CN101177733A - Technology for extracting germanium from germanium-containing coal by ultrasonic-wave assisted acid weak oxidation process - Google Patents
Technology for extracting germanium from germanium-containing coal by ultrasonic-wave assisted acid weak oxidation process Download PDFInfo
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- CN101177733A CN101177733A CNA2006101433443A CN200610143344A CN101177733A CN 101177733 A CN101177733 A CN 101177733A CN A2006101433443 A CNA2006101433443 A CN A2006101433443A CN 200610143344 A CN200610143344 A CN 200610143344A CN 101177733 A CN101177733 A CN 101177733A
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- germanium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to a technology of extracting germanium from germanium coal by a method of ultrasonic acid-aid weak oxidation, which pertains to the technical field of coal comprehensive utilization. The invention takes oxidation, acid soluble and ultrasound as main means, extracts micro germanium element in the germanium coal and comprehensively utilizes the coal on the premise of not damaging the main structure of the germanium coal. The method is that the germanium coal is crushed and ground, and then the acid soluble is oxidized, thereby, a reactant is obtained after completely reaction; under 30-100 DEG C, the ultrasonic reaction is used for leading the reactant to be ultrasonic for more than 5 minutes; under 0.01-2 MPa and 40-120 DEG C, Cl<-> is added to distill the ultrasonic reactant so as to extract the germanium element. The invention has simple technological process, easy operation and low investment cost, and highly improves the recovery rate of the germanium in the coal. Furthermore, the method does not damage the main component in the coal, thus causing the coal to be further and comprehensively utilized and improving a due economic value of the coal.
Description
Technical field:
The invention belongs to coal comprehensive utilization technique field, is that a class is extracted trace germanium element in the coal and applied technical field that coal is fully utilized.
Background technology:
At present, the extracting method of extraction germanium mainly contains following two kinds in the coal:
(1) is solution system with dense HCl, from raw coal, directly extracts germanium.The organic efficiency of germanium generally can reach more than 80% in this method raw coal, but this method hydrochloric acid consumption is too big, and the industrial production cost is too high.
(2), from the burning of coal product, extract germanium with behind the coal combustion.Though this method is simple to operate, the rate of recovery low (50%～80%) is the significant wastage to coal resources, do not given play to the institute of coal inherent economic worth own fully, and burning of coal pollutes the environment.
Summary of the invention:
The purpose of this invention is to provide a class and extract the utilisation technology of germanium from germanic coal, this technical matters flow process is simple, has improved the rate of recovery of germanium to a greater degree, generally can reach more than 94%, and this method cost of investment is low.And this method is not destroyed the main composition of raw coal, has reached the purpose of coal comprehensive utilization.
The present invention is achieved by following technical proposals:
From germanic raw coal, extract germanium, comprise by oxygenant, acid solution and be the prerequisite that main supplementary means constitutes whole process flow by ultrasonic wave.Raw coal is rich germanic coal.Described oxygenant is selected from MnO
2, HNO
3, O
2, H
2O
2, Na
2O
2, K
2O
2, NaClO
4, KClO
4And Na
2O
3In one or more combination.Described acid solution is selected from H
2SO
4, HF, HClO
3, HCl and HClO
4In one or more combination.
The mass ratio of described germanic coal pressed powder and oxygenant is 1: 0.1～1: 5); The volumetric molar concentration of described acid solution is 2-8mol/L; The weight ratio of germanic coal pressed powder and acid solution is 1: 0.1～1: 6.
The method of extracting germanium from germanic coal of the present invention realizes by following steps:
(1) mixes the reactant that obtains reacting completely earlier with the oxygenant oxidation of raw coal powder, and then with acid solution;
(2) with resulting reactant in (1) under 30～100 ℃ of conditions, (ultrasonic wave is meant that generally vibrational frequency is greater than more than the 20KHz to utilize ultrasonic wave, the vibration number of its per second (frequency) is very high, the upper limit (20000Hz) that has exceeded human auditory system, people are called ultrasonic wave with this inaudible sound wave), the ultrasonic time scope is 5min～6h;
(3) with resulting reactant in (2) under 0.01～2MPa, 40～120 ℃ of conditions, add Cl
-Carry out the distillation extraction element Ge.
Brief description of drawings
Fig. 1 is the flow line figure of brief description the inventive method.
In a kind of preferred embodiment of the method for the invention, the granularity of germanic coal pressed powder is 10～600 purpose powder.
In a kind of preferred embodiment of the method for the invention, described oxidant is selected from MnO2、HNO
3、O
2、H
2O
2、Na
2O
2、K
2O
2、NaClO
4、KClO
4And Na2O
3In one or more combination.
In a kind of preferred embodiment of the method for the invention, described acid solution is selected from H2SO
4、HF、HClO
3, HCl and HClO4In one or more combination.
In a kind of preferred embodiment of the method for the invention, hyperacoustic frequency is 20KHz～2MHz.
Because germanium has close Organic, so the enrichment of germanium is arranged in many coal seams; Germanium mainly may be attracted in the coal with free germanium ion form in coal; The sulfide that is SiGe hydrochlorate and germanium is present in the coal; The form that is the organic compound of germanium is present in the coal, and perhaps the form with complex compound exists; With with coal in macromolecular different functional groups bonding, or close with the humic acid huge legendary turtle; Form by surface oxidation reduction reaction and adsorption is present in surface organic in the coal. So mechanism of the present invention is, utilize oxidant and change the existence form of germanium in coal take ultrasonic wave as auxiliary means, perhaps the form with free germanium ion exists, perhaps with coal in little molecular linkage, and then carry out extracting germanium by distillation.
This is ultrasonic to help the acid weak oxidation method to extract the germanium method from germanic coal to compare with conventional method and have following features, technique is simple, easily operation, the germanium recovery rate is high, cost of investment is relatively low, and germanic coal is after utilizing the method to extract germanium, can also carry out to it other comprehensive utilization, such as: the organic matter that coal gasification, coal liquefaction or separation and Extraction are contained, so just can take full advantage of the various components of coal, coal is fully utilized, to improve its added value.
The contrast experiment:
Get coal sample and each 0.5g of original coal sample of utilizing the method to extract germanium, carry out the quantitative analysis of germanium, used analytical method is high-frequency inductive coupling plasma body emission spectrometry (ICP-AES, U.S. PerkinElmer company, Optima4300DV type).
Table 1: the experimental result contrast of having extracted Ge content in the coal sample of germanium and the original coal sample
| Sample | Analytical procedure | Analytical line | ?Ge(μg/g) |
| Do not extract ge content (C) in the coal sample of germanium | ICP-OES | ?209nm | ?1298 |
| Do not extract ge content (C) in the coal sample of germanium | ICP-OES | ?209nm | ?1333 |
| Extracted ge content (C) in the coal sample of germanium | ICP-OES | ?209nm | ?90 |
| Extracted ge content (C) in the coal sample of germanium | ICP-OES | ?209nm | ?81 |
| The ge content of blank sample | ICP-OES | ?209nm | ?6 |
Remarks: the data in the table 1 are among the embodiment.
Test result analysis:
C
1＝[(1298-6)+(1333-6)]/2＝1309.5
C
2＝[(90-6)+(81-6)]/2＝79.5
W＝(C
1-C
2)/C
1＊100％＝93.93％
Wherein C is the content of germanium; W is the rate of recovery of germanium.
By as can be seen above, extract germanium by this method, the rate of recovery of germanium has been reached more than 93%, surpassed the rate of recovery of traditional method.
The specific examples mode:
Enumerate 3 embodiment below, the present invention is further specified, but the present invention is not only limited to these embodiment.
The germanic brown coal that we adopted in an embodiment are from Inner Mongolia Autonomous Region, ultrasonic instrument is the KQ-250B type that Kunshan Ultrasonic Instruments Co., Ltd. produces, adopt high-frequency inductor coupled plasma emission spectrometry (ICP-AES, U.S. PerkinElmer company, Optima4300DV type) carries out test analysis.
Embodiment 1
Experimental procedure comprises germanic brown coal ball mill pulverizing, oxidation, sour molten.In this embodiment, germanic brown coal ball milling to 50 order is taken by weighing 20 grams, add oxygenant and acid solution, oxygenant is an oxygen, and acid is dense HClO
3, utilized dioxygen oxidation 15 minutes; Wherein coal sample is 1: 2.5 with the weight ratio of acid, and acid is 1: 2 with the volume ratio of water; With above-mentioned reaction mixture under 60 ℃, ultrasonic 2 hours, static 3 hours.Then with reactant under 0.8MPa, 100 ℃ of conditions, add Cl
-Ion distillation extraction germanium, wherein Cl
-The molar ratio of the germanic amount in total add-on of ion and the brown coal is 12: 1.The coal that extracts germanium is carried out the quantitative analysis of germanium, and experiment analysis results shows that the rate of recovery of germanium is 95.2%.
Embodiment 2
Adopt the step of embodiment 1, take by weighing germanic brown coal 20 grams of 50 purposes in this embodiment, utilized dioxygen oxidation 10 minutes, acid is dense HClO
3Wherein coal sample and dense HClO
3The weight ratio of acid is 1: 1.8, and acid is 1: 1.8 with the volume ratio of water, ultrasonic 3 hours.Add Cl then
-Ion distillation extraction germanium.The coal that extracts germanium is carried out the quantitative analysis of germanium, and experiment analysis results shows that the rate of recovery of germanium is 94.8%.
Embodiment 3
Adopt the step of embodiment 1, take by weighing germanic brown coal 20 grams of 100 purposes in this embodiment, add oxygenant H
2O
24ml, acid is dense HCl; Wherein the weight ratio of coal sample and dense HCl acid solution is 1: 1, and the volume ratio of acid solution and water is 1: 1.5, ultrasonic 4 hours.Distillation extraction germanium then.The coal that extracts germanium is carried out the quantitative analysis of germanium, and experiment analysis results shows that the rate of recovery of germanium is 94.1%.
Claims (7)
1. a method of extracting germanium from germanic coal is characterized in that with the germanic coal being basic material, in the presence of oxygenant, acid solution and water, and is that supplementary means is extracted germanium from coal with the ultrasonic wave.
2. the method for extraction germanium as claimed in claim 1 is characterized in that described oxygenant is selected from MnO
2, HNO
3, O
2, H
2O
2, Na
2O
2, K
2O
2, NaClO
4, KClO
4And Na
2O
3In one or more combination; Described acid solution is selected from H
2SO
4, HF, HClO
3, HCl and HClO
4In one or more combination.
3. the method for extraction germanium as claimed in claim 1, the weight ratio that it is characterized in that described germanic coal pressed powder and oxygenant is 1: 0.1～1: 5; The weight ratio of described germanic coal pressed powder and acid solution is 1: 0.1～1: 6; Adding entry, acid is configured to volumetric molar concentration is 2～8mol/L; Add Cl
-1Total amount and germanic coal in the mol ratio of germanic amount be 2～16.
4. method of extracting germanium from germanic coal as claimed in claim 1 may further comprise the steps successively:
(1) mixes the reactant that obtains reacting completely earlier with the oxygenant oxidation of germanic coal powder, and then with acid solution and water;
(2), under 30～100 ℃ of conditions, utilize more than the ultrasonic echography 5min with resulting reactant in (1);
(3) under 0.01～2MPa, 40～120 ℃ of conditions, in the reactant of ultrasonic mistake, add Cl
-Distill to extract element Ge;
5. the method for extraction germanium as claimed in claim 4 is characterized in that frequency of ultrasonic is 20KHz～2MHz.
6. the method for extraction germanium as claimed in claim 4 is characterized in that described oxygenant is selected from MnO
2, HNO
3, O
2, H
2O
2, Na
2O
2, K
2O
2, NaClO
4, KClO
4And Na
2O
3In one or more combination; Described acid solution is selected from H
2SO
4, HF, HClO
3, HCl and HClO
4In one or more combination.
7. the method for extraction germanium as claimed in claim 4, the weight ratio that it is characterized in that described germanic coal pressed powder and oxygenant is 1: 0.1～1: 3; The weight ratio of described germanic coal pressed powder and acid solution is 1: 0.1～1: 4; Adding entry, acid is configured to volumetric molar concentration is 2～8mol/L; Add Cl
-1Total amount and germanic coal in the mol ratio of germanic amount be 2～16.
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|---|---|---|---|
| CNA2006101433443A CN101177733A (en) | 2006-11-06 | 2006-11-06 | Technology for extracting germanium from germanium-containing coal by ultrasonic-wave assisted acid weak oxidation process |
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|---|---|---|---|
| CNA2006101433443A CN101177733A (en) | 2006-11-06 | 2006-11-06 | Technology for extracting germanium from germanium-containing coal by ultrasonic-wave assisted acid weak oxidation process |
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| CN101177733A true CN101177733A (en) | 2008-05-14 |
Family
ID=39404147
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101956079A (en) * | 2010-10-29 | 2011-01-26 | 河池市南方有色冶炼有限责任公司 | Rare and noble metal recycling device |
| CN102534268A (en) * | 2010-12-28 | 2012-07-04 | 北京有色金属研究总院 | Production method of high-purity germanium dioxide |
| CN104818397A (en) * | 2015-05-19 | 2015-08-05 | 河北工程大学 | Method for extracting germanium from coal |
| CN104911363A (en) * | 2015-06-24 | 2015-09-16 | 上海交通大学 | Method for recovering germanium in lignite smoke |
| CN105369038A (en) * | 2015-11-05 | 2016-03-02 | 昆明理工大学 | Mixed oxidant and method for recycling germanium from leaching residues in hard zinc through mixed oxidant |
| JP2019528371A (en) * | 2017-07-24 | 2019-10-10 | 韓國電力公社Ｋｏｒｅａ Ｅｌｅｃｔｒｉｃ Ｐｏｗｅｒ Ｃｏｒｐｏｒａｔｉｏｎ | Extraction method of rare metal element from coal ash and extraction device of rare metal element |
| CN114032397A (en) * | 2021-11-18 | 2022-02-11 | 昆明理工大学 | Method for reducing and leaching germanium-containing smoke dust in lead-zinc smelting through ultrasonic enhancement |
| CN116694937A (en) * | 2023-08-08 | 2023-09-05 | 昆明理工大学 | Zinc oxide smoke deep leaching ultrasonic device and valuable metal extraction method |
-
2006
- 2006-11-06 CN CNA2006101433443A patent/CN101177733A/en not_active Withdrawn
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101956079A (en) * | 2010-10-29 | 2011-01-26 | 河池市南方有色冶炼有限责任公司 | Rare and noble metal recycling device |
| CN101956079B (en) * | 2010-10-29 | 2012-08-08 | 河池市南方有色冶炼有限责任公司 | Rare and noble metal recycling device |
| CN102534268A (en) * | 2010-12-28 | 2012-07-04 | 北京有色金属研究总院 | Production method of high-purity germanium dioxide |
| CN104818397A (en) * | 2015-05-19 | 2015-08-05 | 河北工程大学 | Method for extracting germanium from coal |
| CN104911363A (en) * | 2015-06-24 | 2015-09-16 | 上海交通大学 | Method for recovering germanium in lignite smoke |
| CN105369038A (en) * | 2015-11-05 | 2016-03-02 | 昆明理工大学 | Mixed oxidant and method for recycling germanium from leaching residues in hard zinc through mixed oxidant |
| JP2019528371A (en) * | 2017-07-24 | 2019-10-10 | 韓國電力公社Ｋｏｒｅａ Ｅｌｅｃｔｒｉｃ Ｐｏｗｅｒ Ｃｏｒｐｏｒａｔｉｏｎ | Extraction method of rare metal element from coal ash and extraction device of rare metal element |
| CN114032397A (en) * | 2021-11-18 | 2022-02-11 | 昆明理工大学 | Method for reducing and leaching germanium-containing smoke dust in lead-zinc smelting through ultrasonic enhancement |
| CN114032397B (en) * | 2021-11-18 | 2022-12-27 | 昆明理工大学 | Method for reducing and leaching germanium-containing smoke dust in lead-zinc smelting through ultrasonic enhancement |
| CN116694937A (en) * | 2023-08-08 | 2023-09-05 | 昆明理工大学 | Zinc oxide smoke deep leaching ultrasonic device and valuable metal extraction method |
| CN116694937B (en) * | 2023-08-08 | 2023-11-14 | 昆明理工大学 | Zinc oxide smoke deep leaching ultrasonic device and valuable metal extraction method |
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Open date: 20080514 |