CN1603439A - Production method for extracting nickel by pyrogenic process - Google Patents
Production method for extracting nickel by pyrogenic process Download PDFInfo
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- CN1603439A CN1603439A CN 200410081234 CN200410081234A CN1603439A CN 1603439 A CN1603439 A CN 1603439A CN 200410081234 CN200410081234 CN 200410081234 CN 200410081234 A CN200410081234 A CN 200410081234A CN 1603439 A CN1603439 A CN 1603439A
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- vanadium
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 191
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 230000008569 process Effects 0.000 title claims abstract description 12
- 230000001698 pyrogenic effect Effects 0.000 title claims abstract description 7
- 239000002699 waste material Substances 0.000 claims abstract description 58
- 238000003723 Smelting Methods 0.000 claims abstract description 49
- 238000007670 refining Methods 0.000 claims abstract description 42
- 239000000956 alloy Substances 0.000 claims abstract description 40
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 38
- 230000003647 oxidation Effects 0.000 claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 34
- 230000009467 reduction Effects 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 27
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 26
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002893 slag Substances 0.000 claims abstract description 25
- 229910000863 Ferronickel Inorganic materials 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000005303 weighing Methods 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 11
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims abstract description 7
- 239000000571 coke Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 10
- 238000010891 electric arc Methods 0.000 claims description 10
- 239000004571 lime Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 238000005266 casting Methods 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 239000013067 intermediate product Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 230000004907 flux Effects 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- OOJQNBIDYDPHHE-UHFFFAOYSA-N barium silicon Chemical compound [Si].[Ba] OOJQNBIDYDPHHE-UHFFFAOYSA-N 0.000 claims description 2
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 37
- 239000011574 phosphorus Substances 0.000 abstract description 37
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 27
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 7
- 229910052681 coesite Inorganic materials 0.000 abstract description 6
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 6
- 229910052682 stishovite Inorganic materials 0.000 abstract description 6
- 229910052905 tridymite Inorganic materials 0.000 abstract description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- HBVFXTAPOLSOPB-UHFFFAOYSA-N nickel vanadium Chemical compound [V].[Ni] HBVFXTAPOLSOPB-UHFFFAOYSA-N 0.000 abstract 2
- 230000000694 effects Effects 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 5
- 239000004484 Briquette Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- -1 sensors Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910005347 FeSi Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RIBYQLWAMJKWEH-UHFFFAOYSA-N [Ni].[V].[P] Chemical compound [Ni].[V].[P] RIBYQLWAMJKWEH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001285 shape-memory alloy Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a production method for extracting nickel by a pyrogenic process, which is characterized in that waste catalyst and waste desulfurizer which are discarded in the petrochemical industry or high-phosphorus vanadium-containing vanadium which is discarded after vanadium and molybdenum are extracted by a wet methodThe technology for smelting and producing ferronickel alloy by taking secondary pollutants such as low-nickel residues and the like as nickel raw materials comprises the steps of preparing waste materials, weighing and mixing the materials, reducing and smelting the materials and oxidizing and refining the materials under the condition of binary alkalinity CaO%/SiO2Within the range of about 0.8-1.8 percent, coke and ferrosilicon are used as reducing agents to carry out reduction smelting to remove 60-70 percent of phosphorus, and then the binary basicity CaO%/SiO of the slag is carried out2The percent is about 1.2-3.5, and more than 99 percent of phosphorus and more than 98 percent of vanadium are combined to generate CaO & P by adopting an oxygen-iron ore combined oxidation mode2O5And CaO.V2O5The high-phosphorus vanadium-nickel-containing waste material is refined to obtain a qualified nickel-iron alloy product, so that the purpose of extracting nickel from the high-phosphorus vanadium-nickel-containing waste material in a short process, low cost and industrialization is realized, and the method has obvious economic benefits and social environmental protection effects.
Description
The technical field is as follows:
the invention relates to a smelting technology for separating and extracting metals by a pyrogenic process, belongs to the technical field of metallurgical engineering, and particularly relates to a production technology for smelting a nickel-iron alloy from high-phosphorus vanadium-containing nickel waste discarded in petrochemical industry, in particular to a production method for extracting nickel by a pyrogenic process.
Background art:
as is well known, nickel is an important alloy element in the metallurgical industry, and because nickel metal has unique performance, the nickel metal has very wide application in numerous technical fields of producing special steel, high-temperature alloy, precision alloy, heat-resistant alloy, shape memory alloy, hydrogen storage alloy, electronic and electric batteries, magnetic materials, sensors, chemical catalysts and the like, and the nickel alloy material plays an important role in national economic construction and national defense and military construction and belongs to important strategic metal. The method is characterized in that the method is suitable for China with extremely little nickel, the yield of nickel in China is only 30-45 ten thousand tons and only accounts for 4-5% of the world amount for many years, the yield of nickel in China is far from meeting the requirement of nickel consumption, huge cost has to be spent on importing nickel alloy materials from abroad every year, andthe rapid development of the manufacturing industry in China is severely restricted. While in China, only the catalyst and the desulfurizer in the petroleum and chemical industries need to consume thousands of tons of nickel metal every year, and particularly when the nickel-containing catalyst and the desulfurizer used in the petroleum industry perform desulfurization operation on crude oil, the nickel-containing catalyst and the desulfurizer can absorb a large amount of elements such as vanadium, sulfur, phosphorus and the like from the crude oil to generate low-price vanadium (VS and V)2S3) Molybdenum sulfide (MoS)2) And impurities such as phosphorus-containing compounds, and the like, and the catalyst becomes a waste catalyst containing nickel and a waste desulfurizer and is discharged. At present, the nickel-containing waste catalyst and the waste desulfurizer which are discarded every year in petroleum production industries of various countries in the world are huge in quantity, and are accumulated like mountains, so that the waste mountain is a nuisance which seriously threatens the ecological environment and is difficult to solve so far. The waste slag mountain is a valuable resource bank of nickel, vanadium and molybdenum which is urgently required to be developed and utilized by the metallurgical department. After years of research, the company has successfully adopted a wet method to extract vanadium and molybdenum metals from a nickel-containing waste catalyst and a waste desulfurizer and has carried out industrial production of extracting vanadium and molybdenumThe technology has already applied for the invention patent (patent application number: 200410021725.5) to the national intellectual property office, but at present, the nickel-containing residue waste after extracting vanadium and molybdenum by wet method is still abandoned, and at most, the waste is used as the raw material for nickel extraction by wet method. Because it is difficult to extract qualified nickel from the nickel-containing material by using the traditional wet method, the main reasons are that the technical problems of high acid consumption, high operation cost and low nickel leaching rate exist in the wet method for extracting nickel, the purification technology of phosphorus, vanadium and molybdenum is difficult, the nickel plate produced reluctantly is difficult to meet the quality requirement, and according to the existing production practice and the literature records: firing a low-phosphorus nickel-containing material with the phosphorus content of less than 0.05%When the pyrometallurgical method is used for smelting high-phosphorus vanadium-containing nickel materials with the phosphorus content higher than 0.2%, the phosphorus content of the prepared nickel-iron alloy or metal nickel product is as high as more than 2.0% due to the fact that the phosphorus content fluctuates greatly along with the nickel content in the raw materials, and actually, the nickel-iron alloy with the phosphorus content higher than 2.0% has no use value in the material industry, particularly, when the traditional pyrometallurgical approaches such as smelting nickel matte, casting an anode, electrolysis and the like are adopted for the high-phosphorus vanadium-containing low-nickel raw materials, a vulcanizing agent is needed to be added at the early stage of smelting, and the technical problem of sulfur pollution is solved at the later stage. According to the determination, the nickel-containing waste catalyst and waste desulfurizing agent discharged from petroleum industry contains about 2-5% of nickel and V2O5About 8-16%, molybdenum-2-5% and phosphorus-containing quantity is up to 0.3-1%, this is a typical high-phosphorus vanadium-containing low-nickel waste material which is very difficult to treat, so far, the production technology process for industrially extracting nickel by completely adopting waste catalyst containing nickel and waste desulfurizer which are discardedby petroleum industry has not been reported at home and abroad.
The invention content is as follows:
the invention provides a production method for extracting nickel by a pyrogenic process on the basis of the prior metallurgical technology, in particular to a high-phosphorus vanadium-containing nickel waste material discarded by petrochemical industry, which is realized by the following technical scheme:
it is carried out by the following steps in sequence,
(1) preparing waste materials: the method comprises subjecting waste nickel-containing catalyst or waste desulfurizer to surface deoiling treatment, and subjecting the waste nickel-containing catalyst and waste desulfurizer to surface deoiling treatment, or directly using the waste nickel-containing material without agglomeration and briquetting treatment,
(2) weighing and mixing materials: the weight ratio of the raw materials is as follows:
1 part of nickel-containing waste material, namely,
0.01-0.25 portion of reducing agent (coke or ferrosilicon),
0.10-0.50 portion of flux (lime or silica),
wherein the reducing agent can also adopt silicon reducing agents (mainly comprising Si, Ca, Ba and Al) such as silicon calcium, industrial silicon, silicon barium, silicon-aluminum alloy and the like, and can also adopt carbonaceous reducing agents (mainly comprising C) such as coal and the like,
respectively weighing the materials and mixing the materials into a mixture,
(3) reduction smelting: sending the mixed mixture into a smelting furnace for reduction smelting reaction, controlling the reduction smelting temperature to be 1000-1600 ℃ and the reduction smelting time to be 0.5-3 hours,
the reduction smelting reaction of the nickel-containing waste material by the carbonaceous reducing agent (such as coking coal) is as follows:
the reduction smelting reaction of the nickel-containing waste material by a siliceous reducing agent (such as ferrosilicon) is as follows:
after the reduction smelting reaction is completed (the Ni content in the slag is controlled to be lower than 0.2%), opening a slag hole to discharge primary ferronickel slag to prepare nickel-containing intermediate alloy liquid,
(4) oxidation refining: adding raw materials according to the following weight ratio in a smelting furnace for preparing nickel-containing intermediate alloy liquid after primary ferronickel slag is discarded, and carrying out oxidation refining reaction:
1 part of nickel-containing intermediate alloy, namely,
0.2-3.5 portions of flux lime,
0.01-0.30 portion of iron ore,
weighing the materials according to the specified weight proportion, adding the materials into a smelting furnace, blowing oxygen into the furnace for oxidation refining to remove silicon, vanadium and phosphorus, controlling the oxidation refining temperature to be 1000-1700 ℃ and the oxidation refining time to be 1-4 hours,
carrying out the following oxidation refining reaction in a smelting furnace:
after the oxidation refining reaction is completed (based on the requirement of detecting the content of phosphorus), the silicon, the phosphorus and the vanadium respectively generate CaO. SiO2、CaO·P2O5And CaO.V2O5Adding into furnace slag, pouring slag to obtain qualified ferronickel alloy liquid with qualified phosphorus content (lower than 0.02%),
(5) nickel-iron alloy product: casting the ferronickel alloy liquid obtained by oxidation refining, cooling and demoulding to obtain the refined ferronickel alloy product with qualified phosphorus content (lower than 0.02 percent).
The invention uses the waste catalyst containing nickel discarded in petrochemical industry, or the waste desulfurizer containing nickel, or the secondary pollutants of high-phosphorus vanadium-nickel residue discarded after the waste catalyst containing nickel and the waste desulfurizer containing nickel are extracted by chemical wet method to obtain vanadium and molybdenum, and the like as the raw material containing nickel, and CaO%/SiO is used as the binary alkalinity2Within the range of 0.8-1.8, using coke or ferrosilicon as reducing agent, reducing and smelting to remove 60-70% of phosphorus, making nickel-containing intermediate alloy, and then using slag binary alkalinity CaO%/SiO2% 1.2-3.5, oxygen or oxygen-iron ore combined oxidation mode can make more than 99% of phosphorus and silicon in the nickel-containing intermediate alloy combine with more than 98% of vanadium to produce CaO.P2O5、CaO·SiO2And CaO.V2O5The ferronickel alloy with qualified phosphorus content (lower than 0.02 percent) and qualified refining can be prepared after the ferronickel alloy enters the furnace slagThe product and the production method provided by the invention solve the technical problem of separation of high phosphorus and vanadium in the nickel-iron alloy, realize the purpose of extracting nickel from high phosphorus vanadium-nickel-containing waste materials in a short process, low cost and industrialization, widen the mineral source channel of nickel resources which are in short supply in China, and relieve the serious problem of waste residue pollution which exists for a long time in the petrochemical department and is difficult to solve.
The invention also has the following technical characteristics:
in the step of reduction smelting, the nickel-containing intermediate alloy liquid prepared after the primary nickel-iron slag is discarded can be cast, the nickel-containing intermediate alloy ingot is prepared after cooling and demoulding, the nickel-containing intermediate alloy ingot is used as an intermediate product to be intensively put in storage for the next step, and the intermediate product containing the nickel-containing intermediate alloy is intensively subjected to oxidation refining to prepare the refined qualified nickel-iron alloy.
The smelting furnace is a submerged arc furnace or an electric arc furnace, reduction smelting can be carried out in the submerged arc furnace or the electric arc furnace, and oxidation refining is carried out in the electric arc furnace.
Description of the drawings:
the attached figure is a production process flow chart of the invention.
The specific implementation mode is as follows:
the first embodiment is as follows: taking the nickel-containing residue discharged after extracting vanadium and molybdenum by a wet method as a raw material to continuously carry out two-step smelting of reduction smelting and oxidation refining in the same tilting refining electric arc furnace as an example,
the method comprises the following steps:
(1) preparing waste materials: agglomerating the nickel-containing residue discharged after vanadium and molybdenum are extracted by a chemical wet method to prepare a nickel-containing waste briquette, and determining: the nickel-containing waste briquette contains 5 percent of nickel oxide, 5 percent of ferrous oxide, 1 percent of molybdenum trioxide, 1.5 percent of vanadium pentoxide and 0.6 percent of phosphorus pentoxide,
(2) weighing and mixing materials: the weight ratio of the raw materials is as follows:
the nickel-containing scrap is pressed into a block for 5t,
0.5t of ferrosilicon (containing 75 percent of Si),
1.6t of lime is added into the lime,
respectively weighing the materials and mixing the materials into a mixture,
(3) reduction smelting: adding the mixed mixture into a tilting refining electric arc furnace, carrying out reduction smelting reaction, controlling the reduction smelting temperature to be 1400 ℃ and the reduction smelting time to be 2.5 hours, and carrying out the following reduction smelting reaction on the nickel-containing waste briquette by using a reducing agent ferrosilicon (the main component is FeSi):
opening a slag discharge port to dump and discharge primary ferronickel waste slag when the reduction smelting reaction is complete and the Ni content in the slag is controlled to be lower than 0.2 percent, removing 60-70 percent of phosphorus to prepare nickel-containing intermediatealloy liquid,
(4) oxidation refining: weighing 0.9t of lime used in the refining period and 0.06t of iron ore,
in a tilting refining electric arc furnace for preparing nickel-containing intermediate alloy liquid after discarding primary ferronickel waste slag, adding materials in a refining period, blowing oxygen for oxidation refining, and controlling the temperature of the oxidation refining to be 1500 ℃, wherein the furnace has good fluidity, the oxidation refining time is 1 hour, and the following oxidation refining reactions are carried out in the tilting refining electric arc furnace:
after the oxidation refining reaction is thorough, the silicon, the phosphorus and the vanadium respectively generate CaO&SiO2、CaO·P2O5And CaO.V2O5Adding into furnace slag, pouring slag to obtain qualified ferronickel alloy liquid with qualified phosphorus content (lower than 0.02%),
(5) nickel-iron alloy product: injecting the ferronickel alloy liquid obtained by oxidation refining into a ladle for casting, cooling and demoulding to obtain the qualified ferronickel alloy product with the phosphorus content of less than 0.02 percent.
Example two: taking waste catalyst containing nickel (or waste desulfurizer containing nickel) discarded by petrochemical industry as raw material to respectively carry out reduction smelting and oxidation refining in different smelting furnaces as an example,
the method comprises the following steps in sequence:
(1) preparing waste materials: the nickel-containing waste catalyst (or the nickel-containing waste desulfurizer) discarded in the petrochemical industry is subjected to surface deoiling treatment to prepare a nickel-containing waste briquette,
(2) weighing and mixing materials: the raw materials are as follows:
the nickel-containing scrap compact is pressed for 100t,
5t of coke (the fixed carbon content is reduced by 80%),
the lime is 30t, and the lime is,
respectively weighing the materials, mixing the materials into a smelting mixture by a charging machine,
(3) reduction smelting: adding the mixed mixture into a 6000kVA submerged arc ore heating furnace for reduction smelting reaction, controlling the temperature of the 6000kVA submerged arc ore heating internal reduction smelting to 1400 ℃, carrying out reduction smelting for 3 hours, opening a slag iron hole and pouring into a ladle after the reduction smelting reaction is complete (controlling the Ni content in slag to be lower than 0.15%), carrying out slag discharge and casting to obtain an intermediate product casting block containing the nickel intermediate alloy, intensively warehousing for next centralized oxidation refining,
(4) oxidation refining: weighing an intermediate product casting block containing nickel intermediate alloy, adding the intermediate product casting block into a tilting refining electric arc furnace with the specification of 2t,
weighing the following raw materials in parts by weight:
the nickel-containing intermediate alloy 2t is,
the lime is added for 2.8t,
0.1t of iron ore,
during the oxidation refining reaction, the raw materials are added into a tilting refining electric arc furnace, after the charging materials are fed and melted, the temperature of the oxidation refining is controlled to be 1400 ℃, and oxygen is blown in for the oxidation refiningIn 2 hours, after the oxidation refining reaction is complete, the silicon, the phosphorus and the vanadium respectively generate CaO&SiO2、CaO·P2O5And CaO.V2O5Adding into furnace slag, pouring slag to obtain qualified ferronickel alloy liquid with phosphorus content lower than 0.02%,
(5) nickel-iron alloy product: injecting the ferronickel alloy liquid obtained by oxidation refining into a ladle for casting, cooling and demoulding to obtain the ferronickel alloy product with qualified phosphorus content (lower than 0.02%) and qualified refining.
Claims (4)
1. A production method for extracting nickel by a pyrogenic process sequentially comprises the following steps:
(1) preparing waste materials: preparing the nickel-containing waste material for later use,
(2) weighing and mixing materials: according to the specified weight ratio of the raw materials, respectively weighing the materials and mixing the materials into a mixture,
the method is characterized in that:
in the step of preparing the waste material, the nickel-containing waste material is nickel-containing waste catalyst, or nickel-containing waste desulfurizer, or nickel-containing residue discharged after the nickel-containing waste catalyst and the nickel-containing waste desulfurizer are subjected to wet extraction of vanadium and molybdenum,
in the step of weighing and mixing the materials, the specified weight ratio of the raw materials is as follows:
1 part of nickel-containing waste material, namely,
reducing agent: 0.01-0.25 portion of coke or ferrosilicon,
flux: 0.10-0.50 portion of lime or silica,
(3) reduction smelting: sending the mixed mixture into a smelting furnace for reduction smelting reaction, controlling the reduction smelting temperature to be 1000-1600 ℃ and the reduction smelting time to be 0.5-3 hours, removing primary ferronickel slag to prepare nickel-containing intermediate alloy liquid,
(4) oxidation refining: weighing the following materials in parts by weight in a smelting furnace for preparing nickel-containing intermediate alloy liquid after discarding primary ferronickel slag, and adding the materials into the smelting furnace:
1 part of nickel-containing intermediate alloy, namely,
flux: lime 0.2-3.5 portions,
0.01-0.30 portion of iron ore,
blowing oxygen gas into the reactor for oxidation refining, controlling the oxidation refining temperature to be 1000-1700 ℃ and the oxidation refining time to be 1-4 hours, pouring slag to obtain refined ferronickel alloy liquid,
(5) nickel-iron alloy product: and casting the ferronickel alloy liquid obtained by oxidation refining, cooling and demoulding to obtain the refined qualified ferronickel alloy product.
2. The method for producing pyro-extracted nickel according to claim 1, wherein the method comprises the following steps: the reducing agent in the reduction smelting step can also be calcium silicon, industrial silicon, silicon barium, silicon aluminum alloy and coal.
3. A process according to claim 1 or 2, characterized in that: in the step of reduction smelting, the nickel-containing intermediate alloy liquid prepared after the primary nickel-iron slag is discarded is cast to prepare a nickel-containing intermediate alloy ingot which is used as an intermediate product to be intensively put in storage for the next step of oxidation refining.
4. A process according to claim 1 or 2, characterized in that: the smelting furnace is a submerged arc furnace or an electric arc furnace.
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| WO2006045254A1 (en) * | 2005-09-16 | 2006-05-04 | Shenjie Liu | A smelting process of ferronickel with nickel oxide ore containing of crystal water in a blast furnace |
| WO2006050658A1 (en) * | 2005-09-16 | 2006-05-18 | Shenjie Liu | A smelting process of ferronickel with nickel oxide ore free of crystal water in a blast furnace |
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| CN105950873A (en) * | 2016-06-24 | 2016-09-21 | 浙江浙能催化剂技术有限公司 | Method for recycling vanadium, tungsten and titanium from waste SCR denitration catalyst |
| CN106337133A (en) * | 2016-09-30 | 2017-01-18 | 攀枝花学院 | Method for recovering titanium, vanadium and tungsten in waste SCR denitration catalyst |
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