CN105399069A - Ferrophosphorus recycle method - Google Patents
Ferrophosphorus recycle method Download PDFInfo
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- CN105399069A CN105399069A CN201510829381.9A CN201510829381A CN105399069A CN 105399069 A CN105399069 A CN 105399069A CN 201510829381 A CN201510829381 A CN 201510829381A CN 105399069 A CN105399069 A CN 105399069A
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- ferrophosphorus
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
- C01B25/088—Other phosphides containing plural metal
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
The invention discloses a ferrophosphorus recycle method which comprises the following particular steps: adding calcium oxide into a ferrophosphorus raw material to enable the molar ratio of silicon dioxide to calcium oxide in the ferrophosphorus raw material being 1:(1-3), conducting uniform mixing and tabletting, placing into a vacuum furnace, conducting heat preservation for 30-60 min under the condition that the vacuum degree is 10-30 Pa and the temperature is 1200-1500 DEG C, cooling to the room temperature, removing an obtained upper layer residue sample, and collecting a lower layer product for later use; adding nickel powder into the lower layer product a according to the ingredient weight ratio of the product a to the nickel powder of (3-5):1, conducting uniform mixing and tabletting, placing into the vacuum furnace, conducting heat preservation for 30-60 min under the condition that the pressure in the furnace is 10-100 Pa and the temperature is 1000-1500 DEG C, and cooling to the room temperature, so as to obtain the mixture of ferrophosphorus and schreibersite, wherein the total content of phosphide in the mixture is 98% or above and the percentage of Si is less than 0.07%. According to the method, by-product ferrophosphorus in the phosphorus chemical industry is used as the raw material for preparing metal phosphide, a new idea is provided for further recycle of the by-product ferrophosphorus in the phosphorus chemical industry, and the deficiencies of the conventional metal phosphide preparation method are solved.
Description
Technical field
The invention belongs to field of chemical metallurgical technology, be specifically related to a kind of recoverying and utilizing method of ferrophosphorus.
Background technology
Transition metal phosphide has the characteristic of ionic crystal, transition metal and covalency solid concurrently, thus shows unique physicochemical property.Transition metal phosphide, except have good hydrogenating desulfurization (HDS), hydrodenitrification (HDN) and hydrogenation deoxidation (HDO) activity in oil product except, has potential purposes in the catalyzed reaction of selective catalytic hydrogenation, anticorrosive, the field such as sewage disposal and photocatalytic degradation.Wherein, under identical testing conditions, the active order of similar phosphide is: Ni
2p>WP>MoP>CoPGr eatT.GreaT.GTFe
2p.Ni
2p has excellent electroconductibility, thermostability and physical strength, and special crystalline structure and excellent HDS catalytic performance, and its catalytic activity can compare favourably with precious metal, but much lower than precious metal of its cost.Study hotspot in recent years to the preparations and applicatio of transition metal phosphide.
A kind of preparation method of transition metal phosphide in prior art, be adopt, in solvent thermal system, nickel salt and yellow phosphorus are carried out solid-liquid reaction, filter, washing, obtains transition metal phosphide after vacuum-drying.A kind of nickel three phosphorus (Ni
3p) synthetic method is that reaction product is carried out suction filtration and carry out anneal under anaerobic atmosphere by two kinds of metal-salts are carried out hydro-thermal reaction, is washed by work in-process, dries and obtains body phase Ni
3p.The method that pyrolysis gasoline hydrogenation is refining is that roasting obtains containing Ni by metal-salt and hypophosphite, auxiliary agent and complexing agent are dissolved impregnated carrier
2the catalyzer of P thing phase, active ingredient is one or more metallic sulfides in cobalt metal, molybdenum, nickel, tungsten and Ni
2the composite catalyst of P, this catalyst activity is high, good stability, the sulfocompound in pyrolysis gasoline and alkene substantially all can be transformed.Iron mixes a preparation method for catalyst of phosphatizing nickel, is by molysite, nickel salt and urea are carried out hydro-thermal reaction, and cooling suction filtration obtains iron nickel hydrotalcite, add tensio-active agent and phosphoric acid stirring again, solid-liquid separation, washing, dries and obtains Fe2O3 doping catalyst of phosphatizing nickel.
At present, the preparation method of metal phosphide comprises: metal and the direct chemical combination of red phosphorus simple substance, metal halide and phosphine (Na
3p etc.) solid-state cementation, metal phosphate reduction, hypophosphite parco-lubrizing, phosphuret-(t)ed hydrogen parco-lubrizing, solvent-thermal process method, low-temperature plasma reduction method and organometallic compound decomposition etc.In all these preparation methods, some preparation procedures is complicated, the raw material that some needs are very expensive, or produces poisonous by product and cause phosphide to pollute.
Meanwhile, ferrophosphorus is the by product produced in a kind of phosphorous chemical industry production process, containing a small amount of iron in phosphorus ore, at high temperature generates iron phosphide with the phosphorus reaction in ore.By often producing 1t yellow phosphorus by-product ferrophosphorus 0.1 ~ 0.2t estimation, the ferrophosphorus by-product of annual phosphorous chemical industry is at 300,000 more than t, and ferrophosphorus is the by product in the production process such as a kind of hot legal system phosphorus and fused(calcium magnesium)phosphate.Phosphate rock resource is further exhausted, and a large amount of ferrophosphorus by products therefore rationally recycling phosphorous chemical industry generation are just day by day important.Therefore, develop and a kind ofly can recycle a large amount of ferrophosphorus by products that phosphorous chemical industry produces and can solve again the method for technical problem in metal phosphide preparation and be very important.
Summary of the invention
The object of the present invention is to provide a kind of recoverying and utilizing method of ferrophosphorus.
The object of the present invention is achieved like this, and the recoverying and utilizing method of described ferrophosphorus comprises following concrete steps:
A, add calcium oxide by raw material ferrophosphorus, the mol ratio of the silicon-dioxide in raw material ferrophosphorus and calcium oxide is made to be 1:1 ~ 3, insert in vacuum oven after mixing, compressing tablet, be 10 ~ 30Pa in vacuum tightness, temperature is be incubated 30 ~ 60min under 1200 ~ 1500 DEG C of conditions, be cooled to room temperature, obtain upper strata slag specimen and discard, collect lower floor product a for subsequent use;
B, add nickel powder by lower floor product a, ingredients by weight ratio is: product a: nickel powder=3 ~ 5:1, insert in vacuum oven after mixing, compressing tablet, in stove, pressure is 10 ~ 100Pa, temperature is be incubated 30 ~ 60min under 1000 ~ 1500 DEG C of conditions, be cooled to room temperature, obtain phosphide total content more than 98%, the ferrophosphorus of Si% < 0.07% and the mixture of phosphorus ferronickel.
Ferrophosphorus is a kind of by product produced in phosphorous chemical industry production process, and its composition is comparatively complicated, and ferrophosphorus is mainly with FeP, Fe
2p, Fe
3p, Fe
4p and FeP
2exist etc. form, the silicon also containing trace in usual ω (Fe)=50% ~ 75%, ω (P)=18% ~ 30% by-product ferrophosphorus, mainly with silicon-dioxide (SiO
2) form exist, ω (Si)=0.12% ~ 5.20%.Phosphorous chemical industry by-product ferrophosphorus and calcium oxide (analytical pure) are mixed in proportion, the mol ratio of the silicon-dioxide in phosphorous chemical industry by-product ferrophosphorus and calcium oxide is made to be 1:1 ~ 3, compressing tablet, put into vacuum oven, in stove, pressure is 10Pa ~ 100Pa, and temperature is be incubated 30min ~ 60min under 1200 DEG C ~ 1500 DEG C conditions, is down to room temperature, take off layer product as the ferrophosphorus after desiliconization, for subsequent use.Carry out desiliconization process by adding appropriate calcium oxide to ferrophosphorus, its layered effect is obvious.After testing, slag specimen main component in upper strata is Calucium Silicate powder (Ca
2siO
4), abandon.Lower floor's product is as ferrophosphorus (Fe after the desiliconization of next step doping nickel
2p), wherein Si% < 0.08%.Take the ferrophosphorus after 10g ~ 100g desiliconization and nickel powder (analytical pure) again, the amount wherein adding nickel powder is 2g ~ 35g, mixing, compressing tablet, puts into vacuum oven, and in stove, pressure is 10Pa ~ 100Pa, temperature is be incubated 30min ~ 60min under 1000 DEG C ~ 1500 DEG C conditions, and being down to room temperature, is ferrophosphorus (Fe after testing
3p) with phosphorus ferronickel (FeNi
2p) mixture, phosphide total content reaches more than 98%, wherein Si% < 0.07%.This method is that by-product ferrophosphorus carries out further recycling providing new approaches.
The present invention is directed to the technical problem existed in the by product Appropriate application of the deficiency of existing metal phosphide preparation method, the continuous exhaustion of phosphate rock resource and phosphorous chemical industry, with the by product ferrophosphorus of phosphorous chemical industry for metal phosphide prepared by raw material, the by product ferrophosphorus for phosphorous chemical industry carries out the not enough problem solving existing metal phosphide preparation method while recycling provides new approaches further.
Accompanying drawing explanation
Fig. 1 is present invention process schematic flow sheet.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is further illustrated, but limited the present invention never in any form, and any conversion done based on training centre of the present invention or replacement, all belong to protection scope of the present invention.
The recoverying and utilizing method of ferrophosphorus of the present invention, comprises following concrete steps:
A, add calcium oxide by raw material ferrophosphorus, the mol ratio of the silicon-dioxide in raw material ferrophosphorus and calcium oxide is made to be 1:1 ~ 3, insert in vacuum oven after mixing, compressing tablet, be 10 ~ 30Pa in vacuum tightness, temperature is be incubated 30 ~ 60min under 1200 ~ 1500 DEG C of conditions, be cooled to room temperature, obtain upper strata slag specimen and discard, collect lower floor product a for subsequent use;
B, add nickel powder by lower floor product a, ingredients by weight ratio is: product a: nickel powder=3 ~ 5:1, insert in vacuum oven after mixing, compressing tablet, in stove, pressure is 10 ~ 100Pa, temperature is be incubated 30 ~ 60min under 1000 ~ 1500 DEG C of conditions, be cooled to room temperature, obtain phosphide total content more than 98%, the ferrophosphorus of Si% < 0.07% and the mixture of phosphorus ferronickel.
Described ferrophosphorus is the by product produced in phosphorous chemical industry production process.
Described room temperature is 10 ~ 30 DEG C.
The thickness of the compressing tablet described in step A is 5mm ~ 10mm, and diameter is 25mm.
The thickness of the compressing tablet described in step B is 5mm ~ 15mm, and diameter is 25mm.
With concrete case study on implementation, the present invention will be further described below:
Embodiment 1
Ferrophosphorus raw material desiliconization process: by the silicon (SiO in phosphorous chemical industry by-product ferrophosphorus
2% is 1.53%) and the mol ratio of calcium oxide be 1:1, take 60g phosphorous chemical industry by-product ferrophosphorus and 0.9g calcium oxide (analytical pure), mixing, compressing tablet, puts into vacuum oven, is evacuated to 10Pa ~ 30Pa, be warming up to 1300 DEG C of insulation 30min, be cooled to room temperature, a layer product is taken off in blow-on, is the ferrophosphorus (Fe after desiliconization
2p), the silicon in ferrophosphorus takes off to 0.07%.
Take the ferrophosphorus after 10g desiliconization and 2.5g nickel powder (analytical pure), mixing, compressing tablet, puts into vacuum oven, is evacuated to 10Pa ~ 20Pa, and be warming up to 1100 DEG C of insulation 30min, be cooled to room temperature, (after testing) can obtain ferrophosphorus (Fe
3and phosphorus ferronickel (FeNi P)
2p) mixture, phosphide total content reaches 98.51%, and wherein Si% is 0.066%.
Embodiment 2
Ferrophosphorus raw material desiliconization process: by the silicon (SiO in phosphorous chemical industry by-product ferrophosphorus
2% is 1.53%) and the mol ratio of calcium oxide be 1:1.5, take 60g phosphorous chemical industry by-product ferrophosphorus and 1.3g calcium oxide (analytical pure), mixing, compressing tablet, puts into vacuum oven, is evacuated to 10Pa ~ 40Pa, be warming up to 1300 DEG C of insulation 40min, be cooled to room temperature, a layer product is taken off in blow-on, is the ferrophosphorus (Fe after desiliconization
2p), the silicon in ferrophosphorus takes off to 0.075%.
Take the ferrophosphorus after 60g desiliconization and 15g nickel powder (analytical pure), mixing, compressing tablet, puts into vacuum oven, is evacuated to 10Pa ~ 50Pa, and be warming up to 1200 DEG C of insulation 50min, be cooled to room temperature, (after testing) can obtain ferrophosphorus (Fe
3and phosphorus ferronickel (FeNi P)
2p) mixture, phosphide total content reaches 98.13%, and wherein Si% is 0.065%.
Embodiment 3
Ferrophosphorus raw material desiliconization process: by the silicon (SiO in phosphorous chemical industry by-product ferrophosphorus
2% is 1.53%) and the mol ratio of calcium oxide be 1:2, take 300g phosphorous chemical industry by-product ferrophosphorus and 8.5g calcium oxide (analytical pure), mixing, compressing tablet, puts into vacuum oven, is evacuated to 30Pa ~ 80Pa, be warming up to 1400 DEG C of insulation 60min, be cooled to room temperature, a layer product is taken off in blow-on, is the ferrophosphorus (Fe after desiliconization
2p), the silicon in ferrophosphorus takes off to 0.06%.
Take the ferrophosphorus after 100g desiliconization and 20g nickel powder (analytical pure), mixing, compressing tablet, puts into vacuum oven, is evacuated to 10Pa ~ 80Pa, and be warming up to 1300 DEG C of insulation 60min, be cooled to room temperature, a layer product is taken off in blow-on, can obtain ferrophosphorus (Fe
3and phosphorus ferronickel (FeNi P)
2p) mixture, phosphide total content reaches 98.05%, and wherein Si% is 0.04%.
Embodiment 4
Ferrophosphorus raw material desiliconization process: by the silicon (SiO in phosphorous chemical industry by-product ferrophosphorus
2% is 2.67%) and the mol ratio of calcium oxide be 1:1, take 60g phosphorous chemical industry by-product ferrophosphorus and 1.5g calcium oxide (analytical pure), mixing, compressing tablet, puts into vacuum oven, is evacuated to 10Pa ~ 30Pa, be warming up to 1300 DEG C of insulation 30min, be cooled to room temperature, a layer product is taken off in blow-on, is the ferrophosphorus (Fe after desiliconization
2p), the silicon in ferrophosphorus takes off to 0.069%.
Take the ferrophosphorus after 10g desiliconization and 2.0g nickel powder (analytical pure), mixing, compressing tablet, puts into vacuum oven, is evacuated to 10Pa ~ 30Pa, and be warming up to 1100 DEG C of insulation 60min, be cooled to room temperature, a layer product is taken off in blow-on, can obtain ferrophosphorus (Fe
3and phosphorus ferronickel (FeNi P)
2p) mixture, phosphide total content reaches 98.23%, and wherein Si% is 0.065%.
Embodiment 5
Ferrophosphorus raw material desiliconization process: by the silicon (SiO in phosphorous chemical industry by-product ferrophosphorus
2% is 2.67%) and the mol ratio of calcium oxide be 1:1, take 300g phosphorous chemical industry by-product ferrophosphorus and 7.5g calcium oxide (analytical pure), mixing, compressing tablet, puts into vacuum oven, is evacuated to 30Pa ~ 80Pa, be warming up to 1300 DEG C of insulation 60min, be cooled to room temperature, a layer product is taken off in blow-on, is the ferrophosphorus (Fe after desiliconization
2p), the silicon in ferrophosphorus takes off to 0.072%.
Take the ferrophosphorus after 100g desiliconization and 20g nickel powder (analytical pure), mixing, compressing tablet, puts into vacuum oven, is evacuated to 10Pa ~ 80Pa, and be warming up to 1200 DEG C of insulation 50min, be cooled to room temperature, a layer product is taken off in blow-on, can obtain ferrophosphorus (Fe
3and phosphorus ferronickel (FeNi P)
2p) mixture, phosphide total content reaches 98.09%, and wherein Si% is 0.068%.
Embodiment 6
Ferrophosphorus raw material desiliconization process: by the silicon (SiO in phosphorous chemical industry by-product ferrophosphorus
2% is 2.67%) and the mol ratio of calcium oxide be 1:1.5, take 300g phosphorous chemical industry by-product ferrophosphorus and 11g calcium oxide (analytical pure), mixing, compressing tablet, puts into vacuum oven, is evacuated to 30Pa ~ 80Pa, be warming up to 1400 DEG C of insulation 60min, be cooled to room temperature, a layer product is taken off in blow-on, is the ferrophosphorus (Fe after desiliconization
2p), the silicon in ferrophosphorus takes off to 0.067%.
Take the ferrophosphorus after 100g desiliconization and 33g nickel powder (analytical pure), mixing, compressing tablet, puts into vacuum oven, is evacuated to 10Pa ~ 80Pa, and be warming up to 1200 DEG C of insulation 60min, be cooled to room temperature, a layer product is taken off in blow-on, can obtain ferrophosphorus (Fe
3and phosphorus ferronickel (FeNi P)
2p) mixture, phosphide total content reaches 98.38%, and wherein Si% is 0.049%.
Claims (5)
1. a recoverying and utilizing method for ferrophosphorus, is characterized in that the recoverying and utilizing method of described ferrophosphorus comprises following concrete steps:
A, add calcium oxide by raw material ferrophosphorus, the mol ratio of the silicon-dioxide in raw material ferrophosphorus and calcium oxide is made to be 1:1 ~ 3, insert in vacuum oven after mixing, compressing tablet, be 10 ~ 30Pa in vacuum tightness, temperature is be incubated 30 ~ 60min under 1200 ~ 1500 DEG C of conditions, be cooled to room temperature, obtain upper strata slag specimen and discard, collect lower floor product a for subsequent use;
B, add nickel powder by lower floor product a, ingredients by weight ratio is: product a: nickel powder=3 ~ 5:1, insert in vacuum oven after mixing, compressing tablet, in stove, pressure is 10 ~ 100Pa, temperature is be incubated 30 ~ 60min under 1000 ~ 1500 DEG C of conditions, be cooled to room temperature, obtain phosphide total content more than 98%, the ferrophosphorus of Si% < 0.07% and the mixture of phosphorus ferronickel.
2. the recoverying and utilizing method of ferrophosphorus according to claim 1, is characterized in that described ferrophosphorus is the by product produced in phosphorous chemical industry production process.
3. the recoverying and utilizing method of ferrophosphorus according to claim 1, is characterized in that described room temperature is 10 ~ 30 DEG C.
4. the recoverying and utilizing method of ferrophosphorus according to claim 1, it is characterized in that the thickness of the compressing tablet described in step A is 5mm ~ 10mm, diameter is 25mm.
5. the recoverying and utilizing method of ferrophosphorus according to claim 1, it is characterized in that the thickness of the compressing tablet described in step B is 5mm ~ 15mm, diameter is 25mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510829381.9A CN105399069B (en) | 2015-11-25 | 2015-11-25 | A kind of recoverying and utilizing method of ferrophosphorus |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510829381.9A CN105399069B (en) | 2015-11-25 | 2015-11-25 | A kind of recoverying and utilizing method of ferrophosphorus |
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| CN105399069A true CN105399069A (en) | 2016-03-16 |
| CN105399069B CN105399069B (en) | 2017-06-16 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113023699A (en) * | 2021-04-28 | 2021-06-25 | 贵州福泉川东化工有限公司 | Method for separating and purifying ferrophosphorus and calcium silicate composite waste |
| CN115594158A (en) * | 2022-12-01 | 2023-01-13 | 云南布兰特化工有限公司（Cn） | Method for preparing yellow phosphorus from phosphate by using silicothermic reduction and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1149631A (en) * | 1995-11-03 | 1997-05-14 | 朱培基 | Method for preparing ferro-phosphorus from corundum slag |
| CN102796838A (en) * | 2012-08-27 | 2012-11-28 | 黄靖元 | Method for producing pig iron and phosphate using ferro-phosphorus |
| CN104293989A (en) * | 2013-07-17 | 2015-01-21 | 郑州汇金炉料有限公司焦作分公司 | Method for recycling phosphorus iron scraps |
-
2015
- 2015-11-25 CN CN201510829381.9A patent/CN105399069B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1149631A (en) * | 1995-11-03 | 1997-05-14 | 朱培基 | Method for preparing ferro-phosphorus from corundum slag |
| CN102796838A (en) * | 2012-08-27 | 2012-11-28 | 黄靖元 | Method for producing pig iron and phosphate using ferro-phosphorus |
| CN104293989A (en) * | 2013-07-17 | 2015-01-21 | 郑州汇金炉料有限公司焦作分公司 | Method for recycling phosphorus iron scraps |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113023699A (en) * | 2021-04-28 | 2021-06-25 | 贵州福泉川东化工有限公司 | Method for separating and purifying ferrophosphorus and calcium silicate composite waste |
| CN115594158A (en) * | 2022-12-01 | 2023-01-13 | 云南布兰特化工有限公司（Cn） | Method for preparing yellow phosphorus from phosphate by using silicothermic reduction and application |
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| CN105399069B (en) | 2017-06-16 |
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