CN117210688B - Method for recycling tannin germanium slag in quality - Google Patents
Method for recycling tannin germanium slag in quality Download PDFInfo
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- CN117210688B CN117210688B CN202311484008.5A CN202311484008A CN117210688B CN 117210688 B CN117210688 B CN 117210688B CN 202311484008 A CN202311484008 A CN 202311484008A CN 117210688 B CN117210688 B CN 117210688B
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- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 140
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000002893 slag Substances 0.000 title claims abstract description 98
- 229920001864 tannin Polymers 0.000 title claims abstract description 51
- 239000001648 tannin Substances 0.000 title claims abstract description 51
- 235000018553 tannin Nutrition 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000004064 recycling Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 92
- 238000000197 pyrolysis Methods 0.000 claims abstract description 68
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 62
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 39
- 239000011701 zinc Substances 0.000 claims abstract description 34
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 30
- 238000002386 leaching Methods 0.000 claims abstract description 29
- 239000000571 coke Substances 0.000 claims abstract description 26
- 238000000746 purification Methods 0.000 claims abstract description 22
- 238000001556 precipitation Methods 0.000 claims abstract description 16
- 239000003034 coal gas Substances 0.000 claims abstract description 11
- 238000000605 extraction Methods 0.000 claims abstract description 7
- 230000005284 excitation Effects 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- 229910052742 iron Inorganic materials 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 18
- 238000004537 pulping Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000008235 industrial water Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 230000000536 complexating effect Effects 0.000 claims description 13
- 239000008139 complexing agent Substances 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 abstract description 17
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 abstract description 13
- 239000001263 FEMA 3042 Substances 0.000 abstract description 13
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 abstract description 13
- 229940033123 tannic acid Drugs 0.000 abstract description 13
- 235000015523 tannic acid Nutrition 0.000 abstract description 13
- 229920002258 tannic acid Polymers 0.000 abstract description 13
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000012141 concentrate Substances 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 6
- 239000003350 kerosene Substances 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 239000011335 coal coke Substances 0.000 abstract description 2
- 239000011280 coal tar Substances 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000011269 tar Substances 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 150000007824 aliphatic compounds Chemical class 0.000 description 5
- 150000001491 aromatic compounds Chemical class 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
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- 230000001105 regulatory effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a method for recycling tannin germanium slag by mass, belonging to the technical field of germanium extraction.The method comprises 9 working procedures of coordination leaching, neutralization precipitation, inorganic neutralization slag volatilization, arsenic-poor material volatilization, organic pyrolysis coal gas, organic pyrolysis kerosene, organic pyrolysis coke, coke purification and ultraviolet excitation, wherein tannic acid and metal elements can be separated by the coordination leaching, and metals such as arsenic, germanium, zinc and the like in the slag can be separated and recovered by two-stage volatilization of inorganic metal slag, so that the grade of germanium concentrate is improved, and the grade of Ge is over 67.40%; and (3) performing three-stage pyrolysis on the organic matters to generate coal gas, tar and coke, and purifying and ultraviolet exciting the coke to obtain CDs. The invention can separate and recycle inorganic matters and organic matters in the tannin germanium slag into arsenic-rich material, germanium-poor material, coal gas, kerosene and CDs, and can effectively solve the problems that a large amount of organic resources are wasted and a large amount of CO is produced in the oxidizing roasting of the single Ning Zhe slag 2 High impurity content of germanium concentrate and the like.
Description
Technical Field
The invention relates to a method for recycling tannin germanium slag by mass, belonging to the technical field of germanium extraction.
Background
The vast majority of germanium is produced by utilizing a tannin germanium precipitation process, and mainly comprises two steps of countercurrent leaching, tannin germanium precipitation, oxidizing roasting, chloridizing distillation and the like. The tannin germanium precipitation process cost reaches more than 80% of the whole process treatment cost, tannic acid with the mass of 30 times of germanium is needed to be utilized to enrich and extract germanium from milliquantity of germanium solution to form tannic germanium slag with the germanium content of 3-5%, and then the tannic germanium slag is roasted to obtain germanium concentrate with the germanium content of about 25%. The direct roasting of the tannin germanium slag not only wastes a great deal of organic resources, but also generates a great deal of CO 2 And is unfavorable for realizing the double-carbon target.
In order to avoid direct roasting loss of tannic acid and germanium slag, patent document CN202210422432.6 discloses a method for recovering tannic acid from tannic acid and germanium slag based on an ultrasonic external field, wherein germanium in germanium concentrate is subjected to coordination leaching, then the pH value of a system is regulated by NaOH, tannic acid liquid and germanium slag are separated, and the tannic acid liquid is recycled after acid is reversely regulated; patent document CN201810363224.7 discloses a method for improving comprehensive value of tannin germanium slag, which comprises alkaline leaching tannin germanium slag, separating tannin germanium slag from tannic acid solution, adjusting pH value of system with NaOH, separating tannic acid solution from germanium slag, reversely adjusting acid of tannic acid solution, and concentrating to obtain tannin solution. Although the technology can avoid the loss of organic resources to a certain extent, the coordination structure of the recovered tannin is destroyed, and a large amount of organic matters can be introduced in the subsequent germanium precipitation.
Disclosure of Invention
Aiming at the problems that the oxidation roasting of tannin germanium slag in the existing tannin germanium precipitation process wastes a large amount of organic resources and generates a large amount of CO 2 The invention provides a method for recycling tannin germanium slag according to quality, which comprises 9 working procedures of coordination leaching, neutralization precipitation, volatilization of inorganic neutralization slag, volatilization of arsenic-poor materials, pyrolysis of organic matters, pyrolysis of coal gas, pyrolysis of organic matters, pyrolysis of kerosene, coke purification of organic matters and ultraviolet excitation; the coordination leaching can separate tannic acid from metal elements, and the two-stage volatilization of the inorganic metal slag can separate and recycle metals such as arsenic, germanium, zinc and the like in the slag, so that the grade of germanium concentrate is improved, and the grade of Ge is up to 67.40%; and (3) performing three-stage pyrolysis on the organic matters to generate coal gas, tar and coke, and purifying and ultraviolet exciting the coke to obtain CDs. The invention can separate and recycle inorganic matters and organic matters in the tannin germanium slag into arsenic-rich material, germanium-poor material, coal gas, kerosene and CDs, and can effectively solve the problems that a large amount of organic resources are wasted and a large amount of CO is produced in the oxidizing roasting of the single Ning Zhe slag 2 High impurity content of germanium concentrate and the like.
A method for recycling tannin germanium slag according to quality comprises the following specific steps:
(1) Mixing and pulping the tannin germanium slag and industrial water, adding a complexing agent, and carrying out coordination leaching to obtain a coordination leaching solution;
(2) Adding a neutralizing agent into the coordination leaching solution to perform neutralization precipitation reaction, and carrying out solid-liquid separation to obtain inorganic neutralization slag and organic solution;
(3) Performing I-level volatilization on the inorganic neutralization slag to obtain an arsenic-rich material and an arsenic-poor material, and returning the arsenic-rich material to a vacuum arsenic extraction process;
(4) Performing II-stage volatilization on the arsenic-depleted material to obtain a germanium-enriched material and a germanium-depleted material, returning the germanium-enriched material to the chlorination distillation process, and returning the germanium-depleted material to the fuming system;
(5) Drying the organic solution to obtain an organic mixture and water vapor, returning the water vapor to the pulping process of the step (1), and performing I-stage pyrolysis on the organic mixture to obtain coal gas and I-stage pyrolysis organic matters;
(6) Carrying out II-stage pyrolysis on the organic matters obtained by the I-stage pyrolysis to obtain tar and organic matters obtained by the II-stage pyrolysis; wherein the pyrolysis temperature of the section I is less than the pyrolysis temperature of the section II;
(7) Performing III-stage pyrolysis on the organic matters obtained by II-stage pyrolysis to obtain coke; wherein the II-stage pyrolysis temperature is less than the III-stage pyrolysis temperature;
(8) Mixing the coke and the ethanol, and performing ultrasonic purification to obtain a coke-ethanol mixed solution;
(9) Exciting the coke-ethanol mixed solution by using ultraviolet rays, performing liquid-solid separation to obtain CDs and ethanol residual liquid, and returning the ethanol residual liquid to the step (8) for ultrasonic purification.
Based on the mass of the tannin germanium slag as 100%, the tannin germanium slag contains 2-6% of germanium, 1-4% of zinc, 0.1-0.5% of arsenic, 0.2-0.5% of iron and 89-96.7% of organic matters; the pH value of the industrial water is 4-5; the liquid-solid ratio of the industrial water to the tannin germanium slag is mL, g is 2-4:1, the slurrying temperature is 50-70 ℃, and the slurrying time is 15-40 min; the complexing agent is oxalic acid, tartaric acid, citric acid or malic acid, the addition amount of the complexing agent is 5-30% of the mass of the tannin germanium slag, the pH value of the complexing leaching is 1-3, and the complexing leaching time is 30-60 min.
The neutralizer in the step (2) is sodium hydroxide, ammonia water or zinc oxide, the pH of the end point of the neutralization precipitation reaction is 6.5-8, and the temperature of the neutralization precipitation reaction is 50-70 ℃; the mass of the inorganic neutralization slag is 100%, the content of germanium in the inorganic neutralization slag is 22.98% -30.94%, the content of zinc in the inorganic neutralization slag is 11.49% -19.90%, the content of arsenic in the inorganic neutralization slag is 1.15% -2.49%, and the content of iron in the inorganic neutralization slag is 2.49% -17.24%.
The temperature of the I-level volatilization in the step (3) is 300-500 ℃ and the volatilization time is 1-3 h; based on the mass of the arsenic-rich material being 100%, the germanium content in the arsenic-rich material is 5.88% -7.57%, the zinc content is 7.35% -12.61%, the arsenic content is 13.97% -29.95%, and the iron content is 1.47% -13.09%; based on 100% of the mass of the arsenic-poor material, the germanium content in the arsenic-poor material is 32.13-44.70%, the zinc content in the arsenic-poor material is 15.57-27.11%, the arsenic content in the arsenic-poor material is 0.08-0.18%, and the iron content in the arsenic-poor material is 3.39-23.36%.
The temperature of the II-level volatilization in the step (4) is 800-1000 ℃ and the volatilization time is 4-6 h; based on the mass of the germanium-rich material being 100%, the germanium content in the germanium-rich material is 65.48% -67.40%, the zinc content is 1.62% -2.21%, the arsenic content is 0.009% -0.015%, and the iron content is 0.28% -2.43%; based on 100% of the mass of the germanium-poor material, the germanium content in the germanium-poor material is 1.24% -2.55%, the zinc content is 28.49% -66.44%, the arsenic content is 0.15% -0.44%, and the iron content is 8.30% -42.74%.
The drying temperature of the organic solution in the step (5) is 60-80 ℃ and the drying time is 4-6 hours; the pyrolysis temperature of the section I is 200-350 ℃, and the pyrolysis time is 1-2 h; the side chain in the tannic acid structure starts to break and decompose at this stage, and methane, hydrogen, CO, a small amount of light hydrocarbon and other gases are mainly generated.
In the step (6), the pyrolysis temperature of the section II is 350-500 ℃ and the pyrolysis time is 4-6 hours; this stage mainly produces tar such as aliphatic and aromatic compounds.
In the step (7), the pyrolysis temperature of the III section is 500-650 ℃, and the pyrolysis time is 6-8 hours; this stage is mainly the shrinkage of the semicoke, which forms coke.
In the step (8), the liquid-solid ratio of the ethanol to the coke, namely, the g, is 1-3:1, the purification temperature is 20-30 ℃, the purification time is 10-20 min, and the ultrasonic intensity is 0.3-0.5W/cm 2 。
In the step (9), the ultraviolet wavelength is 200-400 nm, and the excitation time is 10-30 min.
The CDs can be used in the fields of heavy metal ion detection and photoelectric devices.
The beneficial effects of the invention are as follows:
(1) According to the invention, a complexing agent substance (oxalic acid, tartaric acid, citric acid or malic acid) with higher coordination coefficient with germanium is added to separate tannin organic matters from germanium, and tannin germanium slag is separated into organic tannic acid and inorganic metal slag for recycling;
(2) According to the invention, the inorganic metal slag is volatilized in two sections, and arsenic is extracted by volatilizing in one section at low temperature, so that the As grade reaches 29.95%; extracting germanium by two-stage high-temperature volatilization, wherein the Ge grade reaches 67.40%; the residual zinc and iron are returned to smelting, and the Zn grade reaches 66.44%;
(3) The method comprises the steps of carrying out three-stage pyrolysis on organic tannic acid, wherein the first-stage pyrolysis generates gases such as methane, hydrogen, CO, a small amount of light hydrocarbon and the like, the second-stage pyrolysis generates tar such as aliphatic compounds and aromatic compounds, the third-stage pyrolysis generates coke, and the coke is purified by ultrasonic to obtain CDs;
(4) The invention can effectively solve the problems that the oxidation roasting of the prior single Ning Zhe slag wastes a large amount of organic resources and generates a large amount of CO 2 High impurity content of germanium concentrate and the like.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is an ultraviolet-visible light absorption curve of CDs prepared in example 2.
Detailed Description
The invention will be described in further detail with reference to specific embodiments, but the scope of the invention is not limited to the description.
Example 1: the main components of the germanium slag of the single Ning Zhe slag of the embodiment are shown in table 1;
TABLE 1 main ingredients (wt.%) of tannin germanium slag
| Ge | Zn | As | Fe | Organic matter |
| 2% | 1% | 0.1% | 0.2% | 96.7% |
A method for recycling tannin germanium slag by mass (see figure 1) comprises the following specific steps:
(1) Mixing and pulping the tannic germanium slag and industrial water, wherein the industrial water is enterprise production backwater, the pH value is 4, the liquid-solid ratio mL of the industrial water and the tannic germanium slag is 2:1, the pulping temperature is 50 ℃, and the pulping time is 15min; then adding a complexing agent (oxalic acid) for carrying out complexing leaching for 30min to obtain a complexing leaching solution; wherein the addition amount of the complexing agent is 5% of the mass of the tannin germanium slag, and the pH value of the complexing leaching is 1;
(2) Adding a neutralizing agent (sodium hydroxide) into the coordination leaching solution, carrying out neutralization precipitation reaction at 50 ℃ until the end point pH is 6.5, and carrying out solid-liquid separation to obtain inorganic neutralization slag and organic solution; the mass of the inorganic neutralization slag is 100%, the germanium content in the inorganic neutralization slag is 30.94%, the zinc content is 15.47%, the arsenic content is 1.55% and the iron content is 3.09%;
(3) Performing I-stage volatilization on the inorganic neutralization slag at the temperature of 300 ℃ for 1h to obtain an arsenic-rich material and an arsenic-poor material, and returning the arsenic-rich material to the vacuum arsenic extraction process; the mass of the arsenic-rich material is 100%, the germanium content in the arsenic-rich material is 5.88%, the zinc content is 7.35%, the arsenic content is 13.97%, and the iron content is 1.47%; the mass of the arsenic-lean material is 100%, the germanium content in the arsenic-lean material is 44.70%, the zinc content is 21.66%, the arsenic content is 0.11%, and the iron content is 4.33%;
(4) Performing II-stage volatilization on the arsenic-depleted material at 800 ℃ for 4 hours to obtain a germanium-enriched material and a germanium-depleted material, returning the germanium-enriched material to a chlorination distillation process, and returning the germanium-depleted material to a fuming system; based on 100% of the germanium-rich material, the germanium content in the germanium-rich material is 67.40%, the zinc content is 1.67%, the arsenic content is 0.009%, and the iron content is 0.33%; based on 100% of the mass of the germanium-poor material, the germanium content in the germanium-poor material is 2.55%, the zinc content is 58.79%, the arsenic content is 0.31% and the iron content is 11.76%;
(5) Drying the organic solution at the loading temperature of 60 ℃ for 4 hours to obtain an organic mixture and water vapor, returning the water vapor to the pulping process of the step (1), and performing I-stage pyrolysis on the organic mixture at the temperature of 200 ℃ for 1 hour to obtain coal gas and I-stage pyrolysis organic matters; the side chain in the tannic acid structure starts to break and decompose, and gases such as methane, hydrogen, CO, a small amount of light hydrocarbon and the like are mainly generated;
(6) Carrying out II-stage pyrolysis on the organic matters obtained by the I-stage pyrolysis at the temperature of 350 ℃ for 4 hours to obtain tar and organic matters obtained by the II-stage pyrolysis; this stage mainly produces tar such as aliphatic and aromatic compounds;
(7) Performing III-stage pyrolysis on the II-stage pyrolysis organic matters at the temperature of 500 ℃ for 6 hours to obtain coke; the semicoke is mainly contracted to form coke;
(8) Mixing the coke and the ethanol, and performing ultrasonic purification to obtain a coke-ethanol mixed solution; wherein the liquid-solid ratio of the ethanol to the coke, namely, the g, is 1:1, the purification temperature is 20 ℃, the purification time is 10min, and the ultrasonic intensity is 0.3W/cm 2 ；
(9) Exciting the coke-ethanol mixed solution for 10min by using ultraviolet rays with the wavelength of 200nm, and performing liquid-solid separation to obtain CDs and ethanol residual liquid, wherein the ethanol residual liquid returns to the step (8) for ultrasonic purification; the prepared CDs can be used in the fields of heavy metal ion detection and photoelectric devices.
Example 2: the main components of the germanium slag of the single Ning Zhe slag of the embodiment are shown in table 2;
TABLE 2 main ingredients (wt.%) of tannin germanium slag
| Ge | Zn | As | Fe | Organic matter |
| 4% | 2% | 0.2% | 0.3% | 93.5% |
A method for recycling tannin germanium slag by mass (see figure 1) comprises the following specific steps:
(1) Mixing and pulping the tannic germanium slag and industrial water, wherein the industrial water is enterprise production backwater, the pH value is 4.5, the liquid-solid ratio mL of the industrial water and the tannic germanium slag is 3:1, the pulping temperature is 60 ℃, and the pulping time is 30min; then adding a complexing agent (tartaric acid) for carrying out complexing leaching for 45min to obtain a complexing leaching solution; wherein the addition amount of the complexing agent is 15% of the mass of the tannin germanium slag, and the pH value of the complexing leaching is 2;
(2) Adding a neutralizing agent (ammonia water) into the coordination leaching solution, carrying out neutralization precipitation reaction at the temperature of 60 ℃ until the end point pH is 7, and carrying out solid-liquid separation to obtain inorganic neutralization slag and organic solution; the mass of the inorganic neutralization slag is 100%, the germanium content in the inorganic neutralization slag is 22.98%, the zinc content is 11.49%, the arsenic content is 1.15% and the iron content is 17.24%;
(3) Performing I-stage volatilization on the inorganic neutralization slag for 2 hours at the temperature of 400 ℃ to obtain an arsenic-rich material and an arsenic-poor material, and returning the arsenic-rich material to the vacuum arsenic extraction process; based on 100% of the mass of the arsenic-rich material, the germanium content in the arsenic-rich material is 6.98%, the zinc content is 8.73%, the arsenic content is 16.58% and the iron content is 13.09%; based on 100% of the mass of the arsenic-lean material, the germanium content in the arsenic-lean material is 32.13%, the zinc content is 15.57%, the arsenic content is 0.08% and the iron content is 23.36%;
(4) Performing II-stage volatilization on the arsenic-depleted material at 900 ℃ for 5 hours to obtain a germanium-enriched material and a germanium-depleted material, returning the germanium-enriched material to a chlorination distillation process, and returning the germanium-depleted material to a fuming system; based on 100% of the germanium-rich material, the germanium content in the germanium-rich material is 65.48%, the zinc content is 1.62%, the arsenic content is 0.009% and the iron content is 2.43%; based on 100% of the mass of the germanium-poor material, the germanium content in the germanium-poor material is 1.24%, the zinc content is 28.49%, the arsenic content is 0.15% and the iron content is 42.74%;
(5) Drying the organic solution at 70 ℃ for 5 hours to obtain an organic mixture and water vapor, returning the water vapor to the pulping process of the step (1), and performing I-stage pyrolysis on the organic mixture at 300 ℃ for 1.5 hours to obtain coal gas and I-stage pyrolysis organic matters; the side chain in the tannic acid structure starts to break and decompose, and gases such as methane, hydrogen, CO, a small amount of light hydrocarbon and the like are mainly generated;
(6) Carrying out II-stage pyrolysis on the organic matters obtained by the I-stage pyrolysis at the temperature of 450 ℃ for 5 hours to obtain tar and organic matters obtained by the II-stage pyrolysis; this stage mainly produces tar such as aliphatic and aromatic compounds;
(7) Performing III-stage pyrolysis on the II-stage pyrolysis organic matters at 600 ℃ for 7 hours to obtain coke; the semicoke is mainly contracted to form coke;
(8) Mixing the coke and the ethanol, and performing ultrasonic purification to obtain a coke-ethanol mixed solution; wherein the liquid-solid ratio of the ethanol to the coke is mL, g is 2:1, the purification temperature is 25 ℃, the purification time is 15min, and the ultrasonic intensity is 0.4W/cm 2 ；
(9) Exciting the coke-ethanol mixed solution for 20min by using ultraviolet rays with the wavelength of 300nm, and performing liquid-solid separation to obtain CDs and ethanol residual liquid, wherein the ethanol residual liquid returns to the step (8) for ultrasonic purification;
the uv-vis absorption curve of CDs prepared in this example is shown in fig. 2, and it can be seen from fig. 2 that CDs generate a fluorescence absorption peak at 220 nm, corresponding to pi-pi transition of c=c bonds in the carbon core; the fluorescence characteristic can be used in the fields of heavy metal ion detection and photoelectric devices.
Example 3: the main components of the germanium slag of the single Ning Zhe slag of the embodiment are shown in table 3;
table 3 Single Ning Zhe slag main component (wt.%)
| Ge | Zn | As | Fe | Organic matter |
| 6% | 4% | 0.5% | 0.5% | 89% |
A method for recycling tannin germanium slag by mass (see figure 1) comprises the following specific steps:
(1) Mixing and pulping the tannin germanium slag and industrial water, wherein the industrial water is enterprise production backwater, the pH value is 5, the liquid-solid ratio mL of the industrial water to the tannin germanium slag is 4:1, the pulping temperature is 70 ℃, and the pulping time is 40min; then adding complexing agent (citric acid) for carrying out complexing leaching for 60min to obtain complexing leaching solution; wherein the addition amount of the complexing agent is 30% of the mass of the tannin germanium slag, and the pH value of the complexing leaching is 3;
(2) Adding a neutralizing agent (zinc oxide) into the coordination leaching solution, carrying out neutralization precipitation reaction at 70 ℃ until the end point pH is 8, and carrying out solid-liquid separation to obtain inorganic neutralization slag and organic solution; the mass of the inorganic neutralization slag is 100%, the germanium content in the inorganic neutralization slag is 29.85%, the zinc content is 19.90%, the arsenic content is 2.49% and the iron content is 2.49%;
(3) Performing I-stage volatilization on the inorganic neutralization slag at the temperature of 500 ℃ for 3 hours to obtain an arsenic-rich material and an arsenic-poor material, and returning the arsenic-rich material to the vacuum arsenic extraction process; based on 100% of the mass of the arsenic-rich material, the germanium content in the arsenic-rich material is 7.57%, the zinc content is 12.61%, the arsenic content is 29.95% and the iron content is 1.58%; the mass of the arsenic-lean material is 100%, the germanium content in the arsenic-lean material is 41.95%, the zinc content is 27.11%, the arsenic content is 0.18% and the iron content is 3.39%;
(4) Performing II-stage volatilization on the arsenic-depleted material at the temperature of 1000 ℃ for 6 hours to obtain a germanium-enriched material and a germanium-depleted material, returning the germanium-enriched material to a chlorination distillation process, and returning the germanium-depleted material to a fuming system; based on 100% of the germanium-rich material, the germanium content in the germanium-rich material is 67.14%, the zinc content is 2.21%, the arsenic content is 0.015% and the iron content is 0.28%; based on 100% of the mass of the germanium-poor material, the germanium content in the germanium-poor material is 2.16%, the zinc content is 66.44%, the arsenic content is 0.44% and the iron content is 8.30%;
(5) Drying the organic solution at the temperature of 80 ℃ for 6 hours to obtain an organic mixture and water vapor, returning the water vapor to the pulping process of the step (1), and performing I-stage pyrolysis on the organic mixture at the temperature of 350 ℃ for 2 hours to obtain coal gas and I-stage pyrolysis organic matters; the side chain in the tannic acid structure starts to break and decompose, and gases such as methane, hydrogen, CO, a small amount of light hydrocarbon and the like are mainly generated;
(6) Carrying out II-stage pyrolysis on the organic matters obtained by the I-stage pyrolysis at the temperature of 500 ℃ for 6 hours to obtain tar and organic matters obtained by the II-stage pyrolysis; this stage mainly produces tar such as aliphatic and aromatic compounds;
(7) Carrying out III-stage pyrolysis on the organic matters obtained by II-stage pyrolysis at the temperature of 650 ℃ for 8 hours to obtain coke; the semicoke is mainly contracted to form coke;
(8) Mixing the coke and the ethanol, and performing ultrasonic purification to obtain a coke-ethanol mixed solution; wherein the liquid-solid ratio of the ethanol to the coke, namely, the g, is 3:1, the purification temperature is 30 ℃, the purification time is 20min, and the ultrasonic intensity is 0.5W/cm 2 ；
(9) Exciting the coke-ethanol mixed solution for 30min by using ultraviolet rays with the wavelength of 400nm, and performing liquid-solid separation to obtain CDs and ethanol residual liquid, wherein the ethanol residual liquid returns to the step (8) for ultrasonic purification; the prepared CDs can be used in the fields of heavy metal ion detection and photoelectric devices.
While the present invention has been described in detail with reference to the drawings, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. The method for recycling the tannin germanium slag according to quality is characterized by comprising the following specific steps:
(1) Mixing and pulping the tannin germanium slag and industrial water, adding a complexing agent, and carrying out coordination leaching to obtain a coordination leaching solution;
(2) Adding a neutralizing agent into the coordination leaching solution to perform neutralization precipitation reaction, and carrying out solid-liquid separation to obtain inorganic neutralization slag and organic solution;
(3) Performing I-level volatilization on the inorganic neutralization slag to obtain an arsenic-rich material and an arsenic-poor material, and returning the arsenic-rich material to a vacuum arsenic extraction process;
(4) Performing II-stage volatilization on the arsenic-depleted material to obtain a germanium-enriched material and a germanium-depleted material, returning the germanium-enriched material to the chlorination distillation process, and returning the germanium-depleted material to the fuming system;
(5) Drying the organic solution to obtain an organic mixture and water vapor, returning the water vapor to the pulping process of the step (1), and performing I-stage pyrolysis on the organic mixture to obtain coal gas and I-stage pyrolysis organic matters;
(6) Carrying out II-stage pyrolysis on the organic matters obtained by the I-stage pyrolysis to obtain tar and organic matters obtained by the II-stage pyrolysis; wherein the pyrolysis temperature of the section I is less than the pyrolysis temperature of the section II;
(7) Performing III-stage pyrolysis on the organic matters obtained by II-stage pyrolysis to obtain coke; wherein the II-stage pyrolysis temperature is less than the III-stage pyrolysis temperature;
(8) Mixing the coke and the ethanol, and performing ultrasonic purification to obtain a coke-ethanol mixed solution;
(9) Exciting the coke-ethanol mixed solution by using ultraviolet rays, performing liquid-solid separation to obtain CDs and ethanol residual liquid, and returning the ethanol residual liquid to the step (8) for ultrasonic purification.
2. The method for recycling the tannin germanium slag according to the quality of claim 1, which is characterized in that: based on the mass of the tannin germanium slag as 100%, the tannin germanium slag contains 2-6% of germanium, 1-4% of zinc, 0.1-0.5% of arsenic, 0.2-0.5% of iron and 89-96.7% of organic matters; the pH value of the industrial water is 4-5; the ratio of liquid to solid of the industrial water to the tannin germanium slag is mL, g is 2-4:1, the slurrying temperature is 50-70 ℃, and the slurrying time is 15-40 min; the complexing agent is oxalic acid, tartaric acid, citric acid or malic acid, the addition amount of the complexing agent is 5-30% of the mass of the tannin germanium slag, the pH value of the complexing leaching is 1-3, and the complexing leaching time is 30-60 min.
3. The method for recycling the tannin germanium slag according to the quality of claim 1, which is characterized in that: the neutralizer in the step (2) is sodium hydroxide, ammonia water or zinc oxide, the pH of the end point of the neutralization precipitation reaction is 6.5-8, and the temperature of the neutralization precipitation reaction is 50-70 ℃; the mass of the inorganic neutralization slag is 100%, the content of germanium in the inorganic neutralization slag is 22.98% -30.94%, the content of zinc in the inorganic neutralization slag is 11.49% -19.90%, the content of arsenic in the inorganic neutralization slag is 1.15% -2.49%, and the content of iron in the inorganic neutralization slag is 2.49% -17.24%.
4. The method for recycling the tannin germanium slag according to the quality of claim 1, which is characterized in that: the temperature of the I-level volatilization in the step (3) is 300-500 ℃, and the volatilization time is 1-3 h; based on the mass of the arsenic-rich material being 100%, the germanium content in the arsenic-rich material is 5.88% -7.57%, the zinc content is 7.35% -12.61%, the arsenic content is 13.97% -29.95%, and the iron content is 1.47% -13.09%; based on 100% of the mass of the arsenic-poor material, the germanium content in the arsenic-poor material is 32.13-44.70%, the zinc content in the arsenic-poor material is 15.57-27.11%, the arsenic content in the arsenic-poor material is 0.08-0.18%, and the iron content in the arsenic-poor material is 3.39-23.36%.
5. The method for recycling the tannin germanium slag according to the quality of claim 1, which is characterized in that: the temperature of the II-level volatilization in the step (4) is 800-1000 ℃ and the volatilization time is 4-6 h; based on the mass of the germanium-rich material being 100%, the germanium content in the germanium-rich material is 65.48% -67.40%, the zinc content is 1.62% -2.21%, the arsenic content is 0.009% -0.015%, and the iron content is 0.28% -2.43%; based on 100% of the mass of the germanium-poor material, the germanium content in the germanium-poor material is 1.24% -2.55%, the zinc content is 28.49% -66.44%, the arsenic content is 0.15% -0.44%, and the iron content is 8.30% -42.74%.
6. The method for recycling the tannin germanium slag according to the quality of claim 1, which is characterized in that: in the step (5), the drying temperature of the organic solution is 60-80 ℃ and the drying time is 4-6 hours; the pyrolysis temperature of the section I is 200-350 ℃, and the pyrolysis time is 1-2 h.
7. The method for recycling the tannin germanium slag according to the quality of claim 1, which is characterized in that: in the step (6), the pyrolysis temperature of the section II is 350-500 ℃ and the pyrolysis time is 4-6 h.
8. The method for recycling the tannin germanium slag according to the quality of claim 1, which is characterized in that: in the step (7), the pyrolysis temperature of the III section is 500-650 ℃, and the pyrolysis time is 6-8 h.
9. The method for recycling the tannin germanium slag according to the quality of claim 1, which is characterized in that: in the step (8), the liquid-solid ratio of the ethanol to the coke, namely, the g, is 1-3:1, the purification temperature is 20-30 ℃, the purification time is 10-20 min, and the ultrasonic intensity is 0.3-0.5W/cm 2 。
10. The method for recycling the tannin germanium slag according to the quality of claim 1, which is characterized in that: in the step (9), the ultraviolet wavelength is 200-400 nm, and the excitation time is 10-30 min.
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