CN106636682A

CN106636682A - Equipment and method for preparing high purity gallium

Info

Publication number: CN106636682A
Application number: CN201611198374.4A
Authority: CN
Inventors: 赵兴雷; 李国涛; 马瑞; 钟振成; 翁力
Original assignee: Shenhua Group Corp Ltd; National Institute of Clean and Low Carbon Energy
Current assignee: China Energy Investment Corp Ltd; National Institute of Clean and Low Carbon Energy
Priority date: 2016-12-22
Filing date: 2016-12-22
Publication date: 2017-05-10
Anticipated expiration: 2036-12-22
Also published as: CN106636682B

Abstract

The invention relates to the field of high purity gallium preparation, and discloses equipment and a method for preparing high purity gallium. The invention relates to equipment for preparing high purity gallium. The equipment comprises a closed crystallization tank 1 provided with a cone bottom; the crystallization tank 1 is internally provided with a suction pipe 12 arranged along the axial direction, a circulation hot water pipe 13 surrounding the suction pipe 12, and a first circulation cold water pipe 14 surrounding the circulation hot water pipe 13; the lower end of the suction pipe 12 is close to the conical point of the cone bottom of the crystallization tank 1; and the upper end of the suction pipe 12 stretches out of the crystallization tank 1 upwards. The invention also relates to a method for preparing high purity gallium. With the adoption of the equipment and the method for gallium crystallization, the purity and the yield of gallium can be raised, and the crystallization time can be shortened.

Description

A kind of apparatus and method for preparing high purity gallium

Technical field

The present invention relates to high purity gallium preparation field, in particular it relates to a kind of apparatus and method for preparing high purity gallium.

Background technology

High purity gallium is a kind of important dissipated metal material, is widely used in semicon industry, electronic information and new forms of energy Fields such as (such as photovoltaic, LED illuminations).At present the consumption of whole world high purity gallium is about 200 tons/year, and annual with super The speed for crossing 20% increases sharply.Shenhua Group possesses the gallium ore resources of global maximum, and reserves are up to 850,000 tons, accounts for the whole world and visits The 82% of bright reserves.In March, 2013 No. 3, Zhun Neng companies of Shenhua aluminum oxide pilot plant produces first purity for 99.99% (4N) gallium.And the high purity gallium purity required for the CIGS thin-film of photovoltaic field is at least 5N, semiconductor row The purity that industry needs is at least 6N.

For purity can be up to the preparation method of the high purity gallium of 5N to 7N it has been reported that wherein in prior art, specifically Preparation method can substantially be divided into electrolytic purification method, zone melting method, crystal pulling method, Laue method again etc. for solidifying by melt, Such as patent application CN101386923A discloses a kind of preparation method of high purity gallium, and the method is crystal pulling method, specifically, its system Preparation Method includes being cleaned with electron level deionized water after organic container, drying；The gallium material of 2kg-25kg is added into heat fusing, will be molten The liquid gallium for melting is added in cylindrical organic container；Environment temperature is controlled at 20 DEG C -25 DEG C, and cylindrical organic container is placed in into 15 In DEG C -25 DEG C of circulator bath, the liquid level of gallium liquid is less than water-bath liquid level, and the flow control of recirculated water is existed 1.0L/h-3.0L/h；By 5g-10g, purity >=7N gallium even application in one end of cylindrical bar, make seed crystal；By cylinder The other end of bar is connected with the end of weighing of balance；Step 5：Being partially disposed in behind Jia Ye centers of seed crystal will be scribbled on cylindrical bar, The volumetric expansion occurred when being solidified using gallium, the accurate Solidification Quality and Solidification Quality fraction for obtaining solidification gallium；Work as Solidification Quality When fraction reaches 60%-90%, solid gallium is taken out, liquid is poured out carries out separation of solid and liquid；The solid Ga of acquisition, and in this, as Gallium material；Step 7：Repeat step (1)-(6) two to seven times, obtains the high purity gallium of 6N-8N.The defect of the method is crystallization Speed is relatively low and crystallization content is less, it is impossible to realize fairly large continuous production, while the stability of operation is also poor.In addition, Patent application CN1566380A discloses a kind of purification process for manufacturing the high purity gallium of compound semiconductor, concrete open , the method includes：While stirring is mounted in the gallium material of the liquid condition in container, while making the freezing interface of tubular from the appearance The internal face of device is gradually solidified undergauge towards the method in container central authorities, and is made before the whole raw materials solidification in container The liquid phase for being present in container middle body is separated with liquid-solid phase.Wherein, its stirring is the rotor by placing in crystallizer Magnetic agitation realizing, but, centre position is provided with suction pipe in crystallizer, rotor may encounter the lower end of suction pipe, from And cause in crystallization process rotor cannot normal work, the reliability of crystallization operation is relatively low.

In sum, several gallium methods of purification announced at present there are problems that fluctuation of service, be badly in need of A kind of reliability is higher and can improve the method for crystallising and equipment of gallium purity.

The content of the invention

The invention aims to the reliability for overcoming gallium purity in prior art relatively low and crystallizing is relatively low lack Fall into, there is provided a kind of apparatus and method for preparing high purity gallium.

Therefore, to achieve these goals, the present invention provides a kind of equipment for preparing high purity gallium, and the equipment includes thering is cone The crystallization tank of the closing of shape bottom, the crystallization tank be internally provided with axially arrange suction pipe, arrange around the suction pipe Circulating hot water pipe and the first circulation cold water pipe arranged around the circulating hot water pipe, wherein, the lower end of the suction pipe is near the knot The cone point of the conical lower portion of brilliant groove, the upper end of the suction pipe extends upward the crystallization tank.

Preferably, the equipment also includes weighing device, and the weighing device includes residual liquid container and weighing component, described The upper end of suction pipe extends upwardly to and is connected with the residual liquid container.

It is highly preferred that the weighing device also includes the pressure regulating part for adjusting the residual liquid container internal pressure Part.

Preferably, the cone angle of the conical lower portion of the crystallization tank is 5-80 degree, preferably 10-60 degree, more preferably 20-50 Degree.

Preferably, the circulating hot water pipe and the first circulation cold water pipe are respectively and are axially arranged around the crystallization tank The helix tube of cloth.

Preferably as the vertical range at top edge and the top of the crystallization tank of the helix tube of first circulation cold water pipe To crystallize the 2-20% of groove height.

The screw diameter of helix tube preferably as circulating hot water pipe and the helix tube as first circulation cold water pipe it Than for 1：1.5-5, more preferably 1：2-4；

It is 1 preferably as the screw diameter of helix tube and the ratio of the radial dimension of crystallization tank of first circulation cold water pipe： 8-30, more preferably 1：10-20.

Preferably as first circulation cold water pipe helix tube lower limb be located at the crystallization tank conical lower portion with On.

Preferably, the equipment also includes the second circulation cold water pipe being arranged on the crystallization tank outer wall.

Preferably, the equipment is also included for placing crystallization tank and causing the gallium in crystallization tank conical lower portion to keep liquid The hot water water bath of state.

On the other hand, the invention provides a kind of employing the said equipment method for preparing high purity gallium, the method includes：Lazy Property atmosphere under, will liquid metallic gallium feedstock add crystallization tank in crystallized, wherein, during crystallization, using circulation The temperature in circulating water regulation and control crystallization tank in circulating hot water and first circulation cold water pipe in hot-water line, the raffinate of generation leads to Cross suction pipe and discharge crystallization tank.

Preferably, methods described also includes：Before the metallic gallium feedstock by liquid adds crystallization tank, using circulating hot water The circulating water in circulating hot water and first circulation cold water pipe in pipe is by the temperature adjustment in crystallization tank to more than 35 DEG C.

Preferably, during crystallization, the temperature for controlling the circulating water in first circulation cold water pipe is 0-15 DEG C.

Preferably, during crystallization, the coolant-temperature gage that enters of the circulating hot water in the circulating hot water pipe is 35-80 DEG C, Flow is 5-30L/h；The coolant-temperature gage that enters of the circulating water in the first circulation cold water pipe is 2-25 DEG C, and flow is 10-80L/ h。

Preferably, according to the testing result of the weight of the raffinate discharged by suction pipe judging the terminal of single crystallization；

It is highly preferred that when the weight of the raffinate discharged accounts for the 1.4-2% for adding the metallic gallium feedstock weight in crystallization tank, Stop crystallization.

Preferably, the method also includes：After crystallization is stopped, by the circulation in the raising first circulation cold water pipe The temperature of cold water causes the watery fusion that first circulation cold water pipe outer wall is adhered to, and by keeping the conical lower portion of the crystallization tank Temperature cause the watery fusion being deposited in the conical lower portion of crystallization tank, then repeatedly crystallization process.

Preferably, it is added without crystal seed in crystallization process.

The invention provides a kind of control crystallization direction along crystallization tank axially from top to bottom, along crystallization tank radially by first Circulating water pipe starts the high purity gallium preparation technology to inside and outside melting recrystallization repeatedly, the equipment and crystallization side using the present invention Method, it is possible to achieve the further purification (more than 4N wherein, 4N represents the purity of 99.99 weight % to gallium purity) of gallium. Compared to prior art, the method for the present invention and equipment mainly have the advantage that：(1) magnetic agitation is cancelled, by crystallizing Cheng Fanfu aspirates and returns raffinate, realizes the stirring of process, and preferably carrys out real-time monitoring crystallization degree by weighing raffinate weight With control crystallization terminal；(2) using the crystallization tank with conical lower portion, because the bottom is taper, with constant slope, because This, can as far as possible make crystallization raffinate by self gravitation stream to crystallization trench bottom.Further, since by central tube as close possible to The cone point of the conical lower portion of crystallization tank, therefore, it can extract all crystallization raffinates as far as possible, while reducing crystallization process repeatedly The complex operations of mobile original center pipette.

Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.

Description of the drawings

Fig. 1 is a kind of apparatus and method schematic diagram for preparing high purity gallium of preferred embodiment of the invention；

Fig. 2 is the schematic diagram of a kind of first circulation cold water pipe of specific embodiment of the invention and circulating hot water pipe；

A kind of set-up mode of the crystallization tank point for measuring temperature of specific embodiment of Fig. 3 present invention；Wherein, Fig. 3 a are that crystallization tank is surveyed The top view that warm spot is arranged, Fig. 3 b are the side views that crystallization tank point for measuring temperature is arranged；

Fig. 4 is that the temperature change of each point for measuring temperature is bent in crystallization tank during gallium crystallization experiment in the embodiment of the present invention 1 Line；

Fig. 5 is the comparison diagram of impurity content in raw material and product in the embodiment of the present invention 1.

Description of reference numerals

1 crystallization tank

The inert gas of 11 lid, 12 suction pipe, 13 circulating hot water pipe, 14 first circulation cold water pipe, 15 inert gas entrance 16 Export the circulating hot water of 17 charging aperture, 18 second circulation cold water pipe, 19 hot water water bath, 131 circulating hot water pipe's suction line 132 The first circulation cold water pipe of 133 circulating hot water pipe's outlet line of pipe spiral part, 141 first circulation cold water pipe suction line 142 The first circulation cold water pipe outlet line of spiral part 143

2 weighing devices

The pressure regulating part of 21 residual liquid container, 22 weighing component 23

Specific embodiment

The specific embodiment of the present invention is described in detail below.It should be appreciated that described herein concrete Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.

Herein the end points and any value of disclosed scope is not limited to the accurate scope or value, these scopes or Value should be understood to the value comprising close these scopes or value.For number range, between the endpoint value of each scope, respectively Between the endpoint value of individual scope and single point value, and individually one or more can be obtained with combination with one another between point value New number range, these number ranges should be considered concrete open herein.

The invention provides a kind of equipment for preparing high purity gallium, as shown in figure 1, the equipment includes the envelope with conical lower portion The crystallization tank 1 for closing, the crystallization tank 1 is internally provided with the suction pipe 12 for axially arranging, the circulation arranged around the suction pipe 12 Hot-water line 13 and the first circulation cold water pipe 14 arranged around the circulating hot water pipe 13, wherein, the lower end of the suction pipe 12 is near institute The cone point of the conical lower portion of crystallization tank 1 is stated, the upper end of the suction pipe 12 extends upward the crystallization tank 1.

According to equipment of the present invention, to the shape of crystallization tank 1, there is no particular limitation, and for example it can be pros Shape, tubular etc..

According to equipment of the present invention, the purpose that the top of crystallization tank 1 is provided with lid 11 to realize closing such that it is able to External dust etc. is avoided to the pollution inside crystallization tank 1, and then ensure that the cleanliness factor of crystalline environment.

According to equipment of the present invention, inert gas entrance 15 is also provided with the lid and inert gas goes out Mouth 16 and the charging aperture 17 connected with raw material tank, the inert gas entrance 15 and inert gas outlet 16 are respectively used to be passed through With discharge inert gas to keep crystallization process in inert gas atmosphere in crystallization tank.

According to equipment of the present invention, in a preferred embodiment, the equipment also includes weighing device 2, institute Weighing device 2 is stated including residual liquid container 21 and weighing component 22, the upper end of the suction pipe 12 extends upwardly to and holds with the raffinate Device 21 is connected such that it is able to which the testing result of the weight of raffinate that weighing is discharged by suction pipe 12 is judging end of single crystallization Point.Wherein, the weighing component 22 can be various conventional weighing components, for example, can be balance.

According to equipment of the present invention, it is highly preferred that the weighing device 2 is also included for adjusting the residual liquid container The pressure regulating part 23 of 21 internal pressures such that it is able to by the internal pressurization of the residual liquid container 21 or decompression passing through Raffinate in the suction crystallization tank 1 of the suction pipe 12.Wherein, when the internal pressure of residual liquid container 21 is reduced, by suction pipe 12 from knot The conical lower portion of brilliant groove 1 suctions out raffinate, when the internal pressure of residual liquid container 21 is raised, by suction pipe 12 by residual liquid container 21 Raffinate is sent back in the conical lower portion of crystallization tank 1.The aspiration procedure of the raffinate can not only judge the terminal of single crystallization, can be with Crystal solution in crystallization tank 1 is well mixed.

According to equipment of the present invention, it is preferable that the cone angle of the conical lower portion of the crystallization tank 1 is 5-80 degree, more excellent Elect 10-60 degree, most preferably 20-50 degree as such that it is able to so that crystallization raffinate relies on self gravitation stream to crystallization trench bottom, and Crystallization raffinate is all extracted as far as possible to residual liquid container 21, to improve the accuracy of single crystallization endpoint.

According to equipment of the present invention, it is preferable that the circulating hot water pipe 13 and the first circulation cold water pipe 14 are each From for around the helix tube of the axial arranging of the crystallization tank 1.

As illustrated in fig. 1 and 2, in a kind of specific embodiment of the invention, the circulating hot water pipe 13 have be interconnected Circulating hot water pipe's suction line 131, circulating hot water pipe's spiral part 132 and circulating hot water pipe's outlet line 133, and cycling hot Pipe inlet pipeline 131 is fixed on the lid 11 of crystallization tank 1, for the circulating hot water outside crystallization tank 1 to be passed through into cycling hot In water pipe spiral part 132；Circulating hot water pipe's outlet line 133 is fixed on the lid 11 of crystallization tank 1, for circulating The circulating hot water of the bottom of hot-water line spiral part 132 leads to the outside of crystallization tank 1.

As illustrated in fig. 1 and 2, in another kind specific embodiment of the invention, the first circulation cold water pipe 14 has phase Intercommunicated first circulation cold water pipe suction line 141, first circulation cold water pipe spiral part 142 and first circulation cold water pipe go out Mouthful pipeline 143, and first circulation cold water pipe suction line 141 is fixed on the lid 11 of crystallization tank 1, for by outside crystallization tank 1 The first circulation cold water in portion is passed through in first circulation cold water pipe spiral part 142；The first circulation cold water pipe outlet line 143 It is fixed on the lid 11 of crystallization tank 1, for the first circulation cold water of the bottom of first circulation cold water pipe spiral part 142 to be led to The outside of crystallization tank 1.

According to equipment of the present invention, it is preferable that the top edge and institute as the helix tube of first circulation cold water pipe 14 The vertical range for stating the top of crystallization tank 1 is the 2-20% for crystallizing groove height.Further, since crystallization process along crystallization tank 1 by Up to carry out down, the crystallization that the initial stage produces can swim in the surface of crystal solution, it is therefore preferred that will be used as first circulation cold water The top edge of the helix tube of pipe 14 and the 5-15% that the vertical range at the top of the crystallization tank 1 is crystallization groove height, such energy Crystallization contact with the lid 11 at the top of crystallization tank on the surface of crystal solution is enough avoided, also can be avoided with the growth of crystalline volume Its risk that lid 11 may be burst.

According to equipment of the present invention, the circulating hot water pipe 13 and first circulation cold water pipe 14 are non-contiguously arranged, The first circulation cold water pipe 14 is non-contiguously arranged with the crystallization tank 1 such that it is able to is controlled the intercrystalline direction of crystallization tank 1 and is existed It is inwardly outer by first circulation cold water pipe 14 in the radial direction to extend.

In the preferred embodiment of the present invention, it is cold with as first circulation as the helix tube of circulating hot water pipe 13 The ratio of the screw diameter of the helix tube of water pipe 14 is 1：1.5-5, more preferably 1：2-4 such that it is able to more accurately control crystallization The direction that groove 1 is radially crystallized.Here, the screw diameter of helix tube refers to the external diameter of spiral part.

In another kind of preferred embodiment of the present invention, as the screw diameter of the helix tube of first circulation cold water pipe 14 It is 1 with the ratio of the radial dimension of crystallization tank 1：8-30, more preferably 1：10-20 such that it is able to avoid the side of the intercrystalline of crystallization tank 1 To from the beginning of the position of close its inwall.Here, when crystallization tank 1 is tubular, the radial dimension of its crystallization tank 1 refers to the tubular Internal diameter.

According to equipment of the present invention, it is preferable that be located at as the lower limb of the helix tube of first circulation cold water pipe 14 More than the conical lower portion of the crystallization tank 1 such that it is able to avoid producing crystallization, Jin Erbao in the conical lower portion of the crystallization tank 1 The quality of card crystallization.

In the preferred embodiment of the present invention, the equipment also includes the be arranged on the outer wall of the crystallization tank 1 Two circulating water pipes 18, wherein second circulation cold water pipe 18 can be the spiral around the outer wall axial arranging of the crystallization tank 1 Pipe such that it is able to ensure certain thermograde, and control crystallization direction.

According to equipment of the present invention, it is preferable that the equipment is also included for placing crystallization tank 1 and causing crystallization tank 1 Gallium in conical lower portion keeps the hot water water bath 19 of liquid such that it is able to avoid in the conical lower portion of the crystallization tank 1 Crystallization is produced, and then is ensured the quality of crystallization and is crystallized efficiently separating for residual night.

According to equipment of the present invention, the equipment can also include raw material tank, and the raw material tank connects with crystallization tank 1 It is logical.

According to equipment of the present invention, crystallization tank 1, raw material tank, first circulation cold water pipe 14 and circulating hot water pipe's 13 Material is preferably polytetrafluoroethylene (PTFE) such that it is able to the pollution problem that may be present of effectively solving equipment material.

In a kind of specific embodiment of the invention, the equipment also includes：8-10 thermometer being arranged in crystallization tank, These thermometers are randomly provided in crystallization tank 1, and its upper end is fixed on lid 11, and lower end extends to the difference in crystallization tank 1 Depth, for example, as shown in figure 3, be randomly provided 8 thermometers in crystallization tank 1, respectively T1, T2, T3, T4, T5, T6, T7 and T8.Wherein, T1, T2 are arranged on the position between circulating hot water pipe 13 and first circulation cold water pipe 14, are 16cm relative to height Crystallization tank 1, the corresponding depth of T1 be 9-12cm, the corresponding depth of T2 be 12-13cm；T3, T4, T5, T6, T7 and T8 set at random Put the position between the inwall of first circulation cold water pipe 14 and crystallization tank 1, relative to height for 16cm crystallization tank 1, T3 pair The depth answered is 6-8cm, and the corresponding depth of T4 is 8-10cm, and the corresponding depth of T5 is 10-12cm, and the corresponding depth of T6 is 12- The corresponding depth of 14cm, T7 is 13-14cm, and the corresponding depth of T8 is 14-15cm.

Of the present invention being fixed on lid 11 refers to that pipeline or thermometer are laterally fixed irremovable and up and down may be used Movably it is fixed on lid.

On the other hand, the invention provides a kind of employing the said equipment method for preparing high purity gallium, the method includes：Lazy Property atmosphere under, will liquid metallic gallium feedstock add crystallization tank 1 in crystallized, wherein, during crystallization, using circulation The temperature in circulating water regulation and control crystallization tank 1 in circulating hot water and first circulation cold water pipe 14 in hot-water line 13, generation Raffinate discharges crystallization tank 1 by suction pipe 12.

Can carry out in clean operating desk in the crystallization process of the present invention, to ensure the cleanliness factor of crystalline environment.This In bright, the inert atmosphere can be provided by any inert gas not reacted with gallium, for example, can be provided by nitrogen.

According to method of the present invention, it is preferable that the method also includes：Before crystallization, by inert gas entrance 15 are passed through under the conditions of high pure nitrogen into crystallization tank 1, and raw material tank, crystallization tank 1, residual liquid container 21 are cleaned with water and them are connected Pipeline inside.After cleaning, then drying is purged with high pure nitrogen, until hygronom is shown as zero, and from crystallization tank top Observation exists without the globule and moisture.Wherein, the water can be deionized water.In the present invention, high pure nitrogen can be 99.999-99.9999 the nitrogen of weight %.

According to method of the present invention, it is preferable that the method also includes：Crystallization is added in the metallic gallium feedstock by liquid Before groove 1, using the circulating water in the circulating hot water in circulating hot water pipe 13 and first circulation cold water pipe 14 by crystallization tank 1 Temperature adjustment to be more than 35 DEG C, it is highly preferred that by liquid metallic gallium feedstock add crystallization tank 1 before, by circulating hot water Circulating hot water temperature control in pipe 13 controls its discharge for 5-15L/h in the range of 50-70 DEG C, and first circulation is cold The temperature control of the circulating water in water pipe 14 controls its discharge for 15-25L/h in the range of 40-50 DEG C.

According to method of the present invention, it is preferable that the method also includes：Observation 8 point for measuring temperature thermometers of crystallization tank The temperature change of (T1, T2, T3, T4, T5, T6, T7 and T8), and gradually adjust the circulating hot water and first in circulating hot water pipe 13 The desired temperature of the circulating water in circulating water pipe 14 so that the temperature of each point for measuring temperature is not less than 35 DEG C, and stable 10min More than.

According to method of the present invention, it is preferable that the method also includes：It is passed through in raw material tank and crystallization tank 1 respectively High pure nitrogen, and ensure that the flow-rate ratio that nitrogen is passed through in raw material tank and crystallization tank 1 is 4-5：1, then detect clean operating desk and Cleanliness factor in crystallization tank, when the number of particles that cleanliness factor is less than 0.5 micron is less than 10000, then by raw material tank Liquid metallic gallium feedstock add crystallization tank 1 in.

According to method of the present invention, it is preferable that the method also includes：By control in raw material tank and crystallization tank 1 By the flow of high pure nitrogen, the metallic gallium feedstock of the liquid in raw material tank is pressed in crystallization tank 1, it is highly preferred that raw material tank It is 5-10 with the flow-rate ratio that nitrogen is passed through in crystallization tank 1：1.High Purity Nitrogen is kept to be passed through by charging process such that it is able to prevent Impurity is mixed in gas, it is ensured that the cleanliness factor of crystalline environment.In the present invention, can by the weight change of crystallization tank 1 come It is determined that the addition of crystallization raw material.

According to method of the present invention, it is preferable that during crystallization, following in first circulation cold water pipe 14 is controlled The temperature of ring cold water is 0-15 DEG C, it is highly preferred that in crystallization tank after the gallium of addition liquid, when the temperature of each point for measuring temperature is tieed up Keep steady fixed (each point for measuring temperature keeps a temperature value at least 10min) when, then reduce the circulation in first circulation cold water pipe 14 The temperature of cold water is crystallized to 0-15 DEG C.Wherein, the temperature of circulating water in first circulation cold water pipe 14 is reduced to 0-15 DEG C it is preferably and gradually lowers the temperature, the speed of the cooling is 0.2-2 DEG C/min.In control crystallization process in first circulation cold water pipe 14 The mode of temperature of circulating water can be：Circulating water in by controlling first circulation cold water pipe 14 enter coolant-temperature gage and Realizing, can for example control the circulating water in the first circulation cold water pipe 14 enters coolant-temperature gage for 2-25 (preferably to flow For 2-12 DEG C), flow be 10-80L/h (preferably 10-40L/h) to realize crystallization process in circulating water temperature in 0-15 In the range of DEG C.

Temperature according to method of the present invention, during crystallization, to the circulating hot water in circulating hot water pipe 13 Without special requirement, as long as so that the gallium passed through in suction pipe keeps liquid.For example can be by following described in control Circulating hot water in ring hot-water line 13 enters coolant-temperature gage for 35-80 DEG C (preferably 40-70 DEG C), flow be 5-30L/h (preferably 10-30L/h) to realize crystallization process in circulating hot water temperature in the range of 35-60 DEG C.

According to method of the present invention, it is preferable that according to the testing result of the weight of the raffinate discharged by suction pipe 12 To judge the terminal of single crystallization；It is highly preferred that the weight for working as the raffinate discharged accounts for the metallic gallium feedstock weight added in crystallization tank 1 During the 1.4-2% of amount, stop crystallization such that it is able to which the relation for considering impurity content with crystallization yield is to accurately determine knot Brilliant terminal.

In a kind of specific embodiment of the invention, substantially judge what is crystallized by observing the temperature change of each point for measuring temperature Terminal, when the temperature of each point for measuring temperature tends towards stability, such as when can not change at least 10min, it can be determined that crystallization Close terminal.For the cost that saves manpower and time, it is preferable that the change for first passing through point for measuring temperature temperature substantially judges the end for crystallizing Point, further according to the raffinate discharged by suction pipe 12 weight testing result judging the terminal of single crystallization exactly.

Those skilled in the art knows that crystallization is reached after terminal, and the raffinate discharged finally by suction pipe 12 is not returned again to To crystallization tank 1, but discharged by residual liquid container 21, then cause the watery fusion in crystallization tank 1 to repeat above-mentioned crystallization Process.Wherein crystallize the content and metal of the number of times according to foreign ion of interest in the product for finally needing to obtain of repetition Yield, the purity of gallium and determine, for example if necessary to by final products content of impurities control below 0.0005 weight %, And the yield of gallium is controlled more than 87 weight %, purity be 5N levels and its more than, can repeatedly crystallization 5-8 time.

In a kind of specific embodiment of the invention, the method can also include：After crystallization is stopped, by improving institute The temperature of circulating water in first circulation cold water pipe 14 is stated so that the watery fusion of the outer wall of first circulation cold water pipe 14 attachment, and The watery fusion being deposited in the conical lower portion of crystallization tank 1 is caused by keeping the temperature of the conical lower portion of the crystallization tank 1.Its In, the temperature of circulating water in the first circulation cold water pipe 14 can be improved to 40-50 DEG C, treat that the temperature of each point for measuring temperature is equal After more than 35 DEG C and stably after 20min, heating process is completed, then repeatedly crystallization process.

According to method of the present invention, after crystallization process is finally stopped, the resultant metal gallium that can be taken in crystallization tank 1 enters Row composition measurement.After yield, purity in measure impurity content and gallium reaches requirement, crystal solution can be discharged and to system The equipment of standby high purity gallium carries out overall cleaning, wherein, 1-5mol/L KOH solutions cleaning device and pipeline 2-3 is respectively adopted It is secondary, then with high-purity water washing device and pipeline 2-3 time, in liquid to be cleaned without residual gallium drop and cleaning fluid pH value for 7 or so when, clearly Washed journey terminates.Cleaning is purged after terminating with High Purity Nitrogen, until hygronom is shown as zero end.All power supplys are cut off, closing is followed Ring water pump and High Purity Nitrogen source of the gas, experiment terminates.

According to method of the present invention, it is preferable that be added without crystal seed in crystallization process such that it is able to reduce answering for operation Polygamy.

Hereinafter will be described the present invention by embodiment.

Elementary analysis is completed by Shanghai Inorganic Material Analysis test center of silicate research institute.Specifically detection method is GDMS explication de textes.

Embodiment 1

The present embodiment is used to illustrate the apparatus and method for preparing high purity gallium of the present invention.

(1) equipment for preparing high purity gallium as Figure 1-3, it is by polytetrafluoroethylene (PTFE) raw material tank, with conical lower portion The tubular polytetrafluoroethylene (PTFE) crystallization tank 1 of closing and hot water water bath 19 and weighing device 2 are constituted, and are surrounded on the outer wall of crystallization tank 1 Polytetrafluoroethylene (PTFE) second circulation cold water pipe 18 is provided with, the conical lower portion of crystallization tank 1 is placed in hot water water bath 19, and raw material Groove, crystallization tank 1 and weighing device 2 are interconnected, and the cone angle of conical lower portion is 30 degree, and the top of crystallization tank 1 is provided with lid 11, institute State the charging aperture 17 for inert gas entrance 15 and inert gas outlet 16 being provided with lid and being connected with raw material tank, the knot Brilliant groove 1 be internally provided with axially arrange suction pipe 12, poly- the four of circulating hot water pipe 13 is provided as around the suction pipe 12 PVF helix tube and the polytetrafluoroethylhelix helix tube of first circulation cold water pipe 14 is provided as around the circulating hot water pipe 13, The circulating hot water pipe 13 has the circulating hot water pipe's suction line 131 being interconnected, circulating hot water pipe's spiral part 132 and follows Ring hot-water line outlet line 133, and circulating hot water pipe's suction line 131 is fixed on the lid 11 of crystallization tank 1；The cycling hot Pipe outlet pipeline 133 is fixed on the lid 11 of crystallization tank 1；The first circulation cold water pipe 14 has first for being interconnected Circulating water tube inlet pipeline 141, first circulation cold water pipe spiral part 142 and first circulation cold water pipe outlet line 143, and First circulation cold water pipe suction line 141 is fixed on the lid 11 of crystallization tank 1；The first circulation cold water pipe outlet line 143 are fixed on the lid 11 of crystallization tank 1.As the top edge and the crystallization tank 1 of the helix tube of first circulation cold water pipe 14 Top cover vertical range be crystallize groove height 5%, as circulating hot water pipe 13 helix tube with as first circulation The ratio of the screw diameter of the helix tube of cold water pipe 14 is 1：4, as first circulation cold water pipe 14 helix tube screw diameter with The ratio of the radial dimension of crystallization tank 1 is 1：8, it is located at the crystallization tank as the lower limb of the helix tube of first circulation cold water pipe 14 It is more than 1 conical lower portion, wherein, the lower end of the suction pipe 12 near the conical lower portion of the crystallization tank 1 cone point, the suction pipe 12 Upper end extends upward the crystallization tank 1 and connects to residual liquid container conical flask 21 and with residual liquid container conical flask 21, residual liquid container Conical flask 21 is placed on weighing component balance 22.As best shown in figures 3 a and 3b, 8 thermometers are randomly provided in crystallization tank 1, point Wei not T1, T2, T3, T4, T5, T6, T7 and T8.Wherein, T1, T2 be arranged on circulating hot water pipe 13 and first circulation cold water pipe 14 it Between position, relative to height for 16cm crystallization tank 1, the corresponding depth of T1 be 9cm, the corresponding depth of T2 be 12cm；T3、 T4, T5, T6, T7 and T8 are randomly provided the position between the inwall of first circulation cold water pipe 14 and crystallization tank 1, relative to height For the crystallization tank 1 of 16cm, the corresponding depth of T3 is 6cm, and the corresponding depth of T4 is 8cm, and the corresponding depth of T5 is 10cm, and T6 is corresponding Depth be 12cm, the corresponding depth of T7 be 13cm, the corresponding depth of T8 be 14cm.The said equipment is placed on into clean operating desk It is interior, the inspection of pipeline connection is carried out to the said equipment, i.e. elder generation's check device crystallization tank 1, raw material tank and the connecting tube of residual liquid container 21 Whether firmly road, and checks that whether accurately 8 point for measuring temperature positions, check first circulation cold water pipe 14 and the pipeline of circulating hot water pipe 13 Breakage is whether there is with the pipeline of High Purity Nitrogen, whether joint loosens, the time that the process needs is 0.5h.

(2) power-on：Check whether the connection of each power line normal, it is ensured that power line without breakage with it is exposed after, connect electricity Source.

(3) cleaning of equipment and pipeline：99.999 weight % are passed through into crystallization tank 1 by inert gas entrance 15 high-purity Under condition of nitrogen gas, deionized water is cleaned raw material tank, crystallization tank 1, residual liquid container 21 and connects the inside 2 of their pipeline It is secondary.After cleaning, then drying is purged with high pure nitrogen, until hygronom is shown as zero, and from the observation of crystallization tank top without the globule And moisture is present.The time that the process needs is 3h.

(4) ON cycle water-bath：By the circulation in the circulating water in first circulation cold water pipe 14 and circulating hot water pipe 13 Hot water is opened, and it is 50 DEG C to adjust the temperature of the circulating water in first circulation cold water pipe 14, and discharge is 20L/h, and regulation is followed Circulating hot water temperature in ring hot-water line 13 is 50 DEG C, and discharge is 10L/h；The temperature of the hot water in hot water water bath 19 is all the time Kept for 36 DEG C, observe the temperature change of 8 points for measuring temperature of crystallization tank 1, and gradually adjust the circulation in first circulation cold water pipe 14 The desired temperature of the circulating hot water in cold water and circulating hot water pipe 13 so that the temperature of each point for measuring temperature is not less than 35 DEG C, and surely Determine more than 10min.The time that the process needs is about 2h.

(5) High Purity Nitrogen carrier gas is opened：High Purity Nitrogen source of the gas is opened, it is 20L/h to control its total flow, and control it and enter former Hopper is 4 with the flow proportional of two strands of High Purity Nitrogens of crystallization tank:1.Leave behind behind clean operating desk Qianmen, determined with Particle Size Analyzer Cleanliness factor in clean operating desk and crystallization tank 1, the number of particles controlled less than 0.5 micron is 9000, to meet experimentation Requirement to operating space cleanliness factor.The time that the process needs is about 0.5h.

(6) raw material is added：It is all higher than in the case of 35 DEG C in each point for measuring temperature temperature, by by raw material tank and crystallization tank 1 The flow-rate ratio for being passed through nitrogen is adjusted to 4：1, the gallium of the 6.7kg raw material liquids in raw material tank (is constituted by high pure nitrogen See the table below and 1) be pressed into the weight change that raw material tank is weighed in crystallization tank 1 to determine the gallium quality for adding crystallization tank 1.

(7) single crystallization process：Under conditions of high pure nitrogen is passed through in crystallization tank 1, liquid is added in crystallization tank Gallium after, when the temperature of each point for measuring temperature maintains stable (each point for measuring temperature keeps a temperature value 10min), with 1 DEG C/ The cooling rate of min reduces the temperature of the circulating water in first circulation cold water pipe 14 to 10 DEG C, according to the water-bath stream of crystallization tank Field design, along the axial direction of crystallization tank 1 from top to bottom and along the radial direction of crystallization tank 1 by the outer wall of first circulation cold water pipe 14 Start to proceed by crystallization outside inwardly.Wherein, the temperature of the circulating water in crystallization process in first circulation cold water pipe 14 is controlled Mode for 10 DEG C is：The coolant-temperature gage that enters for controlling the circulating water in the first circulation cold water pipe 14 is 12 DEG C, and flow is 15L/h, the temperature for controlling the circulating hot water in crystallization process in circulating hot water pipe 13 is that 35 DEG C of mode is：Control the circulation The coolant-temperature gage that enters of the circulating hot water in hot-water line 13 is 50 DEG C, and flow is 10L/h.In crystallization process, the temperature of each point for measuring temperature is observed Degree change, specific temperature when the temperature of each point for measuring temperature does not change in 10min, can be sentenced over time referring to Fig. 4 The close terminal of disconnected crystallization, now, causes the internal pressure of residual liquid container 21 to reduce by pressure regulating part 23 so that suction pipe 12 from The conical lower portion of crystallization tank 1 suctions out raffinate into residual liquid container 21, and by balance the weight of the raffinate is read, and the weight of raffinate is first Begin 1.6 weight % for adding the feed metal gallium in crystallization tank 1, the i.e. close terminal of the single crystallization, terminates the crystallization process, leads to Cross the raffinate that suction pipe 12 is expelled in residual liquid container 21 and be no longer back to crystallization tank 1, but by the device for transferring of residual liquid container 21 Outward, it is 1.5h that the crystallization spends the time.

(8) watery fusion repeats crystallization and elementary analysis process：After single crystallization stops, by improving described first The temperature of the circulating water in circulating water pipe 14 to 40 DEG C cause the outer wall of first circulation cold water pipe 14 attachment watery fusions, and It it is 50 DEG C by the temperature for keeping the conical lower portion of the crystallization tank 1 so that the crystallization being deposited in the conical lower portion of crystallization tank 1 Fusing, wherein, after the temperature of each point for measuring temperature is all higher than 35 DEG C and stably after 20min, heating process is completed, then repeat step (6) single crystallization process 7 times.After 7 times are terminated, all liquid metal gallium samples are extracted from crystallization tank 1 by suction pipe Each element analysis is carried out as crystalline product, testing result see the table below 2, and the quality that crystallization terminates to obtain product is 5.8kg.Every time The impurity content in the amount and raw material of raffinate and the impurity in crystalline product is detected in crystallization process, testing result is shown in Fig. 5, should This process needs used time 2h.

(9) device cleaning：Using 1mol/L KOH solutions cleaning device and pipeline 2 times, then with high-purity water washing device with Pipeline 2 times, when without residual gallium drop and cleaning fluid pH being 7 in liquid to be cleaned, cleaning process terminates.Cleaning is blown after terminating with High Purity Nitrogen Sweep, until hygronom is shown as zero end.All power supplys are cut off, water circulating pump and High Purity Nitrogen source of the gas is closed, experiment terminates.The mistake Journey takes 2h.

Embodiment 2

(1) equipment for preparing high purity gallium as Figure 1-3, it is by polytetrafluoroethylene (PTFE) raw material tank, with conical lower portion The tubular polytetrafluoroethylene (PTFE) crystallization tank 1 of closing and hot water water bath 19 and weighing device 2 are constituted, and are surrounded on the outer wall of crystallization tank 1 Polytetrafluoroethylene (PTFE) second circulation cold water pipe 18 is provided with, the conical lower portion of crystallization tank 1 is placed in hot water water bath 19, and raw material Groove, crystallization tank 1 and weighing device 2 are interconnected, and the cone angle of conical lower portion is 35 degree, and the top of crystallization tank 1 is provided with lid 11, institute State the charging aperture 17 for inert gas entrance 15 and inert gas outlet 16 being provided with lid and being connected with raw material tank, the knot Brilliant groove 1 be internally provided with axially arrange suction pipe 12, poly- the four of circulating hot water pipe 13 is provided as around the suction pipe 12 PVF helix tube and the polytetrafluoroethylhelix helix tube of first circulation cold water pipe 14 is provided as around the circulating hot water pipe 13, The circulating hot water pipe 13 has the circulating hot water pipe's suction line 131 being interconnected, circulating hot water pipe's spiral part 132 and follows Ring hot-water line outlet line 133, and circulating hot water pipe's suction line 131 is fixed on the lid 11 of crystallization tank 1；The cycling hot Pipe outlet pipeline 133 is fixed on the lid 11 of crystallization tank 1；The first circulation cold water pipe 14 has first for being interconnected Circulating water tube inlet pipeline 141, first circulation cold water pipe spiral part 142 and first circulation cold water pipe outlet line 143, and First circulation cold water pipe suction line 141 is fixed on the lid 11 of crystallization tank 1；The first circulation cold water pipe outlet line 143 are fixed on the lid 11 of crystallization tank 1.As the top edge and the crystallization tank 1 of the helix tube of first circulation cold water pipe 14 Top cover vertical range be crystallize groove height 4%, as circulating hot water pipe 13 helix tube with as first circulation The ratio of the screw diameter of the helix tube of cold water pipe 14 is 1：3, as first circulation cold water pipe 14 helix tube screw diameter with The ratio of the radial dimension of crystallization tank 1 is 1：10, it is located at the crystallization as the lower limb of the helix tube of first circulation cold water pipe 14 It is more than the conical lower portion of groove 1, wherein, the lower end of the suction pipe 12 near the conical lower portion of the crystallization tank 1 cone point, the suction pipe 12 Upper end extend upward the crystallization tank 1 and connect to residual liquid container conical flask 21 and with residual liquid container conical flask 21, raffinate holds Device conical flask 21 is placed on weighing component balance 22.As best shown in figures 3 a and 3b, 8 thermometers are randomly provided in crystallization tank 1, Respectively T1, T2, T3, T4, T5, T6, T7 and T8.Wherein, T1, T2 are arranged on circulating hot water pipe 13 and first circulation cold water pipe 14 Between position, relative to height for 16cm crystallization tank 1, the corresponding depth of T1 be 9cm, the corresponding depth of T2 be 12cm；T3、 T4, T5, T6, T7 and T8 are randomly provided the position between the inwall of first circulation cold water pipe 14 and crystallization tank 1, relative to height For the crystallization tank 1 of 16cm, the corresponding depth of T3 is 6cm, and the corresponding depth of T4 is 8cm, and the corresponding depth of T5 is 10cm, and T6 is corresponding Depth be 12cm, the corresponding depth of T7 be 13cm, the corresponding depth of T8 be 14cm.The said equipment is placed on into clean operating desk It is interior, the inspection of pipeline connection is carried out to the said equipment, i.e. elder generation's check device crystallization tank 1, raw material tank and the connecting tube of residual liquid container 21 Whether firmly road, and checks that whether accurately 8 point for measuring temperature positions, check first circulation cold water pipe 14 and the pipeline of circulating hot water pipe 13 Breakage is whether there is with the pipeline of High Purity Nitrogen, whether joint loosens, the time that the process needs is 0.5h.

(4) ON cycle water-bath：By the circulation in the circulating water in first circulation cold water pipe 14 and circulating hot water pipe 13 Hot water is opened, and it is 50 DEG C to adjust the temperature of the circulating water in first circulation cold water pipe 14, and discharge is 20L/h, and regulation is followed Circulating hot water temperature in ring hot-water line 13 is 50 DEG C, and discharge is 10L/h；The temperature of the hot water in hot water water bath 19 is all the time Kept for 38 DEG C, observe the temperature change of 8 points for measuring temperature of crystallization tank 1, and gradually adjust the circulation in first circulation cold water pipe 14 The desired temperature of the circulating hot water in cold water and circulating hot water pipe 13 so that the temperature of each point for measuring temperature is not less than 35 DEG C, and surely Determine more than 10min.The time that the process needs is about 2h.

(5) High Purity Nitrogen carrier gas is opened：High Purity Nitrogen source of the gas is opened, it is 20L/h to control its total flow, and control it and enter former Hopper is 4 with the flow proportional of two strands of High Purity Nitrogens of crystallization tank:1.Leave behind behind clean operating desk Qianmen, determined with Particle Size Analyzer Cleanliness factor in clean operating desk and crystallization tank 1, the number of particles controlled less than 0.5 micron is 8000, to meet experimentation Requirement to operating space cleanliness factor.The time that the process needs is about 0.5h.

(6) raw material is added：It is all higher than in the case of 35 DEG C in each point for measuring temperature temperature, by by raw material tank and crystallization tank 1 The flow-rate ratio for being passed through nitrogen is adjusted to 5：1, by high pure nitrogen, by the gallium of the 5kg raw material liquids in raw material tank, (composition is shown in Table 1) press-in crystallization tank 1 in, weigh raw material tank weight change come determine add crystallization tank 1 gallium quality.

(7) single crystallization process：Under conditions of high pure nitrogen is passed through in crystallization tank 1, liquid is added in crystallization tank Gallium after, when the temperature of each point for measuring temperature maintains stable (each point for measuring temperature keeps a temperature value 10min), with 1 DEG C/ The cooling rate of min reduces the temperature of the circulating water in first circulation cold water pipe 14 to 15 DEG C, according to the water-bath stream of crystallization tank Field design, along the axial direction of crystallization tank 1 from top to bottom and along the radial direction of crystallization tank 1 by the outer wall of first circulation cold water pipe 14 Start to proceed by crystallization outside inwardly.Wherein, the temperature of the circulating water in crystallization process in first circulation cold water pipe 14 is controlled Mode for 15 DEG C is：The coolant-temperature gage that enters for controlling the circulating water in the first circulation cold water pipe 14 is 12 DEG C, and flow is 12L/h, the temperature for controlling the circulating hot water in crystallization process in circulating hot water pipe 13 is that 38 DEG C of mode is：Control the circulation The coolant-temperature gage that enters of the circulating hot water in hot-water line 13 is 40 DEG C, and flow is 10L/h.In crystallization process, the temperature of each point for measuring temperature is observed Degree change, when the temperature of each point for measuring temperature does not change in 10min, it can be determined that the close terminal of crystallization, now, is adjusted by pressure Section part 23 causes the internal pressure of residual liquid container 21 to reduce so that suction pipe 12 suctions out raffinate to residual from the conical lower portion of crystallization tank 1 In liquid container 21, the weight of the raffinate is read by balance, the weight of raffinate is the feed metal gallium being initially added in crystallization tank 1 1.3 weight %, the i.e. close terminal of the single crystallization, terminate the crystallization process, are expelled in residual liquid container 21 by suction pipe 12 Raffinate is no longer back to crystallization tank 1, but by the device for transferring of residual liquid container 21 outside, it is 1.5h that the crystallization spends the time.

(8) watery fusion repeats crystallization and elementary analysis process：After single crystallization stops, by improving described first The temperature of the circulating water in circulating water pipe 14 to 40 DEG C cause the outer wall of first circulation cold water pipe 14 attachment watery fusions, and It it is 50 DEG C by the temperature for keeping the conical lower portion of the crystallization tank 1 so that the crystallization being deposited in the conical lower portion of crystallization tank 1 Fusing, wherein, after the temperature of each point for measuring temperature is all higher than 35 DEG C and stably after 20min, heating process is completed, then repeat step (6) single crystallization process 8 times.The quality that crystallization terminates to obtain product is 4.5kg.After 8 times are terminated, by suction pipe from knot All liquid metal gallium samples are extracted in brilliant groove 1 carries out each element analysis as crystalline product, and testing result see the table below 3.This Process needs used time 2h.

Embodiment 3

(1) equipment for preparing high purity gallium as Figure 1-3, it is by polytetrafluoroethylene (PTFE) raw material tank, with conical lower portion The tubular polytetrafluoroethylene (PTFE) crystallization tank 1 of closing and hot water water bath 19 and weighing device 2 are constituted, and are surrounded on the outer wall of crystallization tank 1 Polytetrafluoroethylene (PTFE) second circulation cold water pipe 18 is provided with, the conical lower portion of crystallization tank 1 is placed in hot water water bath 19, and raw material Groove, crystallization tank 1 and weighing device 2 are interconnected, and the cone angle of conical lower portion is 40 degree, and the top of crystallization tank 1 is provided with lid 11, institute State the charging aperture 17 for inert gas entrance 15 and inert gas outlet 16 being provided with lid and being connected with raw material tank, the knot Brilliant groove 1 be internally provided with axially arrange suction pipe 12, poly- the four of circulating hot water pipe 13 is provided as around the suction pipe 12 PVF helix tube and the polytetrafluoroethylhelix helix tube of first circulation cold water pipe 14 is provided as around the circulating hot water pipe 13, The circulating hot water pipe 13 has the circulating hot water pipe's suction line 131 being interconnected, circulating hot water pipe's spiral part 132 and follows Ring hot-water line outlet line 133, and circulating hot water pipe's suction line 131 is fixed on the lid 11 of crystallization tank 1；The cycling hot Pipe outlet pipeline 133 is fixed on the lid 11 of crystallization tank 1；The first circulation cold water pipe 14 has first for being interconnected Circulating water tube inlet pipeline 141, first circulation cold water pipe spiral part 142 and first circulation cold water pipe outlet line 143, and First circulation cold water pipe suction line 141 is fixed on the lid 11 of crystallization tank 1；The first circulation cold water pipe outlet line 143 are fixed on the lid 11 of crystallization tank 1.As the top edge and the crystallization tank 1 of the helix tube of first circulation cold water pipe 14 Top cover vertical range be crystallize groove height 10%, as circulating hot water pipe 13 helix tube with as first circulation The ratio of the screw diameter of the helix tube of cold water pipe 14 is 1：3.2, as the screw diameter of the helix tube of first circulation cold water pipe 14 It is 1 with the ratio of the radial dimension of crystallization tank 1：15, it is located at the knot as the lower limb of the helix tube of first circulation cold water pipe 14 It is more than the conical lower portion of brilliant groove 1, wherein, the lower end of the suction pipe 12 near the conical lower portion of the crystallization tank 1 cone point, the suction pipe 12 upper end extends upward the crystallization tank 1 and connects to residual liquid container conical flask 21 and with residual liquid container conical flask 21, raffinate Container conical flask 21 is placed on weighing component balance 22.As best shown in figures 3 a and 3b, 8 temperature are randomly provided in crystallization tank 1 Meter, respectively T1, T2, T3, T4, T5, T6, T7 and T8.Wherein, T1, T2 are arranged on circulating hot water pipe 13 and first circulation cold water Position between pipe 14, relative to the crystallization tank 1 that height is 16cm, the corresponding depth of T1 is 9cm, and the corresponding depth of T2 is 12cm；T3, T4, T5, T6, T7 and T8 are randomly provided the position between the inwall of first circulation cold water pipe 14 and crystallization tank 1, phase For height is the crystallization tank 1 of 16cm, the corresponding depth of T3 is 6cm, and the corresponding depth of T4 is 8cm, and the corresponding depth of T5 is The corresponding depth of 10cm, T6 is 12cm, and the corresponding depth of T7 is 13cm, and the corresponding depth of T8 is 14cm.The said equipment is placed In clean operating desk, the inspection of pipeline connection is carried out to the said equipment, i.e. elder generation's check device crystallization tank 1, raw material tank and raffinate Whether firmly the connecting line of container 21, and checks that whether accurately 8 point for measuring temperature positions, check first circulation cold water pipe 14 and circulation The pipeline of hot-water line 13 whether there is breakage with the pipeline of High Purity Nitrogen, and whether joint loosens, and the time that the process needs is 0.5h.

(3) cleaning of equipment and pipeline：99.9999 weight % are passed through into crystallization tank 1 by inert gas entrance 15 high Under the conditions of pure nitrogen gas, deionized water is cleaned raw material tank, crystallization tank 1, residual liquid container 21 and connects the inside 2 of their pipeline It is secondary.After cleaning, then drying is purged with high pure nitrogen, until hygronom is shown as zero, and from the observation of crystallization tank top without the globule And moisture is present.The time that the process needs is 3h.

(4) ON cycle water-bath：By the circulation in the circulating water in first circulation cold water pipe 14 and circulating hot water pipe 13 Hot water is opened, and it is 40 DEG C to adjust the temperature of the circulating water in first circulation cold water pipe 14, and discharge is 20L/h, and regulation is followed Circulating hot water temperature in ring hot-water line 13 is 50 DEG C, and discharge is 10L/h；The temperature of the hot water in hot water water bath 19 is all the time Kept for 36 DEG C, observe the temperature change of 8 points for measuring temperature of crystallization tank 1, and gradually adjust the circulation in first circulation cold water pipe 14 The desired temperature of the circulating hot water in cold water and circulating hot water pipe 13 so that the temperature of each point for measuring temperature is not less than 35 DEG C, and surely Determine more than 10min.The time that the process needs is about 2h.

(5) High Purity Nitrogen carrier gas is opened：High Purity Nitrogen source of the gas is opened, it is 20L/h to control its total flow, and control it and enter former Hopper is 4 with the flow proportional of two strands of High Purity Nitrogens of crystallization tank:1.Leave behind behind clean operating desk Qianmen, determined with Particle Size Analyzer Cleanliness factor in clean operating desk and crystallization tank 1, the number of particles controlled less than 0.5 micron is 7000, to meet experimentation Requirement to operating space cleanliness factor.The time that the process needs is about 0.5h.

(6) raw material is added：It is all higher than in the case of 35 DEG C in each point for measuring temperature temperature, by by raw material tank and crystallization tank 1 The flow-rate ratio for being passed through nitrogen is adjusted to 6：1, by high pure nitrogen, by the gallium of the 7kg raw material liquids in raw material tank, (composition is shown in Table 1) press-in crystallization tank 1 in, weigh raw material tank weight change come determine add crystallization tank 1 gallium quality.

(7) single crystallization process：Under conditions of high pure nitrogen is passed through in crystallization tank 1, liquid is added in crystallization tank Gallium after, when the temperature of each point for measuring temperature maintains stable (each point for measuring temperature keeps a temperature value 10min), with 0.9 DEG C/ The cooling rate of min reduces the temperature of the circulating water in first circulation cold water pipe 14 to 12 DEG C, according to the water-bath stream of crystallization tank Field design, along the axial direction of crystallization tank 1 from top to bottom and along the radial direction of crystallization tank 1 by the outer wall of first circulation cold water pipe 14 Start to proceed by crystallization outside inwardly.Wherein, the temperature of the circulating water in crystallization process in first circulation cold water pipe 14 is controlled Mode for 12 DEG C is：The coolant-temperature gage that enters for controlling the circulating water in the first circulation cold water pipe 14 is 10 DEG C, and flow is 22L/h, the temperature for controlling the circulating hot water in crystallization process in circulating hot water pipe 13 is that 40 DEG C of mode is：Control the circulation The coolant-temperature gage that enters of the circulating hot water in hot-water line 13 is 45 DEG C, and flow is 12L/h.In crystallization process, the temperature of each point for measuring temperature is observed Degree change, when the temperature of each point for measuring temperature does not change in 10min, it can be determined that the close terminal of crystallization, now, is adjusted by pressure Section part 23 causes the internal pressure of residual liquid container 21 to reduce so that suction pipe 12 suctions out raffinate to residual from the conical lower portion of crystallization tank 1 In liquid container 21, the weight of the raffinate is read by balance, the weight of raffinate is the feed metal gallium being initially added in crystallization tank 1 1.5 weight %, the i.e. close terminal of the single crystallization, terminate the crystallization process, are expelled in residual liquid container 21 by suction pipe 12 Raffinate is no longer back to crystallization tank 1, but by the device for transferring of residual liquid container 21 outside, it is 1.5h that the crystallization spends the time.

(8) watery fusion repeats crystallization and elementary analysis process：After single crystallization stops, by improving described first The temperature of the circulating water in circulating water pipe 14 to 40 DEG C cause the outer wall of first circulation cold water pipe 14 attachment watery fusions, and It it is 50 DEG C by the temperature for keeping the conical lower portion of the crystallization tank 1 so that the crystallization being deposited in the conical lower portion of crystallization tank 1 Fusing, wherein, after the temperature of each point for measuring temperature is all higher than 35 DEG C and stably after 20min, heating process is completed, then repeat step (6) single crystallization process 7 times.The quality that crystallization terminates to obtain product is 6.29kg.After 7 times are terminated, by suction pipe from All liquid metal gallium samples are extracted in crystallization tank 1 carries out each element analysis as crystalline product, and testing result see the table below 4.Should This process needs used time 2h.

Table 1

Note：It is Mg, Si, Ca, Fe and Zn higher than the element of detection limit.

Table 2

Note：It is Mg, Si and Zn higher than the element of detection limit.

Table 3

Note：It is Mg, Si and Zn higher than the element of detection limit.

Table 4

Note：It is Mg, Si and Zn higher than the element of detection limit.

Fig. 4 lists typical temperature variation curve during gallium crystallization experiment.It is current when not crystallizing out, with The carrying out of operation, the temperature of each point for measuring temperature is gradually reduced.When crystallization is initially formed, the temperature of each point for measuring temperature comparatively fast increases, Caused by this is mainly due to crystallization exotherm.After temperature increase to a certain extent, gradually become steady, this is mainly shown as condensation heat with knot Brilliant heat is roughly the same.With the carrying out of crystallization, crystallization content is gradually reduced so that crystallization heat is gradually less than condensation heat, shows as gold The temperature of category gallium continues to decline.

Finely divide from fig. 5, it can be seen that raw material and the 7th wheel product being delivered to into Shanghai silicate and carrying out further GDMS Analysis, its analysis result is respectively as shown in table 1 (raw material) and table 2 (product).From data in table, by the single crystallization of 7 wheels After process, the major impurity in gallium such as Mg, Ca, Fe, Si and Zn are presented the trend of reduction.By 7 wheel single crystallization mistakes Cheng Hou, the purity of gallium increases to 5N levels (5.19ppm) by 4N levels (25.4ppm), and the quality of crystalline product is by raw material 6.7kg is changed into 5.8kg, and the yield of corresponding crystalline product is 87%.Thus demonstrating the process can realize entering for gallium One step is purified, and prepares the high purity gallium of variable concentrations demand.

Can be seen that in raw material by the data of table 1 and 2 and be higher than impurity Mg, Ca, Fe, Si and Zn total amount of detection limit 0.00254 weight %, using impurity Mg, the Si and Zn total amount in gallium product obtained in the method for the present invention higher than detection limit It is reduced to 0.000519 weight %.The yield of gallium obtained in embodiment 1 is 87 weight %, and purity is 5N levels.

Can be seen that in raw material by the data of table 1 and 3 and be higher than impurity Mg, Ca, Fe, Si and Zn total amount of detection limit 0.00254 weight %, using impurity Mg, the Si and Zn total amount in gallium product obtained in the method for the present invention higher than detection limit It is reduced to 0.000423 weight %.Embodiment 2 is obtained and yield of gallium is 90 weight %, and purity is 5N levels.

Can be seen that in raw material by the data of table 1 and 4 and be higher than impurity Mg, Ca, Fe, Si and Zn total amount of detection limit 0.00254 weight %, using impurity Mg, the Si and Zn total amount in gallium product obtained in the method for the present invention higher than detection limit 0.000498 weight % is reduced to, and the yield of gallium is 89.9 weight %, purity is 5N levels.

The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment Detail, the present invention range of the technology design in, various simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.

It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy is no longer separately illustrated.

Additionally, can also be combined between a variety of embodiments of the present invention, as long as it is without prejudice to this The thought of invention, it should equally be considered as content disclosed in this invention.

Claims

1. a kind of equipment for preparing high purity gallium, it is characterised in that the equipment includes the crystallization tank of the closing with conical lower portion (1), the crystallization tank (1) is internally provided with the suction pipe (12) for axially arranging, the cycling hot arranged around the suction pipe (12) Water pipe (13) and the first circulation cold water pipe (14) arranged around the circulating hot water pipe (13), wherein, the lower end of the suction pipe (12) Near the cone point of the conical lower portion of the crystallization tank (1), the upper end of the suction pipe (12) extends upward the crystallization tank (1).

2. equipment according to claim 1, wherein, the equipment also includes weighing device (2), the weighing device (2) Including residual liquid container (21) and weighing component (22), the upper end of the suction pipe (12) extends upwardly to and the residual liquid container (21) Connection.

3. equipment according to claim 2, wherein, the weighing device (2) is also included for adjusting the residual liquid container (21) pressure regulating part (23) of internal pressure.

4. the equipment according to any one in claim 1-3, wherein, the cone angle of the conical lower portion of the crystallization tank (1) For 5-80 degree, preferably 10-60 degree, more preferably 20-50 degree.

5. equipment according to claim 1, wherein, the circulating hot water pipe (13) and the first circulation cold water pipe (14) Respectively around the helix tube of the crystallization tank (1) axial arranging.

6. equipment according to claim 5, wherein, the top edge and institute as the helix tube of first circulation cold water pipe (14) The vertical range for stating the top of crystallization tank (1) is the 2-20% for crystallizing groove height.

7. equipment according to claim 5, wherein, it is cold with as first circulation as the helix tube of circulating hot water pipe (13) The ratio of the screw diameter of the helix tube of water pipe (14) is 1：1.5-5, preferably 1：2-4；

It is 1 as the screw diameter of helix tube and the ratio of the radial dimension of crystallization tank (1) of first circulation cold water pipe (14)：8- 30, preferably 1：10-20.

8. equipment according to claim 5, wherein, it is located at as the lower limb of the helix tube of first circulation cold water pipe (14) It is more than the conical lower portion of the crystallization tank (1).

9. equipment according to claim 1, wherein, the equipment also includes being arranged on the on the crystallization tank (1) outer wall Two circulating water pipes (18).

10. equipment according to claim 1, wherein, the equipment is also included for placing crystallization tank (1) and causing crystallization tank (1) gallium in conical lower portion keeps the hot water water bath (19) of liquid.

The method that equipment described in any one prepares high purity gallium in a kind of 11. employing claims 1-10, it is characterised in that the party Method includes：Under an inert atmosphere, the metallic gallium feedstock of liquid is added and is crystallized in crystallization tank (1), wherein, in the mistake of crystallization Cheng Zhong, using the circulating water regulation and control crystallization tank in the circulating hot water in circulating hot water pipe (13) and first circulation cold water pipe (14) (1) temperature in, the raffinate of generation discharges crystallization tank (1) by suction pipe (12).

12. methods according to claim 11, wherein, methods described also includes：Add in the metallic gallium feedstock by liquid Before crystallization tank (1), using the circulating water in the circulating hot water in circulating hot water pipe (13) and first circulation cold water pipe (14) By the temperature adjustment in crystallization tank (1) to more than 35 DEG C.

13. methods according to claim 11, wherein, during crystallization, in controlling first circulation cold water pipe (14) Circulating water temperature be 0-15 DEG C.

14. methods according to claim 13, wherein, during crystallization, following in the circulating hot water pipe (13) The coolant-temperature gage that enters of ring hot water is 35-80 DEG C, and flow is 5-30L/h；Circulating water in the first circulation cold water pipe (14) Enter coolant-temperature gage for 2-25 DEG C, flow is 10-80L/h.

15. methods according to any one in claim 11-14, wherein, according to the raffinate discharged by suction pipe (12) Weight testing result judging the terminal of single crystallization；

Preferably, when the weight of the raffinate discharged accounts for the 1.4-2% for adding the metallic gallium feedstock weight in crystallization tank (1), stop Only crystallize.

16. methods according to claim 15, wherein, the method also includes：It is described by improving after crystallization is stopped The temperature of the circulating water in first circulation cold water pipe (14) causes the watery fusion that first circulation cold water pipe (14) outer wall adheres to, And cause the crystallization being deposited in the conical lower portion of crystallization tank (1) by keeping the temperature of the conical lower portion of the crystallization tank (1) Fusing, then repeatedly crystallization process.

17. methods according to claim 11, wherein, crystal seed is added without in crystallization process.