CN111057853B - Method for efficiently recovering multiple valuable substances from waste diamond tool bit raw materials - Google Patents
Method for efficiently recovering multiple valuable substances from waste diamond tool bit raw materials Download PDFInfo
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- 239000010432 diamond Substances 0.000 title claims abstract description 74
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000002994 raw material Substances 0.000 title claims abstract description 50
- 239000002699 waste material Substances 0.000 title claims abstract description 47
- 239000000126 substance Substances 0.000 title claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 79
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 22
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims abstract description 19
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052718 tin Inorganic materials 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 238000002386 leaching Methods 0.000 claims description 68
- 239000002253 acid Substances 0.000 claims description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000002425 crystallisation Methods 0.000 claims description 27
- 230000008025 crystallization Effects 0.000 claims description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 24
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 22
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 20
- 229910001431 copper ion Inorganic materials 0.000 claims description 20
- 239000000706 filtrate Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 18
- 239000012452 mother liquor Substances 0.000 claims description 18
- 238000012360 testing method Methods 0.000 claims description 18
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 17
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000002351 wastewater Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 230000007613 environmental effect Effects 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000002912 waste gas Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 12
- 238000004090 dissolution Methods 0.000 abstract description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 abstract description 3
- -1 heptahydrate ferrous sulfate Chemical class 0.000 abstract description 2
- 229910052804 chromium Inorganic materials 0.000 abstract 1
- 239000011651 chromium Substances 0.000 abstract 1
- 235000003891 ferrous sulphate Nutrition 0.000 abstract 1
- 239000011790 ferrous sulphate Substances 0.000 abstract 1
- 239000011135 tin Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910017518 Cu Zn Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 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
- 239000011230 binding agent Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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
- C01B32/25—Diamond
- C01B32/26—Preparation
-
- 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
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/949—Tungsten or molybdenum carbides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/04—Obtaining tin by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for efficiently recovering various valuable substances from waste diamond tool bit raw materials, which can economically, efficiently and environmentally realize the efficient recovery of various valuable substances from low-chromium waste diamond tool bit raw materials with relatively simple components, iron is directly leached out by dilute sulfuric acid at normal pressure, the leachate is crystallized to obtain a heptahydrate ferrous sulfate product, air is filled into dilute sulfuric acid solution by adopting an innovative nano cavitation device for the residue leached at the first time at normal pressure, the copper dissolution speed is more efficiently improved at lower temperature and sulfuric acid concentration than the common process, the leachate is filtered to obtain a tin mud product, the leached residue is reselected by a table concentrator to obtain diamond and tungsten carbide products, the leachate is crystallized to obtain a blue copperas product, the stepwise recovery of the valuable substances is realized, the process flow is simple, the recovery rate of the valuable substances is high, the production cost is low, high automation degree, low equipment requirement and low industrialization cost.
Description
Technical Field
The invention relates to the technical field of waste hard alloy recovery, in particular to a method for efficiently recovering various valuable substances from waste diamond cutter head raw materials.
Background
The diamond saw blade is a working main body of the diamond saw blade, and the diamond saw blade consists of diamond and a matrix binder. The diamond is a superhard material and plays a role of a cutting edge, and the matrix bonding agent plays a role of fixing the diamond and is composed of metal alloy powder or metal simple substance powder. The application of the diamond tool bit is very wide, but about 10% -15% of the diamond tool bits can not be used and abandoned in the later period of use, and China generates considerable waste diamond tool bits every year.
At present, the methods for treating the waste diamond tool bit mainly comprise a leaching method and an electrolysis method.
The leaching method is most commonly applied, wherein nitric acid or aqua regia and the like are adopted to dissolve other metals except diamond and tungsten carbide in the waste diamond tool bit into a liquid phase, diamond and tungsten carbide solids are obtained by filtration and separation, the separation of diamond and tungsten carbide is realized by the solid through a screening method through particle size difference, and the separation of valuable metals is realized by the liquid phase through chemical precipitation, crystallization and the like. The leaching method has the advantages of relatively simple process flow, high production cost and unstable quality of byproducts, and has the disadvantages of generating a large amount of nitrogen oxides and acid mist which pollute the environment, and consuming a large amount of acid and alkali.
The electrolytic method is often applied to the treatment of raw materials with high content of high added-value metals such as silver and the like. Since the composition of the waste diamond segments is complicated and the composition difference is large, it is difficult to obtain a stable cathode product by the electrolytic method. The waste diamond tool bits have large difference in conductivity and irregular shapes, so that the waste diamond tool bits have low electrolysis efficiency. The electrolysis method cannot be widely applied due to high energy consumption, large equipment investment and poor process adaptability.
Due to the rising price of raw materials such as artificial diamond, tungsten carbide, copper and the like, the manufacturing cost of the diamond tool bit is continuously increased, and in addition, the national requirement on environmental protection is higher and higher, and the recovery value of valuable metals in the waste diamond tool bit is more and more obvious. The efficient and environment-friendly recovery of valuable elements such as diamond, tungsten carbide, copper, iron and the like in the waste diamond tool bit can effectively realize the recovery of secondary resources, reduce the resource waste and reduce the manufacturing cost of the diamond tool bit. For this reason, there is an urgent need to develop an efficient and environmentally friendly method of treating waste diamond segments.
Accordingly, those skilled in the art have provided a method for efficiently recovering a variety of valuable materials from waste diamond segments as a solution to the above-mentioned problems of the background art.
Disclosure of Invention
In order to achieve the purpose, the invention provides the following technical scheme: a method for efficiently recovering multiple valuable substances from waste diamond tool bit raw materials is characterized by comprising the following steps:
s1, raw material pretreatment: pretreating the waste diamond tool bit raw material by using a sodium hydroxide solution with the concentration of 50g/L so as to generate a pretreated raw material and waste liquid A, and performing auxiliary treatment by using an ultrasonic device in the pretreatment process;
s2, primary acid leaching: performing primary acid leaching on the pretreated raw material obtained in the step S1, wherein the liquid-solid mass ratio is 2.5-3: 1, the initial sulfuric acid concentration is 60-80 g/L, the reaction is performed at 50-60 ℃ and under normal pressure, the sulfuric acid concentration and the ferrous ion concentration are continuously tested in the reaction process, when the ferrous ion concentration in the solution is lower than 130g/L, the sulfuric acid concentration is ensured to be stabilized at 50-60 g/L, when the ferrous ion concentration is higher than 130g/L, the acid addition is stopped, the acid remained in the solution continues to react, and the ultrasonic device is adopted for assisting in the acid leaching process;
s3, preparing a ferrous sulfate heptahydrate product: when the concentration of the ferrous ions in the leachate A obtained in the step S2 is not increased any more, filtering the leachate A to form filtrate A and filter residue, returning the filter residue to the step S2, and performing a crystallization process of ferrous sulfate heptahydrate on the filtrate A to prepare a ferrous sulfate heptahydrate product, wherein the mother liquor A is returned to the step S2;
s4, secondary acid leaching: performing secondary acid leaching on the residue A in the S2, wherein the liquid-solid mass ratio is 3.5-4: 1, the initial sulfuric acid concentration is 150-200 g/L, the reaction is performed at 70-75 ℃ and under normal pressure, a nano cavitation device is adopted to introduce air, hot steam and hydrogen peroxide into the solution in the acid leaching process to enhance the oxidation leaching of copper to form a leaching solution B and a residue B, the sulfuric acid concentration and the copper ion concentration are tested uninterruptedly in the reaction process, when the copper ion concentration in the solution is lower than 80g/L, the sulfuric acid concentration is ensured to be stabilized at 90-120 g/L, when the copper ion concentration is higher than 80g/L, the acid addition is stopped, the temperature is increased to 85-90 ℃, the residual acid in the solution continues to react, and an ultrasonic device is adopted to assist in the acid leaching process;
s5, separation of diamond and tungsten carbide: polishing the residue B in the S4, then sorting diamond and tungsten carbide by using a table concentrator, and further realizing effective separation of diamonds with different grain sizes by using a model selecting machine after the obtained diamond product is elutriated;
s6, preparation of tin mud: and when the concentration of copper ions in the leaching solution B in the S4 is not increased any more, filtering the leaching solution B to obtain tin mud and a filtrate B, wherein the tin mud enters a filter cake.
S7, preparation of crude copper sulfate pentahydrate: and (3) carrying out primary cooling crystallization on the filtrate B in the S6 to prepare a crude copper sulfate pentahydrate product, wherein the mother liquor B is returned to S4.
S8, copper sulfate secondary crystallization: dissolving the crude copper sulfate pentahydrate in the step S7, adding hydrogen peroxide, adjusting the pH value of the solution to 3-4 by using sodium hydroxide, filtering to form a copper sulfate solution and impurities, returning the impurities to the step S2, carrying out secondary copper sulfate crystallization on the copper sulfate solution to obtain a copper sulfate pentahydrate product with the mass fraction of 98% +/-0.5%, and returning a copper sulfate secondary crystallization mother liquor C to the step S8 for dissolving the crude copper sulfate pentahydrate;
s9, treating three wastes: the three wastes generated by the process are treated so as to ensure that the three wastes meet the requirement of environmental protection, acid mist generated in the acid leaching process is treated by sodium hydroxide solution, valuable ions such as copper ions and the like are replaced by iron-containing alloy powder in the production wastewater, then a sponge copper product is obtained by filtering, and the filtrate returns to the iron dissolving operation for continuous recycling.
Compared with the prior art, the invention has the beneficial effects that:
(1) the process provided by the invention has relatively simple treatment components, can realize direct leaching of valuable metals by using dilute sulfuric acid under normal pressure, and can recover valuable substances step by step, so that the process is simple, the recovery rate of valuable substances is high, the production cost is lower, the automation degree is high, and the industrial cost is lower.
(2) The invention can obtain good indexes for the raw materials of which the main valuable metals are diamond, tungsten carbide, copper, iron and tin.
(3) The invention adopts an innovative nano cavitation device to fill air, hot steam and hydrogen peroxide into dilute sulfuric acid solution, and the gas-liquid mixture can form nano-scale microbubbles at high speed after being sprayed out, the oxygen content in the leaching solution can be improved by more than 25 percent compared with the common ventilation mode by the nano microbubbles, so that the oxidation potential of the leaching solution is obviously improved, the oxidation leaching speed of copper is improved by more than 40 percent compared with the common heating leaching, and the consumption of the hydrogen peroxide is reduced by more than 70 percent compared with the common dripping mode. Compared with the traditional inflation method, the oxygen content in the leaching solution is improved by more than 25%, the hydrogen peroxide consumption is reduced by more than 70%, the copper oxidation leaching speed is improved by more than 40%, the copper dissolution is realized at lower temperature and sulfuric acid concentration, the production cost is obviously reduced, and the copper dissolution efficiency is greatly improved.
(4) The invention adopts an innovative and optimized ultrasonic assisted leaching process, improves the reaction speed by more than 30 percent compared with the reaction speed without using an ultrasonic device, obviously improves the production capacity and greatly reduces the production cost.
(5) On the basis of fully recovering valuable substances, the waste water, waste gas and waste residues generated in the production can be effectively treated, the waste water and the waste gas meet the environment-friendly discharge requirement on the premise of effective recycling, the waste residues can be effectively recycled, and the valuable substances in the waste diamond tool bit raw materials can be efficiently recovered in an economic, effective and environment-friendly manner.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: referring to fig. 1, the present invention provides a technical solution: a method for efficiently recovering multiple valuable substances from waste diamond tool bit raw materials is characterized by comprising the following steps:
s1, raw material pretreatment: at normal temperature and normal pressure, the waste diamond tool bit raw material is pretreated by adopting a sodium hydroxide solution with the concentration of 50g/L in a rotary cleaning machine, and impurities such as silt, grease and the like on the surface of the raw material are removed. After the raw materials are cleaned, the solid-liquid separation is realized through a screening machine, products on the screen enter a rotary rinsing liquid tank and are rinsed by clear water, and after the materials are rinsed completely, the raw materials enter an acid leaching reaction kettle to be subjected to primary acid leaching.
S2, primary acid leaching: carrying out primary acid leaching on the pretreated raw material obtained in the step S1, wherein the liquid-solid mass ratio is 2.5-3: 1, the initial sulfuric acid concentration is 60-80 g/L, and the raw material is reacted at 50-60 ℃ and normal pressure, and the reaction equation generated in the process is as follows: fe + H2SO4＝FeSO4+H2×) @. The sulfuric acid concentration and the ferrous ion concentration are continuously tested in the reaction process, when the ferrous ion concentration in the solution is lower than 130g/L, the sulfuric acid concentration is guaranteed to be stabilized at 50-60 g/L, when the ferrous ion concentration is higher than 130g/L, acid addition is stopped, the acid remaining in the solution continues to react, and an ultrasonic device is adopted for assisting in acid leaching in the acid leaching process.
S3, preparing a ferrous sulfate heptahydrate product: when the concentration of the ferrous ions in the leachate A obtained in the step S2 is not increased any more, filtering the leachate A to form filtrate A and filter residue, returning the filter residue to the step S2, and performing a crystallization process of ferrous sulfate heptahydrate on the filtrate A to prepare a ferrous sulfate heptahydrate product, wherein the mother liquor A is returned to the step S2;
s4, secondary acid leaching: carrying out secondary acid leaching on the residue A in the S2, wherein the liquid-solid mass ratio is 3.5-4: 1, the initial sulfuric acid concentration is 150-200 g/L, the reaction is carried out at 70-75 ℃ and under normal pressure, a nano cavitation device is adopted to introduce air, hot steam and hydrogen peroxide into the solution in the acid leaching process, so that a gas-liquid mixture is dispersed in dilute sulfuric acid in form of nano-scale microbubbles, the oxygen-containing concentration in the dilute sulfuric acid solution is greatly improved, the oxidation speed of copper can be obviously improved, the oxidation leaching of copper is strengthened, and a leaching solution B and a residue B are formed, and the reaction equation generated in the process is as follows: 2Cu + O2＝2CuO，CuO+H2SO4＝CuSO4+H2And O. The concentration of sulfuric acid and the concentration of copper ions are tested uninterruptedly in the reaction process, when the concentration of copper ions in the solution is lower than 80g/L, the concentration of sulfuric acid is guaranteed to be stabilized at 90-120 g/L, and when the concentration of copper ions is higher than 80g/L
And stopping adding acid after 80g/L, increasing the temperature to 85-90 ℃, continuously reacting the acid remained in the solution, and using an ultrasonic device for assisted leaching in the acid leaching process.
S5, separation of diamond and tungsten carbide: and (4) grinding the residue B in the step S4 at a high speed by using a high-speed grinding machine, so that the color of the diamond is further improved. After polishing, the diamond and the tungsten carbide are separated by a table concentrator, so that the diamond and the tungsten carbide are effectively separated, and the obtained diamond product is elutriated and then is further effectively separated by a model selecting machine.
S6, preparation of tin mud: and when the concentration of copper ions in the leaching solution B in the S4 is not increased any more, filtering the leaching solution B to obtain tin mud and a filtrate B, wherein the tin mud enters a filter cake.
S7, preparation of crude copper sulfate pentahydrate: and (3) performing primary cooling crystallization on the filtrate B in the S6 to prepare a crude copper sulfate pentahydrate product, wherein the mother liquor B is returned to S4, and the crude copper sulfate pentahydrate is washed by clear water to reduce impurities.
S8, copper sulfate secondary crystallization: dissolving the crude blue vitriod in the S7, adding hydrogen peroxide, adjusting the pH value of the solution to 3-4 by using sodium hydroxide, oxidizing ferrous ions into ferric ions and forming ferric hydroxide, wherein the reaction equation generated in the process is as follows: h2O2+2FeSO4+H2SO4＝Fe2(SO4)3+2H2O，Fe2(SO4)3+6NaOH＝2Fe(OH)3↓+3Na2SO4. Filtering to effectively separate iron hydroxide from copper ions to form a copper sulfate solution and impurities, wherein the impurities return to S2, the copper sulfate solution is subjected to copper sulfate secondary crystallization to obtain a copper sulfate pentahydrate product with the mass fraction of about 98%, and a copper sulfate secondary crystallization mother liquor C returns to S8 for dissolving crude copper sulfate pentahydrate;
s9, treating three wastes: treating the three wastes generated by the process so as to ensure that the three wastes meet the environmental protection requirement, treating acid mist generated in the acid leaching process by using a sodium hydroxide solution, replacing valuable ions such as copper ions and the like by using iron-containing alloy powder in the production wastewater, filtering to obtain a sponge copper product, returning the filtrate to the iron dissolving operation for continuous recyclingThe reaction equation for this process is: CuSO4+Fe＝FeSO4+Cu↓。
Example 2: the method is characterized in that waste diamond tool bit raw materials are collected from main granite producing areas in China, and after analysis, main valuable substances in the waste diamond tool bit raw materials comprise diamond, tungsten carbide, copper, cobalt, nickel, zinc, iron, tin and other elements. Through a large number of exploration tests, a process for recovering the valuable substances is provided, then the feasibility of the process is verified through a laboratory small-scale test, and then an industrial test is carried out.
Semi-industrial test:
the chemical analysis of the waste diamond bit raw material is carried out, and the contents of main valuable substances are shown in the following table 1.
TABLE 1 content of main valuable substances in the raw material of waste diamond segments for semi-industrial test
| Components | Fe | Cu | Zn | Diamond | WC | Cr | Sn | Others |
| Content/% | 41.73 | 39.01 | 0.15 | 2.87 | 13.58 | 0.04 | 2.43 | 0.19 |
(1) Pretreatment of raw materials: taking 300kg of waste diamond tool bit raw material, pretreating with sodium hydroxide solution at normal temperature and normal pressure, stirring for 20min, filtering and washing with clear water.
(2) Processing a first batch of raw materials:
1) acid leaching for the first time: under normal pressure, 10kg of pretreated waste diamond tool bit raw material is added into 25L of dilute sulfuric acid with the temperature of 50-60 ℃, the concentration of the sulfuric acid is 70g/L, and the mixture is continuously stirred. The concentration of sulfuric acid and the concentration of ferrous ions are continuously tested in the reaction process, when the concentration of the ferrous ions in the solution is lower than 130g/L, the concentration of the sulfuric acid is guaranteed to be stabilized at 50-60 g/L, when the concentration of the ferrous ions is higher than 130g/L, acid addition is stopped, and the residual acid in the solution continues to react. Filtering after the concentration of ferrous ions in the leachate is not increased any more, washing the residue A with a small amount of clear water for secondary acid leaching, and enabling the cleaning solution and the filtrate to form the leachate A and enter ferrous sulfate heptahydrate crystallization operation together.
2) Preparing a ferrous sulfate heptahydrate product: filtering after the ferrous sulfate heptahydrate crystallization is finished, drying and weighing, and using the crystallization mother liquor A for the first acid leaching operation of the second batch of raw materials.
3) Acid leaching for the second time: adding the residue A after the first acid leaching into 40L of dilute sulfuric acid at the temperature of 70-75 ℃ under normal pressure, wherein the concentration of the sulfuric acid is 150g/L, introducing air, hot steam and hydrogen peroxide into the solution through a nano cavitation device in the acid leaching process, and continuously stirring, wherein the addition amount of the hydrogen peroxide is about 40 g/min. And continuously testing the concentration of sulfuric acid and the concentration of copper ions in the reaction process, ensuring that the concentration of sulfuric acid is stabilized at 90-120 g/L when the concentration of copper ions in the solution is lower than 80g/L, stopping adding acid when the concentration of copper ions is higher than 80g/L, increasing the temperature to 85-90 ℃, and continuously reacting the residual acid in the solution. And after the concentration of copper ions in the leaching solution B is not increased any more, filtering the leaching solution B, feeding tin mud into a filter cake, drying the filter cake and weighing.
4) Separation of diamond and tungsten carbide: and (3) sorting diamond and tungsten carbide by using a shaking table for the residue B generated in the second acid leaching, cleaning the diamond and the tungsten carbide, drying and weighing.
5) Preparation of blue vitriol: cooling and crystallizing the filtrate B by using copper sulfate, and performing secondary acid leaching operation on the crystallized mother liquor B on a second batch of raw materials. And dissolving the first copper sulfate crystal, adding hydrogen peroxide, adjusting the pH value of the solution to 3-4 by using sodium hydroxide, filtering, performing second copper sulfate crystallization on the filtrate, and performing first acid leaching operation on impurities in a second batch of raw materials. Filtering to form mother liquor C after crystallization is completed, and enabling the mother liquor C to enter a second batch of copper sulfate dissolving operation, drying copper sulfate crystals and weighing.
(3) Treating a second batch of material
1) Acid leaching for the first time: under normal pressure, dilute sulfuric acid is supplemented into the crystallization mother liquor A of ferrous sulfate heptahydrate generated in the first batch of raw material treatment, the volume is adjusted to about 25L, the concentration of the sulfuric acid is adjusted to about 70g/L, the temperature is kept at 50-60 ℃, 10kg of pretreated waste diamond tool bit raw material is added, impurities generated before the second crystallization of blue vitriol are added, and other operations and processes are the same as those of the first batch of raw material.
2) Preparing a ferrous sulfate heptahydrate product: the process was the same as when the first batch was processed, and the resulting crystallization mother liquor a was used for the first acid leaching of the third batch.
3) Acid leaching for the second time: under normal pressure, dilute sulfuric acid is supplemented into mother liquor B of first copper sulfate crystallization generated in first raw material treatment, the volume is adjusted to be about 40L, the sulfuric acid concentration is adjusted to be about 150g/L, the temperature is kept at 70-75 ℃, and other operations and processes are the same as those of the first raw material.
4) Separation of diamond and tungsten carbide: the process is the same as when processing the first batch.
5) Preparation of blue vitriol: the process is the same as that of the first batch of raw materials, the first crystallization mother liquor B enters the second acid leaching operation of the third batch of raw materials, the second crystallization mother liquor C enters the third copper sulfate dissolving operation, and impurities enter the first acid leaching operation of the third batch of raw materials.
(4) The steps of processing the first batch of material and the second batch of material are repeated until the process is in equilibrium. The recovery of several valuable substances was calculated and the test results are shown in table 2.
TABLE 2 semi-Industrial test indexes
| Products/elements | Coarse diamond | Fine diamond | Tungsten carbide | Copper (Cu) | Tin (Sn) | Iron |
| Percent recovery% | 98.75 | 97.53 | 91.03 | 98.87 | 70.23 | 96.21 |
The test results show that the process has excellent recovery effect on diamond, tungsten carbide, copper, tin and iron.
Example 3:
and (3) industrial test:
the industrial test was carried out using 10 tons of waste diamond segments as raw materials, the contents of main valuable substances in the raw materials are shown in table 3 below, and the test results are shown in table 4 below.
TABLE 3 content of main valuable substances in the raw material of the waste diamond segments for industrial test
| Components | Fe | Cu | Zn | Diamond | WC | Cr | Sn | Others |
| Content/% | 43.37 | 40.55 | 0.16 | 2.41 | 11.07 | 0.03 | 2.22 | 0.19 |
TABLE 4 Industrial test indices
| Products/elements | Coarse diamond | Fine diamond | Tungsten carbide | Copper (Cu) | Tin (Sn) | Iron |
| Percent recovery% | 97.89 | 96.88 | 90.75 | 97.85 | 69.75 | 94.12 |
The industrial test result shows that the method is successfully industrialized, the result similar to that of a semi-industrial test is obtained, and the process can efficiently recover the main valuable substances in the waste diamond tool bit raw materials.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (1)
1. A method for efficiently recovering multiple valuable substances from waste diamond tool bit raw materials is characterized by comprising the following steps:
s1, raw material pretreatment: pretreating the waste diamond tool bit raw material by adopting a sodium hydroxide solution with the concentration of 50g/L so as to generate a pretreated raw material and waste liquid A;
s2, primary acid leaching: performing primary acid leaching on the pretreated raw material obtained in the step S1, wherein the liquid-solid mass ratio is 2.5-3: 1, the initial sulfuric acid concentration is 60-80 g/L, and reacting at 50-60 ℃ under normal pressure;
s3, preparing a ferrous sulfate heptahydrate product: when the concentration of the ferrous ions in the leachate A obtained in the step S2 is not increased any more, filtering the leachate A to form filtrate A and filter residue, returning the filter residue to the step S2, and performing a crystallization process of ferrous sulfate heptahydrate on the filtrate A to prepare a ferrous sulfate heptahydrate product, wherein the mother liquor A is returned to the step S2;
s4, secondary acid leaching: performing secondary acid leaching on the residue A obtained in the step S2, wherein the liquid-solid mass ratio is 3.5-4: 1, the initial sulfuric acid concentration is 150-200 g/L, the reaction is performed at 70-75 ℃ and normal pressure, and in the acid leaching process, a nano cavitation device is adopted to introduce air, hot steam and hydrogen peroxide into the solution, so that the oxidation leaching of copper is enhanced to form a leaching solution B and a residue B;
s5, separation of diamond and tungsten carbide: polishing the residue B in the S4, then sorting diamond and tungsten carbide by using a table concentrator, and further realizing effective separation of diamonds with different grain sizes by using a model selecting machine after the obtained diamond product is elutriated;
s6, preparation of tin mud: when the concentration of copper ions in the leaching solution B in the S4 is not increased any more, filtering the leaching solution B to obtain tin mud and a filtrate B, and feeding the tin mud into a filter cake;
s7, preparation of crude copper sulfate pentahydrate: carrying out primary cooling crystallization on the filtrate B in the S6 to prepare a crude copper sulfate pentahydrate product, wherein the mother liquor B returns to S4;
s8, copper sulfate secondary crystallization: dissolving the crude copper sulfate pentahydrate in the step S7, adding hydrogen peroxide, adjusting the pH value of the solution to 3-4 by using sodium hydroxide, filtering to form a copper sulfate solution and impurities, returning the impurities to the step S2, carrying out secondary copper sulfate crystallization on the copper sulfate solution to obtain a copper sulfate pentahydrate product with the mass fraction of 98% +/-0.5%, and returning a copper sulfate secondary crystallization mother liquor C to the step S8 for dissolving the crude copper sulfate pentahydrate;
s9, treating three wastes: the three wastes generated by the process are treated so as to enable the three wastes to meet the environmental protection requirement, wherein the waste gas is treated by alkaline liquor, the production wastewater is filtered after copper ions are replaced by iron-containing alloy powder to obtain a sponge copper product, and the filtrate is returned to the iron dissolving operation for continuous recycling;
an ultrasonic device is adopted for auxiliary treatment in the pretreatment process of S1;
s2, continuously testing the sulfuric acid concentration and the ferrous ion concentration in the reaction process, ensuring the sulfuric acid concentration to be stabilized at 50-60 g/L when the ferrous ion concentration in the solution is lower than 130g/L, stopping adding acid when the ferrous ion concentration is higher than 130g/L, continuously reacting the residual acid in the solution, and carrying out assisted leaching by using an ultrasonic device in the acid leaching process;
and S4, continuously testing the sulfuric acid concentration and the copper ion concentration in the reaction process, ensuring the sulfuric acid concentration to be stabilized at 90-120 g/L when the copper ion concentration in the solution is lower than 80g/L, stopping adding acid when the copper ion concentration is higher than 80g/L, raising the temperature to 85-90 ℃, continuously reacting the acid remained in the solution, and using an ultrasonic device for assisting in leaching in the acid leaching process.
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