CN109439897A - Germanic organic matter produces germanium tetrachloride new process - Google Patents
Germanic organic matter produces germanium tetrachloride new process Download PDFInfo
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- CN109439897A CN109439897A CN201811399983.5A CN201811399983A CN109439897A CN 109439897 A CN109439897 A CN 109439897A CN 201811399983 A CN201811399983 A CN 201811399983A CN 109439897 A CN109439897 A CN 109439897A
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- organic matter
- germanium tetrachloride
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- 239000005416 organic matter Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 33
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 title claims abstract description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000000463 material Substances 0.000 claims abstract description 58
- 238000005188 flotation Methods 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 32
- 229910052732 germanium Inorganic materials 0.000 claims description 30
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 30
- 239000000344 soap Substances 0.000 claims description 30
- 238000012216 screening Methods 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 19
- 238000002386 leaching Methods 0.000 claims description 19
- 239000008396 flotation agent Substances 0.000 claims description 17
- 235000010469 Glycine max Nutrition 0.000 claims description 15
- 244000068988 Glycine max Species 0.000 claims description 15
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 15
- 239000000194 fatty acid Substances 0.000 claims description 15
- 229930195729 fatty acid Natural products 0.000 claims description 15
- 150000004665 fatty acids Chemical class 0.000 claims description 15
- 239000012188 paraffin wax Substances 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 15
- 238000000605 extraction Methods 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000012085 test solution Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- -1 hydroxyl oxime Chemical class 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000005660 chlorination reaction Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/012—Organic compounds containing sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/14—Flotation machines
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B41/00—Obtaining germanium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biotechnology (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention provides germanic organic matters to produce germanium tetrachloride new process, includes the following steps: the first step, germanic organic matter is ground, and sieves, is then prepared into pre- slurry, is delivered in flotation device and carries out flotation, the material after flotation is dried, and obtains material dry powder；Material dry powder is carried out the slow oxidation reaction of low temperature by second step；Hydrochloric acid is added in third step, the material for taking second step to obtain thereto, then carries out low temperature distillation, obtains germanium tetrachloride.Present invention process process is simple, improves the output capacity of germanium tetrachloride in organic matter.
Description
Technical field
The present invention relates to metallurgical technology fields, and in particular to germanic organic matter produces germanium tetrachloride new process.
Background technique
Germanium is a kind of important rare and scatter element, wide with the development of science and technology with the raising of living standards of the people
It is general to apply in people's lives and industrial and agricultural production.Germanium is mainly used for making optical fiber, catalyst and infra-red material, and nearly 30 years
Come, germanium increasingly becomes the backing material of certain new and high technologies, germanium be intensively applied in high-tech area.It is shown in the Gulf War
The power of germanium infra-red material, various countries mutually equip with arms oneself with high-tech unexpectedly, optical fiber germanium sustainable growth, produce as polyester fiber
Catalyst germanium also increasing.Germanium occupies more and more important position in the national economic development and national defense construction, and germanium disappears
Consumption can also be growing day by day, and germanium resource lacks on international market, supply falls short of demand.The separation and Extraction of germanium study oneself caused it is more and more
Concern.
Summary of the invention
For the defects in the prior art, the present invention provides germanic organic matter and produces germanium tetrachloride new process.
Germanic organic matter produces germanium tetrachloride new process, includes the following steps:
The first step grinds germanic organic matter, then screening is prepared into pre- slurry, is delivered in flotation device and is floated
Choosing, the material after flotation are dried, and obtain material dry powder；
Material dry powder is carried out the slow oxidation reaction of low temperature by second step；
Hydrochloric acid is added in third step, the material for taking second step to obtain thereto, then carries out low temperature distillation, obtains four chlorinations
Germanium.
It in the present invention, as a kind of perferred technical scheme, in the first step, when grinding, is dry grinded using rod mill, when grinding
Between be 15-20 minutes.
In the present invention, as a kind of perferred technical scheme, in the first step, when screening, sieved using 300 mesh hole wet types
Point.
In the present invention, as a kind of perferred technical scheme, in the first step, it is prepared in pre- slurry, the weight of organic matter
Amount percentage is 10-15wt%, remaining is flotation agent.
In the present invention, as a kind of perferred technical scheme, flotation agent is hydroximic acid, sodium alkyl hydroxamate, soya fatty acid
The mixture of sulphation soap, oxidized paraffin wax soap.
In the present invention, as a kind of perferred technical scheme, hydroximic acid, sodium alkyl hydroxamate, soya fatty acid sulphation soap,
The weight ratio of oxidized paraffin wax soap is 1:1:3:2.
In the present invention, as a kind of perferred technical scheme, in the first step, flotation device is using extension groove type floatation cell.
In the present invention, as a kind of perferred technical scheme, in the first step, screening uses Taylor's bushing screen.
In the present invention, as a kind of perferred technical scheme, in second step, material dry powder is laid in roasting ware, so
It is placed in Muffle furnace, closed fire door, furnace temperature is gradually warmed up from room temperature to 500-525 DEG C through 30-45min, and at this temperature
Then heat preservation 3-4 hours is warming up to 550-600 DEG C again, maintain temperature 2-3 hours.
In the present invention, as a kind of perferred technical scheme, in second step, it is 1:1 that weight ratio is mixed in material dry powder
MnO2.
In the present invention, as a kind of perferred technical scheme, in third step, the material that second step is obtained is added three necks and burns
In bottle, hydrochloric acid leaching germanium is added thereto, during hydrochloric acid leaching, each mouth of three-neck flask will jump a queue closed, wave to prevent hydrochloric acid
Hair, extraction time are 2-3 hours；Concentration of hydrochloric acid in test solution is adjusted to 8-9mol/L and heats distillation；Utilize air setting
Still keeps temperature to be condensed back to 105-107 DEG C,
In the present invention, as a kind of perferred technical scheme, in third step, before heating, boron is added into three-neck flask
Acid and MnO2.
Due to using the technology described above, the invention has the following beneficial effects:
The first step of the invention using hydroximic acid, sodium alkyl hydroxamate, soya fatty acid sulphation soap, oxidized paraffin wax soap it is mixed
It closes object and carries out flotation, can remove most of impurity, reduce and extract germanium feed material directly from organic matter, to reduce hydrochloric acid
Dosage reduces cost；Meanwhile special flotation agent is that inventor obtains by long-term practice, which has fraction heavy, close
Degree is high, viscosity is big, and the oil droplet size dispersed in water is big, and the features such as the speed of organic matter unfolded surface is slow, but hydrophobicity is strong,
The quantity absorbed by organic matter surface pore is few, greatly improves the efficiency of flotation, is that the extraction of subsequent germanium tetrachloride is created
Good condition is made.
Because Ge O after temperature is higher than 350 DEG C, starts to aoxidize and form Ge O2；At 260 DEG C oxygen just occurs for Ge S2
Change and generates Ge O2；Ge S starts to aoxidize and form Ge SO4 at 350 DEG C, when temperature is higher than 350 DEG C, oxidation product
Maximum possible is to form Ge O2；But if temperature is excessively high, and germanium is easy to exist with the solid solution of Ge O2-Si O2 in coal, the solid solution
Form is difficult to by Ore Leaching.Therefore, the mode slowly to heat up is taken in second step of the present invention, while manganese dioxide is added, metal
Germanium can be stayed in calcining matter by manganese dioxide, while the organic carbon in organic matter being removed, and be conducive to further chlorination leaching
It handles out.
In third step of the invention, due to using method of the invention, germanium, which basically forms, in the step is soluble in acid
Ge O2 form, when salt Ore Leaching, Ge O2 is easier to occur with reacting for HCl, so directly salt Ore Leaching at normal temperatures and pressures
Germanium；Germanium is leached under normal temperature and pressure, energy consumption needed for not only having saved heating, but also the equipment anticorrosion solved under the conditions of high temperature concentrated acid are asked
Topic, so that the process flow of salt Ore Leaching distillation can also be simplified.
In conclusion present invention process process is simple, the output capacity of germanium tetrachloride in organic matter is improved.
Specific embodiment
Technical solution of the present invention is described in detail below in conjunction with specific embodiment.Following embodiment is only used for more
Add and clearly demonstrate technical solution of the present invention, therefore be only used as example, and not intended to limit the protection scope of the present invention.
Embodiment 1
Germanic organic matter produces germanium tetrachloride new process, includes the following steps:
The first step grinds germanic organic matter, when grinding, is dry grinded using rod mill, and milling time is 15 minutes, screening,
When screening, using Taylor's bushing screen wet screening in 300 mesh holes, it is then prepared into pre- slurry, is prepared in pre- slurry, it is organic
The weight percent of object is 10wt%, remaining is flotation agent, and flotation agent is hydroximic acid, sodium alkyl hydroxamate, soya fatty acid sulfuric acid
Change the mixture of soap, oxidized paraffin wax soap, the weight of hydroximic acid, sodium alkyl hydroxamate, soya fatty acid sulphation soap, oxidized paraffin wax soap
Than for 1:1:3:2, being delivered in flotation device and carrying out flotation, using groove type floatation cell is hung, the material after flotation carries out flotation device
It is dry, obtain material dry powder；
Material dry powder is carried out the slow oxidation reaction of low temperature by second step, specifically: material dry powder is laid in roasting ware
In, it is subsequently placed in Muffle furnace, closed fire door, furnace temperature is gradually warmed up from room temperature to 500 DEG C through 30min, and is protected at this temperature
Then temperature 3 hours is warming up to 550 DEG C again, maintain temperature 2 hours, and the MnO2 that weight ratio is 1:1 is mixed in material dry powder；
Hydrochloric acid is added in third step, the material for taking second step to obtain thereto, then carries out low temperature distillation, obtains four chlorinations
Germanium, the material for specially obtaining second step are added in three-neck flask, hydrochloric acid leaching germanium are added thereto, in hydrochloric acid leaching process
In, each mouth of three-neck flask to jump a queue it is closed, to prevent hydrochloric acid volatilization, extraction time be 2 hours；Concentration of hydrochloric acid in test solution is adjusted
For 8mol/L, boric acid and MnO2 are added into three-neck flask, and heats distillation；Temperature is kept extremely using air setting still
105 DEG C are condensed back.
Embodiment 2
Germanic organic matter produces germanium tetrachloride new process, includes the following steps:
The first step grinds germanic organic matter, when grinding, is dry grinded using rod mill, and milling time is 20 minutes, screening,
When screening, using Taylor's bushing screen wet screening in 300 mesh holes, it is then prepared into pre- slurry, is prepared in pre- slurry, it is organic
The weight percent of object is 15wt%, remaining is flotation agent, and flotation agent is hydroximic acid, sodium alkyl hydroxamate, soya fatty acid sulfuric acid
Change the mixture of soap, oxidized paraffin wax soap, the weight of hydroximic acid, sodium alkyl hydroxamate, soya fatty acid sulphation soap, oxidized paraffin wax soap
Than for 1:1:3:2, being delivered in flotation device and carrying out flotation, using groove type floatation cell is hung, the material after flotation carries out flotation device
It is dry, obtain material dry powder；
Material dry powder is carried out the slow oxidation reaction of low temperature by second step, specifically: material dry powder is laid in roasting ware
In, it is subsequently placed in Muffle furnace, closed fire door, furnace temperature is gradually warmed up from room temperature to 525 DEG C through 45min, and is protected at this temperature
Then temperature 4 hours is warming up to 600 DEG C again, maintain temperature 3 hours, and the MnO2 that weight ratio is 1:1 is mixed in material dry powder；
Hydrochloric acid is added in third step, the material for taking second step to obtain thereto, then carries out low temperature distillation, obtains four chlorinations
Germanium, the material for specially obtaining second step are added in three-neck flask, hydrochloric acid leaching germanium are added thereto, in hydrochloric acid leaching process
In, each mouth of three-neck flask to jump a queue it is closed, to prevent hydrochloric acid volatilization, extraction time be 3 hours；Concentration of hydrochloric acid in test solution is adjusted
For 9mol/L, boric acid and MnO2 are added into three-neck flask, and heats distillation；Temperature is kept extremely using air setting still
107 DEG C are condensed back.
Embodiment 3
Germanic organic matter produces germanium tetrachloride new process, includes the following steps:
The first step grinds germanic organic matter, when grinding, is dry grinded using rod mill, and milling time is 20 minutes, screening,
When screening, using Taylor's bushing screen wet screening in 300 mesh holes, it is then prepared into pre- slurry, is prepared in pre- slurry, it is organic
The weight percent of object is 12wt%, remaining is flotation agent, and flotation agent is hydroximic acid, sodium alkyl hydroxamate, soya fatty acid sulfuric acid
Change the mixture of soap, oxidized paraffin wax soap, the weight of hydroximic acid, sodium alkyl hydroxamate, soya fatty acid sulphation soap, oxidized paraffin wax soap
Than for 1:1:3:2, being delivered in flotation device and carrying out flotation, using groove type floatation cell is hung, the material after flotation carries out flotation device
It is dry, obtain material dry powder；
Material dry powder is carried out the slow oxidation reaction of low temperature by second step, specifically: material dry powder is laid in roasting ware
In, it is subsequently placed in Muffle furnace, closed fire door, furnace temperature is gradually warmed up from room temperature to 510 DEG C through 42min, and is protected at this temperature
Then temperature 4 hours is warming up to 590 DEG C again, maintain temperature 3 hours, and the MnO2 that weight ratio is 1:1 is mixed in material dry powder；
Hydrochloric acid is added in third step, the material for taking second step to obtain thereto, then carries out low temperature distillation, obtains four chlorinations
Germanium, the material for specially obtaining second step are added in three-neck flask, hydrochloric acid leaching germanium are added thereto, in hydrochloric acid leaching process
In, each mouth of three-neck flask to jump a queue it is closed, to prevent hydrochloric acid volatilization, extraction time be 3 hours；Concentration of hydrochloric acid in test solution is adjusted
For 9mol/L, boric acid and MnO2 are added into three-neck flask, and heats distillation；Temperature is kept extremely using air setting still
105 DEG C are condensed back.
Embodiment 4
Germanic organic matter produces germanium tetrachloride new process, includes the following steps:
The first step grinds germanic organic matter, when grinding, is dry grinded using rod mill, and milling time is 18 minutes, screening,
When screening, using Taylor's bushing screen wet screening in 300 mesh holes, it is then prepared into pre- slurry, is prepared in pre- slurry, it is organic
The weight percent of object is 12wt%, remaining is flotation agent, and flotation agent is hydroximic acid, sodium alkyl hydroxamate, soya fatty acid sulfuric acid
Change the mixture of soap, oxidized paraffin wax soap, the weight of hydroximic acid, sodium alkyl hydroxamate, soya fatty acid sulphation soap, oxidized paraffin wax soap
Than for 1:1:3:2, being delivered in flotation device and carrying out flotation, using groove type floatation cell is hung, the material after flotation carries out flotation device
It is dry, obtain material dry powder；
Material dry powder is carried out the slow oxidation reaction of low temperature by second step, specifically: material dry powder is laid in roasting ware
In, it is subsequently placed in Muffle furnace, closed fire door, furnace temperature is gradually warmed up from room temperature to 515 DEG C through 40min, and is protected at this temperature
Then temperature 3.5 hours is warming up to 580 DEG C again, maintain temperature 2.5 hours, and it is 1:1's that weight ratio is mixed in material dry powder
MnO2；
Hydrochloric acid is added in third step, the material for taking second step to obtain thereto, then carries out low temperature distillation, obtains four chlorinations
Germanium, the material for specially obtaining second step are added in three-neck flask, hydrochloric acid leaching germanium are added thereto, in hydrochloric acid leaching process
In, each mouth of three-neck flask to jump a queue it is closed, to prevent hydrochloric acid volatilization, extraction time be 2.5 hours；By the concentration of hydrochloric acid tune in test solution
Section is 8.5mol/L, boric acid and MnO2 is added into three-neck flask, and heat distillation；Temperature is kept using air setting still
It is condensed back to 106 DEG C.
Embodiment 5
Germanic organic matter produces germanium tetrachloride new process, includes the following steps:
The first step grinds germanic organic matter, when grinding, is dry grinded using rod mill, and milling time is 15 minutes, screening,
When screening, using Taylor's bushing screen wet screening in 300 mesh holes, it is then prepared into pre- slurry, is prepared in pre- slurry, it is organic
The weight percent of object is 15wt%, remaining is flotation agent, and flotation agent is hydroximic acid, sodium alkyl hydroxamate, soya fatty acid sulfuric acid
Change the mixture of soap, oxidized paraffin wax soap, the weight of hydroximic acid, sodium alkyl hydroxamate, soya fatty acid sulphation soap, oxidized paraffin wax soap
Than for 1:1:3:2, being delivered in flotation device and carrying out flotation, using groove type floatation cell is hung, the material after flotation carries out flotation device
It is dry, obtain material dry powder；
Material dry powder is carried out the slow oxidation reaction of low temperature by second step, specifically: material dry powder is laid in roasting ware
In, it is subsequently placed in Muffle furnace, closed fire door, furnace temperature is gradually warmed up from room temperature to 525 DEG C through 30min, and is protected at this temperature
Then temperature 3 hours is warming up to 600 DEG C again, maintain temperature 2 hours, and the MnO2 that weight ratio is 1:1 is mixed in material dry powder；
Hydrochloric acid is added in third step, the material for taking second step to obtain thereto, then carries out low temperature distillation, obtains four chlorinations
Germanium, the material for specially obtaining second step are added in three-neck flask, hydrochloric acid leaching germanium are added thereto, in hydrochloric acid leaching process
In, each mouth of three-neck flask to jump a queue it is closed, to prevent hydrochloric acid volatilization, extraction time be 3 hours；Concentration of hydrochloric acid in test solution is adjusted
For 8mol/L, boric acid and MnO2 are added into three-neck flask, and heats distillation；Temperature is kept extremely using air setting still
107 DEG C are condensed back.
Comparative example 1
The step of with embodiment 4, is almost the same, the difference is that, the present embodiment does not use flotation agent to carry out flotation.
Comparative example 2
The step of with embodiment 4, is almost the same, the difference is that, the flotation agent that the present embodiment uses is light diesel fuel.
Comparative example 3
The step of with embodiment 4, is almost the same, the difference is that, the present embodiment directly 600 DEG C at a temperature of it is aerobic
Roasting.
By obtained germanium tetrachloride compared with weight of material, the output capacity of germanium tetrachloride is obtained, as in the table below:
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme should all cover within the scope of the claims and the description of the invention.
Claims (10)
1. germanic organic matter produces germanium tetrachloride new process, characterized by the following steps:
The first step grinds germanic organic matter, and then screening is prepared into pre- slurry, be delivered in flotation device and carry out flotation, floats
Material after choosing is dried, and obtains material dry powder；
Material dry powder is carried out the slow oxidation reaction of low temperature by second step；
Hydrochloric acid is added in third step, the material for taking second step to obtain thereto, then carries out low temperature distillation, obtains germanium tetrachloride.
2. germanic organic matter as described in claim 1 produces germanium tetrachloride new process, it is characterised in that: in the first step, grinding
When, it is dry grinded using rod mill, milling time is 15-20 minutes.
3. germanic organic matter as claimed in claim 2 produces germanium tetrachloride new process, it is characterised in that: in the first step, screening
When, using 300 mesh hole wet screenings.
4. germanic organic matter as claimed in claim 3 produces germanium tetrachloride new process, it is characterised in that: pre- slurry is prepared
In, the weight percent of organic matter is 10-15wt%, remaining is flotation agent.
5. germanic organic matter as claimed in claim 4 produces germanium tetrachloride new process, it is characterised in that: flotation agent is hydroxyl oxime
Acid, sodium alkyl hydroxamate, soya fatty acid sulphation soap, oxidized paraffin wax soap mixture.
6. germanic organic matter as claimed in claim 5 produces germanium tetrachloride new process, it is characterised in that: hydroximic acid, hydroximic acid
Sodium, soya fatty acid sulphation soap, oxidized paraffin wax soap weight ratio be 1:1:3:2.
7. germanic organic matter as described in claim 1 produces germanium tetrachloride new process, it is characterised in that: in second step, by object
Material dry powder be laid in roasting ware in, be subsequently placed in Muffle furnace, closed fire door, furnace temperature through 30-45min from room temperature be gradually warmed up to
500-525 DEG C, and 3-4 hours are kept the temperature at this temperature, it is then warming up to 550-600 DEG C again, maintains temperature 2-3 hours.
8. germanic organic matter as claimed in claim 7 produces germanium tetrachloride new process, it is characterised in that: in second step, material
The MnO2 that weight ratio is 1:1 is mixed in dry powder.
9. germanic organic matter as described in claim 1 produces germanium tetrachloride new process, it is characterised in that: in third step, by the
The material that two steps obtain is added in three-neck flask, hydrochloric acid leaching germanium is added thereto, during hydrochloric acid leaching, three-neck flask is each
Mouth to jump a queue it is closed, to prevent hydrochloric acid volatilization, extraction time be 2-3 hours；Concentration of hydrochloric acid in test solution is adjusted to 8-9mol/L
And heat distillation；Temperature is kept to be condensed back to 105-107 DEG C using air setting still.
10. germanic organic matter as claimed in claim 9 produces germanium tetrachloride new process, it is characterised in that: in third step, adding
Before heat, boric acid and MnO2 are added into three-neck flask.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102094128A (en) * | 2011-03-02 | 2011-06-15 | 郴州雄风稀贵金属材料股份有限公司 | Method for comprehensively recovering various valuable metals from germanium-containing material by wet process |
| CN105821224A (en) * | 2016-06-06 | 2016-08-03 | 云南临沧鑫圆锗业股份有限公司 | Method for extracting germanium in low-grade germanium concentrates through fluoride roasting process |
| US20160298210A1 (en) * | 2014-12-01 | 2016-10-13 | Yunnan Lincang Xinyuan Germanium Industry Co., Ltd. | Method and apparatus for secondary enrichment and recovery of germanium from low-grade lignite germanium concentrates with by microwave heating in vacuum |
| CN106802093A (en) * | 2015-11-25 | 2017-06-06 | 衡阳恒荣高纯半导体材料有限公司 | A kind of condensing unit for producing high-purity germanium tetrachloride |
-
2018
- 2018-11-22 CN CN201811399983.5A patent/CN109439897A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102094128A (en) * | 2011-03-02 | 2011-06-15 | 郴州雄风稀贵金属材料股份有限公司 | Method for comprehensively recovering various valuable metals from germanium-containing material by wet process |
| US20160298210A1 (en) * | 2014-12-01 | 2016-10-13 | Yunnan Lincang Xinyuan Germanium Industry Co., Ltd. | Method and apparatus for secondary enrichment and recovery of germanium from low-grade lignite germanium concentrates with by microwave heating in vacuum |
| CN106802093A (en) * | 2015-11-25 | 2017-06-06 | 衡阳恒荣高纯半导体材料有限公司 | A kind of condensing unit for producing high-purity germanium tetrachloride |
| CN105821224A (en) * | 2016-06-06 | 2016-08-03 | 云南临沧鑫圆锗业股份有限公司 | Method for extracting germanium in low-grade germanium concentrates through fluoride roasting process |
Non-Patent Citations (1)
| Title |
|---|
| 王玲: ""褐煤中提取锗的工艺研究"", 《工程科技Ⅰ辑》 * |
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