CN115637339B - Production process for extracting phosphorus product and rare earth product from monazite rare earth ore - Google Patents
Production process for extracting phosphorus product and rare earth product from monazite rare earth ore Download PDFInfo
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- CN115637339B CN115637339B CN202211024991.8A CN202211024991A CN115637339B CN 115637339 B CN115637339 B CN 115637339B CN 202211024991 A CN202211024991 A CN 202211024991A CN 115637339 B CN115637339 B CN 115637339B
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 113
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 75
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 64
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000011574 phosphorus Substances 0.000 title claims abstract description 63
- 229910052590 monazite Inorganic materials 0.000 title claims abstract description 40
- -1 monazite rare earth Chemical class 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000003723 Smelting Methods 0.000 claims abstract description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000011084 recovery Methods 0.000 claims abstract description 15
- 238000010298 pulverizing process Methods 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 40
- 239000000843 powder Substances 0.000 claims description 38
- 239000000047 product Substances 0.000 claims description 35
- 239000007789 gas Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 25
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 20
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 18
- 239000011707 mineral Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 239000000853 adhesive Substances 0.000 claims description 13
- 230000001070 adhesive effect Effects 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000003801 milling Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 238000005453 pelletization Methods 0.000 abstract description 6
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 29
- 238000004090 dissolution Methods 0.000 description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920002261 Corn starch Polymers 0.000 description 5
- 239000008120 corn starch Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 3
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 241001062472 Stokellia anisodon Species 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 2
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 240000002234 Allium sativum Species 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000004611 garlic Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a production process for extracting phosphorus products and rare earth products from monazite rare earth ores, which comprises the steps of proportioning, pelletizing, putting spherical materials into a high-temperature smelting furnace for high-temperature smelting to obtain smelted ores, pulverizing the smelted ores, heating, washing with water to prepare acid, dissolving rare earth acid, concentrating phosphoric acid solution and the like, so that the preparation of the rare earth products and the recovery of the phosphorus products are realized, the rare earth yield is high, the economic benefit is good, and the problem of high wastewater treatment cost in the traditional alkali-to-decomposition production process can be avoided.
Description
Technical Field
The invention relates to the technical field of rare earth, in particular to a production process for extracting a phosphorus product and a rare earth product from monazite rare earth ores.
Background
The existing production process for decomposing and extracting rare earth from monazite rare earth ore mainly comprises the steps that in the reaction process of alkali method (sodium hydroxide to alkali) monazite rare earth ore and liquid alkali, rare earth generates water-insoluble rare earth hydroxide, phosphorus is prepared into trisodium phosphate, and the rare earth hydroxide is subjected to optimal dissolution by hydrochloric acid to obtain rare earth chloride.
The alkali-converting and decomposing process of the monazite rare earth ore produces a large amount of industrial alkali water, if the waste water is not treated, serious environmental pollution is caused, the waste water is recycled and treated by various enterprises at present due to environmental protection, the cost of water treatment is high, certain economic loss is brought to the enterprises, the rare earth yield of the alkali-converting and decomposing process of the monazite rare earth ore is less than 94%, and the rare earth loss causes resource waste.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a production process for extracting phosphorus products and rare earth products from monazite rare earth ores, can avoid the problems of large industrial alkali consumption and high wastewater treatment cost in the traditional alkali-to-decomposition production process, has high rare earth yield, can recover phosphorus in the monazite ores while preparing the rare earth products from the monazite ores, and improves economic benefits.
The aim of the invention is realized by the following technical scheme:
a production process for extracting phosphorus products and rare earth products from monazite rare earth ores comprises the following steps:
A. and (3) batching: mixing and proportioning the ground carbon powder and monazite ore, wherein the mass ratio of phosphorus in the monazite ore is as follows: carbon powder=1:0.5-3;
B. ball making: adding a ball-making adhesive into the mixed material prepared in the step A, uniformly mixing, and pressing into balls by a ball machine to obtain a ball-shaped material; the ball-making adhesive accounts for 3-5% of the total mass after mixing;
C. high-temperature smelting: b, placing the spherical material prepared in the step B into a high-temperature smelting furnace for smelting, wherein the smelting temperature is more than 1400 ℃, the smelting time is more than 1 hour, in the smelting process, generating tail gas, entering a tail gas recovery system, and pouring the spherical material subjected to high-temperature smelting out of the furnace after smelting to obtain smelted ores;
D. pulverizing: cooling, crushing and pulverizing the smelting ore to obtain smelting ore powder;
E. rare earth is extracted.
The monazite rare earth ore is smelted at high temperature, and an open smelting furnace is adopted in the smelting process; in the high-temperature smelting process, phosphorus in the monazite rare earth ore is reduced into elemental phosphorus by carbon, most of the elemental phosphorus contacts with oxygen in air, phosphorus pentoxide gas is generated by combustion, and the phosphorus pentoxide gas and a small amount of unreacted elemental phosphorus gas enter a tail gas recovery system for tail gas recovery.
In a specific embodiment of this solution, the step E specifically includes Ea1, ea2, ea3:
ea1, heating: heating the smelting mineral powder in a heating furnace to perform phosphorus conversion, so that elemental phosphorus remained in the mineral powder and oxygen in air are combined to form phosphorus pentoxide, and the temperature in the heating furnace is 41-200 ℃ in the heating process;
ea2, washing with water to prepare acid: adding the heated smelting mineral powder into a washing tank, adding hot water, and performing pentoxide treatment
The phosphorus reacts with hot water to form phosphoric acid, and a phosphoric acid solution and a rare earth filter cake are obtained through plate-frame filter pressing;
ea3, rare earth acid dissolution: and (3) putting the rare earth filter cake into a dissolving tank, adding hydrochloric acid for dissolving, stirring, and filtering to obtain rare earth chloride solution and filter residues. The filter residues are waste residues and are piled up uniformly.
Further, the hot water temperature in the step Ea2 is greater than 70 ℃.
The reaction equation of step Ea1 is
4P+5O2＝2P2O5；
The reaction equation of step Ea2 is
P2o5+3h2o=2h3po4 (hot water).
In a specific embodiment of this solution, the step E specifically includes Eb1, eb2, eb3:
eb1, rare earth alkaline washing: adding potassium hydroxide or sodium hydroxide solution into an alkali rotating tank, starting stirring, slowly adding smelting mineral powder, stirring, and filtering to obtain rare earth ore cakes;
eb2, washing: washing the rare earth ore cake with water to neutrality to obtain a neutral rare earth ore cake;
eb3, rare earth acid dissolution: adding hydrochloric acid with the mass concentration of 30% into an acid dissolving tank, then adding water, wherein the volume ratio of the hydrochloric acid to the water is 3:1, adding neutral rare earth ore cakes, stirring for 30-50 minutes, and filtering to obtain a rare earth chloride solution and filter residues. The filter residues are waste residues and are piled up uniformly.
Step Eb2 washes the rare earth ore cake, so that the rare earth ore cake is washed to be neutral, and the use amount of hydrochloric acid in the subsequent rare earth acid dissolution step is reduced.
In a specific embodiment of this solution, the step E specifically includes:
adding hydrochloric acid with the mass concentration of 30% into an acid dissolving tank, then adding water, wherein the volume ratio of the hydrochloric acid to the water is 3:1, starting stirring, slowly adding smelting mineral powder, and filtering to obtain rare earth chloride solution and filter residues. The filter residues are waste residues and are piled up uniformly.
Further preferably, in the step D, the pulverizing temperature does not exceed 40 ℃.
The powder-making temperature is controlled by inert gas protection or other modes, so that the powder-making temperature is not higher than 40 ℃ to avoid spontaneous combustion of the phosphorus element in the powder-making process.
Further preferably, the tail gas recovery system in the step C is provided with a hot water spray tower. And (3) the tail gas enters a hot water spray tower and is absorbed by hot water to obtain phosphoric acid solution and yellow phosphorus products.
Oxygen in the air during the phosphorus combustion is combined into phosphorus pentoxide gas, and the phosphorus pentoxide can be sprayed by hot water or dilute phosphoric acid in an exhaust gas recovery system and then is continuously enriched to form a phosphoric acid product; and spraying by adopting a hot water spray tower, wherein the hot water can absorb phosphorus pentoxide in the tail gas to produce a phosphoric acid product, and the elemental phosphorus in the tail gas is sprayed by the hot water to obtain liquid yellow phosphorus, wherein the liquid yellow phosphorus is insoluble in water, so that a phosphoric acid solution and a yellow phosphorus product can be obtained by subsequent separation.
Further preferably, in the step a, the particle size of the carbon powder is 1 to 200 mesh.
Still more preferably, in the step B, the powder particle size is 200 to 400 mesh.
Optionally, the adhesive is an organic adhesive. The binder can bind the powder, particulate matter into a unitary mass.
Alternatively, the organic binder is corn starch.
Further preferably, the high-temperature melting temperature is 1600 to 2600 ℃.
The beneficial effects of the invention are as follows: (1) According to the scheme, rare earth smelting ores are obtained through the modes of proportioning, pelletizing and high-temperature smelting, then rare earth products are obtained through subsequent steps, the rare earth yield of the optimized process can reach 98%, the process flow is simple, the economic benefit is high, and meanwhile, 70-80% of phosphorus in the monazite rare earth ores can be recovered through the tail gas recovery system, so that the recovery of phosphorus resources is realized, and the economic benefit of the process is greatly improved;
(2) In the scheme, 20-30% of phosphorus is remained in a smelted ore after smelting at a high temperature, and in the preferred scheme, hot water is adopted to react with the part of phosphorus after heating and conversion to obtain a phosphoric acid solution and a rare earth filter cake, and the phosphoric acid solution is concentrated to obtain a phosphoric acid product with high content, so that the recovery of phosphorus resources is further realized, and the economic benefit is improved;
(3) The rare earth is prepared by adopting a high-temperature smelting mode, so that a large amount of industrial alkaline water generated by the traditional alkaline-to-decomposing production process is avoided, and environmental pollution caused by a large amount of industrial alkaline water is avoided, thereby reducing the wastewater treatment cost.
Drawings
FIG. 1 is a process flow diagram of example 1.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to the accompanying drawings, but the scope of the present invention is not limited to the following description.
Example 1
The production process for extracting the phosphorus product and the rare earth product from the monazite rare earth ore comprises the following steps:
s1, proportioning: mixing and proportioning ground carbon powder with 1-200 meshes and monazite ore, wherein the mass ratio of phosphorus in the monazite ore is as follows: carbon powder = 1:2;
s2, ball making: adding a ball-making adhesive corn starch into the mixed material prepared in the step A, uniformly mixing, and pressing into balls by a ball machine to obtain a ball-shaped material; wherein, the adding amount of the corn starch is 3% of the total mass after mixing;
s3, high-temperature smelting: b, placing the spherical material prepared in the step B into a high-temperature smelting furnace for smelting, wherein the smelting temperature is 1600 ℃, the smelting time is 3 hours, pouring the spherical material out of the furnace after high-temperature smelting to obtain a smelting ore, and enabling tail gas generated in the smelting process to enter a tail gas recovery system through a pipeline;
s4, pulverizing: cooling, crushing and pulverizing the smelting ore to obtain smelting ore powder; wherein, the powder preparation granularity is 200-400 meshes, the powder preparation process is carried out under the inert gas environment, and the powder preparation temperature is not more than 40 ℃;
s5, heating: heating the smelting mineral powder in a heating furnace to perform phosphorus conversion, so that elemental phosphorus remained in the mineral powder and oxygen in air are combined to form phosphorus pentoxide, and the temperature in the heating furnace is 41-200 ℃ in the heating process;
s6, washing with water to prepare acid: adding the heated smelting mineral powder into a washing tank, adding hot water at 75 ℃, reacting phosphorus pentoxide in the ore with the hot water to form phosphoric acid, and carrying out plate-frame filter pressing to obtain a phosphoric acid solution and a rare earth filter cake;
s7, rare earth acid dissolution: putting the rare earth filter cake into a dissolving tank, adding hydrochloric acid for dissolving, stirring, and filtering to obtain rare earth chloride solution and filter residues;
and S8, concentrating the phosphoric acid solution obtained in the step S6 to obtain a high-content phosphoric acid product.
Further, in the present embodiment, the exhaust gas recovery system is provided with a hot water spray tower.
In the embodiment, the rare earth leaching rate of the rare earth chloride solution obtained in the step S7 is calculated to be 98.18%; and uniformly stacking the filter residues.
The process flow route of this embodiment is shown in fig. 1.
Example 2
The difference between this example and example 1 is only that in step S1, the mass ratio of phosphorus in the monazite ore of this example: carbon powder=1:0.5.
The rare earth leaching rate of the rare earth chloride solution prepared by the embodiment is 94.3 percent.
Example 3
The difference between this example and example 1 is only that in step S1, the mass ratio of phosphorus in the monazite ore of this example: carbon powder = 1:3.
In this embodiment, the rare earth leaching rate of the rare earth chloride solution obtained in the step S7 is calculated to be 98.1%.
Example 4
The production process for extracting the phosphorus product and the rare earth product from the monazite rare earth ore comprises the following steps:
s1, mixing and proportioning finely ground carbon powder (1-200 meshes) and monazite ore, wherein the mass ratio of phosphorus in the monazite ore is as follows: carbon powder = 1:2;
s2, pelletizing, namely adding a pelletizing adhesive into the mixed material prepared in the step S1, wherein the adhesive is corn starch, uniformly mixing, and then pressing into pellets by a pelletizer, wherein the mass of the added adhesive is 3% of the total mass after mixing;
s3, high-temperature smelting, namely putting the spherical material prepared in the step S2 into a high-temperature smelting furnace to smelt, wherein the smelting temperature is 1600 ℃, the smelting time is 3 hours, phosphorus in monazite rare earth ore is reduced into elemental phosphorus by carbon and is combusted to generate phosphorus gas, and the phosphorus gas enters a tail gas recovery system, and pouring out the spherical material after high-temperature smelting to obtain smelted ore;
s4, milling, namely cooling, crushing and milling the smelting ore to obtain smelting ore powder, wherein the milling granularity is 200-400 meshes, the milling process is carried out in an inert gas environment, and the milling temperature is not more than 40 ℃;
s5, after smelting ore to prepare powder, adding hydrochloric acid with the mass concentration of 30% into an acid dissolving tank, adding water, wherein the ratio of the hydrochloric acid to the water is 3:1 (volume ratio), starting stirring, slowly adding the smelting ore powder, and at the moment, a fire phenomenon, namely that a large number of fires are generated on the surface of liquid, stirring for 30 minutes, and filtering to obtain a rare earth chloride solution.
The ignition phenomenon in the step S5 is caused by that elemental phosphorus in mineral powder encounters chlorine in hydrochloric acid to generate phosphorus chloride, and the phenomenon is that the higher the acidity is, the faster the charging is, the more fires are, and conversely, the lower the acidity is, the slower the charging is, and the fewer fires are.
The reaction equation of phosphorus with chlorine:
when a small amount of chlorine is used:
2p+3cl2=2pcl3 (conditional ignition)
When a large amount of chlorine gas is generated:
2p+5cl2=2pcl5 (conditional ignition)
Phosphorus chloride is a toxic substance.
The rare earth chloride solution is obtained in the embodiment, the rare earth leaching rate is calculated to be 96.5%, and the filter residues are uniformly stacked.
The rare earth leaching rate of the production process route of the embodiment can meet the production process requirement, but toxic phosphorus chloride can be generated in the actual operation process, so that the scheme cannot be used for large-scale production, and the environment pollution and the physical damage to operators are caused.
Example 5
The production process for extracting the phosphorus product and the rare earth product from the monazite rare earth ore comprises the following steps:
s1, mixing and proportioning finely ground carbon powder (1-200 meshes) and monazite ore, wherein the mass ratio of phosphorus in the monazite ore is as follows: carbon powder = 1:2;
s2, pelletizing, namely adding a pelletizing adhesive into the mixed material prepared in the step S1, wherein the adhesive is corn starch, the mass of the added adhesive is 3% of the total mass, and uniformly mixing and then pressing into pellets by a pelletizer;
s3, high-temperature smelting, namely putting the spherical material prepared in the step S2 into a high-temperature smelting furnace to smelt, wherein the smelting temperature is 1600 ℃, the smelting time is 3 hours, phosphorus in monazite rare earth ore is reduced into elemental phosphorus by carbon and is combusted to generate phosphorus gas, and the phosphorus gas enters a tail gas recovery system, and pouring out the spherical material after high-temperature smelting to obtain smelted ore;
s4, pulverizing: cooling, crushing and pulverizing the smelting ore to obtain smelting ore powder, wherein the pulverizing granularity is 200-400 meshes, the pulverizing process is carried out in an inert gas environment, and the pulverizing temperature is not more than 40 ℃;
s5, rare earth alkali washing: after smelting ore is prepared into powder, adding potassium hydroxide solution into an alkali rotating tank, starting stirring, slowly adding 20g of smelting ore powder, and reacting phosphorus in the smelting ore powder with potassium hydroxide to generate potassium hypophosphite and phosphine gas; the reaction equation:
3KOH+4P+3H2O＝3KH2PO2+PH3↑
phosphine (PH 3) gas is colorless and extremely toxic.
Stirring for 1 hour, filtering, wherein the liquid is potassium hypophosphite, and the solid is rare earth ore cakes;
volatilizing a smell of garlic in the process of stirring and ore feeding;
s6, washing: washing the rare earth ore cake with water to neutrality to obtain a neutral rare earth ore cake;
s6, rare earth acid dissolution: adding hydrochloric acid with the mass concentration of 30% into an acid dissolving tank, adding water, wherein the ratio of the hydrochloric acid to the water is 3:1 (volume ratio), adding neutral rare earth ore cakes, stirring for 30 minutes, filtering to obtain 250ml of rare earth chloride solution, uniformly stacking filter residues which are waste residues, and calculating the leaching rate of the rare earth to be 95.3%.
The production process route of the example cannot be used in actual production, firstly, the production of highly toxic phosphine gas, and secondly, the dephosphorization with potassium hydroxide produces a large amount of alkaline water.
In this example, 50ml of pure water was measured in a measuring cylinder, and 63g of KOH was added to prepare a saturated solution (30 ℃ C.).
Experimental example 1
Experiment for roasting monazite smelting mineral powder
(1) Taking 100g of the smelting ore prepared in the step S3 of the example 1, grinding the blocky smelting ore into powder to obtain 300-mesh smelting ore powder, and dividing the 300-mesh smelting ore powder into two 50g samples, wherein the samples are numbered as a baked raw ore A and a baked raw ore B;
(2) Placing 50g of baked raw ore B in an open crucible, placing in a muffle furnace for low-temperature roasting, and setting the temperature to 170 ℃; the temperature in the furnace is not increased after the temperature is increased from 28 ℃ to 200 ℃ (about 15 minutes), the electric heating switch is turned off, and the electric heating switch is taken out the next day to obtain smelted ores roasted at low temperature, and the smelted ores are marked as a roasted product B';
sending the sample to analysis room for detection (TREO, F, P and distribution), and the detection results are shown in Table 1;
appearance: the color gray of the smelted ore after low-temperature roasting is yellow, and the smelted ore is slightly yellow compared with a sample (gray) burnt at 50 ℃.
TABLE 1 detection results
Acid dissolution test (to detect whether flame is generated): firstly adding hydrochloric acid and water, then heating, and then adding a roasting product B', wherein no flame phenomenon is generated in the feeding process, which indicates that the elemental phosphorus is converted into phosphorus oxide;
conclusion of experiment: the monazite smelted ore is roasted at low temperature, the phosphorus content of the front and rear samples is basically unchanged, the smelted ore is roasted again by heating, only the elemental phosphorus coated by impurities of the smelted ore is combusted to produce phosphorus oxide, the phosphorus is not volatilized into the air in a gaseous state, and the phosphorus in the smelted ore powder can be recovered by adopting hot water washing.
Experimental example 2
Heating experiment of smelting mineral powder:
the steps are as follows: 25g of the powdered smelting mineral powder ground in the step S4 of the example 1 is placed in an open crucible, the temperature is set to be 50 ℃, and the heating is stopped when the time is 13:22; the temperature change process is as in table 2:
table 2 temperature change table
Analysis:
appearance: the color of the roasted smelting ore is hardly changed to be grey, and the temperature is naturally increased from 50 ℃ to 122 ℃ because the process of converting elemental phosphorus into phosphorus oxide is a combustion exothermic process in the heating process.
Smelting ore acid dissolution experiment:
taking 20g of the heated smelting ore in the experimental example, washing with hot water at 75 ℃, and filtering to obtain smelting ore filter residues; then adding 100ml of hydrochloric acid and a proper amount of H2O into the slag of the smelting ore, reacting for 30min at the temperature t of more than 95 ℃, and vacuum filtering to obtain an acid solution and acid solution slag;
volume of acid solution V:482ml;
acid solution: rare earth liquid concentration C:26.89g/l- -modified by CeO2 partition: 28.25g/l;
H+：1.17N；
F：94mg/l；
P：6mg/l；
acid sludge (oven dried) weight G:5.5g;
acid solution slag: TREO:7.28% - -modified by CeO 2: 7.99%;
F：1931ppm；
P：120ppm
the rare earth yield after acid dissolution is calculated as follows: 98.2%.
Conclusion of experiment: the sum of the P content in the acid slag and the acid solution is obviously smaller than the P content in the smelted raw ore A detected in the experimental example 1, which shows that the hot water can extract the P in the smelted ore after heating to obtain a phosphoric acid product.
In the invention, the rare earth acid dissolution adopts a low-concentration or high-concentration hydrochloric acid solution, because the concentration of the hydrochloric acid is only related to the extraction rate of the rare earth, and the higher the concentration is, the shorter the extraction time is.
In the heating step, the smelting mineral powder is heated in a heating furnace to perform phosphorus conversion, the temperature in the heating furnace is between 41 and 200 ℃, and the upper limit of the temperature is 200 ℃ which is a preferable temperature value so as to meet the requirement of saving energy.
The foregoing is merely a preferred embodiment of the invention, and it is to be understood that the invention is not limited to the form disclosed herein but is not to be construed as excluding other embodiments, but is capable of numerous other combinations, modifications and environments and is capable of modifications within the scope of the inventive concept, either as taught or as a matter of routine skill or knowledge in the relevant art. And that modifications and variations which do not depart from the spirit and scope of the invention are intended to be within the scope of the appended claims.
Claims (7)
1. The production process for extracting the phosphorus product and the rare earth product from the monazite rare earth ore is characterized by comprising the following steps of:
A. proportioning materials
Mixing and proportioning the ground carbon powder and monazite ore, wherein the mass ratio of phosphorus in the monazite ore is as follows: carbon powder=1:0.5-3;
B. ball making
Adding a ball-making adhesive into the mixed material prepared in the step A, uniformly mixing, and pressing into balls by a ball machine to obtain a ball-shaped material; the ball-making adhesive accounts for 3% -5% of the total mass after mixing;
C. high temperature smelting
B, placing the spherical material prepared in the step B into a high-temperature smelting furnace for smelting, wherein the smelting temperature is more than 1400 ℃, the smelting time is more than 1 hour, in the smelting process, generating tail gas, entering a tail gas recovery system, and pouring the spherical material subjected to high-temperature smelting out of the furnace after smelting to obtain smelted ores;
D. pulverizing into powder
Cooling, crushing and pulverizing the smelting ore to obtain smelting ore powder;
E. extracting rare earth;
the step E specifically comprises Ea1, ea2 and Ea3:
ea1, heating
Heating the smelting mineral powder in a heating furnace to perform phosphorus conversion, so that elemental phosphorus remained in the mineral powder and oxygen in air are combined to form phosphorus pentoxide, and the temperature in the heating furnace is 41-200 ℃ in the heating process;
ea2, washing with water to prepare acid
Adding the heated smelting mineral powder into a washing tank, adding hot water, reacting phosphorus pentoxide in the mineral with the hot water to form phosphoric acid, and carrying out plate-frame filter pressing to obtain a phosphoric acid solution and a rare earth filter cake;
ea3, rare earth acid-soluble
Putting the rare earth filter cake into a dissolving tank, adding hydrochloric acid for dissolving, stirring, and filtering to obtain rare earth chloride solution and filter residues; or (b)
The step E specifically comprises Eb1, eb2 and Eb3:
eb1, rare earth alkali washing
Adding potassium hydroxide or sodium hydroxide solution into an alkali rotating tank, starting stirring, slowly adding smelting mineral powder, stirring, and filtering to obtain rare earth ore cakes;
eb2, washing with water
Washing the rare earth ore cake with water to neutrality to obtain a neutral rare earth ore cake;
eb3, rare earth acid-soluble
Adding hydrochloric acid with the mass concentration of 30% into an acid dissolving tank, then adding water, wherein the volume ratio of the hydrochloric acid to the water is 3:1, adding neutral rare earth ore cakes, stirring for 30-50 minutes, and filtering to obtain a rare earth chloride solution and filter residues.
2. The process for extracting phosphorus and rare earth products from monazite rare earth ores according to claim 1, wherein the hot water temperature in step Ea2 is greater than 70 ℃.
3. A process for the extraction of phosphorus and rare earth products from rare earth ores of monazite according to any one of claims 1 or 2, wherein in step D, the milling temperature is not higher than 40 ℃.
4. A process for extracting phosphorus and rare earth products from rare earth ores as claimed in any one of claims 1 or 2, wherein the tail gas recovery system in step C is provided with a hot water spray tower.
5. The process for extracting phosphorus products and rare earth products from monazite rare earth ores according to any one of claims 1 or 2, wherein in the step a, the granularity of carbon powder is 1-200 meshes.
6. The process for extracting phosphorus products and rare earth products from monazite rare earth ores according to any one of claims 1 or 2, wherein in the step B, the powder preparation granularity is 200-400 meshes.
7. A process for the extraction of phosphorus and rare earth products from monazite rare earth ores according to any one of claims 1 or 2, wherein the binder is an organic binder.
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