CN113233454A - Method for producing high-purity graphite by using recovered acid - Google Patents
Method for producing high-purity graphite by using recovered acid Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000002253 acid Substances 0.000 title claims abstract description 87
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 78
- 239000010439 graphite Substances 0.000 title claims abstract description 78
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000002699 waste material Substances 0.000 claims abstract description 29
- 239000007800 oxidant agent Substances 0.000 claims abstract description 21
- 239000008139 complexing agent Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000001590 oxidative effect Effects 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000000967 suction filtration Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000010517 secondary reaction Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000003825 pressing Methods 0.000 claims abstract description 6
- 230000007935 neutral effect Effects 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- BHQCQFFYRZLCQQ-UHFFFAOYSA-N (3alpha,5alpha,7alpha,12alpha)-3,7,12-trihydroxy-cholan-24-oic acid Natural products OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 BHQCQFFYRZLCQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004380 Cholic acid Substances 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- BHQCQFFYRZLCQQ-OELDTZBJSA-N cholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 BHQCQFFYRZLCQQ-OELDTZBJSA-N 0.000 claims description 3
- 229960002471 cholic acid Drugs 0.000 claims description 3
- 235000019416 cholic acid Nutrition 0.000 claims description 3
- KXGVEGMKQFWNSR-UHFFFAOYSA-N deoxycholic acid Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 KXGVEGMKQFWNSR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- -1 polypropylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims 1
- 229920004934 Dacron® Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 description 34
- 239000011573 trace mineral Substances 0.000 description 7
- 235000013619 trace mineral Nutrition 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000005086 pumping Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/215—Purification; Recovery or purification of graphite formed in iron making, e.g. kish graphite
Abstract
The invention relates to the field of graphite deep processing, and discloses a method for producing high-purity graphite by using recovered acid, which comprises the following steps: (1) preparing a recovered acid; (2) carrying out a primary reaction, mixing graphite powder with carbon content of 80-90% and recovered acid according to a certain proportion, and reacting for 10-14 hours at 80-90 ℃; (3) carrying out primary suction filtration; (4) carrying out secondary reaction, adding the recovered acid and the oxidant into the graphite obtained in the step (3) in proportion, uniformly mixing the recovered acid and the oxidant, and reacting for 6-12 hours at the temperature of 60-80 ℃; (5) carrying out secondary suction filtration; (6) carrying out a third reaction, and mixing the graphite obtained in the step (5) with a complexing agent, an oxidant and clear water according to a certain proportion; reacting for 5-10 hours at 50-80 ℃; (7) washing to be neutral; (8) performing filter pressing; (9) and (5) drying. The invention solves the problems that waste acid generated by the preparation method of high-purity graphite in the prior art needs to be treated and the production cost is increased.
Description
Technical Field
The invention belongs to the field of graphite deep processing, and particularly relates to a method for producing high-purity graphite by using recovered acid.
Background
In the 21 st century, China's economy has come to a way of resource conservation, environmental friendliness and high-quality development, market competition is becoming more and more intense, and enterprises must pay attention to the premise of environmental protection and reaching standards and reduce cost to establish the market in a non-abortive way. As a natural graphite deep processing industry, the graphite has to be survived and developed only by reducing the cost on the premise of reaching the environmental protection standard, so that enterprises in the industry practice internal work, reduce the cost, innovate and break through, and improve the competitiveness. One of the most important directions for the deep processing of natural graphite is to improve the purity of graphite, namely to improve the carbon content; the method comprises two commonly used methods, namely a chemical purification method and a high-temperature method, wherein the high-temperature method is high in cost, and the most commonly used method in the industry is the chemical purification method, namely, the method comprises the steps of reacting acid, alkali and graphite under certain conditions to remove impurities in the graphite, washing out the acid and alkali, and drying to obtain high-purity graphite, particularly a hydrofluoric acid method in the chemical purification method.
Disclosure of Invention
In order to solve the problems that waste acid generated in the traditional preparation method of high-purity graphite needs to be treated and the production cost is increased in the prior art, the invention provides a method for producing high-purity graphite by using recovered acid.
The invention adopts the specific scheme that: a method for producing high purity graphite using recovered acid, the method comprising the steps of:
(1) collecting the waste acid liquid, filtering to remove insoluble large-particle impurities, then feeding the waste acid liquid into a closed evaporator, evaporating at high temperature to obtain gas in the waste acid, feeding the gas into a spray tower to be combined with pure water in the spray tower, and dissolving the gas in the pure water under high pressure to obtain recovered acid, wherein the concentration of the recovered acid is 5-30%;
(2) carrying out a primary reaction, mixing graphite powder with carbon content of 80-90% and recovered acid according to a certain proportion, and reacting for 10-14 hours at 80-90 ℃;
(3) carrying out primary suction filtration, and discharging the waste acid liquor;
(4) carrying out secondary reaction, adding the recovered acid, the oxidant and the complexing agent into the graphite obtained in the step (3) in proportion, uniformly mixing, and reacting for 6-12 hours at the temperature of 60-80 ℃;
(5) carrying out secondary suction filtration, and discharging the waste acid liquor;
(6) carrying out third reaction, and mixing the graphite obtained in the step (5) with a complexing agent, an oxidant and clear water in proportion; reacting for 5-10 hours at 50-80 ℃;
(7) washing, namely deacidifying the material obtained by the reaction, and then adding pure water to wash the material to be neutral;
(8) performing filter pressing, and performing squeezing dehydration under the pressure of 0.5-1.0 MPa;
(9) and (4) drying, namely drying at 350-500 ℃ until the water content is less than 0.2% to obtain the high-purity graphite.
The oxidant is one or two selected from hydrogen peroxide, peroxyacetic acid, chlorine, concentrated sulfuric acid, nitric acid, concentrated hydrochloric acid and perchloric acid.
The complexing agent is one or two selected from hydrofluoric acid, phosphoric acid, hydrochloric acid, cholic acid and EDTA.
The mass ratio of the graphite powder to the recovered acid in the step (2) is 1: 2 to 4.
And (5) performing suction filtration operation in the steps (3) and (5), wherein a Roots vacuum pump is adopted, strong acid corrosion resistant and high temperature resistant terylene and polypropylene fiber filter cloth is adopted, and 300-mesh 1500-mesh filter cloth is selected according to different particle sizes of graphite products.
Graphite in the secondary reaction in the step (4): acid recovery: oxidizing agent: the mass ratio of the complexing agent is 1: 0.5-4: 0.05-0.5: 0.15 to 1.5.
Graphite in the third reaction in the step (6): complexing agent: oxidizing agent: the clean water is in a mass ratio of 1: 0.3-1.0: 0.1-0.5: 1-3.
Compared with the prior art, the invention has the following beneficial effects:
the method adopts the medium-carbon graphite with lower carbon content to replace the high-carbon graphite, the price of the medium-carbon graphite is only 1/2 of the high-carbon graphite, the cost is saved, the generated waste acid is fully utilized to react with the medium-carbon graphite, the purity of the medium-carbon graphite is improved to the purity of the high-purity graphite under the condition of not increasing new acid consumption, all indexes of trace elements and ash can reach the standard, the cost is reduced by 1/3-1/2 compared with the cost of the original production method, the waste acid is recycled, the environment-friendly sewage treatment cost is reduced, the method is environment-friendly, and the method conforms to the idea of green chemistry.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Example 1:
1) preparing recovered acid, collecting waste acid liquor obtained by primary reaction and secondary reaction filter pressing or centrifugation on a production line into a PP container, pumping the waste acid liquor in the PP container into an acid liquor filtering filter press, wherein filter cloth of the filter press for filtering the acid liquor is acid-resistant and alkali-resistant 1500-mesh 2000-mesh, and the filtered waste acid liquor enters a standby waste acid pool; the concentration of the recovered acid is 5%; 2) performing primary reaction, mixing 1.6 tons of graphite powder with 80 percent of carbon content and 100 meshes of granularity with 3.5 tons of recovered acid, reacting for 14 hours at 80 ℃, performing suction filtration for 30min, and feeding the filtered waste acid liquid into a waste acid pool for later use; 3) performing secondary reaction, namely sequentially adding 1000kg of filtered recovered acid, 100kg of concentrated hydrochloric acid serving as an oxidant, 300kg of nitric acid serving as an oxidant and 500kg of hydrofluoric acid serving as a complexing agent into a reaction tank, uniformly mixing, and reacting 150kg of cholic acid serving as a complexing agent for 14 hours at 80 ℃; performing secondary suction filtration, and pumping and filtering the acid liquor into a waste acid pool for later use; 4) carrying out third reaction, namely adding 1350kg of complexing agent hydrochloric acid, 450kg of oxidant nitric acid and 1800kg of clear water into a reaction tank, uniformly mixing, and reacting for 5 hours at the temperature of 80 ℃; 5) washing, namely squeezing and deacidifying the reacted materials, and then adding pure water to wash until the pH value is more than 4.5; 6) press-filtering, and dewatering under 1.0 MPa; 9) drying to obtain 1440kg of high-purity flake graphite.
The carbon content of the product is 99.965% according to GB/T3521-95 method, and the trace element indexes of the product are shown in the table (see table 1) by a Plasma1000 type ICP-AES test:
TABLE 1
As can be seen from Table 1, the values of various physical and chemical indexes of the obtained product all reach or exceed the quality standard of the industry.
Example 2:
1) the method for preparing the recovered acid is the same as that of example 1, and the concentration of the recovered acid is 30%; 2) carrying out primary reaction, mixing 2000kg of spherical graphite powder with the carbon content of 95% and the specification of SG17, wherein the median diameter is 17.5 microns with 4200kg of recovered acid, reacting for 10 hours at 90 ℃, carrying out suction filtration for 30min, and feeding the filtered waste acid liquid into a waste acid pool for later use; 3) carrying out secondary reaction, namely adding 2100kg of filtered recovered acid, 350kg of oxidant nitric acid and 800kg of complexing agent hydrofluoric acid into a reaction tank in sequence, and reacting for 10 hours at 90 ℃; performing secondary suction filtration, and pumping and filtering the acid liquor into a waste acid pool for later use; 4) performing third reaction, namely adding 500kg of nitric acid serving as an oxidant, 1500kg of hydrochloric acid serving as a complexing agent and 2200kg of clear water into a reaction tank, uniformly mixing, and reacting for 10 hours at the temperature of 50 ℃; 5) washing, namely squeezing and deacidifying the reacted materials, and then adding pure water to wash until the pH value is 5; 6) filter pressing, and squeezing, filtering and dehydrating under the pressure of 1.0 MPa; 9) drying to obtain 2179kg of high-purity spherical graphite with the specification of SG 17.
The carbon content was 99.968% according to GB/T3521-95 method, and the trace element index of the test by Plasma1000 type ICP-AES is shown in Table 2:
TABLE 2
It can be seen from table 2 that the purity of the obtained high-purity graphite is high, which reaches 99.968%, and the index content of trace elements such as iron, aluminum, copper and the like is low, which reaches or is lower than the control standard in the industry.
Example 3:
1) the method for preparing the recovered acid is the same as that of example 1, and the concentration of the recovered acid is 15%; 2) carrying out primary reaction, mixing 3000kg of spherical graphite powder with 94% of carbon content and SG10 specification of 10.8 microns in median diameter with 6000kg of recovered acid, reacting for 12 hours at 85 ℃, carrying out suction filtration for 30min, and feeding the filtered waste acid liquid into a waste acid pool for later use; 3) performing secondary reaction, namely adding 3100kg of filtered recovered acid, 100kg of oxidant hydrogen peroxide, 330kg of oxidant nitric acid and 1000kg of complexing agent concentrated hydrochloric acid into a reaction tank in sequence; 500kg of complexing agent hydrofluoric acid is uniformly mixed and reacts for 12 hours at the temperature of 85 ℃; performing secondary suction filtration, and pumping and filtering the acid liquor into a waste acid pool for later use; 4) carrying out third reaction, namely adding 600kg of oxidant nitric acid, 1800kg of complexing agent hydrochloric acid, 200kg complexing agent EDTA and 3000 clear water into a reaction tank, uniformly mixing, and reacting for 8 hours at the temperature of 60 ℃; 5) washing, namely squeezing and deacidifying the reacted materials, and then adding pure water to wash until the pH value is 5; 6) filter pressing, and squeezing, filtering and dehydrating under the pressure of 0.8 MPa; 9) drying to obtain 2179kg of high-purity spherical graphite with the specification of SG 10.
The carbon content can reach 99.979% according to GB/T3521-95; the trace element index of the test specimen by ICP-AES, type 1000 Plasma, is shown in Table 3.
TABLE 3
As can be seen from Table 3, the purity of the obtained high-purity graphite reached ultra-high purity 99.979%.
Example 4:
by adopting the method of example 1, the carbon content of the primary reaction in the step (2) is 80% of the granularity and is replaced by 50-mesh crystalline flake graphite.
Test results of high-purity graphite prepared from flake graphite with a particle size of 450 meshes by using the method disclosed by the invention
Example 5:
by adopting the method of example 1, the carbon content of the primary reaction in the step (2) is 80% of the granularity and is replaced by 80-mesh crystalline flake graphite.
Test results of high-purity graphite prepared from scale graphite with 580 meshes by using method disclosed by invention
Example 6:
the method of example 1 was used, and in step (2) the reaction was carried out once, replacing the flake graphite with-100 mesh carbon having a carbon content of 80% particle size.
Table 6-100 mesh flake graphite test results for high purity graphite prepared by the method of the present invention
Example 7:
the method of example 1 was used, and in step (2), the reaction was carried out once to replace the graphite particles having a carbon content of 80% by spherical graphite particles having a particle size of 16.06. mu.m.
TABLE 716.06 μm spheroidal graphites test results for high purity graphites prepared by the method of the invention
Example 8:
the method of example 1 was used, and in step (2), the reaction was carried out once to replace the graphite particles having a carbon content of 80% by spherical graphite particles having a size of 22.93 μm.
TABLE 8.22.93 μm spheroidal graphites test results for high purity graphites prepared by the method of the invention
As can be seen from the above examples, the present invention is used for graphite of other forms having different carbon contents, and the high purity graphite produced by the method of the present invention has a carbon content of 99.95% or more and an ash content of 0.05% or less, and contains trace elements of 50ppm or less of iron (Fe), 5ppm or less of chromium (Cr), 5ppm or less of nickel (Ni), 50ppm or less of aluminum (Al), 50ppm or less of sodium (Na), 50ppm or less of chlorine (Cl) and 50ppm or less of fluorine (F), and thus can completely satisfy the requirements of customers for various indexes of products, and has wide adaptability.
Because the carbon content of the medium-carbon graphite is low and the internal impurity content is high, the process of purifying the medium-carbon graphite to the high-purity graphite is more, and the cost is high; therefore, the high-purity graphite produced by the natural graphite deep processing industry is produced by using high-carbon graphite with the carbon content of more than 93 percent as a raw material. The reaction is carried out twice, the first reaction adopts mixed acid of hydrofluoric acid and hydrochloric acid, and the mixed acid mainly reacts with the impurity SiO2 in the graphite to generate water-soluble silicate which is filtered and removed; the hydrochloric acid and nitric acid are reacted for the second time to prepare aqua regia which reacts with the iron, aluminum, copper and other metal oxides in the graphite to generate water-soluble compounds and water, and the high-purity graphite is obtained after filtering, removing and drying. If the high-carbon graphite can be replaced by the medium-carbon graphite with lower carbon content and the price is only 1/2 of the high-carbon graphite, and the recovered acid is used for replacing part of industrial acid to reduce the cost, namely, the waste acid generated in the production method is fully utilized to react with the medium-carbon graphite, the purity of the medium-carbon graphite is improved to the purity of high-purity graphite under the condition of not increasing new acid consumption, the suction filtration method is adopted for discharging for 1 time, the original twice discharging and washing processes are reduced to one discharging process, all indexes of trace elements and ash can reach the standard, the cost can be reduced by 1/3-1/2 compared with the cost of the original production method, the waste acid is recycled, the cost for treating the environment-friendly sewage is reduced, and two purposes are achieved.
In the invention, high-purity graphite can be obtained only by adding a certain amount of chemical reagent in the second and third reactions, and compared with the existing method in the industry, the method has the advantages of lower cost and more convenient operation.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. A method for producing high purity graphite using recovered acid, comprising the steps of:
(1) preparation of the recovered acid: collecting the waste acid liquid, filtering to remove insoluble large-particle impurities, then feeding the waste acid liquid into a closed evaporator, evaporating at high temperature to obtain gas in the waste acid, feeding the gas into a spray tower to be combined with pure water in the spray tower, and dissolving the gas in the pure water under high pressure to obtain recovered acid, wherein the concentration of the recovered acid is 5-30%;
(2) carrying out a primary reaction, mixing graphite powder with carbon content of 80-90% and recovered acid according to a certain proportion, and reacting for 10-14 hours at 80-90 ℃;
(3) carrying out primary suction filtration, and discharging the waste acid liquor;
(4) carrying out secondary reaction, adding the recovered acid, the oxidant and the complexing agent into the graphite obtained in the step (3) in proportion, uniformly mixing, and reacting for 6-12 hours at the temperature of 60-80 ℃;
(5) carrying out secondary suction filtration, and discharging the waste acid liquor;
(6) carrying out a third reaction, and mixing the graphite obtained in the step (5) with a complexing agent, an oxidant and clear water according to a certain proportion; reacting for 5-10 hours at 50-80 ℃;
(7) washing, namely deacidifying the material obtained by the reaction, and then adding pure water to wash the material to be neutral;
(8) performing filter pressing, and performing squeezing dehydration under the pressure of 0.5-1.0 MPa;
(9) and (4) drying, namely drying at 350-500 ℃ until the water content is less than 0.2%, so as to obtain the high-purity graphite.
2. The method for producing high-purity graphite by using the recovered acid as claimed in claim 1, wherein the oxidant is one or two selected from hydrogen peroxide, peracetic acid, chlorine gas, concentrated sulfuric acid, nitric acid, concentrated hydrochloric acid and perchloric acid.
3. The method for producing high-purity graphite by using the recovered acid as claimed in claim 1, wherein the complexing agent is one or two selected from hydrofluoric acid, phosphoric acid, hydrochloric acid, cholic acid, and EDTA.
4. The method for producing high-purity graphite by using the recovered acid as claimed in claim 1, wherein the mass ratio of the graphite powder to the recovered acid in the step (2) is 1: 1.5 to 3.0.
5. The method for producing high-purity graphite by using recovered acid as claimed in claim 1, wherein the suction filtration operation in the steps (3) and (5) is performed by using a Roots vacuum pump, using filter cloth made of Dacron and polypropylene which are resistant to strong acid corrosion and high temperature, and selecting filter cloth of 300 meshes and 1500 meshes according to the different particle sizes of graphite products.
6. The method for producing high-purity graphite using recovered acid according to claim 1, wherein in the secondary reaction in step (4), the ratio of graphite: acid recovery: oxidizing agent: the mass ratio of the complexing agent is 1: 0.5-4: 0.05-0.5: 0.15 to 1.5.
7. The method for producing high purity graphite using recovered acid according to claim 1, wherein the graphite in the third reaction in the step (6): complexing agent: oxidizing agent: the clean water is in a mass ratio of 1: 0.3-1.0: 0.1-0.5: 1-3.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115611277A (en) * | 2022-10-24 | 2023-01-17 | 苏州中材非金属矿工业设计研究院有限公司 | Preparation process of high-purity graphite |
| CN117049533A (en) * | 2023-09-26 | 2023-11-14 | 黑龙江工业学院 | Method for purifying graphite by electric field induced graphite acid method and application |
| CN117049533B (en) * | 2023-09-26 | 2024-04-30 | 黑龙江工业学院 | Method for purifying graphite by electric field induced graphite acid method and application |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0238781A1 (en) * | 1986-03-27 | 1987-09-30 | VOEST-ALPINE INDUSTRIEANLAGENBAU GESELLSCHAFT m.b.H. | Process for winning high-purity graphite from natural graphite |
| CN1049856A (en) * | 1989-09-02 | 1991-03-13 | 大连理工大学 | The chemical deliming method of natural graphite and coal |
| CN1616347A (en) * | 2004-07-28 | 2005-05-18 | 汤世伟 | High purity graphite purfying process |
| JP2005270687A (en) * | 2004-03-22 | 2005-10-06 | Nissan Motor Co Ltd | Catalyst-carrying carbon material and its production method |
| CN1919729A (en) * | 2006-09-11 | 2007-02-28 | 洛阳市冠奇工贸有限责任公司 | Ultra-high purity purifying technique for native graphite |
| CN101983917A (en) * | 2010-11-02 | 2011-03-09 | 黑龙江省牡丹江农垦奥宇石墨深加工有限公司 | Preparation method of high purity graphite |
| CN205590302U (en) * | 2016-04-29 | 2016-09-21 | 乌兰察布市大盛石墨新材料股份有限公司 | Spent acid regenerating unit |
| CN108821276A (en) * | 2018-09-03 | 2018-11-16 | 东莞市鸿亿导热材料有限公司 | The manufacturing method of expansible graphite |
-
2021
- 2021-06-24 CN CN202110704441.XA patent/CN113233454A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0238781A1 (en) * | 1986-03-27 | 1987-09-30 | VOEST-ALPINE INDUSTRIEANLAGENBAU GESELLSCHAFT m.b.H. | Process for winning high-purity graphite from natural graphite |
| CN1049856A (en) * | 1989-09-02 | 1991-03-13 | 大连理工大学 | The chemical deliming method of natural graphite and coal |
| JP2005270687A (en) * | 2004-03-22 | 2005-10-06 | Nissan Motor Co Ltd | Catalyst-carrying carbon material and its production method |
| CN1616347A (en) * | 2004-07-28 | 2005-05-18 | 汤世伟 | High purity graphite purfying process |
| CN1919729A (en) * | 2006-09-11 | 2007-02-28 | 洛阳市冠奇工贸有限责任公司 | Ultra-high purity purifying technique for native graphite |
| CN101983917A (en) * | 2010-11-02 | 2011-03-09 | 黑龙江省牡丹江农垦奥宇石墨深加工有限公司 | Preparation method of high purity graphite |
| CN205590302U (en) * | 2016-04-29 | 2016-09-21 | 乌兰察布市大盛石墨新材料股份有限公司 | Spent acid regenerating unit |
| CN108821276A (en) * | 2018-09-03 | 2018-11-16 | 东莞市鸿亿导热材料有限公司 | The manufacturing method of expansible graphite |
Non-Patent Citations (1)
| Title |
|---|
| 魏丽丹 等: ""氢氟酸法处理石墨酸回收研究"", 《环境科学导刊》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115611277A (en) * | 2022-10-24 | 2023-01-17 | 苏州中材非金属矿工业设计研究院有限公司 | Preparation process of high-purity graphite |
| CN117049533A (en) * | 2023-09-26 | 2023-11-14 | 黑龙江工业学院 | Method for purifying graphite by electric field induced graphite acid method and application |
| CN117049533B (en) * | 2023-09-26 | 2024-04-30 | 黑龙江工业学院 | Method for purifying graphite by electric field induced graphite acid method and application |
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