CN100348477C - Process for preparing phosphor copper ingots with phosphor sludge as raw material - Google Patents
Process for preparing phosphor copper ingots with phosphor sludge as raw material Download PDFInfo
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- CN100348477C CN100348477C CNB2006100108543A CN200610010854A CN100348477C CN 100348477 C CN100348477 C CN 100348477C CN B2006100108543 A CNB2006100108543 A CN B2006100108543A CN 200610010854 A CN200610010854 A CN 200610010854A CN 100348477 C CN100348477 C CN 100348477C
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- phosphorus
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- phosphorus mud
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000002994 raw material Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 239000010802 sludge Substances 0.000 title abstract 5
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 title description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 98
- 239000011574 phosphorus Substances 0.000 claims abstract description 97
- 239000010949 copper Substances 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 51
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 35
- 239000000956 alloy Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 150000001879 copper Chemical class 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000002844 melting Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000010025 steaming Methods 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 20
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 12
- 230000004927 fusion Effects 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- 239000012265 solid product Substances 0.000 claims description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 230000005587 bubbling Effects 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 229960003280 cupric chloride Drugs 0.000 claims description 3
- 230000002829 reductive effect Effects 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 16
- 238000002360 preparation method Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000002893 slag Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 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 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004737 colorimetric analysis Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- KWUUWVQMAVOYKS-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe][Mo][Mo] KWUUWVQMAVOYKS-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000002798 spectrophotometry method Methods 0.000 description 3
- 238000000207 volumetry Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- -1 phosphorus compound Chemical class 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a method for preparing P-Cu mother alloy, which prepares the P-Cu mother alloy by using phosphorus sludge as raw material via the steps of melting phosphorus, evaporating phosphorus to generate phosphorus steam which can react with the water solution of soluble copper salt, separating solid from liquid, drying, etc. because the raw material used by the present invention is soluble copper salt and white phosphorus produced waste material-phosphorus sludge, the method has the advantages of simple preparation process, easy realization and obvious environmental, economical and social benefit, and the method can solve the problem of processing and treating phosphorus sludge. The P-Cu mother alloy prepared by the method provided by the present invention has good product quality and has the P content of at least 14.5% and the Cu and P content of at least 97.75%. The method is suitable for the industrial preparation of P-Cu mother alloy, and is also suitable for the comprehensive utilization of phosphorus sludge.
Description
One, technical field
The present invention relates to a kind of P-Cu mother alloy production method, belong to meticulous phosphorous chemical industry preparation field.
Two, background technology
Phosphor-copper is that a kind of outward appearance is silver gray solid metal phosphide, and is water insoluble, has higher chemistry and thermo-chemical stability, hard and crisp, higher thermal, electrical conductivity arranged, the mixture of normally following three kinds of structure types: Cu
3P, CuP
2, Cu
2P
7, Cu wherein
3P has industrial application value most.As a kind of basic function material, be mainly used in copper and copper alloy reductor, phosphor bronze, solder flux, scolder, powder metallurgy, the production of ultra-fine copper lead.In actual application, the form of adding phosphorus in the various materials and mainly be with phosphor-copper adds.General custom claims that phosphorous 10～15% phosphor-copper is a P-Cu mother alloy, and its main component is Cu
3P.Industrialized preparing process mainly contains at present: heat phosphorus ore, copper mine and coke mixture 1.; 2. heated oxide copper, phosphoric acid and charcoal mixt; 3. copper, cupric oxide, cupric sulfide and phosphuret-(t)ed hydrogen reaction; 4. cupric oxide electrolysis in the metaphosphate molten mass; 5. metallic copper and element phosphor are directly synthetic; 6. red phosphorus is scattered in electrolysis in the vitriolated copper-bath; 7. copper-bath and element phosphor reaction, chemical reaction equation is:
96H
2O+60CuSO
4+11P
4→20Cu
3P+60H
2SO
4+24H
3PO
4
Known P-Cu mother alloy production method is a raw material with high purity metal copper and element phosphor generally, and reaction generates under conditions such as heat, electrolysis, thereby has problems such as raw materials cost height, production process complexity, energy consumption height.Disclose from yellow phosphorus as Chinese patent CN1532298A (2004), in the copper liquid of fusing, added dehydration yellow phosphorus, under the effect of catalyzer, produced the method for P-Cu mother alloy; Russ P RU2177511C2 (1999) discloses sheet or granular metal copper and the red phosphorus method of heat production P-Cu mother alloy altogether; Russ P RU2171310C1 (2001) discloses the method for melt production P-Cu mother alloy under high temperature (1350 ℃～1550 ℃) such as the mixture that utilizes calcium oxide, phosphorated material, reductive agent;
If use low-cost phosphorous, copper raw material, adopt the simple production technology of normal temperature and pressure, not only can reduce the P-Cu mother alloy production cost and can increase economic efficiency, strengthen product market competitiveness.
In the phosphorus production furnace gas, except phosphorous vapor, carbon monoxide, also have dust and other sublimate, during by fly-ash separator, materials such as unsegregated dust form difficult isolating phosphorus-dirt-water mixture---phosphorus mud in condensation phase and gaseous state phosphorus.The physical condition of phosphorus mud can be regarded as the emulsoid that yellow phosphorus, dust and water are formed, and less than phosphorus, so the separation of phosphorus mud is extremely difficult greater than water for proportion.Phosphorus content is very high in the phosphorus mud, and the phosphorus stove of electric precipitator particularly is not installed, and has 10%～15% yellow phosphorus to enter in the phosphorus mud, produces 1 ton of yellow phosphorus and can produce phosphorus mud more than 500 kilograms.Still be that the environment protection angle considers that the recovery of phosphorus is all extremely important in the phosphorus mud no matter from economic benefit.Conventional phosphorus mud treatment process has three classes:
1. recovery phosphorus
(1) hot method: divide recirculation method, vacuum filtration method and distillation method again; (2) liquid phase method: divide physics method, centrifuging, extraction process and chemical method again;
2. produce phosphorus compound
(1) thermochemical method generates phosphoric acid with phosphorus mud in specific stove internal combustion, and this is the domestic method that generally adopts; (2) chemical method can get hypophosphite, phosphite and phosphuret-(t)ed hydrogen with phosphorus mud with alkaline purification.
The method that adopts yellow phosphorus in the polar solvent extraction with carbon disulfide recovery phosphorus mud is disclosed as Chinese patent CN1071394A; CN85104781A discloses the method for producing Sodium phosphate dibasic with phosphorus mud; CN1174166A discloses with compound digestion agent, flocculating aids and has administered the method that the high-quality high-purity yellow phosphorus is dyed and therefrom reclaimed to the phosphorus dirt; CN1236750A discloses the method with peparing phosphoric acid from P-poor slime; CN1324759A discloses the method for phosphorus mud being carried out technologies recovery yellow phosphorus such as heating and melting, filtration; Russ P RU2248937C1 discloses in phosphorus mud and water mixture and has added chromic acid, the method for Separation and Recovery yellow phosphorus; US6620396B2 discloses in phosphorus mud and water mixture and has added phosphoric acid salt, the method for Separation and Recovery yellow phosphorus; US4379132 discloses the method that phosphorus mud and calcium hydroxide reaction are produced sodium hypophosphite.
Cu in the element phosphor and the aqueous solution
2+Chemical reaction as the formula (1) can take place
96H
2O+60CuSO
4+11P
4→20Cu
3P+60H
2SO
4+24H
3PO
4 (1)
With phosphorus mud be raw material directly and the soluble copper reactant salt produce P-Cu mother alloy, treating processes is carried out under lesser temps and normal pressure, make full use of the useful component in the phosphorus mud, cleaning is harmlessly handled mud phosphorus, finally the phosphorus in the mud phosphorus is converted into the P-Cu mother alloy of high value, has remarkable economic efficiency and environmental benefit.U.S. Pat 4192853 discloses the method for utilizing copper sulfate solution to handle phosphorus mud and yellow phosphoric tail gas, can obtain mainly to contain phosphorized copper through handling, modification and refining raw material that the solid product that contains the compositions such as silicate of the muriate of basic metal and silicon and fluorochemical, calcium and aluminium simultaneously, this product are mainly made as hypereutectoid aluminum silicon alloy and P-Cu mother alloy.But the copper-containing raw material that this method is used only limits to copper sulfate, and because the employing copper-bath is direct and phosphorus mud reacts, water-fast solid impurity easily is present in the gained solid product with solid-liquid separation in the phosphorus mud, so product still contains more impurity after separating, products therefrom needs just can obtain P-Cu mother alloy through further processing treatment.
Three, technology contents
The object of the invention is to provide a kind of production method of P-Cu mother alloy, and reluctant waste from phosphorus production---phosphorus mud produces phosphorous vapor through molten phosphorus, steaming phosphorus, makes phosphorous vapor and soluble copper salt produce P-Cu mother alloy in liquid phase reaction.P-Cu mother alloy P content 〉=14.5%, Cu+P 〉=97.75%.It is not only applicable to the P-Cu mother alloy industrial production and is applicable to the comprehensive utilization of phosphorus mud yet, has also solved the treatment and disposal problem of phosphorus mud.
Flow process of the present invention is invented and is finished according to the following steps as shown in Figure 1,
1, feedstock production
(1), in phosphorus-melting groove, drop into phosphorus mud, be heated to 45 ℃～95 ℃ so that the fusion under the temperature that is higher than yellow phosphorus fusing point (44.1 ℃) of phosphorus mud;
(2), select copper sulfate, cupric chloride or cupric nitrate as soluble copper salt, be mixed with the mantoquita mass percentage concentration and be 30%～50% copper salt solution;
2, in phosphorus-steaming pot, add the water that is equivalent to pot volume 1/6～1/2, then the phosphorus mud after the fusion is introduced in the phosphorus-steaming pot, phosphorus mud coefficient of loading 50%～80%, be heated to 285～400 ℃, in the temperature-rise period, when temperature rises to 100 ℃, mainly based on moisture evaporation, continuing to heat up makes the element phosphor in the phosphorus mud change phosphorous vapor under the temperature that is higher than yellow phosphorus boiling point (282 ℃), temperature is not higher than 400 ℃, to prevent that red phosphorus from producing, best steaming phosphorus temperature is 300 ℃, and the solid phosphorus slag that steaming phosphorus end back produces is discharged by the phosphorus-steaming pot slag notch;
When 3, producing phosphorous vapor phosphorous vapor being fed reactor reacts with the mantoquita that is preheated to 45～80 ℃, generate P-Cu mother alloy, for guaranteeing the efficient and the speed of reaction, reactor temperature is controlled at 45 ℃～80 ℃, 4～6 hours reaction times (also for steaming the phosphorus time), the water-fast gas in reaction back is discharged by the gas reactor outlet, reactor is the Gas-Liquid Absorption device, comprising and stir a kind of in bubbling reactor, packing tower, wet-wall tower, spray column, the bubble tower, is good to stir the bubbling reactor;
4, contain solid-liquid biphase mixture after the reaction and separate by equipment for separating liquid from solid, filtrate is mixed the back Returning reactor and is recycled with copper salt solution, and must be adjusted to mass percent concentration 30%～50% this moment with mantoquita concentration in the mixed solution;
5, solid-liquid separation gained solid product main component is a phosphor-copper, continues with the water flushing, filters that no cupric ion and element phosphor detect pH value 6-8 in filtrate;
6, at 100～120 ℃ of normal pressure hot-air dries or drying under reduced pressure to water content below 5%, obtain the P-Cu mother alloy finished product.
Compare the present invention with known technology following advantage arranged:
1, adopting phosphorus mud and soluble copper salt is raw material, and it is wide, cheap to have a source, and the more traditional method of production cost is low;
2, P-Cu mother alloy is produced in phosphorous vapor and the copper salt solution reaction that produces by steaming phosphorus, directly compares with the technology of copper-bath reaction treatment phosphorus mud production phosphorized copper with phosphorus mud, and products obtained therefrom impurity is few, purity is high;
3, present method need not processing such as raw material dewaters, reaction conditions gentleness need not technologies such as High Temperature High Pressure, electrolysis, thereby this technology are belonged to energy-saving technology.
Four, description of drawings
Fig. 1 is a process flow sheet of the present invention.
Five, embodiment
Embodiment 1
1. in phosphorus-melting groove, drop into element phosphor quality percentage composition and be 10 kilograms in 50% phosphorus mud, be heated to 80 ℃ and make the fusion of phosphorus mud; The preparation mass percentage concentration is 40% copper-bath, and is transferred to stirring bubbling reactor reactor after primary heater unit is preheated to 60 ℃;
2. add the water that is equivalent to pot volume 1/3 in phosphorus-steaming pot, then the phosphorus mud after the fusion is introduced in the phosphorus-steaming pot, phosphorus mud coefficient of loading 70% is heated to 300 ℃, steams the phosphorus process and continues 5 hours; Steaming the solid phosphorus slag that produces after phosphorus finishes is discharged by the phosphorus-steaming pot slag notch;
3. phosphorous vapor is fed from phosphorus-steaming pot and stir the bubbling reactor, reactor temperature is controlled at 60 ℃, and feeding speed is 1 kilogram/hour, reactor temperature is controlled at 50-70 ℃, in the 5 hours reaction times (also for steaming the phosphorus time), the water-fast gas in reaction back is discharged by the gas reactor outlet;
4. contain solid-liquid biphase mixture and separate by filtration unit after the reaction, filtrate mixes with copper salt solution afterwards that Returning reactor recycles, and makes that mantoquita concentration maintains mass percent concentration 40% in the mixed solution;
Solid-liquid separation gained solid product repeatedly with water flushing, filter that no cupric ion and element phosphor detect in filtrate;
6.115 ℃ vacuum-drying 1 hour, be dried to water content below 5%, obtain 30.1 kilograms of P-Cu mother alloy finished products, the key technical indexes is Cu+P99.77%, Cu84.92% (EDTA volumetry), P14.85% (molybdenum blue spectrophotometric method), Sn0.008% (hypophosphite Vr method), Pb0.009% (atomic absorption method), Fe0.035% (iron molybdenum blue colorimetric method) meets phosphor copper A grade standard (15CuPA).
Embodiment 2
1. in phosphorus-melting groove, drop into element phosphor quality percentage composition and be 10 kilograms in 25% phosphorus mud, be heated to 45 ℃ and make the fusion of phosphorus mud; The preparation mass percentage concentration is 50% copper nitrate solution, and feeds bubble absorbing tower after primary heater unit is preheated to 50 ℃;
2. add the water that is equivalent to pot volume 1/4 in phosphorus-steaming pot, then the phosphorus mud after the fusion is introduced in the phosphorus-steaming pot, phosphorus mud coefficient of loading 70% is heated to 350 ℃, steams the phosphorus process and continues 6 hours; Steaming the solid phosphorus slag that produces after phosphorus finishes is discharged by the phosphorus-steaming pot slag notch;
3. phosphorous vapor is fed bubble absorbing tower from phosphorus-steaming pot, it is 0.4 kilogram/hour that the interior temperature of tower is controlled at 50 ℃ of feeding speed, and reactor temperature is controlled at 45～60 ℃, the 6 hours reaction times (also for steaming the phosphorus time), the water-fast gas in reaction back is discharged by the gas reactor outlet;
4. containing solid-liquid biphase mixture after the reaction separates by filtration unit, filtrate with return bubble absorbing tower after copper salt solution mixes and recycle, and according to the flow of filtrate and the concentration of mantoquita wherein, the copper salt solution concentration and the flow that adjust to add make that mantoquita concentration maintains mass percent concentration 50% in the mixed solution;
Solid-liquid separation gained solid product repeatedly with water flushing, filter that no cupric ion and element phosphor detect pH value 7 in filtrate;
6.105 ℃ vacuum-drying 1 hour, be dried to water content below 5%, obtain 15 kilograms of P-Cu mother alloy finished products, the key technical indexes is Cu+P99.80%, Cu84.90% (EDTA volumetry), P14.80% (molybdenum blue spectrophotometric method), Sn0.008% (hypophosphite Vr method), Pb0.009% (atomic absorption method), Fe0.045% (iron molybdenum blue colorimetric method) meets phosphor copper A grade standard (15CuPA).
Embodiment 3
1. in phosphorus-melting groove, drop into element phosphor quality percentage composition and be 10 kilograms in 40% phosphorus mud, be heated to 60 ℃ and make the fusion of phosphorus mud; The preparation mass percentage concentration is 40% cupric chloride copper solutions, and feeds bubble absorbing tower after primary heater unit is preheated to 70 ℃;
2. add the water that is equivalent to pot volume 1/4 in phosphorus-steaming pot, then the phosphorus mud after the fusion is introduced in the phosphorus-steaming pot, phosphorus mud coefficient of loading 60% is heated to 400 ℃, steams the phosphorus process and continues 4 hours; Steaming the solid phosphorus slag that produces after phosphorus finishes is discharged by the phosphorus-steaming pot slag notch;
3. phosphorous vapor is fed spray absorber from phosphorus-steaming pot, temperature is controlled at 70 ℃ in the tower, and feeding speed is 1 kilogram/hour, reactor temperature is controlled at 65-80 ℃, in the 4 hours reaction times (also for steaming the phosphorus time), the water-fast gas in reaction back is discharged by the gas reactor outlet;
4. containing solid-liquid biphase mixture after the reaction separates by filtration unit, filtrate with return spray absorber after copper salt solution mixes and recycle, and according to the flow of filtrate and the concentration of mantoquita wherein, the copper salt solution concentration and the flow that adjust to add make that mantoquita concentration maintains mass percent concentration 40% in the mixed solution;
Solid-liquid separation gained solid product repeatedly with water flushing, filter that no cupric ion and element phosphor detect pH value 7 in filtrate;
6.120 ℃ dry air 1 hour, be dried to water content below 5%, obtain 24 kilograms of P-Cu mother alloy finished products, the key technical indexes is Cu+P99.50%, Cu84.90% (EDTA volumetry), P14.60% (molybdenum blue spectrophotometric method), Sn0.007% (hypophosphite Vr method), Pb0.008% (atomic absorption method), Fe0.050% (iron molybdenum blue colorimetric method) meets phosphor copper A grade standard (15CuPA).
Claims (7)
1, a kind of is the method for raw material production P-Cu mother alloy with phosphorus mud, and it is characterized in that: method is finished according to the following steps,
1), feedstock production
(1), in phosphorus-melting groove, drop into phosphorus mud, be heated above fusion under the temperature of yellow phosphorus fusing point;
(2), select copper sulfate, cupric chloride or cupric nitrate as soluble copper salt, be mixed with the mantoquita mass percentage concentration and be 30%～50% copper salt solution;
2), in phosphorus-steaming pot, add the water be equivalent to pot volume 1/6～1/2, then the phosphorus mud after the fusion is introduced in the phosphorus-steaming pot, phosphorus mud coefficient of loading 50%～80% is heated to 285～400 ℃, produces phosphorous vapor;
3), when producing phosphorous vapor phosphorous vapor being fed Gas-Liquid Absorption reactor and mantoquita reacts the generation P-Cu mother alloy;
4), containing solid-liquid biphase mixture after the reaction separates by equipment for separating liquid from solid;
5), solid-liquid separation gained solid product continues with the water flushing, filters that no cupric ion and element phosphor detect in filtrate;
6), the gained solid product is dried to water content below 5%, obtains the P-Cu mother alloy finished product.
2, according to claim 1 is the method for raw material production P-Cu mother alloy with phosphorus mud, it is characterized in that: the phosphorus mud in the described phosphorus-melting groove is heated to 45 ℃～95 ℃.
3, according to claim 1 is the method for raw material production P-Cu mother alloy with phosphorus mud, it is characterized in that: the described mantoquita that enters reactor is preheated to 45～80 ℃ earlier.
4, according to claim 1 is the method for raw material production P-Cu mother alloy with phosphorus mud, it is characterized in that: described reactor temperature is controlled at 45 ℃～80 ℃, 4～6 hours reaction times.
5, according to claim 1 is the method for raw material production P-Cu mother alloy with phosphorus mud, it is characterized in that: described reactor is for stirring a kind of in bubbling reactor, packing tower, wet-wall tower, spray column, the bubble tower.
6, according to claim 1 is the method for raw material production P-Cu mother alloy with phosphorus mud, it is characterized in that: filtrate is mixed the back Returning reactor and is recycled with copper salt solution.
7, according to claim 1 is the method for raw material production P-Cu mother alloy with phosphorus mud, it is characterized in that: described solid product is dry with 100～120 ℃ of normal pressure hot-air dries or drying under reduced pressure.
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| CN2543966Y (en) * | 2002-05-28 | 2003-04-09 | 陆良春 | Copper-phosphorus parent alloy produciton equipment |
| CN1740358A (en) * | 2005-09-09 | 2006-03-01 | 陆良春 | P-Cu mother alloy |
| CN1740355A (en) * | 2005-09-09 | 2006-03-01 | 陆良春 | Prepn process of P-Cu mother alloy |
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| CN2543966Y (en) * | 2002-05-28 | 2003-04-09 | 陆良春 | Copper-phosphorus parent alloy produciton equipment |
| CN1740358A (en) * | 2005-09-09 | 2006-03-01 | 陆良春 | P-Cu mother alloy |
| CN1740355A (en) * | 2005-09-09 | 2006-03-01 | 陆良春 | Prepn process of P-Cu mother alloy |
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