CN106241860A - A kind of crude titanic chloride is except the method for vanadium - Google Patents
A kind of crude titanic chloride is except the method for vanadium Download PDFInfo
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- CN106241860A CN106241860A CN201610585009.2A CN201610585009A CN106241860A CN 106241860 A CN106241860 A CN 106241860A CN 201610585009 A CN201610585009 A CN 201610585009A CN 106241860 A CN106241860 A CN 106241860A
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- C01G23/00—Compounds of titanium
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- C01G23/022—Titanium tetrachloride
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Abstract
The present invention relates to titanium tetrachloride field of refinement, disclose a kind of crude titanic chloride except the method for vanadium, the method includes: content of vanadium crude titanic chloride more than 0.3 weight % is contacted except vanadium reagents carries out first by (1) with organic, and the product that the first contact obtains is carried out solid-liquid separation, the content of vanadium in the liquid phase that described first contact makes solid-liquid separation obtain is reduced to below 0.2 weight %；(2) liquid phase that step (1) solid-liquid separation obtains is carried out aluminium powder except vanadium.The method using the present invention processes the crude titanic chloride of high content of vanadium, makes full use of existing aluminium powder and removes the intact device of vanadium, and level of residue is few, and except vanadium is effective, the settling property of the solid of generation is good.
Description
Technical field
The present invention relates to titanium tetrachloride field of refinement, in particular it relates to a kind of crude titanic chloride is except the method for vanadium.
Background technology
Titanium tetrachloride is that chloridising produces titanium white and Kroll process produces the most important intermediate products of titanium sponge.Thick four chlorinations
Titanium refers to the most purified titanium tetrachloride, its a kind of rufous or the turbid solution of buff, and its color contains with impurity therein
Measure relevant.In crude titanic chloride, impurity component is sufficiently complex, a kind of main impurity element during wherein vanadium is crude titanic chloride, it
With VOCl3Form is contained therein.VOCl3In containing oxygen element, after it is reduced, oxygen element may enter with four times of concentration
Titanium sponge, causes oxygen content in titanium sponge to raise, and Brinell hardness increases, and causes titanium sponge to be demoted.If containing 0.2 weight in raw material
The VOCl of amount %3Impurity, the oxygen element content in titanium sponge can increase by 0.0052 weight %, makes titanium sponge hardness increase by 4 numbers
Amount unit, has a strong impact on the mechanical performance of product.The titanium tetrachloride high with vanadium content produces titanium white, and titanium dioxide can be made to colour and shadow
Ring titanium white performance.Therefore, crude titanic chloride removes the important process process that vanadium is refining titanic chloride.
VOCl3Boiling point be 127 DEG C, TiCl4Boiling point be 136 DEG C, front and back both relative volatilities are 1.22, both
Boiling-point difference and relative volatility smaller, the biggest for reaching reflux ratio needed for separation requirement and theoretical cam curve, institute
With in the industrial production, the most do not use rectificating method (i.e. physics removes vanadium method) to remove vanadium, but use chemical method except vanadium.Chemical method
Except vanadium is to add a kind of chemical reagent in crude titanic chloride, make VOCl3Impurity is reduced by selectivity or selective precipitation, generates
The vfanadium compound of indissoluble and and TiCl4It is separated from each other.At present, that applies in the industrial production has following four kinds of methods, i.e. copper removes
Vanadium, aluminium powder are except vanadium, hydrogen sulfide are except vanadium and Organic substance are except vanadium method.Presently the most conventional is that aluminium powder removes vanadium and Organic substance except vanadium method.
Although Organic substance is cheap and easy to get except vanadium raw material, but Organic substance is except producing a large amount of polymerism, thickness during vanadium
, bulky residue liquid, residue scabs the most on the wall, has a strong impact on heat transfer；Except the titanium tetrachloride after vanadium contains
A small amount of Organic substance is had to be not readily separated removing, if in titanium sponge production, making the carbon content in the titanium sponge of production increase, shortcoming
More.Aluminium powder is more except the advantage of vanadium method, owing to technique is simple, standby except advantages such as vanadium efficiency are high, level of residue is few, vanadium is recyclable
Concerned.But aluminium powder is only applicable to, except vanadium method, the raw material that content of vanadium is relatively low, if removing the crude titanic chloride that content of vanadium is higher, will
Increase the usage amount of aluminium powder, not only increase the solid content in distillating still, have a strong impact on heat transfer, and can make in final products
Aluminum chloride exceeds standard.
In the crude titanic chloride that China produces at present, foreign matter of vanadium content is the most higher, the part that such as Tianjin Chemical Plant prepares
Crude titanic chloride is containing vanada quality about 0.3 weight %, and steel climbing high slag carries the crude titanic chloride vanadium content that titanium technique produces
About up to 0.5 weight %.
So, for height crude titanic chloride Han vanadium, exploitation is a kind of except vanadium is effective, mild condition, and can be fully sharp
The method removing vanadium device with existing aluminium powder is the most necessary.
Summary of the invention
For height crude titanic chloride Han vanadium, in order to avoid using the existing aluminium powder of titanium sponge factory to make gained final except vanadium technology
The defect that in product, aluminum chloride is the most up to standard, makes full use of existing aluminium powder and removes the intact device of vanadium, and overcome Organic substance to remove
The residue that vanadium causes glues the defect of wall, a kind of method that the invention provides titanium tetrachloride vanadium removal, uses the side that the present invention provides
Method, except vanadium is effective, condition is gentleer.
Specifically, the invention provides a kind of method that crude titanic chloride removes vanadium, the method includes:
(1) content of vanadium crude titanic chloride more than 0.3 weight % is contacted except vanadium reagents carries out first with organic, and will
The product that first contact obtains carries out solid-liquid separation, the content of vanadium fall in the liquid phase that described first contact makes solid-liquid separation obtain
Below as little as 0.2 weight %；
(2) liquid phase that step (1) solid-liquid separation obtains is carried out aluminium powder except vanadium；
Wherein, the temperature of described first contact is 25-100 DEG C, relative to the described crude titanic chloride of 100 weight portions, institute
Stating organic consumption except vanadium reagents is 0.5-10 weight portion.
Organic substance except vanadium and aluminium powder are except the method associating of vanadium, is processed high content of vanadium (more than 0.3 weight %) by the present invention
Crude titanic chloride, makes full use of existing aluminium powder and removes the intact device of vanadium, and level of residue is few, except vanadium is effective, the solid of generation
Settling property is good, all has greater advantage except vanadium and aluminium powder with being used alone Organic substance, specifically, to content of vanadium be compared with vanadium
The crude titanic chloride of 0.5 weight %, is used alone Organic substance except the method for vanadium, and the level of residue of generation is many, and has slight residual
Slag glues the phenomenon of wall；And it being used alone the method that aluminium powder removes vanadium, the aluminium powder amount of consumption is big, and the content of the aluminum chloride in product
Higher, the level of residue of generation is many.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that described herein specifically
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The end points of scope disclosed in this article and any value are not limited to this accurate scope or value, these scopes or
Value should be understood to the value comprised close to these scopes or value.For numerical range, between the endpoint value of each scope, respectively
Between endpoint value and the single point value of individual scope, and can obtain one or more between single point value with combination with one another
New numerical range, these numerical rangies should be considered the most specifically to disclose.
The invention provides a kind of method that crude titanic chloride removes vanadium, wherein, the method includes:
(1) content of vanadium crude titanic chloride more than 0.3 weight % is contacted except vanadium reagents carries out first with organic, and will
The product that first contact obtains carries out solid-liquid separation, the content of vanadium fall in the liquid phase that described first contact makes solid-liquid separation obtain
Below as little as 0.2 weight %；
(2) liquid phase that step (1) solid-liquid separation obtains is carried out aluminium powder except vanadium；
Wherein, the temperature of described first contact is 25-100 DEG C, relative to the described crude titanic chloride of 100 weight portions, institute
Stating organic consumption except vanadium reagents is 0.5-10 weight portion.
In the present invention, the temperature of described first contact can change in a big way.Such as, described first contact
The purpose of the present invention can be realized when temperature is 25-100 DEG C, but in order to reach more preferable effect, the temperature of described first contact
Degree is preferably 30-90 DEG C, more preferably 35-80 DEG C.The time of described first contact has no particular limits, such as, can be 10
More than minute.Preferably, the time of described first contact is 0.5-3 hour, more preferably 0.5-1.5 hour.In order to make thick four
Titanium chloride is fully contacted except vanadium reagents with organic, and described first contact is the most under agitation carried out.
Implication and the source of the crude titanic chloride in the present invention are well known to those skilled in the art, such as, and thick four chlorinations
Titanium can be that chloridising produces titanium white and the intermediate product of Kroll process production titanium sponge process, is commonly referred to as the most purified
Titanium tetrachloride containing impurity.Carrying out the crude titanic chloride except vanadium in the present invention can be thick four chlorinations without any process
Titanium, it is also possible to be the crude titanic chloride through pretreatment.Without the crude titanic chloride of any process can contain 0.3-1 weight
The VOCl of amount %3, the FeCl of 0.1-0.3 weight %3, the AlCl of 0.15-0.3 weight %3, the SiCl of 0.1-0.2 weight %4With
98.2-99.3 the TiCl of weight %4And inevitable other trace impurity.According to a kind of preferably embodiment party of the present invention
Formula, before carrying out except vanadium, the pretreatment carrying out crude titanic chloride distilling includes SiCl to remove4Miscellaneous at interior low boiling
Matter.The step of described distillation and condition are the conventional selection of this area, do not repeat them here.Carrying out in step (1) first connects
The content of vanadium in crude titanic chloride before Chuing can be 0.3-1 weight %, preferably 0.5-1 weight %, the content of titanium tetrachloride
Can be 98.2-99.7 weight %.Additionally, step (1) carries out the crude titanic chloride before the first contact generally possibly together with 0.1-
The FeCl of 0.3 weight %3AlCl with 0.15-0.3 weight %3。
It addition, without specified otherwise, in the present invention, all of content of vanadium refers to VOCl3(vanadium oxytrichloride) is counted
Content of vanadium.
According to the present invention, in step (1), to described crude titanic chloride with described organic there is no spy except the consumption of vanadium reagents
Other restriction, can be the conventional selection of this area.Such as, relative to the described crude titanic chloride of 100 weight portions, described organic
Except the consumption of vanadium reagents can be 0.5-10 weight portion, preferably 0.8-8 weight portion, more preferably 1-6 weight portion.
According to the present invention, in step (1), there is no particular limitation for described organic kind except vanadium reagents, can be this
The conventional selection in field.Such as, described organic except vanadium reagents can be fatty acid, soaps, amine, aphthenic acids, mineral oil, animal
One or more in oil, vegetable oil, oil, Cera Flava and paraffin.In view of the economy of raw material with except the effect of vanadium, described in have
Machine is preferably one or more in fatty acid, mineral oil, animal oil and vegetable oil except vanadium reagents.Described fatty acid can be full
With fatty acid and/or unsaturated fatty acid.The chain length of described satisfied fatty acid can be C5-C9, described unsaturated fatty acid
Chain length can be C10-C30.According to a kind of preferred embodiment of the present invention, described organic except vanadium reagents be Heptoic Acid
One or more in (positive enanthic acid), n-nonanoic acid, palmitoleic acid, oleic acid, linoleic acid and mineral oil.
According to the present invention, in step (1), there is no particular limitation for the mode of solid-liquid separation, can be the conventional choosing of this area
Select, such as, can realize solid-liquid separation by the way of being centrifuged, filter, staticly settling.Preferably implement according to the present invention is a kind of
Mode, the mode of solid-liquid separation is for staticly settling.The described time staticly settled can be 0.5-10 hour, and preferably 1-6 is little
Time.There is no particular limitation for the described temperature staticly settled, such as, can carry out under room temperature (20-30 DEG C).
According to the present invention, described in after the process that staticly settles terminates, sample in differing heights section, solid by carrying out after centrifugal
Assay.Solid content in the liquid phase that step (1) obtains is less than 10g/L, preferably 1-9g/L, i.e. takes solid content and meets above-mentioned
The liquid phase of standard carries out follow-up aluminium powder except vanadium process.Content of vanadium in described liquid phase is 0.01-0.2 weight %.Solid content is
Refer to take the sample of unit volume and be centrifuged separating (industrial solid content be usually centrifugal then just can measure) after drying
The content of the solid obtained.
In the present invention, in step (1), solid-liquid separation is in addition to obtaining liquid phase, and the solid-liquid mixed phase of lower floor is also obtained,
Can be referred to as lower floor's mud Han vanadium.Described lower floor mud Han vanadium may be used for ensuing industry vanadium extraction, the tool of vanadium extraction
Step and the condition of body are well known to those skilled in the art, and do not repeat them here.
Except the step of vanadium and condition, there is no particular limitation to the described aluminium powder in step (2) for the present invention, can be all
The conventional selection in field.In order to aluminium powder is illustrated except vanadium technique, this specification introduces the full text of documents below: four chlorinations
Titanium aluminium powder is except vanadium technical study (Xu Liyan, national titanium dioxide industry nd Annual Meeting collection in 2011), aluminium powder are except vanadium serosity quality shadow
Sound Elements research (He Hualin, material Leader, the S1 phase in 2015, page 348) and crude titanic chloride is refined and aluminium powder is except vanadium mechanism
Research (He Hualin, Chengdu University of Technology's Master's thesis in 2015).
According to one of the present invention preferred embodiment, described aluminium powder includes except the step of vanadium: prepare titanous chloride. serosity,
And liquid phase step (1) obtained carries out second with described titanous chloride. serosity and contacts.
Wherein, the preparation process of described titanous chloride. serosity can be the conventional selection of this area, such as can be in trichlorine
Change under conditions of aluminum exists and prepare titanous chloride. serosity with aluminium powder and titanium tetrachloride, it is also possible under conditions of logical chlorine, use aluminium powder
Titanous chloride. serosity is prepared with titanium tetrachloride.
Preferred embodiment, the present invention uses aluminium powder and four chlorinations under conditions of using logical chlorine to one according to the present invention
Titanium prepares titanous chloride. serosity.Specifically, under an inert atmosphere, refining titanic chloride is mixed with aluminium powder, to above-mentioned mixture
System is passed through chlorine, when temperature is increased to 115-125 DEG C, stops being passed through of chlorine, can be prepared by described titanous chloride. serosity.
Described titanous chloride. serosity at least contains titanium tetrachloride, titanous chloride. and aluminum chloride.Wherein, described refining titanic chloride refers to
Be titanium tetrachloride content be the titanium tetrachloride of more than 99.9 weight %.The pressure (gauge pressure) of described chlorine can be 60-
80kPa.Relative to the described refining titanic chloride of 100 weight portions, the addition of described aluminium powder can be 1-5 weight portion, preferably
For 1.5-4.5 weight portion.In described titanous chloride. serosity, on the basis of the gross weight of described titanous chloride. serosity, tri-chlorination
The content of titanium can be 3-12 weight %, preferably 5-10 weight %；The content of aluminum chloride can be 1-8 weight %, preferably
For 2-7 weight %；The content of titanium tetrachloride can be 80-96 weight %, preferably 83-93 weight %.
According to the present invention, in step (2), the condition of described second contact can be the conventional selection of this area.Such as,
The condition of described second contact includes: temperature can be 135-145 DEG C, preferably 137-140 DEG C；Time can be that 0.5-2 is little
Time, preferably 0.6-1.5 hour.
According to the present invention, the ratio carrying out liquid phase that the described step (1) of the second contact obtains and titanous chloride. serosity can
Think the conventional selection of this area.Such as, the liquid phase obtained relative to the step (1) of 100 weight portions, described titanous chloride. serosity
Consumption can be 5-15 weight portion, preferably 7-13 weight portion.
Aluminium powder used in the present invention can be the conventional selection of this area.The particle diameter of described aluminium powder is typically not greater than 80
Micron.Described aluminium powder can be commercially available, such as, can be the aluminium powder that the trade mark is Gb2086-89 purchased from Xin Ao aluminium powder producer.
According to the present invention, aluminium powder is selected except the routine that the method that the mixture obtained after vanadium processes can be this area
Select, such as, can be removed by distillation high-boiling-point impurity such as aluminum chloride, one-level rectification removing low boiling impurity, two-stage rectification
Remove high-boiling-point impurity such as ferric chloride.Concrete step and parameter are those skilled in the art and know, the most superfluous at this
State.
Hereinafter will be described the present invention by embodiment.In following example, the performance of product is by following
Method records:
1) content of vanadium (in terms of vanadium oxytrichloride) by plasma photo-electric direct reading spectrometer (ICP spectrogrph, company: Li Man,
Model: prodigy7) record.
2) without specified otherwise, the crude titanic chloride used in embodiment and comparative example contains 0.5 weight %
VOCl3, the FeCl of 0.2 weight %3, the AlCl of 0.3 weight %3TiCl with 99 weight %4And inevitable other trace
Impurity.
3) assay method of solid content in liquid phase: after staticly settling end, the liquid phase taking unit volume is centrifuged separating
The content of the solid removed after supernatant and be dried to obtain.
4) mineral oil is the product that the trade mark is K125X purchased from Xin Neng petrochemical industry company limited of Sichuan Province；Aluminium powder is purchased from pungent
The product that the trade mark is Gb2086-89 of aluminium powder producer difficult to understand.
Embodiment 1
The crude titanic chloride that the present embodiment provides for the present invention is described is except the method for vanadium
(1) in a round-bottomed flask, add the mineral of crude titanic chloride 500g and 15g that content of vanadium is 0.5 weight %
Oil, stirs 1 hour at 45 DEG C.Do not occur that residue glues the phenomenon of wall.Mixture in round-bottomed flask is placed in the graduated cylinder of 1L
In, carry out staticly settling at 25 DEG C 3 hours, obtain 419g liquid phase and the 94g lower floor mud Han vanadium.Then at the different height of liquid phase
Degree section sampling, carries out solid content and the mensuration of content of vanadium (taking supernatant after Li Xin to record) by centrifugal.Wherein, the consolidating of liquid phase part
Content maximum is 9g/L.Through analyzing, the content of vanadium in liquid phase is 0.1336 weight %.
(2) under nitrogen protection, according to 1L refining titanic chloride: the proportions suspension of 50g aluminium powder, pressure is then passed to
Power is 80kPa chlorine, stops being passed through of chlorine, prepare titanous chloride. serosity when temperature is increased to 120 DEG C.With described three
On the basis of the gross weight of titanium chloride serosity, the content of described aluminum chloride is 5 weight %, and the content of described titanous chloride. is 7 weights
Amount %, the content of described titanium tetrachloride is 88 weight %.
The liquid phase of the 419g obtained in step (1) is added the titanous chloride. serosity of 43g, is heated to 137 DEG C and protects
Hold backflow 30min, collect the condensate of 136 DEG C in reflux condensation mode outlet, be refined titanic chloride.This refined titanic chloride is carried out
Aluminum chloride content and content of vanadium measure.Through analyzing, the content of aluminum chloride is 0.001009 weight %, content of vanadium < 0.00015
Weight %.
Embodiment 2
The crude titanic chloride that the present embodiment provides for the present invention is described is except the method for vanadium
(1) in a round-bottomed flask, add the nonyl of crude titanic chloride 500g and 2.5g that content of vanadium is 0.5 weight %
Acid and the oleic acid of 2.5g, stir 0.5 hour at 80 DEG C.Do not occur that residue glues the phenomenon of wall.By the mixing in round-bottomed flask
Thing is placed in the graduated cylinder of 1L, carries out staticly settling 1 hour at 30 DEG C, obtains 404g liquid phase and the 97g lower floor mud Han vanadium.Then
Differing heights section in liquid phase samples, and carries out solid content and content of vanadium mensuration by centrifugal.Wherein, the solid content of liquid phase part is
Big value is 10g/L.Through analyzing, the content of vanadium in liquid phase is 0.1109 weight %.
(2) under nitrogen protection, according to 1L refining titanic chloride: the proportions suspension of 25g aluminium powder, pressure is then passed to
Power is 70kPa chlorine, stops being passed through of chlorine, prepare titanous chloride. serosity when temperature is increased to 125 DEG C.With described three
On the basis of the gross weight of titanium chloride serosity, the content of described aluminum chloride is 2 weight %, and the content of described titanous chloride. is 5 weights
Amount %, the content of described titanium tetrachloride is 93 weight %.
The liquid phase of the 404g obtained in step (1) is added the titanous chloride. serosity of 52g, is heated to 140 DEG C and protects
Hold backflow 1.5 hours, collect the condensate of 136 DEG C in reflux condensation mode outlet, be refined titanic chloride.This refined titanic chloride is entered
Row aluminum chloride content and content of vanadium measure.Through analyzing, the content of aluminum chloride is 0.001108 weight %, content of vanadium <
0.00015 weight %.
Embodiment 3
The crude titanic chloride that the present embodiment provides for the present invention is described is except the method for vanadium
(1) in a round-bottomed flask, add the grape flower of crude titanic chloride 500g and 30g that content of vanadium is 0.5 weight %
Acid, stirs 1.5 hours at 35 DEG C.Do not occur that residue glues the phenomenon of wall.Mixture in round-bottomed flask is placed in the amount of 1L
In Tong, carry out staticly settling at 20 DEG C 6 hours, obtain 416g liquid phase and the 111g lower floor mud Han vanadium.Then in liquid phase not
With height section sampling, carry out solid content and content of vanadium mensuration by centrifugal.Wherein, the solid content maximum of liquid phase part is
9.5g/L.Through analyzing, the content of vanadium in liquid phase is 0.1547 weight %.
(2) under nitrogen protection, according to 1L refining titanic chloride: the proportions suspension of 75g aluminium powder, pressure is then passed to
Power is 60kPa chlorine, stops being passed through of chlorine, prepare titanous chloride. serosity when temperature is increased to 115 DEG C.With described three
On the basis of the gross weight of titanium chloride serosity, the content of described aluminum chloride is 7 weight %, and the content of described titanous chloride. is 10 weights
Amount %, the content of described titanium tetrachloride is 83 weight %.
The liquid phase of the 416g obtained in step (1) is added the titanous chloride. serosity of 30g, is heated to 140 DEG C and protects
Hold backflow 1 hour, collect the condensate of 136 DEG C in reflux condensation mode outlet, be refined titanic chloride.This refined titanic chloride is carried out
Aluminum chloride content and content of vanadium measure.Through analyzing, the content of aluminum chloride is 0.001185 weight %, content of vanadium < 0.00015
Weight %.
Embodiment 4
The crude titanic chloride that the present embodiment provides for the present invention is described is except the method for vanadium
(1) carry out according to method in embodiment 1, except for the difference that, crude titanic chloride contains the VOCl of 0.3 weight %3、
The FeCl of 0.15 weight %3, the AlCl of 0.35 weight %3TiCl with 99.2 weight %4And inevitably other trace is miscellaneous
Matter.Do not occur that residue glues the phenomenon of wall.Obtain 427g liquid phase and the 86g lower floor mud Han vanadium.The solid content of liquid phase part is maximum
Value is 8g/L.Content of vanadium in liquid phase is 0.098 weight %.
(2) carry out according to the method in embodiment 1.The refined titanic chloride obtained is carried out aluminum chloride content and content of vanadium
Measure.Through analyzing, the content of aluminum chloride is 0.0013 weight %, content of vanadium < 0.00015 weight %.
Embodiment 5
The crude titanic chloride that the present embodiment provides for the present invention is described is except the method for vanadium
(1) carry out according to the method in embodiment 1, except for the difference that, in step (1), in round-bottomed flask, add thick tetrachloro
Stir 3 hours at 25 DEG C after changing titanium and mineral oil.Do not occur that residue glues the phenomenon of wall.Obtain 417g liquid phase and 96g lower floor
Containing vanadium mud.The solid content maximum of liquid phase part is 12g/L, and the content of vanadium in liquid phase is 0.1926 weight %.
(2) carrying out according to method in embodiment 1, the content of the aluminum chloride in described titanium tetrachloride is 0.00239 weight
Amount %, content of vanadium is 0.00135 weight %.
Embodiment 6
The crude titanic chloride that the present embodiment provides for the present invention is described is except the method for vanadium
Carrying out according to the method in embodiment 1, except for the difference that, the consumption of mineral oil is 4g.Do not occur that residue glues wall
Phenomenon.Obtain 421g liquid phase and the 89g lower floor mud Han vanadium.The solid content maximum of liquid phase part is 8g/L, and the vanadium in liquid phase contains
Amount is 0.1832 weight %.
(2) carrying out according to method in embodiment 1, the content of the aluminum chloride in described titanium tetrachloride is
0.00205 weight %, content of vanadium is 0.00187 weight %.
Embodiment 7
The crude titanic chloride that the present embodiment provides for the present invention is described is except the method for vanadium
Carrying out according to the method in embodiment 1, except for the difference that, the consumption of mineral oil is 50g.Do not occur that residue glues wall
Phenomenon.Obtain 434g liquid phase and the 114g lower floor mud Han vanadium.The solid content maximum of liquid phase part is 9g/L, and the vanadium in liquid phase contains
Amount is 0.1205 weight %.
(2) carrying out according to method in embodiment 1, the content of the aluminum chloride in described titanium tetrachloride is 0.001381 weight
Amount %, content of vanadium < 0.00015 weight %.
Comparative example 1
This comparative example is for illustrating the crude titanic chloride method except vanadium of reference
In a round-bottomed flask, add the crude titanic chloride 500g that content of vanadium is 0.5 weight %, be heated to 136 DEG C
And make steam reflux in vacuum condensation pipe, in round-bottomed flask, then add 5 grams of mineral oil, rise high-temperature and to 139 DEG C and protect
Hold backflow 1 minute, then heat to 140 DEG C, collect the condensate of 136.4 DEG C in reflux condensation mode outlet, be refined four chlorinations
Titanium.Through analyzing, content of vanadium < 0.00015 weight % in this refining titanic chloride.In round-bottomed flask, the weight of residue is 20.9g, has
Slight residue glues the phenomenon of wall.
Comparative example 2
This comparative example is for illustrating the crude titanic chloride method except vanadium of reference
Adding content of vanadium in a round-bottomed flask is the crude titanic chloride 500g of 0.5 weight %, add 51g according to reality
Titanous chloride. serosity prepared by the method in example 1 of executing, is heated to system 137 DEG C and maintains the reflux for 30min, going out at reflux condensation mode
Mouth collects the condensate of 136 DEG C, is refined titanic chloride.Through analyzing, in this refined titanic chloride, the content of aluminum chloride is
0.0605 weight %, content of vanadium is 0.0732 weight %, and the level of residue in flask is 11.3g.
Comparative example 3
This comparative example is for illustrating the crude titanic chloride method except vanadium of reference
Carrying out according to the method for comparative example 2, except for the difference that, the addition of described titanous chloride. serosity is 70g.Gained essence four
In titanium chloride, the content of aluminum chloride is 0.0837 weight %, and content of vanadium is 0.0001 weight %, and the level of residue in flask is
12.5g。
From the result of embodiment and comparative example it can be seen that process thick four chlorinations of high content of vanadium (more than 0.3 weight %)
Titanium, both can make full use of existing aluminium powder and remove the intact device of vanadium, and level of residue is few simultaneously, except vanadium is effective, and the solid of generation
Settling property good, compared with vanadium, all have greater advantage except vanadium and aluminium powder with being used alone Organic substance, specifically, to content of vanadium be
The crude titanic chloride of 0.5 weight %, is used alone Organic substance except the method for vanadium, and the level of residue of generation is many, and has slight residual
Slag glues the phenomenon of wall；And it being used alone the method that aluminium powder removes vanadium, the aluminium powder amount of consumption is big, and the content of the aluminum chloride in product
Higher, the level of residue of generation is many.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the technology concept of the present invention, technical scheme can be carried out multiple simple variant, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, at not lance
In the case of shield, can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to various can
The compound mode of energy illustrates the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a crude titanic chloride is except the method for vanadium, it is characterised in that the method includes:
(1) content of vanadium crude titanic chloride more than 0.3 weight % is contacted except vanadium reagents carries out first with organic, and by first
The product that contact obtains carries out solid-liquid separation, and the content of vanadium in the liquid phase that described first contact makes solid-liquid separation obtain is reduced to
Below 0.2 weight %；
(2) liquid phase that step (1) solid-liquid separation obtains is carried out aluminium powder except vanadium；
Wherein, described first contact temperature be 25-100 DEG C, relative to the described crude titanic chloride of 100 weight portions, described in have
Machine is 0.5-10 weight portion except the consumption of vanadium reagents.
Method the most according to claim 1, wherein, the temperature of described first contact is 30-90 DEG C, preferably 35-80 DEG C；
Preferably, the time of described first contact is 0.5-3 hour, more preferably 0.5-1.5 hour.
Method the most according to claim 1, wherein, the content of vanadium in described crude titanic chloride is 0.3-1 weight %, preferably
For 0.5-1 weight %, the content of titanium tetrachloride is 98.2-99.7 weight %.
Method the most according to claim 1, wherein, in step (1), relative to described thick four chlorinations of 100 weight portions
Titanium, described organic consumption except vanadium reagents is 0.8-8 weight portion, preferably 1-6 weight portion.
Method the most according to claim 1, wherein, in step (1), described organic except vanadium reagents be fatty acid, mineral
One or more in oil, animal oil and vegetable oil, preferably Heptoic Acid, n-nonanoic acid, palmitoleic acid, oleic acid, linoleic acid and ore deposit
One or more in thing oil.
Method the most according to claim 1, wherein, in step (1), the mode of solid-liquid separation is for staticly settling, described standing
The time of precipitation is 0.5-10 hour, preferably 1-6 hour.
Method the most according to claim 1, wherein, the solid content in the liquid phase that step (1) obtains is less than 10g/L, preferably
For 1-9g/L；Preferably, the content of vanadium in described liquid phase is 0.01-0.2 weight %.
Method the most according to claim 1, wherein, described aluminium powder includes except the step of vanadium: prepare titanous chloride. serosity, and
Liquid phase step (1) obtained carries out second with described titanous chloride. serosity and contacts；Preferably, described titanous chloride. serosity contains
There are titanium tetrachloride, titanous chloride. and aluminum chloride；It is highly preferred that on the basis of the gross weight of described titanous chloride. serosity, trichlorine
The content changing titanium is 3-12 weight %, more preferably 5-10 weight %；The content of aluminum chloride is 1-8 weight %, enters one
Step is preferably 2-7 weight %.
Method the most according to claim 8, wherein, the temperature of described second contact is 135-145 DEG C, preferably 137-
140℃；Time is 0.5-2 hour, preferably 0.6-1.5 hour；It is highly preferred that obtain relative to the step (1) of 100 weight portions
Liquid phase, the consumption of described titanous chloride. serosity can be 5-15 weight portion, preferably 7-13 weight portion.
Method the most according to claim 8, wherein, the method preparing described titanous chloride. serosity includes: at inert atmosphere
Under, refining titanic chloride is mixed with aluminium powder, in above-mentioned mixed system, is passed through chlorine, when temperature is increased to 115-125 DEG C
Stop being passed through of chlorine, i.e. prepare described titanous chloride. serosity；Preferably, relative to described refined four chlorinations of 100 weight portions
Titanium, the addition of described aluminium powder is 1-5 weight portion, more preferably 1.5-4.5 weight portion；It is further preferred that described aluminium powder
Particle diameter is less than 80 microns.
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Cited By (12)
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| CN106745217A (en) * | 2017-03-14 | 2017-05-31 | 江苏展钛科技有限公司 | A kind of method and reactor that titanium trichloride is produced for aluminum reduction titanium tetrachloride |
| CN107381630A (en) * | 2017-08-04 | 2017-11-24 | 攀钢集团研究院有限公司 | The method that high content of vanadium crude titanic chloride removes vanadium in advance |
| CN109264776A (en) * | 2018-11-08 | 2019-01-25 | 龙蟒佰利联集团股份有限公司 | Method for removing impurity tin in crude titanium tetrachloride |
| CN109928424A (en) * | 2019-04-29 | 2019-06-25 | 渤海大学 | A kind of vanadium slag minimizing crude titanic chloride is except vanadium technique compounding organic matter and preparation method thereof |
| CN109956498A (en) * | 2019-04-29 | 2019-07-02 | 渤海大学 | A kind of crude titanic chloride efficiently removes vanadium compounding organic matter and preparation method thereof |
| CN110040772A (en) * | 2019-04-29 | 2019-07-23 | 渤海大学 | A kind of crude titanic chloride is stable except vanadium compounding organic matter and preparation method thereof |
| CN110054217A (en) * | 2019-04-29 | 2019-07-26 | 渤海大学 | Crude titanic chloride quickly removes vanadium compounding organic matter and preparation method thereof |
| CN110078117A (en) * | 2019-04-29 | 2019-08-02 | 渤海大学 | High whiteness titanium tetrachloride compounds organic matter and preparation method thereof except prepare by vanadium for a kind of thick titanium |
| CN111087016A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Method for removing vanadium from crude titanium tetrachloride |
| CN112645381A (en) * | 2020-12-31 | 2021-04-13 | 仙桃市中星电子材料有限公司 | Method for reducing carbon content in titanium tetrachloride |
| CN113149068A (en) * | 2021-06-08 | 2021-07-23 | 攀钢集团攀枝花钢铁研究院有限公司 | Method and system for removing vanadium from crude titanium tetrachloride |
| CN114702064A (en) * | 2022-04-25 | 2022-07-05 | 宜宾天原科创设计有限公司 | Crude titanium tetrachloride vanadium removal reagent and crude titanium tetrachloride vanadium removal method |
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| CN106745217A (en) * | 2017-03-14 | 2017-05-31 | 江苏展钛科技有限公司 | A kind of method and reactor that titanium trichloride is produced for aluminum reduction titanium tetrachloride |
| CN106745217B (en) * | 2017-03-14 | 2018-02-06 | 江苏展钛科技有限公司 | A kind of method and reactor that titanium trichloride is produced for aluminum reduction titanium tetrachloride |
| CN107381630A (en) * | 2017-08-04 | 2017-11-24 | 攀钢集团研究院有限公司 | The method that high content of vanadium crude titanic chloride removes vanadium in advance |
| CN111087016A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Method for removing vanadium from crude titanium tetrachloride |
| CN109264776A (en) * | 2018-11-08 | 2019-01-25 | 龙蟒佰利联集团股份有限公司 | Method for removing impurity tin in crude titanium tetrachloride |
| CN110078117A (en) * | 2019-04-29 | 2019-08-02 | 渤海大学 | High whiteness titanium tetrachloride compounds organic matter and preparation method thereof except prepare by vanadium for a kind of thick titanium |
| CN110040772A (en) * | 2019-04-29 | 2019-07-23 | 渤海大学 | A kind of crude titanic chloride is stable except vanadium compounding organic matter and preparation method thereof |
| CN110054217A (en) * | 2019-04-29 | 2019-07-26 | 渤海大学 | Crude titanic chloride quickly removes vanadium compounding organic matter and preparation method thereof |
| CN109956498A (en) * | 2019-04-29 | 2019-07-02 | 渤海大学 | A kind of crude titanic chloride efficiently removes vanadium compounding organic matter and preparation method thereof |
| CN109928424A (en) * | 2019-04-29 | 2019-06-25 | 渤海大学 | A kind of vanadium slag minimizing crude titanic chloride is except vanadium technique compounding organic matter and preparation method thereof |
| CN109928424B (en) * | 2019-04-29 | 2021-08-03 | 渤海大学 | Compound organic matter for vanadium slag reduction crude titanium tetrachloride vanadium removal process and preparation method thereof |
| CN109956498B (en) * | 2019-04-29 | 2021-08-03 | 渤海大学 | Compound organic matter for efficiently removing vanadium from crude titanium tetrachloride and preparation method thereof |
| CN110040772B (en) * | 2019-04-29 | 2021-10-08 | 渤海大学 | Compound organic matter for stably removing vanadium from crude titanium tetrachloride and preparation method thereof |
| CN110054217B (en) * | 2019-04-29 | 2022-01-04 | 渤海大学 | Compound organic matter for quickly removing vanadium from crude titanium tetrachloride and preparation method thereof |
| CN112645381A (en) * | 2020-12-31 | 2021-04-13 | 仙桃市中星电子材料有限公司 | Method for reducing carbon content in titanium tetrachloride |
| CN113149068A (en) * | 2021-06-08 | 2021-07-23 | 攀钢集团攀枝花钢铁研究院有限公司 | Method and system for removing vanadium from crude titanium tetrachloride |
| CN114702064A (en) * | 2022-04-25 | 2022-07-05 | 宜宾天原科创设计有限公司 | Crude titanium tetrachloride vanadium removal reagent and crude titanium tetrachloride vanadium removal method |
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