CN110357150A - Titanium tetrachloride rectificating method - Google Patents
Titanium tetrachloride rectificating method Download PDFInfo
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- CN110357150A CN110357150A CN201910731322.6A CN201910731322A CN110357150A CN 110357150 A CN110357150 A CN 110357150A CN 201910731322 A CN201910731322 A CN 201910731322A CN 110357150 A CN110357150 A CN 110357150A
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- titanium tetrachloride
- distillation column
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
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- 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
- C01G23/024—Purification of tetrachloride
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Abstract
The present invention provides a kind of titanium tetrachloride rectificating methods.Method includes the following steps: carrying out first time rectification process to titanium tetrachloride using first rectifying column, the first product is obtained；And second of rectification process is carried out to the first product using Second distillation column, obtain titanium tetrachloride purification；Wherein, the internals in first rectifying column and/or Second distillation column are wire packing.For sieve plate or float valve, wire packing has the characteristics that big flux, low pressure drop, ultrahigh in efficiency, the liquid stream decline passway tortuous change of wire packing soak titanium tetrachloride liquid sufficiently in filler surface, uniform liquid film is formed, preferable mass transfer effect is reached.Therefore in the case where same tower height, number of theoretical plate can be greatly increased using wire packing, and in the case where same number of theoretical plate, tower height can be substantially reduced, civil engineering risk is reduced.
Description
Technical field
The present invention relates to titanium tetrachlorides to purify field, in particular to a kind of titanium tetrachloride rectificating method.
Background technique
Titanium tetrachloride is the important intermediate for producing Titanium and its compound, is to produce titanium sponge and Titanium Dioxide Produced by Chloride Procedure
Primary raw material, the quality of quality directly affects the quality of titanium sponge and titanium dioxide.Titanium tetrachloride impurity is complex, includes
Low-boiling point material, high boiling substance and the close substance of boiling point, predominantly SiCl4、CH2ClCOCl、POCL3、CHCl2COCl、
CCl3COCl、CH3COCl、SnCl4、VOCl3、AsCl3、VCl4、Al Cl3、Fe Cl3Deng the type and quantity of these impurity are direct
The color of titanium tetrachloride is influenced, it is very big to the performance hazards of subsequent product.
Two rectifying columns interconnected are generallyd use at present, rectification and purification is carried out to titanium tetrachloride, however, because in impurity
SnCl4、VOCl3、AsCl3、VCl4Deng with TiCl4Boiling point is very close, and high-purity titanium tetrachloride requires the content control of each impurity
System is in 0.1~1ppbw, this just makes titanium tetrachloride purification difficulty bigger, and each rectifying column of inevitable requirement has high number of theoretical plate.High
The height that number of theoretical plate inevitable requirement increases tower can greatly increase civil engineering risk especially for the lesser tower of diameter.Cause
How this, reduce the height of titanium tetrachloride rectifying column, for high-purity titanium tetrachloride while guaranteeing titanium tetrachloride refining effect
Purification production it is most important.
Summary of the invention
The main purpose of the present invention is to provide a kind of titanium tetrachloride rectificating methods, to solve high-purity tetrachloro in the prior art
The problem of rectifying tower height is excessively high in change titanium subtractive process, Yi Yinqi civil engineering risk.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of titanium tetrachloride rectificating method, including
Following steps: first time rectification process is carried out to titanium tetrachloride using first rectifying column, obtains the first product；And use second
Rectifying column carries out second of rectification process to the first product, obtains titanium tetrachloride purification；Wherein, first rectifying column and/or
Internals in two rectifying columns are wire packing.
Further, the internals in first rectifying column and Second distillation column are wire packing, the filler of first rectifying column
Height is 20~50m；The packed height of Second distillation column is 20~50m.
Further, first time rectification process is to take off to handle again, and second of rectification process is de- light processing；Or for the first time
Rectification process is de- light processing, and second of rectification process is handled again to be de-；Wherein, the tower top of first rectifying column and Second distillation column
Pressure is respectively 0.01~0.2MPa of gauge pressure, and tower top temperature is respectively 138~185 DEG C；Tower reactor pressure be respectively gauge pressure 0.02~
0.21MPa, bottom temperature are respectively 143~185 DEG C.
Further, in the step of first time rectification process, a part in material that first rectifying column tower reactor is discharged
It is back in first rectifying column after being heated by the first reboiler, and when first time rectification process is to take off to handle again, it will
Another part in the material of first rectifying column tower reactor discharge is discharged as impurity；When first time rectification process is de- light processing
When, another part in material that first rectifying column tower reactor is discharged is as the first product.
Further, in the step of second of rectification process, a part in material that Second distillation column tower reactor is discharged
It is back in Second distillation column after being heated by the second reboiler, and when second of rectification process is de- light processing, it will
Another part in the material of Second distillation column tower reactor discharge is as titanium tetrachloride purification；When second of rectification process is de- weight
When processing, another part in material that Second distillation column tower reactor is discharged is discharged as impurity.
Further, in the step of first time rectification process, first rectifying column tower top is discharged using the first condenser
Material is condensed to obtain the first lime set, and a part in the first lime set is back in first rectifying column, and when for the first time
Rectification process is when taking off to handle again, using another part in the first lime set as the first product；When first time rectification process is de-
When light processing, it is discharged another part in the first lime set as impurity；Preferably, the reflux entry ratio of the first condenser is 1
~20.
Further, in the step of second of rectification process, Second distillation column tower top is discharged using the second condenser
Material is condensed to obtain the second lime set, and a part in the second lime set is back in Second distillation column, and when second
When rectification process is de- light processing, it is discharged another part in the second lime set as impurity；When second of rectification process is de-
When handling again, using another part in the second lime set as titanium tetrachloride purification；Preferably, the reflux entry of the second condenser
Than being 1~20.
Further, before the step of carrying out first time rectification process to titanium tetrachloride, method further includes using preceding de-
Heavy distillation column carries out the de- pretreated step of weight to titanium tetrachloride.
Further, the internals of preceding de- heavy distillation column are sieve plate or float valve.
Further, it takes off in the pretreated step of weight, a part in the material of preceding de- heavy distillation column tower reactor discharge is led to
Third reboiler is crossed to be heated and refluxed for into preceding de- heavy distillation column, it will be another in the material of preceding de- heavy distillation column tower reactor discharge
A part is discharged as impurity.
Further, it takes off in the pretreated step of weight, the object that preceding de- heavy distillation column tower top is discharged using third condenser
Material is condensed to obtain third lime set, before a part in third lime set is back in de- heavy distillation column, and by third lime set
In another part carry out first time rectification process；Preferably, the reflux entry ratio of third lime set is 1~5；Preferably, preceding de-
The tower top pressure of heavy distillation column is 0.01~0.2MPa of gauge pressure, and tower top temperature is 138~185 DEG C；Tower reactor pressure is gauge pressure 0.06
~0.25MPa, bottom temperature are 155~192 DEG C.
Internals in traditional titanium tetrachloride rectifying column are usually sieve plate or float valve, in the present invention by first rectifying column and/
Or the internals in Second distillation column are configured differently than the wire packing of sieve plate and float valve.For sieve plate or float valve, silk
Net filler has the characteristics that big flux, low pressure drop, ultrahigh in efficiency, the liquid stream decline passway tortuous change of wire packing make tetrachloro
Change titanium liquid sufficiently to soak in filler surface, forms uniform liquid film, reach preferable mass transfer effect.It is based on the above original
Cause, wire packing can achieve 5 pieces of theoretical plate/rice, and sieve plate or float valve are only 1~2 piece of theoretical plate/rice.Therefore in same tower
In the case where height, number of theoretical plate can be greatly increased using wire packing, and in the case where same number of theoretical plate, it can be significantly
Tower height is reduced, civil engineering risk is reduced.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 shows titanium tetrachloride rectifier unit schematic diagram according to an embodiment of the present；
Fig. 2 shows the titanium tetrachloride rectifier unit schematic diagrames of another embodiment according to the present invention；
Fig. 3 shows the titanium tetrachloride rectifier unit schematic diagram of another embodiment according to the present invention；And
Fig. 4 shows the titanium tetrachloride rectifier unit schematic diagram of another embodiment according to the present invention.
Wherein, the above drawings include the following reference numerals:
10, first rectifying column；11, the first reboiler；12, the first condenser；13, the first return tank；14, the first reflux
Pump；15, the first feed pump；20, Second distillation column；21, the second reboiler；22, the second condenser；23, the second return tank；24,
Second reflux pump；30, preceding de- heavy distillation column；31, third reboiler；32, third condenser；33, third return tank；34, third
Reflux pump.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.The present invention will be described in detail below with reference to the accompanying drawings and embodiments.
The application is described in further detail below in conjunction with specific embodiment, these embodiments should not be understood as limitation originally
Apply for range claimed.
As described in background technology part, there are rectifying towers in high-purity titanium tetrachloride subtractive process in the prior art
The problem of height is excessively high, Yi Yinqi civil engineering risk.
In order to solve this problem, the present invention provides a kind of titanium tetrachloride rectificating methods, as illustrated in fig. 1 and 2 comprising
Following steps: first time rectification process is carried out to titanium tetrachloride using first rectifying column 10, obtains the first product；And using the
Two rectifying columns 20 carry out second of rectification process to the first product, obtain titanium tetrachloride purification；Wherein, first rectifying column 10
And/or the internals in Second distillation column 20 are wire packing.The internals of traditional titanium tetrachloride rectifying column are usually sieve plate or float
The internals of first rectifying column 10 and/or Second distillation column 20 are configured differently than the silk screen of sieve plate and float valve in the present invention by valve
Filler.For sieve plate and float valve, wire packing has the characteristics that big flux, low pressure drop, ultrahigh in efficiency, wire packing
Liquid stream decline passway tortuous change, soaks titanium tetrachloride liquid sufficiently in filler surface, forms uniform liquid film, reaches preferable
Mass transfer effect.It is based on the above reason, wire packing can achieve 5 pieces of theoretical plate/rice, and sieve plate or float valve are only 1~2
Block theoretical plate/rice.Therefore in the case where same tower height, number of theoretical plate can be greatly increased using wire packing, and same
In the case where number of theoretical plate, tower height can be substantially reduced, reduces civil engineering risk.
In addition to higher number of theoretical plate, also had the advantage that using wire packing
Wire packing operating flexibility is high, due to flowing similar capillary stream of the gas-liquid two-phase in wire packing, has
Biggish specific surface area, lower gas-liquid load, that is, wettable filler surface, the operating flexibility of wire packing can reach 50~
150%.For example design value is 100%, the operating flexibility of wire packing is 50~150%, exactly when tower internal loading is that design is negative
When the 50% of lotus and 150%, tower can also be operated normally.
Wire packing pressure drop is small, for the tower of same theory plate number, the tower top and tower bottom pressure difference of sieve plate or valve tower
For 0.05~0.3MPa, and the tower top of wire packing tower and tower bottom pressure difference are 0.01~0.02MPa.When using differential pressure thermal coupling skill
When art, tower pressure drop is small particularly important.When fixed 10 tower top pressure of first rectifying column, after internals are changed to wire packing, tower is set
Standby pressure drop reduces, and the tower reactor pressure and temperature of first rectifying column 10 reduces, then the tower top pressure of Second distillation column 20 coupled thereto
Power and temperature reduce, so that the tower reactor pressure and temperature of Second distillation column 20 reduces, and then can reduce Second distillation column 20 again
Boil the quality of device heat source vapor.
In a preferred embodiment, the internals in first rectifying column 10 and Second distillation column 20 are that silk screen is filled out
The packed height of material, first rectifying column 10 and Second distillation column 20 is 20~50, and tower height is 30~70m.In this way, in lower tower
Under the conditions of height, there is higher refining effect when refining using above-mentioned titanium tetrachloride rectifier unit to titanium tetrachloride.
In a preferred embodiment, first time rectification process is to take off to handle again, and second of rectification process is de- light
Processing.In this way, as shown in Figure 1, titanium tetrachloride first through first rectifying column 10 remove high-boiling-point impurity after, enter back into Second distillation column
20 carry out de- light removal low boiling impurity.Alternatively, first time rectification process is de- light processing, second of rectification process is located again to be de-
Reason.In this way, as shown in Fig. 2, titanium tetrachloride first after first rectifying column 10 carries out de- light removal low boiling impurity, enters back into second
Rectifying column 20 removes high-boiling-point impurity.Preferably, the tower top pressure of first rectifying column 10 and Second distillation column 20 is respectively gauge pressure
0.01~0.2MPa, tower top temperature are respectively 138~185 DEG C；Tower reactor pressure is respectively 0.02~0.21MPa of gauge pressure, tower reactor temperature
Degree is respectively 143~185 DEG C.Because material is all high-purity material, titanium tetrachloride purity is all in the operation ginseng of 99% or more, two tower
Number is almost the same.
In a preferred embodiment, in the step of first time rectification process, by 10 first tower reactor of first rectifying column
Outlet is back in first rectifying column 10 after being heated by the first reboiler 11, and when again first time rectifying is to take off to handle
When, it is discharged using the first tower reactor extraction mouth as impurity；When first time rectification process is de- light processing, the first tower reactor produces mouth and makees
For the first product.
In a preferred embodiment, in the step of second of rectification process, by the second tower of Second distillation column 20
Kettle outlet is back in Second distillation column 20 after being heated by the second reboiler 21, and when second of rectification process is de- light
When processing, the second tower reactor produces mouth as titanium tetrachloride purification；When second of rectification process is to take off to handle again, the second tower reactor
Mouth is produced to be discharged as impurity.
In a preferred embodiment, in the step of first time rectification process, using the first condenser 12 by first
The material of 10 tower top of rectifying column discharge is condensed to obtain the first lime set, and a part in the first lime set is back to the first essence
It evaporates in tower 10, and when first time rectification process is to take off to handle again, using another part in the first lime set as the first product；When
When first time rectification process is de- light processing, it is discharged another part in the first lime set as impurity.
Preferably, the reflux entry ratio of the first condenser 12 is 1~20.
In a preferred embodiment, in the step of second of rectification process, using the second condenser 22 by second
The material of 20 tower top of rectifying column discharge is condensed to obtain the second lime set, and a part in the second lime set is back to the second essence
It evaporates in tower 20, and when second of rectification process is de- light processing, is discharged another part in the second lime set as impurity；When
Second of rectification process is when taking off to handle again, using another part in the second lime set as titanium tetrachloride purification.
Preferably, the reflux entry ratio of the second condenser 22 is 1~20.
When the solid content in titanium tetrachloride is higher, in a preferred embodiment, as shown in Figures 3 and 4, to four
Before titanium chloride carries out the step of first time rectification process, method further includes being carried out using preceding de- heavy distillation column 30 to titanium tetrachloride
The de- pretreated step of weight.
It is blocked due to being be easy to cause in tower when solid content is higher, in order to reduce the blocking risk of preceding de- heavy distillation column 30,
In a kind of preferred embodiment, the internals of preceding de- heavy distillation column 30 are sieve plate or float valve.
In a preferred embodiment, it takes off in the pretreated step of weight, by the third tower reactor of preceding de- heavy distillation column 30
Outlet is heated and refluxed for by third reboiler 31 into preceding de- heavy distillation column 30, and third tower reactor produces mouth and arranges as impurity
Out.In a preferred embodiment, it takes off in the pretreated step of weight, using third condenser 32 by preceding de- heavy distillation column 30
The material of tower top discharge is condensed to obtain third lime set, de- heavy distillation column 30 before a part in third lime set is back to
In, and another part in third lime set is subjected to first time rectification process.Mentioning for titanium tetrachloride can further be improved in this way
Pure effect.
Preferably, the reflux entry ratio of third lime set is 1~5；
Preferably, the tower top pressure of preceding de- heavy distillation column 30 is 0.01~0.2MPa of gauge pressure, and tower top temperature is 138~185
℃；Tower reactor pressure is 0.06~0.25MPa of gauge pressure, and bottom temperature is 155~192 DEG C.
According to another aspect of the present invention, a kind of titanium tetrachloride rectifier unit, as illustrated in fig. 1 and 2, the tetrachloro are additionally provided
Changing titanium rectifier unit includes first rectifying column 10 interconnected and Second distillation column 20, for carrying out at rectifying to titanium tetrachloride
Reason, and the upstream of Second distillation column 20 is arranged in first rectifying column 10, wherein first rectifying column 10 and/or Second distillation column 20
In internals be wire packing.
Internals in traditional titanium tetrachloride rectifying column are usually sieve plate or float valve, by first rectifying column 10 in the present invention
And/or the internals in Second distillation column 20 are configured differently than the wire packing of sieve plate and float valve.Compared to sieve plate and float valve
Speech, wire packing have the characteristics that big flux, low pressure drop, ultrahigh in efficiency, the liquid stream decline passway tortuous change of wire packing make
Titanium tetrachloride liquid is sufficiently soaked in filler surface, forms uniform liquid film, reaches preferable mass transfer effect.It is based on above
Reason, wire packing can achieve 5 pieces of theoretical plate/rice, and sieve plate or float valve are only 1~2 piece of theoretical plate/rice.Therefore same
In the case where tower height, number of theoretical plate can be greatly increased using wire packing, and in the case where same number of theoretical plate, Ke Yi great
It is big to reduce tower height, reduce civil engineering risk.
In a preferred embodiment, the filler in first rectifying column 10 and Second distillation column 20 is that silk screen is filled out
Material, the packed height of first rectifying column 10 are 20~50, and tower height is 30~70m；The packed height of Second distillation column 20 be 20~
50, tower height is 30~70m.In this way, under the conditions of lower tower height, using above-mentioned titanium tetrachloride rectifier unit to titanium tetrachloride into
There is higher refining effect when row purification.
In a kind of preferred embodiment, the tower top of first rectifying column 10 is provided with the first tower top outlet, first rectifying column
10 tower bottom is provided with the outlet of the first tower reactor and the first tower reactor produces mouth；Wherein, first rectifying column 10 is weight-removing column, the second rectifying
Tower 20 is lightness-removing column, and the first tower top outlet is connected with the feed inlet of Second distillation column 20；Or first rectifying column 10 is lightness-removing column,
Second distillation column 20 is weight-removing column, and the first tower reactor extraction mouth is connected with the feed inlet of Second distillation column 20.Specific first tower reactor
Outlet and the first tower reactor extraction mouth can be all disposed on tower, and the first tower reactor extraction mouth is for producing.It is highly preferred that the first rectifying
The lower part of tower 10 is additionally provided with the first kettle liquid refluxing opening, and titanium tetrachloride rectifier unit further includes the first reboiler 11, and first boils again
The import of device 11 is connected with the outlet of the first tower reactor, and the first kettle liquid refluxing opening is connected with the outlet of the first reboiler 11, and when first
When rectifying column 10 is weight-removing column, the first tower reactor produces mouth as de- heavy seeds outlet, the removing of first rectifying column 10 is discharged
Impurity；When first rectifying column 10 is lightness-removing column, the first tower reactor extraction mouth is connected with the feed inlet of Second distillation column 20.
In a preferred embodiment, the tower top of first rectifying column 10 is provided with the first tower top outlet, the first rectifying
The tower bottom of tower 10 is provided with the outlet of the first tower reactor and the first tower reactor produces mouth；Wherein, as shown in Figure 1, first rectifying column 10 is de-
Weight tower, Second distillation column 20 are lightness-removing column, and the first tower top outlet is through condenser partial condensation liquid after cooling and Second distillation column
20 feed inlet is connected.In this way, titanium tetrachloride first through first rectifying column 10 remove high-boiling-point impurity after, enter back into Second distillation column
20 carry out de- light removal low boiling impurity.Alternatively, Second distillation column 20 is de- as shown in Fig. 2, first rectifying column 10 is lightness-removing column
Weight tower, the first tower reactor extraction mouth are connected with the feed inlet of Second distillation column 20.In this way, titanium tetrachloride first through first rectifying column 10 into
After the de- light removal low boiling impurity of row, enters back into Second distillation column 20 and remove high-boiling-point impurity.
In a preferred embodiment, the lower part of first rectifying column 10 is additionally provided with the first kettle liquid refluxing opening, tetrachloro
Changing titanium rectifier unit further includes the first reboiler 11, and the import of the first reboiler 11 is connected with the outlet of the first tower reactor, the first kettle liquid
Refluxing opening is connected with the outlet of the first reboiler 11, and when first rectifying column 10 is weight-removing column, the first tower reactor produces mouth conduct
First de- heavy seeds outlet, the impurity of the removing of first rectifying column 10 is discharged；When first rectifying column 10 is lightness-removing column, first
Tower reactor produces mouth as the first out-of branch, and the first out-of branch is connected with the feed inlet of Second distillation column 20.Again using first
The liquid of tower reactor can be heated to be gas by boiling device 11, provide gas phase.
In a preferred embodiment, the tower top of Second distillation column 20 is provided with the second tower top outlet, the second rectifying
The tower bottom of tower 20 is provided with the outlet of the second tower reactor and the second tower reactor produces mouth, and the lower part of Second distillation column 20 is provided with the second kettle liquid
Refluxing opening, titanium tetrachloride rectifier unit further include the second reboiler 21, and import and the second tower reactor of the second reboiler 21 export phase
Even, the outlet of the second reboiler 21 is connected with the second kettle liquid refluxing opening, and when Second distillation column 20 is lightness-removing column, the second tower reactor
It produces mouth to export as refined product, for the rectifying product of titanium tetrachloride to be discharged；When Second distillation column 20 is weight-removing column, the
Two tower reactors produce mouth as the second de- heavy seeds outlet, for the impurity of the removing of Second distillation column 20 to be discharged.Similarly, it is arranged second
Reboiler 21 is capable of providing gas phase.
In a preferred embodiment, the top of first rectifying column 10 is additionally provided with the first condensate liquid refluxing opening, and four
Titanium chloride rectifier unit further includes the first condenser 12, and the import of the first condenser 12 is connected with the first tower top outlet, and first is cold
The outlet of condenser 12 is connected with the first condensate liquid refluxing opening, and when first rectifying column 10 is weight-removing column, the first condenser 12
It exports and is provided with the second out-of branch, the second out-of branch and Second distillation column on the pipeline being connected with the first condensate liquid refluxing opening
20 feed inlet is connected；When first rectifying column 10 is lightness-removing column, the outlet of the first condenser 12 and the first condensate liquid refluxing opening
The first de- light impurity outlet is provided on connected pipeline, for the impurity of the removing of first rectifying column 10 to be discharged.It is cold to be arranged first
Condenser 12 can condense the high-temperature steam that 10 tower top of first rectifying column is discharged, and then will be partly refluxed to first rectifying column
10。
In a preferred embodiment, the top of Second distillation column 20 is additionally provided with the second condensate liquid refluxing opening, and four
Titanium chloride rectifier unit further includes the second condenser 22, and the import of the second condenser 22 is connected with the second tower top outlet, and second is cold
The outlet of condenser 22 is connected with the second condensate liquid refluxing opening, and when Second distillation column 20 is lightness-removing column, the second condenser 22
It exports and is provided with the second de- light impurity outlet on the pipeline being connected with the second condensate liquid refluxing opening, for the second condenser 22 to be discharged
The impurity of removing；When Second distillation column 20 is weight-removing column, the outlet of the second condenser 22 is connected with the second condensate liquid refluxing opening
Pipeline on be provided with refined product outlet, for the rectifying product of titanium tetrachloride to be discharged.It similarly, in this way can also be by the second essence
It evaporates the high temperature vapor condensation that tower 20 steams and a part flows back.
When the solid content in titanium tetrachloride is higher, in a preferred embodiment, as shown in Figures 3 and 4, four chlorinations
Titanium rectifier unit de- heavy distillation column 30 before further including, preceding de- heavy distillation column 30 are connected with first rectifying column 10 and are arranged in the first essence
The upstream for evaporating tower 10 is handled again for take off to titanium tetrachloride.In this way can enter first rectifying column 10 before, first with
Preceding de- heavy distillation column 30 removes the higher high-boiling components of solid content in titanium tetrachloride, to mitigate the pressure of subsequent two tower.
It is blocked due to being be easy to cause in tower when solid content is higher, in order to reduce the blocking risk of preceding de- heavy distillation column 30,
In a kind of preferred embodiment, the internals of preceding de- heavy distillation column 30 are sieve plate or float valve.
In a preferred embodiment, titanium tetrachloride rectifier unit further includes third reboiler 31, preceding de- rectifying again
The tower bottom of tower 30 is provided with the outlet of third tower reactor and third tower reactor produces mouth, and the lower part of preceding de- heavy distillation column 30 is provided with third kettle
The import of liquid refluxing opening, third reboiler 31 is connected with the outlet of third tower reactor, and the outlet of third reboiler 31 and third kettle liquid are returned
Head piece is connected, and third tower reactor produces mouth as third and takes off heavy seeds outlet, the impurity removed for heavy distillation column 30 de- before being discharged.
The removal effect of high-boiling-point impurity can further be improved in this way.
In a preferred embodiment, titanium tetrachloride rectifier unit further includes third condenser 32, preceding de- rectifying again
The tower top of tower 30 is provided with third tower top outlet, and the top of preceding de- heavy distillation column 30 is provided with third condensate liquid refluxing opening, third
The import of condenser 32 is connected with third tower top outlet, and the outlet of third condenser 32 is connected with third condensate liquid refluxing opening, the
It is additionally provided with third out-of branch on the pipeline that the outlet of three condensers 32 is connected with third condensate liquid refluxing opening, and third goes out liquid
Branch is connected with the import of first rectifying column 10.The refining effect of titanium tetrachloride can further be improved in this way.
Preferably, as shown in Figures 1 to 4, on the pipeline that the outlet of the first condenser 12 is connected with the first condensate liquid refluxing opening
It is additionally provided with the first return tank 13；It is additionally provided on the pipeline that the outlet of second condenser 22 is connected with the second condensate liquid refluxing opening
Second return tank 23；Third reflux is additionally provided on the pipeline that the outlet of third condenser 32 is connected with third condensate liquid refluxing opening
Tank 33；
Preferably, as shown in Figures 1 to 4, on the pipeline being connected between the first return tank 13 and the first condensate liquid refluxing opening also
It is provided with the first reflux pump 14；Second is additionally provided on the pipeline being connected between second return tank 23 and the second condensate liquid refluxing opening
Reflux pump 24；Third reflux pump 34 is additionally provided on the pipeline being connected between third return tank 33 and third condensate liquid refluxing opening.
Preferably, as shown in Figures 2 and 4, when first rectifying column 10 is lightness-removing column, on the feeding pipe of Second distillation column 20
It is additionally provided with the first feed pump 15.
Beneficial effects of the present invention are further illustrated by the following examples:
Titanium tetrachloride mass content is 99.8%, and crude titanic chloride liquid treating capacity of the solid content less than 0.5% is 5000kg/
H, product requirement reach high-purity titanium tetrachloride index.Embodiment 1 is identical with 1 process of comparative example, all uses Fig. 1 shown device and stream
Journey, the tower internals of embodiment 1 use wire packing, and the tower internals of comparative example 1 uses valve tower.
The key factor for influencing refining effect is number of theoretical plate and reflux entry ratio, for comparison tower internals to technological parameter,
The influence of heat source and tower height, the number of theoretical plate and reflux entry of embodiment 1 and comparative example 1 are than identical, the temperature of top of tower
Degree and pressure are also identical, and the technological parameter control of embodiment 1 and comparative example 1 is shown in Table 1.As seen from table, tower internals is changed to by float valve
After wire packing, reboiler heat source quality is reduced.
1 tower process parameter lookup table of 1 embodiment 1 of table and comparative example
| Parameter | Embodiment 1 | Comparative example 1 |
| 1 column overhead pressure (MPa) | 0.10 | 0.10 |
| 1 column overhead temperatures (DEG C) | 135 | 135 |
| 1 tower tower reactor pressure (MPa) | 0.11 | 0.16 |
| 1 tower bottom temperature (DEG C) | 139 | 155 |
| 1 tower steam pressure and temperature (MPa, DEG C) | 0.6,158 | 0.9,175 |
| 2 column overhead pressure (MPa) | 0.2 | 0.2 |
| 2 column overhead temperatures (DEG C) | 137 | 137 |
| 2 tower tower reactor pressure (MPa) | 0.21 | 0.26 |
| 2 tower bottom temperatures (DEG C) | 167 | 177 |
| 2 tower steam pressures and temperature (MPa, DEG C) | 1.2,188 | 1.5,198 |
Since the treating capacity and reflux entry of embodiment 1 and comparative example 1 are than identical, therefore tower diameter is identical, only not because of internals
With causing device height different, two kinds of tower internals device height controls are shown in Table 2.As seen from table, the identical number of theoretical plate the case where
Under, after tower internals is changed to wire packing by float valve, tower height is greatly reduced.
The 1 tower table of comparisons of 2 embodiment 1 of table and comparative example
It can be seen from the above description that the above embodiments of the present invention realized the following chievements: in the present invention
Internals in first rectifying column and/or Second distillation column are configured differently than to the wire packing of sieve plate and float valve.Compared to sieve
For plate and float valve, wire packing has the characteristics that big flux, low pressure drop, ultrahigh in efficiency, the liquid stream decline passway of wire packing
Tortuous change soaks titanium tetrachloride liquid sufficiently in filler surface, forms uniform liquid film, reaches preferable mass transfer effect.
Be based on the above reason, wire packing can achieve 5 pieces of theoretical plate/rice, and sieve plate or float valve be only 1~2 piece of theoretical plate/
Rice.Therefore in the case where same tower height, number of theoretical plate can be greatly increased using wire packing, and in same number of theoretical plate
In the case of, tower height can be substantially reduced, civil engineering risk is reduced.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (11)
1. a kind of titanium tetrachloride rectificating method, comprising the following steps:
First time rectification process is carried out to titanium tetrachloride using first rectifying column (10), obtains the first product；And
Second of rectification process is carried out to first product using Second distillation column (20), obtains titanium tetrachloride purification；
It is characterized in that, the internals in the first rectifying column (10) and/or the Second distillation column (20) are wire packing.
2. titanium tetrachloride rectificating method according to claim 1, which is characterized in that the first rectifying column (10) and described
Internals in Second distillation column (20) are wire packing, and the packed height of the first rectifying column (10) is 20~50m；It is described
The packed height of Second distillation column (20) is 20~50m.
3. titanium tetrachloride rectificating method according to claim 1 or 2, which is characterized in that
The first time rectification process is to take off to handle again, and second of rectification process is de- light processing；Or
The first time rectification process is de- light processing, and second of rectification process is handled again to be de-；
Wherein, the tower top pressure of the first rectifying column (10) and Second distillation column (20) is respectively 0.01~0.2MPa of gauge pressure,
Tower top temperature is respectively 138~185 DEG C；Tower reactor pressure is respectively 0.02~0.21MPa of gauge pressure, and bottom temperature is respectively 143~
185℃。
4. titanium tetrachloride rectificating method according to claim 3, which is characterized in that the step of the first time rectification process
In, it is returned after a part in the material of the first rectifying column (10) tower reactor discharge is heated by the first reboiler (11)
It flow in the first rectifying column (10), and
When the first time rectification process be it is de- handle again when, will be another in the material of the first rectifying column (10) tower reactor discharge
A part is discharged as impurity；
It, will be another in the material of the first rectifying column (10) tower reactor discharge when the first time rectification process is de- light processing
A part is used as first product.
5. titanium tetrachloride rectificating method according to claim 3, which is characterized in that the step of second of rectification process
In, it is returned after a part in the material of the Second distillation column (20) tower reactor discharge is heated by the second reboiler (21)
It flow in the Second distillation column (20), and
It, will be another in the material of the Second distillation column (20) tower reactor discharge when second of rectification process is de- light processing
A part is used as the titanium tetrachloride purification；
When second of rectification process be it is de- handle again when, will be another in the material of the Second distillation column (20) tower reactor discharge
A part is discharged as impurity.
6. titanium tetrachloride rectificating method according to claim 5, which is characterized in that the step of the first time rectification process
In, it is condensed the material that the first rectifying column (10) tower top is discharged to obtain the first lime set using the first condenser (12),
And a part in first lime set is back in the first rectifying column (10), and
When the first time rectification process is to take off to handle again, produced another part in first lime set as described first
Object；
When the first time rectification process is de- light processing, it is discharged another part in first lime set as impurity；
Preferably, the reflux entry ratio of first condenser (12) is 1~20.
7. titanium tetrachloride rectificating method according to claim 5, which is characterized in that the step of second of rectification process
In, it is condensed the material that the Second distillation column (20) tower top is discharged to obtain the second lime set using the second condenser (22),
And a part in second lime set is back in the Second distillation column (20), and
When second of rectification process is de- light processing, it is discharged another part in second lime set as impurity；
When second of rectification process is to take off to handle again, using another part in second lime set as four chlorination
Titanium purification；
Preferably, the reflux entry ratio of second condenser (22) is 1~20.
8. titanium tetrachloride rectificating method according to claim 1 or 2, which is characterized in that carried out to the titanium tetrachloride
Before the step of first time rectification process, the method also includes utilizing preceding de- heavy distillation column (30) to the titanium tetrachloride
Carry out the de- pretreated step of weight.
9. titanium tetrachloride rectificating method according to claim 8, which is characterized in that de- heavy distillation column (30) is interior before described
Part is sieve plate or float valve.
10. titanium tetrachloride rectificating method according to claim 8, which is characterized in that in the de- pretreated step of weight,
A part before will be described in the material of de- heavy distillation column (30) tower reactor discharge is heated and is returned by third reboiler (31)
It flow in preceding de- heavy distillation column (30), another part work in material that preceding de- heavy distillation column (30) tower reactor is discharged
For impurity discharge.
11. titanium tetrachloride rectifier unit according to claim 10, which is characterized in that the de- pretreated step of weight
In, it is condensed the material of heavy distillation column (30) tower top discharge de- before described to obtain third using third condenser (32) solidifying
A part in the third lime set is back in preceding de- heavy distillation column (30) by liquid, and will be in the third lime set
Another part carries out the first time rectification process；
Preferably, the reflux entry ratio of the third lime set is 1~5；
Preferably, the tower top pressure of de- heavy distillation column (30) is 0.01~0.2MPa of gauge pressure before described, tower top temperature is 138~
185℃；Tower reactor pressure is 0.06~0.25MPa of gauge pressure, and bottom temperature is 155~192 DEG C.
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