiling furnace, the CaCl2 and the MgCl2 are accumulated along with the reaction and are difficult to be taken out of the chlorination furnace, and the CaCl2 form agglomerates in a bed layer and powdery raw materials, and along with the growth of the agglomerates, the sieve plate of the chlorination furnace is quickly blocked, so that production fluctuation is caused by light persons, and the bed collapse is caused by heavy persons, and the production cannot be continued.
Secondly, as only a small amount of SiCl4 is generated from SiO2 in the raw materials, most of the SiO2 cannot be gasified and is deposited at the bottom of the bed layer, and with the accumulation of the charging materials, the SiO2 is more and more in the chlorination furnace, and finally the sieve plate is blocked and the chlorination efficiency is greatly reduced, so that the content of the SiO2 in the raw materials is generally required to be controlled below 2 wt%.
Thirdly, because the chlorination furnace is operated at high temperature, a large amount of heat is released in the reaction process, and chlorine gas is very strong in corrosivity at high temperature, so that a thick-lined heat-insulating brick and a corrosion-resistant wear-resistant brick are required in the chlorination furnace, in order to protect the outer shell of the chlorination furnace, outer wall water spraying is usually adopted to remove excessive heat, the service life of the lining brick in the chlorination furnace is short and is usually less than one year due to the severe environment in the furnace, the cost for replacing the lining brick is huge and the consumed time is long, so that the furnace preparation must be considered, which is one of the reasons that the investment and the operation cost of a chlorination process titanium white or sponge titanium factory are high, in order to prevent a collapsing bed and blocking a sieve plate, nitrogen gas or air quantity is periodically increased to blow accumulated SiO2 and agglomerates out of the furnace, a large amount of raw materials are not chlorinated, and huge waste is caused.
Fourthly, because the existing chlorination operation is usually operated under the pressure of 0.2MpaG to 0.4MpaG, the pressure is lower, the diameter of the chlorination furnace must be enlarged or more chlorination furnaces must be operated in parallel to obtain high-yield titanium tetrachloride, the external diameter of the chlorination furnace in China reaches more than 7m for a 6 ten thousand ton/year chlorination process titanium white device, and if the capacity of the device continues to increase, more chlorination furnaces must be considered for parallel production. The investment and maintenance costs increase.
Disclosure of Invention
Aiming at the problems in the background art, the invention provides a titanium tetrachloride production system, which adopts an entrained flow bed technology and utilizes the 'along gravity' operation to overcome a series of problems caused by the 'anti-gravity' operation of the existing boiling chlorination. The chlorination operation pressure is improved, and the equipment size is greatly reduced. The slag-resistant technology overcomes the problems of equipment corrosion and abrasion by using slag, and a coil pipe water-cooled wall structure is adopted, so that the chlorination furnace is protected from being damaged by overtemperature, and meanwhile, 0.7MPaG low-pressure steam can be byproduct for the rectification process. It is important that the contents of impurities such as CaO and MgO in the raw materials are basically not required. The chlorination furnace does not need to be provided with a furnace, so that the investment, maintenance, operation and production cost is greatly reduced.
The specific technical scheme is as follows: a titanium tetrachloride production system, which is characterized in that,
comprises a slag coke powder conveying device, a chlorination device and a titanium tetrachloride collecting device;
the slag and coke powder conveying device comprises a slag and coke powder bin 3, a high-pressure lock hopper 4 and a high-pressure feeding tank 5 which are sequentially arranged from high to low, a fluidization coil pipe is arranged at the bottom of the high-pressure feeding tank 5, the tops of the slag and coke powder bin 3, the high-pressure lock hopper 4 and the high-pressure feeding tank 5 are respectively communicated with a dust removal and emptying pipe through a bag filter, and the upper parts of the high-pressure lock hopper 4 and the high-pressure feeding tank 5 are communicated with a high-pressure nitrogen pipe;
the top inlet of the slag-coke powder bin 3 is communicated with a raw material pipeline, the bottom outlet of the slag-coke powder bin 3 is communicated with the top inlet of the high-pressure lock hopper 4 through a valve pipeline, and the bottom outlet of the high-pressure lock hopper 4 is communicated with the top inlet of the high-pressure charging tank 5 through a valve pipeline;
the chlorination device comprises a waste heat boiler 6, a waste heat boiler circulating pump 7, a dust filter 1, a chlorine compressor 2 and a chlorination furnace 9;
a bottom spray combined nozzle 8 is arranged at a top feed inlet of the chlorination furnace 9, a slag breaker 10 is arranged at a bottom discharge outlet of the chlorination furnace 9, and a water-cooling coil pipe is arranged in an interlayer of a gasification chamber of the chlorination furnace 9;
a cooling coil is arranged at the bottom in the waste heat boiler 6, a steam drum is arranged at the top, and the cooling coil is communicated with an external demineralized water pipeline;
the bottom outlet pipeline of the high-pressure charging tank 5 is communicated with a feeding hole of a downward-spraying combined type nozzle 8, the cooling coil water inlet pipeline of the waste heat boiler 6 is communicated with the cooling coil water outlet of the downward-spraying combined type nozzle 8 and is communicated with the water cooling coil water outlet in the interlayer of the gasification chamber of the chlorination furnace 9, the cooling coil water outlet of the waste heat boiler 6 is communicated with the cooling coil water inlet of the downward-spraying combined type nozzle 8 through the circulating pump 7 pipeline of the waste heat boiler and is communicated with the water cooling coil water inlet in the interlayer of the gasification chamber of the chlorination furnace 9, and the water inlet pipeline at the bottom of the shell pass of the waste heat boiler 6 is communicated with an external boiler water feeding pipeline;
an inlet of the dust filter 1 is communicated with a chlorine outlet of the bag filter at the oxidation section through a pipeline, an outlet of the dust filter is communicated with an inlet of the chlorine compressor 2, and an outlet of the chlorine compressor 2 is communicated with a corresponding inlet of the downward spraying combined type nozzle 8;
the titanium tetrachloride collecting device comprises a slag lock hopper 11, a Venturi tube 12, a washing tower 13, a crude titanium tetrachloride collecting tank 14 and a cooler 16; the top outlet of the washing tower 13 is communicated with the condensation recovery process of the crude titanium tetrachloride through a pipeline, the upper spray pipe of the washing tower 13 is communicated with the crude titanium tetrachloride outlet of the cooler 16 through a pipeline,
the chilling chamber at the lower part of the chlorination furnace 9 is communicated with the inlet section of a Venturi tube 12 through a pipeline,
the bottom outlet of the slag breaker 10 is communicated with the top inlet of a slag lock hopper 11 through a valve pipeline, the bottom of the slag lock hopper 11 is provided with a slag discharge port, the upper part of the slag lock hopper 11 is communicated with a high-pressure nitrogen pipe, the top outlet of the slag lock hopper 11 is communicated with the lower part of a washing tower 13 through a valve pipeline, the bottom pipeline of the washing tower 13 is communicated with the inlet of a crude titanium tetrachloride collecting tank 14, the outlet of the crude titanium tetrachloride collecting tank 14 is divided into three paths after passing through a crude titanium tetrachloride pump 15 and a heat exchanger 16 in sequence, one pipeline is communicated with a main spray inlet of a Venturi tube 12, the other pipeline is communicated with a nozzle above a chilling chamber of a chlorination furnace 9, and the other pipeline is communicated with a spray pipe interface at the upper part of the washing tower 13; the outlet of the crude titanium tetrachloride pump 15 is communicated with a refining process of crude titanium tetrachloride through a pipeline;
the diffusion section of the venturi tube 12 is in pipe communication with the lower portion of the scrubber 13.
Further, a gasification chamber at the upper part of the chlorination furnace 9 is made of Yingkang materials and is lined with a high-alumina brick layer;
the cooling coil is made of Yingkang materials;
the chilling chamber at the lower part of the chlorination furnace 9 is lined with a heat-insulating brick layer and a high-alumina brick layer, and the high-alumina brick layer completely covers the heat-insulating brick layer;
the design pressure of an inner cylinder of the chlorination furnace 9 is 1.5-1.8 MPaG, the design temperature is 1100-1300 ℃, and the design temperature of an outer shell is 300-350 ℃.
Further, a steam outlet of the waste heat boiler 6 is sent to the rectification process of the crude titanium tetrachloride through a pipeline.
Furthermore, a nozzle above a chilling chamber of the chlorination furnace 9 is communicated with a rectification process of crude titanium tetrachloride through a pipeline, and vanadium-removing slurry refined from the crude titanium tetrachloride is introduced into the chilling chamber at the lower part of the chlorination furnace 9 and is used for recovering the crude titanium tetrachloride in the slurry.
Further, the lower spraying combined type nozzle 8 is communicated with a low-pressure nitrogen pipeline, and nitrogen is introduced under the pressure of 0.5 MPaG-0.8 MPaG, so that the internal gas of the chlorination furnace 9 is replaced and cooled when the chlorination furnace is started and stopped.
The invention also comprises a method for producing titanium tetrachloride by using the titanium tetrachloride production system,
the method comprises the following steps:
step (1): adding the materials in the raw materials,
the top import of slag coke powder feed bin 3 lets in the raw materials through the raw materials pipeline, and the raw materials are high titanium slag and petroleum coke of misce bene, and the mass ratio of high titanium slag and petroleum coke is 4:1 to 4;
firstly, closing a communication valve between a high-pressure lock hopper 4 and a high-pressure charging tank 5 and a high-pressure nitrogen inlet valve of the high-pressure lock hopper 4, opening an outlet valve of a bag filter above the high-pressure lock hopper 4 to ensure that the high-pressure lock hopper 4 and a slag coke powder bin 3 are both at normal pressure, then opening the communication valve between the high-pressure lock hopper 4 and the slag coke powder bin 3, and enabling slag coke powder stored in the slag coke powder bin 3 to fall into the high-pressure lock hopper 4 under the action of gravity;
when the slag coke in the high-pressure lock hopper 4 reaches a set material level, closing a communication valve between the high-pressure lock hopper 4 and the slag coke powder bin 3 and a bag filter outlet valve above the high-pressure lock hopper 4, then opening a high-pressure nitrogen inlet valve of the high-pressure lock hopper 4, when the internal pressure of the high-pressure lock hopper 4 reaches the same as the internal pressure of the high-pressure charging tank 5, then opening a communication valve between the high-pressure lock hopper 4 and the high-pressure charging tank 5, allowing the slag coke powder stored in the high-pressure lock hopper 4 to fall into the high-pressure charging tank 5 under the action of gravity, after discharging, closing the communication valve between the high-pressure lock hopper 4 and the high-pressure charging tank 5 and the high-pressure nitrogen inlet valve of the high-pressure lock hopper 4, opening a bag filter outlet valve above the high-pressure lock hopper 4, releasing the pressure of the high-pressure lock hopper 4, and then entering the next round of operation cycle;
step (2): the chlorination reaction is carried out, and the reaction condition,
when the chlorination furnace 9 is started, introducing natural gas and oxygen into the downward spraying combined type nozzle 8, wherein the molar ratio of the natural gas to the oxygen is 1;
when the bag filter at the oxidation section returns chlorine, the chlorine is dedusted by the dust filter 1 and pressurized to 0.9MPaG to 1.2MpaG by the chlorine compressor 2, liquid chlorine is introduced into the combined burner 8, and the flow of oxygen is regulated so that the operation temperature of the chlorination furnace 9 is maintained between 1000 ℃ and 1200 ℃, and the operation pressure is maintained between 0.9MpaG and 1.2MpaG;
when the temperature in the chlorination furnace 9 reaches 900 ℃, starting a circulating pump 7 of the waste heat boiler, and timely transferring the reaction heat of the lower spraying combined nozzle 8 and a gasification chamber at the upper part of the chlorination furnace 9 out to the waste heat boiler 6 for producing steam as a byproduct through desalted water closed-loop circulation;
and (3): the slag is discharged,
opening a crude titanium tetrachloride pump 15, introducing crude titanium tetrachloride into a chilling chamber at the lower part of a chlorination furnace 9, chilling a high-temperature product of chlorination reaction, unreacted slag coke and the crude titanium tetrachloride, rapidly cooling to 150-170 ℃, enabling more than 98wt% of chloride and unreacted slag coke to become solids and fall below the chilling chamber, crushing the chloride and the unreacted slag coke by a slag breaker 10 and then fall into a slag lock hopper 11, circularly discharging slag from the slag lock hopper 11, and after the slag lock hopper 11 is emptied, pressurizing the slag lock hopper 11 again by high-pressure nitrogen and connecting the slag breaker 10;
and (4): the titanium tetrachloride is collected, and then the titanium tetrachloride is collected,
the temperature of the dust-containing titanium tetrachloride gas discharged from a chilling chamber at the lower part of the chlorination furnace 9 is 150-170 ℃, the pressure is 0.9MpaG to 1.2MpaG, the dust-containing titanium tetrachloride gas is contacted with the crude titanium tetrachloride liquid from the heat exchanger 16 through the venturi 12, the dust-containing titanium tetrachloride gas is wetted and cooled and then enters the washing tower 13, the contact temperature of the uncondensed crude titanium tetrachloride gas in the washing tower 13 and the crude titanium tetrachloride liquid from the heat exchanger 16 is reduced to 100-125 ℃, the uncondensed gas phase goes to a condensation recovery process through the top of the washing tower 13, and the liquid phase crude titanium tetrachloride at the bottom of the washing tower 13 flows into the crude titanium tetrachloride collecting tank 14 under the action of gravity.
The beneficial technical effects of the invention are as follows:
1. the invention adopts the entrained flow bed technology, utilizes the entrained flow bed chlorination furnace to produce the titanium tetrachloride, the raw materials are subjected to violent reaction similar to combustion in the downward-spraying combined nozzle, the temperature is over 1000 ℃, the pressure is over 0.9MpaG, the reaction is rapid, and the conversion rate of the titanium-rich material or the high-titanium slag is improved by over 5 percent relative to a boiling method.
2. The invention adopts reactants such as chlorine, slag coke and the like to perform the downward spraying combustion reaction under the condition of 'along gravity' in the downward spraying combined nozzle, thereby overcoming the problem which is difficult to overcome and is caused by the prior 'anti-gravity' operation of boiling chlorination (the slag coke needs to float in ascending air flow), such as the strict requirement of the boiling method on the content of calcium, magnesium and the like in the raw materials;
meanwhile, bed collapse and blockage do not occur, the requirement on the impurity content of the raw materials is not high, and even the raw materials with the TiO2 content of more than 70wt% can be adopted for production, so that the cost of the raw materials is greatly reduced, and the raw materials are wider in source and easy to purchase.
3. According to the chlorination furnace, the cooling coil is wound on the outer wall of the inner cylinder of the gasification chamber at the upper part of the chlorination furnace, the cooling coil and the cooling coil of the waste heat boiler form closed circulation through the circulating pump of the waste heat boiler, and the waste heat boiler produces 0.7MpaG pressure steam for a refining process.
4. The invention adopts the principle of slag resistance, in the chlorination furnace gasification chamber, chlorides generated by reaction at high temperature are coated on the inner wall of the gasification chamber with lower temperature in a molten state, and stronger reactant airflow simultaneously scours the inner wall of the gasification chamber, so that the thickness of the slag coated on the inner wall of the gasification chamber forms dynamic balance, the slag effectively protects high-alumina bricks on the inner wall of the gasification chamber, and the furnace preparation does not need to be considered like a boiling method, thereby greatly saving the investment and the maintenance cost.
5. The invention adopts higher pressure to produce titanium tetrachloride, has the same production capacity, smaller chlorination furnace size, quiet and stable operation and lighter weight, and the existing low-pressure boiling chlorination furnace has large diameter, heavy weight and vibration in the production process, thereby not only having large equipment investment, but also having higher requirements on building structures.
Drawings
Fig. 1 is a system diagram of a titanium tetrachloride production system according to the present invention.
Wherein: the device comprises a dust filter 1, a chlorine compressor 2, a slag coke powder bin 3, a high-pressure lock hopper 4, a high-pressure feeding tank 5, a waste heat boiler 6, a waste heat boiler circulating pump 7, a downward spraying combined nozzle 8, a chlorination furnace 9, a slag breaking machine 10, a slag lock hopper 11, a venturi 12, a washing tower 13, a crude titanium tetrachloride collecting tank 14, a crude titanium tetrachloride pump 15 and a cooler 16.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
See fig. 1, a titanium tetrachloride production system,
comprises a slag coke powder conveying device, a chlorination device and a titanium tetrachloride collecting device;
the slag and coke powder conveying device comprises a slag and coke powder bin 3, a high-pressure lock hopper 4 and a high-pressure feeding tank 5 which are sequentially arranged from high to low, a fluidization coil pipe is arranged at the bottom of the high-pressure feeding tank 5, the tops of the slag and coke powder bin 3, the high-pressure lock hopper 4 and the high-pressure feeding tank 5 are respectively communicated with a dust removal and emptying pipe through a bag filter, and the upper parts of the high-pressure lock hopper 4 and the high-pressure feeding tank 5 are communicated with a high-pressure nitrogen pipe;
the top inlet of the slag coke powder bin 3 is communicated with a raw material pipeline, the bottom outlet of the slag coke powder bin 3 is communicated with the top inlet of the high-pressure lock hopper 4 through a valve pipeline, and the bottom outlet of the high-pressure lock hopper 4 is communicated with the top inlet of the high-pressure feeding tank 5 through a valve pipeline;
the chlorination device comprises a waste heat boiler 6, a waste heat boiler circulating pump 7, a dust filter 1, a chlorine compressor 2 and a chlorination furnace 9;
a bottom spray combined nozzle 8 is arranged at a top feed inlet of the chlorination furnace 9, a slag breaker 10 is arranged at a bottom discharge outlet of the chlorination furnace 9, and a water-cooling coil pipe is arranged in an interlayer of a gasification chamber of the chlorination furnace 9;
a cooling coil is arranged at the bottom in the waste heat boiler 6, a steam drum is arranged at the top, and the cooling coil is communicated with an external demineralized water pipeline;
the bottom outlet pipeline of the high-pressure feeding tank 5 is communicated with a feeding hole of a downward-spraying combined type nozzle 8, the pipeline of a cooling coil water inlet of the waste heat boiler 6 is communicated with a cooling coil water outlet of the downward-spraying combined type nozzle 8 and is simultaneously communicated with a water cooling coil water outlet in a gasification chamber interlayer of the chlorination furnace 9, the water outlet of the cooling coil of the waste heat boiler 6 is communicated with a cooling coil water inlet of the downward-spraying combined type nozzle 8 through a circulating pump 7 pipeline of the waste heat boiler and is simultaneously communicated with a water cooling coil water inlet in the gasification chamber interlayer of the chlorination furnace 9, and the pipeline of a water inlet at the bottom of a shell pass of the waste heat boiler 6 is communicated with an external boiler water feeding pipeline;
an inlet of the dust filter 1 is communicated with a chlorine outlet of the bag filter at the oxidation section through a pipeline, an outlet of the dust filter is communicated with an inlet of the chlorine compressor 2, and an outlet of the chlorine compressor 2 is communicated with a corresponding inlet of the downward spraying combined type nozzle 8;
the titanium tetrachloride collecting device comprises a slag lock hopper 11, a venturi tube 12, a washing tower 13, a crude titanium tetrachloride collecting tank 14 and a cooler 16; the top outlet of the washing tower 13 is communicated with the condensation recovery process of the crude titanium tetrachloride through a pipeline, the upper spray pipe of the washing tower 13 is communicated with the condensation process of the crude titanium tetrachloride through a pipeline,
the chilling chamber at the lower part of the chlorination furnace 9 is communicated with the inlet section of the venturi tube 12 through a pipeline,
the bottom outlet of the slag breaker 10 is communicated with the top inlet of a slag lock hopper 11 through a valve pipeline, the bottom of the slag lock hopper 11 is provided with a slag discharge port, the upper part of the slag lock hopper 11 is communicated with a high-pressure nitrogen pipe, the top outlet of the slag lock hopper 11 is communicated with the lower part of a washing tower 13 through a valve pipeline, the bottom pipeline of the washing tower 13 is communicated with the inlet of a crude titanium tetrachloride collecting tank 14, the outlet of the crude titanium tetrachloride collecting tank 14 is divided into three paths after passing through a crude titanium tetrachloride pump 15 and a heat exchanger 16 in sequence, one pipeline is communicated with a main spray inlet of a Venturi tube 12, the other pipeline is communicated with a nozzle above a chilling chamber of a chlorination furnace 9, and the other pipeline is communicated with a spray pipe interface at the upper part of the washing tower 13; the outlet of the crude titanium tetrachloride pump 15 is communicated with a refining process of crude titanium tetrachloride through a pipeline;
the diffusion section of the venturi tube 12 is in pipe communication with the lower portion of the scrubber 13. The gasification chamber at the upper part of the chlorination furnace 9 is made of Yingkang material and is lined with a high-alumina brick layer;
the cooling coil is made of Yingkang materials;
the chilling chamber at the lower part of the chlorination furnace 9 is lined with a heat-insulating brick layer and a high-alumina brick layer, and the high-alumina brick layer completely covers the heat-insulating brick layer;
the design pressure of an inner cylinder of the chlorination furnace 9 is 1.5-1.8 MPaG, the design temperature is 1100-1300 ℃, and the design temperature of an outer shell is 300-350 ℃.
And a steam outlet of the waste heat boiler 6 is sent to a rectification process of the crude titanium tetrachloride through a pipeline.
A nozzle above the chilling chamber of the chlorination furnace 9 is communicated with a rectification process of crude titanium tetrachloride through a pipeline, and vanadium-removing slurry refined from the crude titanium tetrachloride is introduced into the chilling chamber at the lower part of the chlorination furnace 9 and is used for recovering the crude titanium tetrachloride in the slurry.
The lower spraying combined type nozzle 8 is communicated with a low-pressure nitrogen pipeline, the pressure of the introduced nitrogen is 0.5 MPaG-0.8 MPaG, and the lower spraying combined type nozzle is used for replacing and cooling the gas in the chlorination furnace 9 when the chlorination furnace is started and stopped.
Example 2
A method for producing titanium tetrachloride in a titanium tetrachloride production system of example 1,
the method comprises the following steps:
step (1): adding the materials in the raw materials,
the top import of slag coke powder feed bin 3 lets in the raw materials through the raw materials pipeline, and the raw materials are high titanium slag and petroleum coke of misce bene, and the mass ratio of high titanium slag and petroleum coke is 4:1 to 4;
firstly, closing a communication valve between a high-pressure lock hopper 4 and a high-pressure charging tank 5 and a high-pressure nitrogen inlet valve of the high-pressure lock hopper 4, opening an outlet valve of a bag filter above the high-pressure lock hopper 4 to ensure that the high-pressure lock hopper 4 and a slag coke powder bin 3 are both at normal pressure, then opening the communication valve between the high-pressure lock hopper 4 and the slag coke powder bin 3, and allowing slag coke powder stored in the slag coke powder bin 3 to fall into the high-pressure lock hopper 4 under the action of gravity;
when the slag coke in the high-pressure lock hopper 4 reaches a set material level, closing a communication valve between the high-pressure lock hopper 4 and the slag coke powder bin 3 and a bag filter outlet valve above the high-pressure lock hopper 4, then opening a high-pressure nitrogen inlet valve of the high-pressure lock hopper 4, when the internal pressure of the high-pressure lock hopper 4 reaches the same as the internal pressure of the high-pressure charging tank 5, then opening a communication valve between the high-pressure lock hopper 4 and the high-pressure charging tank 5, allowing the slag coke powder stored in the high-pressure lock hopper 4 to fall into the high-pressure charging tank 5 under the action of gravity, after discharging, closing the communication valve between the high-pressure lock hopper 4 and the high-pressure charging tank 5 and the high-pressure nitrogen inlet valve of the high-pressure lock hopper 4, opening a bag filter outlet valve above the high-pressure lock hopper 4, releasing the pressure of the high-pressure lock hopper 4, and then entering the next round of operation cycle;
step (2): the chlorination reaction is carried out, and the reaction condition,
when the chlorination furnace 9 is started, introducing natural gas and oxygen into the downward spraying combined type nozzle 8, wherein the molar ratio of the natural gas to the oxygen is 1;
when the chlorine gas returns to the bag filter at the oxidation section, the chlorine gas is dedusted by the dust filter 1 and is pressurized to 0.9MPaG to 1.2MpaG by the chlorine gas compressor 2, liquid chlorine is introduced into the combined burner 8, the oxygen flow is regulated, the operation temperature of the chlorination furnace 9 is maintained between 1000 ℃ and 1200 ℃, and the operation pressure is maintained between 0.9MpaG and 1.2MpaG;
when the temperature in the chlorination furnace 9 reaches 900 ℃, starting a circulating pump 7 of the waste heat boiler, and timely transferring the reaction heat of the lower spraying combined nozzle 8 and a gasification chamber at the upper part of the chlorination furnace 9 out to the waste heat boiler 6 for producing steam as a byproduct through closed circulation of desalted water;
the chlorination reaction is as follows:
main reaction:
TiOR 2 R(S)＋ 2ClR 2 (g) ＋ 2C R(S) = TiClR 4 (g) R ＋ 2CO (g)
TiOR 2 R(S)＋ 2ClR 2 (g) ＋ C R(S) = TiClR 4 (g) R ＋ 2CO 2 (g)
the main side reaction:
CaO + Cl 2 + C= CaCl 2 + CO
MnO+ Cl 2 + C= MnCl 2 + CO
MgO+ Cl 2 + C= MgCl 2 + CO
Fe 2 O 3 + 3Cl 2 + 3C=2FeCl 3 + 3CO
FeO+ Cl 2 + C= FeCl 2 + CO
Al 2 O 3 + 3Cl 2 + 3C=2AlCl 3 + 3CO
SiO 2 + 2Cl 2 +2C= SiCl 4 + 2CO
C+O 2 =CO 2
CO 2 +C=2CO
and (3): the slag is discharged,
opening a crude titanium tetrachloride pump 15, introducing crude titanium tetrachloride into a chilling chamber at the lower part of a chlorination furnace 9, chilling a high-temperature product of chlorination reaction, unreacted slag coke and the crude titanium tetrachloride, rapidly cooling to 150-170 ℃, enabling more than 98wt% of chloride and unreacted slag coke to become solids and fall below the chilling chamber, crushing the chloride and the unreacted slag coke by a slag breaker 10 and then fall into a slag lock hopper 11, circularly discharging slag from the slag lock hopper 11, and after the slag lock hopper 11 is emptied, pressurizing the slag lock hopper 11 again by high-pressure nitrogen and connecting the slag breaker 10;
and (4): the titanium tetrachloride is collected, and then the titanium tetrachloride is collected,
the temperature of the dust-containing titanium tetrachloride gas discharged from a chilling chamber at the lower part of the chlorination furnace 9 is 150-170 ℃, the pressure is 0.9MpaG-1.2MpaG, the dust-containing titanium tetrachloride gas is contacted with crude titanium tetrachloride liquid from a heat exchanger 16 through a Venturi 12, the dust-containing titanium tetrachloride gas is wetted and cooled and then enters a washing tower 13, the spraying contact temperature of the uncondensed crude titanium tetrachloride gas in the washing tower 13 and the crude titanium tetrachloride from the heat exchanger 16 is reduced to 100-125 ℃, the uncondensed gas phase goes to a condensation recovery process through the top of the washing tower 13, and the liquid phase crude titanium tetrachloride at the bottom of the washing tower 13 flows into a crude titanium tetrachloride collecting tank 14 under the action of gravity.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (6)
1. A titanium tetrachloride production system is characterized in that:
comprises a slag coke powder conveying device, a chlorination device and a titanium tetrachloride collecting device;
the slag and coke powder conveying device comprises a slag and coke powder bin (3), a high-pressure lock hopper (4) and a high-pressure feeding tank (5) which are sequentially arranged from high to low, wherein a fluidization coil pipe is arranged at the bottom of the high-pressure feeding tank (5), the tops of the slag and coke powder bin (3), the high-pressure lock hopper (4) and the high-pressure feeding tank (5) are respectively communicated with a dust removal and emptying pipe through a bag filter, and the upper parts of the high-pressure lock hopper (4) and the high-pressure feeding tank (5) are communicated with a high-pressure nitrogen pipe;
the top inlet of the slag-coke powder bin (3) is communicated with a raw material pipeline, the bottom outlet of the slag-coke powder bin (3) is communicated with the top inlet of the high-pressure lock hopper (4) through a valve pipeline, and the bottom outlet of the high-pressure lock hopper (4) is communicated with the top inlet of the high-pressure charging tank (5) through a valve pipeline;
the chlorination device comprises a waste heat boiler (6), a waste heat boiler circulating pump (7), a dust filter (1), a chlorine compressor (2) and a chlorination furnace (9);
a lower spraying combined type nozzle (8) is arranged at a top feed inlet of the chlorination furnace (9), a slag breaking machine (10) is arranged at a bottom discharge outlet of the chlorination furnace (9), and a water cooling coil pipe is arranged in an interlayer of a gasification chamber of the chlorination furnace (9);
a cooling coil is arranged at the bottom in the waste heat boiler (6), a steam drum is arranged at the top, and the cooling coil is communicated with an external demineralized water pipeline;
the bottom outlet pipeline of the high-pressure feeding tank (5) is communicated with a feeding hole of a downward-spraying combined type nozzle (8), a cooling coil water inlet pipeline of the waste heat boiler (6) is communicated with a cooling coil water outlet of the downward-spraying combined type nozzle (8) and is simultaneously communicated with a water cooling coil water outlet in a gasification chamber interlayer of the chlorination furnace (9), the cooling coil water outlet of the waste heat boiler (6) is communicated with a cooling coil water inlet of the downward-spraying combined type nozzle (8) through a waste heat boiler circulating pump (7) pipeline and is simultaneously communicated with a water cooling coil water inlet in the gasification chamber interlayer of the chlorination furnace (9), and a water inlet pipeline at the bottom of a shell pass of the waste heat boiler (6) is communicated with an external boiler water feeding pipeline;
an inlet of the dust filter (1) is communicated with a chlorine outlet of the bag filter at the oxidation section through a pipeline, an outlet of the dust filter is communicated with an inlet of a chlorine compressor (2), and an outlet of the chlorine compressor (2) is communicated with a corresponding inlet of a downward spraying combined type nozzle (8);
the titanium tetrachloride collecting device comprises a slag lock hopper (11), a Venturi tube (12), a washing tower (13), a crude titanium tetrachloride collecting tank (14) and a cooler (16); the top outlet of the washing tower (13) is communicated with a condensation recovery process of crude titanium tetrachloride through a pipeline, a chilling chamber at the lower part of the chlorination furnace (9) is communicated with the inlet section of a Venturi tube (12) through a pipeline,
the bottom outlet of the slag breaker (10) is communicated with the top inlet of a slag lock hopper (11) through a valve pipeline, the bottom of the slag lock hopper (11) is provided with a slag discharge port, the upper part of the slag lock hopper (11) is communicated with a high-pressure nitrogen pipe, the top outlet of the slag lock hopper (11) is communicated with the lower part of a washing tower (13) through a valve pipeline, the bottom pipeline of the washing tower (13) is communicated with the inlet of a crude titanium tetrachloride collecting tank (14), the outlet of the crude titanium tetrachloride collecting tank (14) is divided into three paths after passing through a crude titanium tetrachloride pump (15) and a heat exchanger (16) in sequence, one path of pipeline is communicated with a main spray inlet of a Venturi tube (12), the other path of pipeline is communicated with a nozzle above a chilling chamber of a chlorination furnace (9), and the other path of pipeline is communicated with a spray pipe interface at the upper part of the washing tower (13); the outlet of the crude titanium tetrachloride pump (15) is communicated with a refining process of crude titanium tetrachloride through a pipeline;
the diffusion section pipeline of the Venturi tube (12) is communicated with the lower part of the washing tower (13).
2. The titanium tetrachloride production system according to claim 1, wherein: the gasification chamber at the upper part of the chlorination furnace (9) is made of Yingkang material and is lined with a high-alumina brick layer;
the cooling coil is made of Yingkang materials;
the chilling chamber at the lower part of the chlorination furnace (9) is lined with a heat-insulating brick layer and a high-alumina brick layer, and the high-alumina brick layer completely covers the heat-insulating brick layer;
the pressure of the inner cylinder design of the chlorination furnace (9) is 1.5-1.8 MPaG, the design temperature is 1100-1300 ℃, and the design temperature of the outer shell is 300-350 ℃.
3. The titanium tetrachloride production system according to claim 1, wherein: and a steam outlet of the waste heat boiler (6) is sent to the rectification process of the crude titanium tetrachloride through a pipeline.
4. The titanium tetrachloride production system according to claim 1, wherein: a nozzle above a chilling chamber of the chlorination furnace (9) is communicated with a rectification process of crude titanium tetrachloride through a pipeline, and vanadium-removing slurry refined from the crude titanium tetrachloride is introduced into the chilling chamber at the lower part of the chlorination furnace (9) and is used for recovering the crude titanium tetrachloride in the slurry.
5. The titanium tetrachloride production system according to claim 1, wherein: the lower spraying combined type nozzle (8) is communicated with a low-pressure nitrogen pipeline, and the pressure of introduced nitrogen is 0.5 MPaG-0.8 MPaG, so that the gas in the chlorination furnace (9) is replaced and cooled when the chlorination furnace is started and stopped.
6. The method of producing titanium tetrachloride in a titanium tetrachloride production system according to claim 1, wherein:
the method comprises the following steps:
step (1): the materials are added in the raw materials,
the top import of sediment coke powder feed bin (3) lets in the raw materials through the raw materials pipeline, and the raw materials are the high titanium sediment and the petroleum coke of misce bene, and the mass ratio of high titanium sediment and petroleum coke is 4:1 to 4;
firstly, closing a communication valve between a high-pressure lock hopper (4) and a high-pressure charging tank (5) and a high-pressure nitrogen inlet valve of the high-pressure lock hopper (4), opening an outlet valve of a bag filter above the high-pressure lock hopper (4) to ensure that the high-pressure lock hopper (4) and a slag coke powder bin (3) are both at normal pressure, then opening the communication valve between the high-pressure lock hopper (4) and the slag coke powder bin (3), and allowing slag coke powder stored in the slag coke powder bin (3) to fall into the high-pressure lock hopper (4) under the action of gravity;
when the slag coke in the high-pressure lock hopper (4) reaches a set material level, closing a communication valve between the high-pressure lock hopper (4) and the slag coke powder bin (3) and a bag filter outlet valve above the high-pressure lock hopper (4), then opening a high-pressure nitrogen inlet valve of the high-pressure lock hopper (4), when the internal pressure of the high-pressure lock hopper (4) reaches the same as the internal pressure of the high-pressure charging tank (5), opening a communication valve between the high-pressure lock hopper (4) and the high-pressure charging tank (5), allowing the slag coke powder stored in the high-pressure lock hopper (4) to fall into the high-pressure charging tank (5) under the action of gravity, after unloading, closing a communication valve between the high-pressure lock hopper (4) and the high-pressure charging tank (5) and the high-pressure nitrogen inlet valve of the high-pressure lock hopper (4), opening the bag filter outlet valve above the high-pressure lock hopper (4), releasing the pressure lock hopper (4), and then entering the next round of operation cycle;
step (2): the chlorination reaction is carried out, and the reaction condition,
when the chlorination furnace (9) is opened, introducing natural gas and oxygen into the downward spraying combined type nozzle (8), wherein the molar ratio of the natural gas to the oxygen is 1;
when the bag filter at the oxidation section returns chlorine, the chlorine is dedusted by the dust filter (1) and pressurized to 0.9MPaG to 1.2MpaG by the chlorine compressor (2), liquid chlorine is introduced into the downward spraying combined nozzle (8), and the flow of oxygen is adjusted, so that the operation temperature of the chlorination furnace (9) is maintained between 1000 ℃ and 1200 ℃, and the operation pressure is maintained between 0.9MpaG to 1.2MpaG;
when the temperature in the chlorination furnace (9) reaches 900 ℃, starting a circulating pump (7) of the waste heat boiler, and timely transferring reaction heat of a lower spraying combined type nozzle (8) and a gasification chamber at the upper part of the chlorination furnace (9) out to the waste heat boiler (6) through closed circulation of demineralized water to produce steam as a byproduct;
and (3): the slag is discharged,
the method comprises the following steps of starting a crude titanium tetrachloride pump (15), introducing crude titanium tetrachloride into a chilling chamber at the lower part of a chlorination furnace (9), chilling a high-temperature product of chlorination reaction, unreacted slag coke and the crude titanium tetrachloride, rapidly cooling to 150-170 ℃, changing more than 98wt% of chloride and the unreacted slag coke into solids, allowing the solids to fall below the chilling chamber, crushing the chloride and the unreacted slag coke by a slag breaker (10), allowing the crushed chloride and the unreacted slag coke to fall into a slag lock hopper (11), circularly discharging slag by the slag lock hopper (11), and pressurizing the slag lock hopper (11) by high-pressure nitrogen again after the slag lock hopper (11) is emptied and connecting the slag lock hopper (11) with the slag breaker (10);
and (4): the titanium tetrachloride is collected, and then the titanium tetrachloride is collected,
the temperature of dust-containing titanium tetrachloride gas discharged from a chilling chamber at the lower part of a chlorination furnace (9) is 150-170 ℃, the pressure is 0.9MpaG to 1.2MpaG, the dust-containing titanium tetrachloride gas is contacted with crude titanium tetrachloride liquid from a heat exchanger (16) through a Venturi tube (12), wetted and cooled, then the dust-containing titanium tetrachloride gas enters a washing tower (13), the uncondensed crude titanium tetrachloride gas in the washing tower (13) and the crude titanium tetrachloride liquid from the heat exchanger (16) are sprayed and contacted to the temperature of 100-125 ℃, the uncondensed gas phase goes to a condensation recovery process through the top of the washing tower (13), and the liquid phase crude titanium tetrachloride at the bottom of the washing tower (13) flows into a crude titanium tetrachloride collecting tank (14) under the action of gravity.
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| GB768867A (en) * | 1954-02-04 | 1957-02-20 | New Jersey Zinc Co | Improved production of titanium tetrachloride |
| CN101462767A (en) * | 2007-12-19 | 2009-06-24 | 贵阳铝镁设计研究院 | Preparation of crude titanic chloride |
| CN103112888B (en) * | 2013-03-15 | 2014-06-25 | 金川集团股份有限公司 | Titanium tetrachloride production system and method for recycling titanium tetrachloride from slurry |
| CN103466694B (en) * | 2013-08-16 | 2015-12-02 | 东华工程科技股份有限公司 | A kind of chloridating gas cooling system |
| JP6211940B2 (en) * | 2014-01-27 | 2017-10-11 | 株式会社大阪チタニウムテクノロジーズ | Titanium tetrachloride production method |
| CN105197989B (en) * | 2015-08-20 | 2017-01-25 | 四川宏达(集团)有限公司 | Flash suspension chlorination method for raw materials containing titanium |
| CN106587143A (en) * | 2016-12-05 | 2017-04-26 | 东华工程科技股份有限公司 | Improvement on chlorination dedusting technology used for chloride process titanium dioxide apparatus |
| CN109721099B (en) * | 2019-03-14 | 2021-06-04 | 攀枝花攀钢集团设计研究院有限公司 | Comprehensive reaction furnace for preparing titanium tetrachloride through low-temperature chlorination |
| CN112266013B (en) * | 2020-11-04 | 2021-06-11 | 宝钛华神钛业有限公司 | System and process for producing titanium tetrachloride from high-calcium magnesium titanium dioxide |
| CN113277553B (en) * | 2021-06-29 | 2023-11-24 | 蚌埠中瓷纳米科技有限公司 | Two-stage dust removal device and dust removal method for preparing titanium tetrachloride |
| CN113501541B (en) * | 2021-08-12 | 2023-01-24 | 上海驰春节能科技有限公司 | System and process for preparing titanium tetrachloride by liquid chlorination of titanium-containing blast furnace slag |
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