CN105329865B

CN105329865B - A kind of method and preparation process preparing yellow phosphorus using low-grade phosphate ore

Info

Publication number: CN105329865B
Application number: CN201510677012.2A
Authority: CN
Inventors: 罗宗恬
Original assignee: CHENGDU LESHI CHEMICAL ENGINEERING Co Ltd
Current assignee: Chengdu Tianyu new phosphorus Technology Co., Ltd.
Priority date: 2015-07-30
Filing date: 2015-10-16
Publication date: 2018-08-17
Anticipated expiration: 2035-10-16
Also published as: CN105329865A

Abstract

The present invention relates to a kind of methods preparing yellow phosphorus using low-grade phosphate ore, it is characterized in that, Silicon-rich or poor silicon measure selectively being taken for different phosphorus ores in the mining stage and removing iron containing compounds in crushing stage to obtain the ground phosphate rock of suitable silicon, low iron, the mode of the phosphorus ore pelletizing by way of drying, calcining or direct flotation or reverse flotation and after drying, consolidation balling-up carries out first time enrichment P respectively₂O₅With second of enrichment P₂O₅.The preparation method of the present invention is at low cost, it is efficient, environmentally friendly, improve yellow phosphorus quality, and efficiently solve knot arch, accidents or the failure such as the material that collapses, broken Electrode, ensure that electric furnace is safe and stable, efficiently runs.

Description

A kind of method and preparation process preparing yellow phosphorus using low-grade phosphate ore

Technical field

The present invention relates to yellow phosphorus preparation field more particularly to a kind of methods and cycle preparing yellow phosphorus using low-grade phosphate ore Preparation process, this method and cycle preparation process are specially the total solution that electrothermal way prepares the environmental protection of yellow phosphorus.

Background technology

200.16 hundred million tons of phosphorus ore reserves have been verified in China, and 90% or more is low-grade phosphate ore, and rich phosphorus ore is less than 8%.Nearly ten Since phosphate chemical industry development is rapid over year, phosphorus ore grade constantly declines.Although production of phosphate fertilizer is solved by ore dressing and is asked with mine Topic, but yellow phosphorus is constantly reduced with mine grade, and the material consumption of phosphorus production, energy consumption, production cost are continuously increased, and become long-standing problem Huang The a great problem of phosphorus enterprise.

Chinese yellow phosphorus manufacturing enterprise is for many years in order to save energy consumption, reduce production cost, and phosphorus ore raw material used is with rich ore Based on (P₂O₅Mass fraction >=28%).Through exhaustive exploitation for many years, there is not much left for rich ore, it is difficult to ensure that phosphorus production needs.It is special The serious is do not adopt block and abandon powder, adopt richness and abandon poor, a large amount of low-grade phosphate ore resource is caused to be unable to get the utilization of science, resource It destroys serious.

Now most phosphorus production enterprise due to raw material grade it is too low, cause high energy consumption, material consumption high.With 10000 tons/year of yellow phosphorus Process units calculates, and year, the direct losses amount of money was up to 10,000,000 yuan or more.

With the development of technique of preparing, the great attention that especially country develops and uses phosphor resource, low-grade phosphate ore is Positive (anti-) floatation process is largely used to carry out flotation.The special ground phosphate rock P of gained yellow phosphorus₂O₅Average grade reaches 30% or more (such as needle Yellow phosphorus enterprise is needed, can be less than 30%), SiO₂It is also enriched with simultaneously.But be directed to phosphorus production feature, need to fit silicon, low iron, The special ground phosphate rock of yellow phosphorus of low-carbon does not draw attention.

The special ground phosphate rock electrothermal way of yellow phosphorus prepares yellow phosphorus there are more technical barrier, and main cause is the special phosphorus ore of yellow phosphorus Powder diameter is thin, and the organic binder (such as sodium humate) of a large amount of use cost costlinesses of other pellets on the market, though it can protect It demonstrate,proves feedstock transportation to need, but after entering yellow phosphorus electric furnace, because the carburizing temperature of organic binder is low, does not arrive yellow phosphorus electric furnace reaction Qu Shi, organic binder have just been carbonized, and the special ground phosphate rock pelletizing of yellow phosphorus, that is, a large amount of dusting, the special ground phosphate rock of yellow phosphorus can be with yellow phosphorus Furnace gas enters yellow phosphorus-refined system, and mud phosphorus amount is caused to increase, and phosphorous recovery reduces, and increases yellow phosphorus-refined difficulty and is refined into This, causes yellow phosphorus special ground phosphate rock waste, at the same also cause material in yellow phosphorus electric furnace, pressure it is unstable.In addition, using silicic acid The general inorganic binders such as sodium, sodium fundamental mode bentonite roast after balling-up through the dry and long period, though it can guarantee that feedstock transportation needs It wants, but due to binder itself NaO, Al₂O₃Etc. harmful components bring into, molten condition furnace charge viscosity increases, and phosphorus stove is caused to be slagged tap Yellow phosphorus-refined system can be entered with furnace gas by reacting the prodan of generation in difficulty, especially yellow phosphorus electric furnace under the condition of high temperature, no Only increase yellow phosphorus-refined difficulty and refined cost, will also seriously affect yellow phosphorus quality.

In addition, the adjustment of yellow phosphorus electric furnace operating parameter, there is also many problems.Yunnan of China yellow phosphorus main producing region, Guizhou, The many enterprises in Sichuan, it is existing using nut coke, also have using anthracite, also have using semi-coke, using coking coal powder, semi-coke powder and The enterprise of anthracite powder is seldom.Yellow phosphorus electric furnace enters stove material moisture, dusting amount controls bad, slag acidity, clinker residual P₂O₅Control It is extensive, knot arch, the material that collapses, the accident of broken Electrode, Frequent Troubles.Also waste gas utilization rate is low, the SiF in tail gas₄It is mostly directly outer Row, environmental pollution are very big.Furthermore the mud phosphorus of phosphorus production Main By product, generally all with turn pot receive phosphorus or directly burn mud phosphoric acid. But residue is not utilized, and directly works as waste dumps, also results in many environmental pollutions.Due to the continuous expansion of phosphorus production scale Greatly, the yield of ferrophosphorus is also increasing, and the market demand is limited, wherein rich in 18%~26% phosphorus, how to be visited using also worth Rope.

Chinese patent CN 1911790A disclose a kind of method of preparing yellow phosphorus from phosphate rock, and specifically disclose with Lower feature：It is P with grade₂O₅>=17% rock phosphate in powder is raw material, and the silica and raw material weight of the 15-22% of raw material weight is added 15-18% carbonaceous reductant, grind the mixture for 0.01-0.5mm after mixing, the 1- of mixture weight be added The coal of 5% water or/and the 10-14% of caking index >=45 is pressed into the agglomerate of a diameter of 10-50mm after remixing uniformly, It is placed in vacuum drying oven, is evacuated to 10-200Pa, begin to warm up and be warming up to 200-400 DEG C, keep the temperature 20-60 minutes, be sintered, It is continuously heating to 900-1500 DEG C later, keeps the temperature 60 to 120 minutes, extracts, the yellow phosphorus steam of generation is laggard through filter Enter water-cooling device, finished product industry grade yellow phosphorus.The invention proposes solution for low-grade phosphate ore so that low-grade phosphorus Mine is utilized on preparing yellow phosphorus, while reducing production cost to a certain extent, and the invention prepares yellow phosphorus generation Tail gas concentrate it is disposable, compared to burning be vented, it is more environmentally-friendly.But the invention does not prepare yellow phosphorus to low-grade phosphate ore Carry out more deep discussion, it is urgently to be resolved hurrily using low-grade phosphate ore to still have many technical problems in actual conditions：

(1) low-grade phosphate ore and concentrate difference, it comprises more impurity, although can be by floatation process to low product Position phosphorus ore carries out enrichment, reduces a part of impurity, but effect is not obvious, in preparation process energy consumption and material consumption still occupy It is high not under, this is because in phosphorus ore caused by various impurity.Moreover, different phosphorus ores prepare its material proportion for using of yellow phosphorus and Environmental parameter is also to be not quite similar, and general preparation method specific aim is not strong, ineffective.

(2) ground phosphate rock balling-up is to prepare the important link of yellow phosphorus process, how both to have ensured that ball-formation quality was good, is not pulverized easily, Can be also again simultaneously this field urgent problem to be solved to avoid bringing into for harmful components in binder；

(3) electric furnace operating parameter is also the big factor of influence yellow phosphorus preparation process not only influences yellow phosphorus if control is bad Yield, by-product cannot efficiently use and then generate environmental issue, and be easy to cause the accidents such as knot arch, the material that collapses, broken Electrode Occur.

(4) by-product how is efficiently used, accomplishes zero-emission as possible, it is also trend of the times to improve environmental protection and economy benefit.

Therefore, be badly in need of it is a kind of for low-grade phosphate ore prepare the slave phosphorus ore source of yellow phosphorus, material proportion, furnace parameter and The solution of the system of by-product recovery processing, it is a kind of while having both at low cost, efficient, environmentally friendly solution.

Invention content

For the deficiency of the prior art, of the invention provides the technical solution that yellow phosphorus is prepared with low-grade phosphate ore, tool Body design is：

1, since phosphorus ore source, the component for being unfavorable for phosphorus production is reduced, removes iron, removes MgCO₃、CaCO₃And organic matter, Remove extra SiO₂, first time enrichment P₂O₅Prepare the special ground phosphate rock of yellow phosphorus.High-carbon hydrochlorate, high organic type phosphorus ore are used Yellow phosphoric tail gas or other fuel dryers, calcining, rapidly remove CO₂And organic matter, first time enrichment P₂O₅Prepare the special phosphorus ore of yellow phosphorus Powder.For the carbonate-type phosphorus ore of content of MgO >=5%, with enrichment P of reverse flotation₂O₅Prepare the special ground phosphate rock of yellow phosphorus.To silicon Hydrochlorate type phosphorus ore, extra SiO is removed with direct flotation₂, first time enrichment P₂O₅Prepare the special ground phosphate rock of yellow phosphorus.

2, the special ground phosphate rock of yellow phosphorus after first time enrichment is added modified raw phosphoric acid binder and carries out second of enrichment, It is pressed into pelletizing after infiltration, then is matched through drying, consolidation, and by phosphorus production, supplying carbon (carbon dust) and silica (silica flour) are sent Enter yellow phosphorus electric furnace production yellow phosphorus.Different characteristics of the present invention according to various regions phosphorus ore, by the special phosphorus ore of yellow phosphorus after first time enrichment After dried bean noodles is dry, balling-up is carried out after adding modified raw phosphoric acid binder infiltration, the effect of secondary enrichment has not only been played but also has had binder Effect.Alternatively, by being pressed into phosphorus ore pelletizing after binder infiltration to the special ground phosphate rock of yellow phosphorus after first time enrichment, And second of enrichment is carried out by way of drying, consolidation, second of enrichment at this time is appreciated that solidification enrichment, that is, passes through first Second of enrichment is realized in secondary consolidation.Only stable lattice structure need to be formed on phosphorus ore pelletizing surface when consolidation, ball can be improved Group's compression strength and tumbler index ensure the not dusting in yellow phosphorus raw material workshop section transmission process of phosphorus ore pelletizing, do not rupture, reduce Energy consumption is roasted, the phosphorus ore pellet roasting time is made to greatly shorten, reduce phosphorus ore waste and reduces environment protection treating expense.Utilize yellow phosphorus electricity Furnace gas sensible heat carries out the second secondary consolidation in stove, can further control pelletizing pulverization rate in stove, reduces mud phosphorus amount, improves phosphorus recycling Rate, while causing the special ground phosphate rock of yellow phosphorus to waste into yellow phosphorus-refined system with furnace gas after avoiding phosphorus ore pelletizing dusting, again Yellow phosphorus-refined quality can be improved, reduces and refines cost.

3, different according to the raw material components of supplying, yellow phosphorus is made in across-the-board regulation electric furnace operating parameter.Control yellow phosphorus electric furnace enters Stove material moisture, dusting amount well solve and finish arch, the material that collapses, the accident of broken Electrode, failure, ensure electric furnace it is safe and stable, Effec-tive Function.

4, tail gas passes through Na₂CO₃With NaOH liquid scrubbings, by SiF therein₄Na is produced in recycling₂SiF₆And Na₂SiO₃.It is yellow Phosphorus produces the mud phosphorus residue of Main By product and the phosphorus ore after first time enrichment presses 1:1~3 ratio mixing, the modified thick phosphorus of addition Pelletizing is pressed into after acid, all recycling are used for phosphorus production.This two belong to the measure of curbing environmental pollution.

5, add binder before balling-up as needed (while can be added carbon dust and silicon by production yellow phosphorus conventional formulation Powder), and the binder added is by controlling the Na in binder₂O、Al₂O₃Etc. harmful components content to a certain extent to keep away Na is exempted from₂O、Al₂O₃Etc. harmful components bring into yellow phosphorus electric furnace, it is ensured that the mobility of molten condition furnace charge in yellow phosphorus electric furnace, to Ensure that its smooth is slagged tap.It especially limits reaction and generates prodan with yellow phosphorus furnace gas into yellow phosphorus-refined system, reduce Yellow phosphorus-refined difficulty and refined cost, improve yellow phosphorus quality.

The specific technical solution of the present invention is：

One aspect of the present invention provides a kind of method preparing yellow phosphorus using low-grade phosphate ore, is directed in the mining stage Different phosphorus ores selectively take Silicon-rich or poor silicon measure and remove iron containing compounds in crushing stage to obtain suitable silicon, low iron Ground phosphate rock, the mode point of the phosphorus ore pelletizing by way of drying, calcining or direct flotation or reverse flotation and after drying, consolidation balling-up It Jin Hang not first time enrichment P₂O₅With second of enrichment P₂O₅.It is sent after the ground phosphate rock of enrichment twice is pressed into phosphorus ore pelletizing Enter to reaction in yellow phosphorus electric furnace to which yellow phosphorus be made.

According to a preferred embodiment, two are carried out to the ground phosphate rock pelletizing that the ground phosphate rock Jing Guo first time enrichment is pressed into Secondary consolidation measure, wherein the phosphorus ore pelletizing by first time enrichment is carried out before entering yellow phosphorus electric furnace by drying and consolidating machine First secondary consolidation so that the surface of the phosphorus ore pelletizing forms stable lattice structure, and the phosphorus ore Jing Guo first time enrichment Pelletizing carry out first consolidation while in high temperature under the action of also carry out second of enrichment P₂O₅, by the first secondary consolidation When phosphorus ore pelletizing afterwards reacts in yellow phosphorus electric furnace the second secondary consolidation is carried out using the furnace gas sensible heat in stove.

According to a preferred embodiment, carried out by way of the phosphorus ore pelletizing after drying, consolidation balling-up described the Secondary enrichment P₂O₅The step of be replaced by：Pass through the special phosphorus ore of yellow phosphorus after the modified raw phosphoric acid binder to the first enrichment of addition The mode of powder carries out second of enrichment P₂O₅。

According to a preferred embodiment, the ground phosphate rock pelletizing that the ground phosphate rock Jing Guo enrichment twice is pressed into is carried out twice Consolidation measure, wherein the phosphorus ore pelletizing Jing Guo enrichment twice carries out first before entering yellow phosphorus electric furnace by drying and consolidating machine Secondary consolidation so that the surface of the phosphorus ore pelletizing forms stable lattice structure, and the phosphorus ore pelletizing after the first secondary consolidation exists In yellow phosphorus electric furnace the second secondary consolidation is carried out using the furnace gas sensible heat in stove when reaction.

According to a preferred embodiment, the described method comprises the following steps：

Make to be crushed, except the ground phosphate rock after iron carried out by way of dry, calcining or reverse flotation or direct flotation it is rich for the first time Change P₂O₅, obtain the special ground phosphate rock of yellow phosphorus；

Addition inorganic binder makes the repressed formation phosphorus ore pelletizing of the special ground phosphate rock of yellow phosphorus, and in addition inorganic bond It is added while agent for controlling one kind in inorganic binder in the silicate, sepiolite and bentonit of harmful components or more Kind；

It is dried and the first secondary consolidation before phosphorus ore pelletizing is entered yellow phosphorus electric furnace so that the surface of the phosphorus ore pelletizing Form stable lattice structure.

According to a preferred embodiment, the method further includes second of enrichment P₂O₅, second of enrichment P₂O₅It is It is carried out by the way that modified raw phosphoric acid binder is added into the special ground phosphate rock of yellow phosphorus after first time enrichment, and the special phosphorus of yellow phosphorus Miberal powder is pressed into phosphorus ore pelletizing after the modified raw phosphoric acid binder infiltration, wherein the original of the modified raw phosphoric acid binder Material component includes raw phosphoric acid, inorganic binder, dispersant and one or more in silicate, sepiolite and bentonit Conditioning agent.

According to another preferred embodiment, the method further includes second enrichment P2O5, second of enrichment P₂O₅ It is to be carried out in consolidating process by being added into the special ground phosphate rock of yellow phosphorus after first time enrichment after binder and balling-up, In, the raw material components of binder include inorganic binder, dispersant and one kind in silicate, sepiolite and bentonit or A variety of conditioning agents.

According to a preferred embodiment, the method further includes adding carbon before ground phosphate rock is pressed into phosphorus ore pelletizing Powder and silica flour so that the carbon dust and the silica flour are pressed into phosphorus ore pelletizing together after being mixed with ground phosphate rock.

According to a preferred embodiment, the method further includes that basis enters the different adjustment yellow phosphorus electric furnaces of stokehold raw material composition Operating parameter, the adjustment of the operating parameter is to control slag acidity, carbon according to the activity and resistivity of the carbon dust used Excess coefficient, clinker remain P₂O₅Content and electric furnace secondary voltage；

Wherein, carbon dust is coke, and the slag acidity is 0.78~0.82, and the carbon excess coefficient is -2~7%, described Clinker remains P₂O₅Content be 1.1~1.7%, the electric furnace secondary voltage be 360~390V；Or

Wherein, carbon dust is semi-coke, and the slag acidity is 0.80~0.84, and the carbon excess coefficient is 0~6%, described Clinker remains P₂O₅Content be 1.5~2.5%, the electric furnace secondary voltage be 370~400V；Or

Wherein, carbon dust is anthracite, and the slag acidity is 0.83~0.87, and the carbon excess coefficient is 0~5%, described Clinker remains P₂O₅Content be 2.0~3.0%, the electric furnace secondary voltage be 380~420V.

According to a preferred embodiment, the phosphorus ore is high-carbon hydrochlorate, high organic type phosphorus ore, and when mining carries out Silicon-rich Measure, and CO therein is removed by yellow phosphoric tail gas or other fuel dryers, calcining phosphorus ore₂It is realized for the first time with organic matter Enrichment P₂O₅；Or

The phosphorus ore is carbonate-type phosphorus ore, and when mining carries out Silicon-rich measure, and realizes first by reverse flotation mode Secondary enrichment P₂O₅；Or

The phosphorus ore is silicate-type phosphorus ore, and when mining carries out poor silicon measure, and removes phosphorus ore by direct flotation mode In extra SiO₂Realize first time enrichment P₂O₅。

According to a preferred embodiment, by first time enrichment P₂O₅The special ground phosphate rock of yellow phosphorus afterwards carries out second of richness Change P₂O₅The step of include：

It adds for controlling one kind in inorganic binder in the silicate, sepiolite and bentonit of harmful components or more Kind, wherein harmful components are Na₂O and Al₂O₃；

Add dispersant；

Add first time enrichment P₂O₅The special ground phosphate rock of yellow phosphorus afterwards carries out homocline, infiltration, to second of enrichment P₂O₅。

According to a preferred embodiment, second of enrichment P₂O₅The step of further include：

Raw phosphoric acid is prepared, sulfuric acid progress as raw material and is added using ground phosphate rock according to conventional wet phosphoric acid by dihydrate preparation process It prepares, and saves concentration and cleaning procedure in preparation process, while controlling the P that dissociates in solution₂O₅And SO₃Content difference Between the 20~30% of solution total amount between 1.5-3%, wherein a concentration of the 28~35% of raw phosphoric acid obtained, and In second of enrichment P₂O₅During the dosage of raw phosphoric acid be into the 3~14% of stove material total amount.

According to a preferred embodiment, the pressure that the phosphorus ore pelletizing applies 4~23MPa by ball press is pressed into Grain size is the phosphorus ore pelletizing of 5~30mm.

According to a preferred embodiment, the phosphorus ore pelletizing is by drying and consolidating machine at a temperature of 180~1200 DEG C It is dried and the first secondary consolidation.It is highly preferred that first time consolidation temperature is 400 DEG C, 650 DEG C, 800 DEG C, 950 DEG C or 1200 ℃。

According to a preferred embodiment, carbon dust and silicon are optionally added when phosphorus ore pelletizing enters yellow phosphorus electric furnace Powder, wherein the moisture of carbon dust and silica flour is 0~3%, and the additive amount of carbon dust and silica flour is into the 0~20% of stove material total amount.

Another aspect of the present invention provides a kind of preparation process preparing yellow phosphorus using low-grade phosphate ore, the preparation Technique includes：

Silicon-rich measure is carried out to low-grade phosphate ore when mining or poor silicon measure is carried out to high-grade phosphorus ore；

It carries out broken to phosphorus ore and removes iron；

First time enrichment P is carried out by way of drying, calcining or reverse flotation or direct flotation₂O₅, obtain the special phosphorus ore of yellow phosphorus Powder；

Second of richness is carried out by the way that modified raw phosphoric acid binder is added into the special ground phosphate rock of yellow phosphorus after first time enrichment Change P₂O₅, and the special ground phosphate rock of yellow phosphorus is pressed into phosphorus ore pelletizing after the modified raw phosphoric acid binder infiltration, alternatively, passing through Phosphorus ore pelletizing is pressed into after binder infiltration, and pass through drying, solid to the special ground phosphate rock of yellow phosphorus after first time enrichment The mode of knot carries out second of enrichment；

It is dried and the first secondary consolidation before phosphorus ore pelletizing is entered yellow phosphorus electric furnace so that the surface of the phosphorus ore pelletizing Form stable lattice structure；Activity according to the carbon dust used adjusts slag acidity, carbon excess coefficient, clinker with resistivity Remain P₂O₅Content and electric furnace secondary voltage, and be fed through the phosphorus ore pelletizing of yellow phosphorus electric furnace using the furnace gas sensible heat in stove Carry out the second secondary consolidation；

Yellow phosphoric tail gas is passed through Na₂CO₃It is washed in NaOH solution, to recycle SiF₄；

Continue to be used to prepare yellow phosphorus after mud phosphorus residue is mixed with the special ground phosphate rock of yellow phosphorus after first time enrichment so that mud Phosphorus residue is recycled.

According to a preferred embodiment, system carries out Silicon-rich by way of adopting silicon-rich layer or the high silicon phosphorus ore of supplying when mining Measure so that the content satisfaction of silicon prepares the production requirement of yellow phosphorus in phosphorus ore.

According to another preferred embodiment, poor silicon measure is carried out by way of washing or flotation so that phosphorus when mining The content satisfaction of silicon prepares the production requirement of yellow phosphorus in mine.

According to a preferred embodiment, the preparation process is included in first time enrichment P₂O₅The special phosphorus ore of yellow phosphorus afterwards Inorganic binder is added in powder and makes the repressed formation phosphorus ore pelletizing of the special ground phosphate rock of yellow phosphorus, and in addition inorganic binder It is added simultaneously one or more in the silicate, sepiolite and bentonit of harmful components in inorganic binder for controlling.

According to a preferred embodiment, the preparation process is included in first time enrichment P₂O₅The special phosphorus ore of yellow phosphorus afterwards It is directly added into modified raw phosphoric acid binder in powder and carries out second of enrichment P₂O₅, and the special ground phosphate rock of yellow phosphorus is thick through the modification Phosphoric acid binder infiltration after be pressed into phosphorus ore pelletizing, wherein the raw material components of the modified raw phosphoric acid binder include raw phosphoric acid, Inorganic binder, dispersant and one or more conditioning agents in silicate, sepiolite and bentonit.

According to a preferred embodiment, the preparation process is included in is pressed into the addition before of phosphorus ore pelletizing by ground phosphate rock Carbon dust and silica flour so that the carbon dust and the silica flour are pressed into phosphorus ore pelletizing together after being mixed with ground phosphate rock.

The beneficial effects of the invention are as follows：

1, present invention Silicon-rich (to low silicon mine) or poor silicon (to high silicon mine) since phosphorus ore source removes iron, removes MgCO₃、 CaCO₃And organic matter, an enrichment P₂O₅The special ground phosphate rock of yellow phosphorus is prepared, the component for being unfavorable for phosphorus production is reduced, to obtain Volatile matter is few, the simply rich phosphorus ore of ingredient.Because of P₂O₅And SiO₂Component content rises, silica and coke when subsequent production yellow phosphorus ( Can be semi-coke or anthracite) proportioning reduce, consumption of electrode reduces, along with flotation removes most of organic matter and CO₂, energy consumption It will all be substantially reduced with material consumption, cost can also decrease, and improve comprehensive resource utilization rate.

2, the first secondary consolidation and the second secondary consolidation of the invention can reduce roasting energy consumption, ensure the special phosphorus ore sphere of powder of yellow phosphorus Group conveys in yellow phosphorus raw material workshop section, and not dusting, unburstable while mud phosphorus can also be reduced controlling pelletizing in yellow phosphorus electric furnace Amount, improves phosphorous recovery, and primary recovery enters after avoiding the special ground phosphate rock pelletizing dusting of yellow phosphorus with furnace gas up to 92% or more Yellow phosphorus-refined system reduces the special ground phosphate rock waste of yellow phosphorus.

3, the present invention is one or more in silicate, sepiolite and bentonit by being added, and controls inorganic binder Middle Na₂O、Al₂O₃Etc. the harmful components amount of bringing into, it is ensured that the mobility of molten condition furnace charge in yellow phosphorus electric furnace, to ensure that its is smooth It slags tap, especially limits reaction and generate prodan with yellow phosphorus furnace gas into yellow phosphorus-refined system, reduce yellow phosphorus-refined difficulty Degree and refined cost, improve yellow phosphorus quality.

4, control yellow phosphorus electric furnace enter stove silica flour (silica), carbon dust (carbon) moisture be 0~3%, enter the total powder amount of stove be 0~ 20%, the accident or failure for finishing arch, the material that collapses, broken Electrode are well solved, ensure that electric furnace is safe and stable, Effec-tive Function.

5, the special ground phosphate rock pelletizing grade of finished phosphorus of the invention is high, and uniform particle sizes, grading is reasonable, good permeability, at Point stablize, reactivity is high, and moisture content is low, and reaction is more abundant, compares blocky phosphorus ore production yellow phosphorus, hence it is evident that reduce phosphorus slag amount and Residual phosphorus rate.

6, the present invention is given birth to due to that can supply carbon dust and silica flour by production yellow phosphorus formula while adding binder in yellow phosphorus The raw material workshop section of production can no longer be incorporated silica (silica flour) or carbon (carbon dust).Not only solve the unserviceable difficulty of silica mine powder Topic, and turn waste into wealth, the resource utilization of silica is improved, is also solved because silica flour stacks the environmental issue brought.

7, the more traditional pelletizing ore production technology of the present invention, consolidates at twice, saves long period pellet roasting this energy consumption Equipment had both saved investment, and had also reduced energy consumption.

8, tail gas passes through Na₂CO₃With NaOH liquid scrubbings, by SiF therein₄Na is produced in recycling₂SiF₆And Na₂SiO₃；It is yellow Phosphorus produces the mud phosphorus residue of Main By product and the phosphorus ore after an enrichment presses 1:1~3 ratio mixing, adds modified raw phosphoric acid Pelletizing is pressed into after binder, all recycling are used for phosphorus production, solve problem of environmental pollution.

Description of the drawings

Fig. 1 is the method flow diagram that the present invention prepares yellow phosphorus using low-grade phosphate ore；With

Fig. 2 is the preparation technology flow chart that the present invention prepares yellow phosphorus using low-grade phosphate ore.

Specific implementation mode

It is described in detail below in conjunction with the accompanying drawings.

Referring to Fig. 1, the present invention prepares yellow phosphorus using low-grade phosphate ore and mainly includes the following steps that：

Step 1：Silicon-rich measure or poor silicon measure are carried out to low-grade phosphate ore；

Step 2：Rock phosphate in powder is crushed, and removes iron containing compounds wherein included；

Step 3：Broken ground phosphate rock is subjected to first time enrichment P₂O₅, obtain the special ground phosphate rock of yellow phosphorus；

Step 4：The modified raw phosphoric acid binder of addition carries out second of enrichment P to the special ground phosphate rock of yellow phosphorus₂O₅；

Step 5：Balling-up is suppressed, ground phosphate rock pelletizing is obtained；

Step 6：Ground phosphate rock pelletizing is dried by drying and consolidating machine and the first secondary consolidation；

Step 7：Activity and resistivity according to the carbon dust used adjust yellow phosphorus electric furnace operating parameter；

Step 8：Phosphorus ore pelletizing reacts in yellow phosphorus electric furnace, and carries out the second secondary consolidation using furnace gas sensible heat in stove；

Step 9：Yellow phosphorus is made after reaction；

According to a preferred embodiment, step 4 can be replaced by：Binder to the special ground phosphate rock of yellow phosphorus is added to infiltrate, Carry out second of enrichment.

Referring to Fig. 2, on the basis of Fig. 1, Fig. 2 increases following steps：

Step 10：Yellow phosphoric tail gas is passed through Na₂CO₃With NaOH liquid scrubbings, Na is generated₂SiF₆And Na₂SiO₃, to recycle SiF in tail gas₄；

Step 11：Mud phosphorus residue is mixed with the ground phosphate rock after first time enrichment, continues, to subsequent production, to follow to reach The purpose that ring utilizes.

According to a preferred embodiment, in step 1 Silicon-rich measure be：System adopts silicon-rich layer or the high silicon phosphorus of supplying when mining Mine.Poor silicon measure is in step 1：The mode of washing or flotation carries out poor silicon measure when mining.Silica is phosphorus production mistake Indispensable fluxing agent in journey, it can reduce reaction temperature, accelerate reduction rate, improves phosphatic reduction rate, to reaction Process and slag fluidity also have large effect.Dioxide-containing silica is too low, and Phosphate ore reduction rate is relatively low.Dioxide-containing silica mistake Height, the poor fluidity of clinker, reduction reaction temperature increase, and clinker and ferrophosphorus form eutectic and carry a large amount of ferrophosphorus secretly, when clinker water Explosion is also easy to produce when quenching.Therefore, content of the control silica in furnace charge has great importance.Prior art production technology In do not draw attention to the content of silicon so that the reduction rate of ore is not high.The present invention is to the lower carbonate-type phosphorus of silicon content Mine, high organic type phosphorus ore increase the content of silicon by Silicon-rich measure, to improve the reduction rate of ore.For silicon content compared with High silicate-type phosphorus ore, extra silica of being gone out by direct flotation, to prevent generating explosion when furnace slag granulating.According to one Preferred embodiment, it is specially to remove Fe that iron containing compounds are removed in step 2₂O₃And Fe₃O₄, step is：After phosphorus ore is broken Fe is removed by conventional concentration equipment₂O₃And Fe₃O₄.After enrichment, the Fe of the special ground phosphate rock of yellow phosphorus₂O₃Content≤0.9%.By In Fe₂O₃And Fe₃O₄Reduction temperature than phosphorus in rock phosphate in powder is low, Fe₂O₃And Fe₃O₄It is reduced agent first and is reduced to fe, in height Under temperature, phosphorus simple substance is obtained after rock phosphate in powder reduction, iron contacts i.e. generation iron phosphide with phosphorus simple substance, changes the resistance of melt.Therefore, Excessively high iron content makes power consumption increase, and phosphorus yield reduces.

According to a preferred embodiment, step 4 may alternatively be：Control control is added while adding binder It is one or more in the silicate, sepiolite and bentonit of harmful components in binder.Wherein, the binder that the present invention uses For inorganic binder, wherein harmful components refer specifically to Na₂O and Al₂O₃.And the phosphorus ore pelletizing after balling-up is carried out solid for the first time Knot is carried out at the same time second of enrichment, so that the performance component in pelletizing is played away, carry due to high temperature action while consolidation High P₂O₅Grade.

According to a preferred embodiment, before step 5, silica flour and carbon are added according to the conventional proportions of phosphorus production Powder.The moisture of carbon dust and silica flour is 0~3%, and the additive amount of carbon dust and silica flour is into the 0~20% of stove material total amount.The step So that in the raw material workshop section of phosphorus production, that is, silica (silica flour) can be no longer incorporated by entering in stove material, solving silica can not utilize Problem, improve the resource utilization of silica, and avoid the environmental issue generated because silica flour is stacked.Produce raw phosphoric acid The ardealite of generation is converted using temperature control with yellow phosphoric tail gas, produces land plaster so that the present invention relates to all by-products by again Secondary recycling sufficiently achieves the effect of environmental protection.

According to a preferred embodiment, phosphorus ore pelletizing is pressed by the pressure of 4~23MPa of ball press application in step 5 The phosphorus ore pelletizing that grain size is 5~30mm is made.

According to a preferred embodiment, temperature of the phosphorus ore pelletizing by drying and consolidating machine at 180~1200 DEG C in step 6 Under be dried and the first secondary consolidation.It is highly preferred that first time consolidation temperature is 400 DEG C, 650 DEG C, 800 DEG C, 950 DEG C or 1200 ℃。

According to a preferred embodiment, mud phosphorus residue is pressed with the special ground phosphate rock of yellow phosphorus after first time enrichment in step 11 1:1.0~3.0 ratio mixing.

It is now directed to different type phosphorus ore, to first time enrichment P₂O₅The step of illustrate.

1, high-carbon hydrochlorate, high organic type phosphorus ore

CO therein is removed by yellow phosphoric tail gas or other fuel dryers, calcining phosphorus ore₂It is realized for the first time with organic matter Enrichment P₂O₅.Specifically, being dried through 0~15S, 0~10S calcinings remove CO₂With organic matter (removal rate >=95%), P₂O₅With SiO₂Grade improves >=2.5%.

2, carbonate-type phosphorus ore

First time enrichment P is realized by reverse flotation mode₂O₅.Specifically, removing MgCO with reverse flotation₃And CaCO₃.It is anti-floating P after choosing₂O₅Content can be increased to 31% or so, CO₂Content≤2.8%, P₂O₅、SiO₂, CaO mass ratio be 1:0.6~ 0.9:1.27.The additive amount of flotation agent is 0.05%~0.08%.The reverse flotation agent of the present invention is special from Le Shi companies LSF-1。

3, silicate-type phosphorus ore

SiO extra in phosphorus ore is removed by direct flotation mode₂Realize first time enrichment P₂O₅.Specifically, with direct flotation side Formula removes extra SiO₂.P after direct flotation₂O₅Content can be increased to 27% or so.It is yellow in production for silicate-type phosphorus ore When phosphorus, SiO can be not added with or added less₂, therefore the effect after enrichment can be with P after flotation₂O₅Achieve the effect that 31% is similar. SiO₂Removal rate be controlled by phosphorus production proportioning.By direct flotation by extra SiO₂Removal.P₂O₅、SiO₂, CaO quality Than being 1:0.9~1.08:1.27.Direct flotation medicament used is respectively the special LSZ-2 of Le Shi companies, and additive amount is 0.05%~ 0.08%.

Now to second of enrichment P of the present invention₂O₅The step of be described in detail.

Second of enrichment P₂O₅The step of include：

Raw phosphoric acid is prepared, sulfuric acid progress as raw material and is added using ground phosphate rock according to conventional wet phosphoric acid by dihydrate preparation process It prepares, and saves concentration and cleaning procedure in preparation process, while controlling the P that dissociates in solution₂O₅And SO₃Content difference Between the 20~30% of solution total amount between 1.5-3%, wherein a concentration of the 28~35% of raw phosphoric acid obtained, and In second of enrichment P₂O₅During the dosage of raw phosphoric acid be into the 3~14% of stove material total amount；

Add dispersant；

The raw material components of the modification raw phosphoric acid binder of the present invention include raw phosphoric acid, inorganic binder, dispersant and are selected from One or more conditioning agents in silicate, sepiolite and bentonit.When being added without raw phosphoric acid, i.e., imitated without second of enrichment Fruit.

According to a preferred embodiment, second of enrichment P of the invention₂O₅The step of can be replaced by：

Binder infiltration is added in the special ground phosphate rock of yellow phosphorus, moisture is removed by dry after compacting balling-up, enters back into consolidation Process, 400-1200 DEG C of consolidation temperature effectively remove the CO in phosphorus ore ball₂And organic matter, to promote P₂O₅Quality reaches two Secondary enrichment effect.

Wherein, the raw material components of binder include inorganic binder, dispersant and selected from silicate, sepiolite and bentonit In one or more conditioning agents.

The adjustment for the electric furnace operating parameter for now preparing yellow phosphorus to the present invention illustrates, in particular for different carbon dusts. The adjustment of operating parameter is activity and resistivity according to the carbon dust that uses come what is carried out, and the parameter specifically adjusted is clinker acid Degree, carbon excess coefficient, clinker remain P₂O₅Content and electric furnace secondary voltage.

1, coke

Electric furnace operating parameter is：Slag acidity is 0.78~0.82, and carbon excess coefficient is -2~7%, and clinker remains P₂O₅'s Content is 1.1~1.7%, and electric furnace secondary voltage is 360~390V.

2, semi-coke

Electric furnace operating parameter is：Slag acidity is 0.80~0.84, and carbon excess coefficient is 0~6%, and clinker remains P₂O₅'s Content is 1.5~2.5%, and electric furnace secondary voltage is 370~400V.

3, anthracite

Electric furnace operating parameter is：Slag acidity is 0.83~0.87, and carbon excess coefficient is 0~5%, and clinker remains P₂O₅'s Content is 2.0~3.0%, and electric furnace secondary voltage is 380~420V.

The preparation method of the present invention is further described below by embodiment.

Embodiment 1

With the P for taking mining Silicon-rich measure₂O₅The low-grade phosphate ore that content is 22.5% carries out the by reverse flotation mode Enrichment P₂O₅, obtain the special ground phosphate rock of yellow phosphorus.Iron containing compounds are removed when phosphorus ore is crushed.Addition 4% is modified raw phosphoric acid extremely Then the special ground phosphate rock of yellow phosphorus carries out the compacting balling-up processing of 19MPa pressure.Screening obtains the phosphorus ore ball of 5mm~30mm sphere diameters Group carries out secondary consolidation, Huang is made in final reaction by phosphorus ore pelletizing after consolidation machine consolidation using furnace gas sensible heat in yellow phosphorus electric furnace Phosphorus.Wherein, it is 650 DEG C into the first time consolidation temperature before yellow phosphorus electric furnace.

In the present embodiment, pass through the special ground phosphate rock P of yellow phosphorus after reverse flotation mode first time enrichment₂O₅Content be 31.5%, moisture content 10%~12%, 200 80% or more mesh sieving rates, CO₂Content 2.68%.Ground phosphate rock pelletizing compression strength For 87kg/cm², tumbler index 86%, the special ground phosphate rock pelletizing quality of yellow phosphorus obtained is：P₂O₅32.03%, CaO 42.24%, SiO₂18.10%, CO₂2.68%, Fe₂O₃0.65%.

Yellow phosphorus, energy consumption of electric furnace 13008kwh/t are produced with nut coke, silica, pelletizing consumes 7.69t/t, and nut coke consumes 1.42t/ T, silica consume 1.26t/t, phosphorous recovery 93%.Yellow phosphorus is produced compared with 22.5% grade lump ore, power consumption reduces 4773kwh/t, drop Low 26.8%, phosphorus ore consumption reduces 3.79t/t, reduces by 33%, nut coke consumption reduces 0.69t/t, reduces by 32.7%.Yellow phosphorus unit 2466 yuan/t of cost reduction.Clinker yield drops to 6.55t/t from 12t/t, reduces by 45.4%.Tail gas (CO) is from 2993Nm³It reduces To 2014Nm³, 32.7% is reduced, corresponding CO₂Directly reduce 32.7%.

Embodiment 2

With the P for taking mining Silicon-rich measure₂O₅The low-grade phosphate ore that content is 22.5% carries out the by reverse flotation mode Enrichment P₂O₅, obtain the special ground phosphate rock of yellow phosphorus.Iron containing compounds are removed when phosphorus ore is crushed.4% binder is added to yellow phosphorus Then special ground phosphate rock carries out the compacting balling-up processing of 19MPa pressure.Screening obtains the phosphorus ore pelletizing of 5mm~30mm sphere diameters, will Phosphorus ore pelletizing carries out secondary consolidation, yellow phosphorus is made in final reaction after consolidation machine consolidation using furnace gas sensible heat in yellow phosphorus electric furnace.Its In, it is 650 DEG C into the first time consolidation temperature before yellow phosphorus electric furnace.

Embodiment 3

Use SiO₂Content 35%, P₂O₅The low-grade phosphate ore direct flotation mode that content is 22.5% obtains the special phosphorus ore of yellow phosphorus Powder.Iron containing compounds are removed when phosphorus ore is crushed.By the special ground phosphate rock of yellow phosphorus in 100~300 DEG C of dryings (control special phosphorus of yellow phosphorus Moisture content after miberal powder drying is that modified raw phosphoric acid 0.6%) is added afterwards.The compacting balling-up of 14MPa pressure is carried out after stirring homogenizing Processing, screening obtain the special ground phosphate rock pelletizing of yellow phosphorus of 5mm~30mm sphere diameters, then by the special ground phosphate rock pelletizing of yellow phosphorus through consolidating machine After consolidation, secondary consolidation is carried out using furnace gas sensible heat in yellow phosphorus electric furnace, yellow phosphorus is made in final reaction.Wherein, into yellow phosphorus electric furnace Preceding first time consolidation temperature is 650 DEG C.

In the present embodiment, it is generally by the moisture content of the special ground phosphate rock of yellow phosphorus after direct flotation mode first time enrichment 10%~12%, special ground phosphate rock moisture content≤0.6% of yellow phosphorus after drying.The special ground phosphate rock P of yellow phosphorus₂O₅Content be 31%, 200 80% or more mesh sieving rates, CO₂Content 1.64%.Ground phosphate rock pelletizing compression strength is 130kg/cm², tumbler index is 85%.Ground phosphate rock pelletizing quality obtained is：P₂O₅31.53%, CaO 34.5%, SiO₂27.0%, CO₂1.64%, Fe₂O₃0.55%.

Yellow phosphorus, energy consumption of electric furnace 12080kwh/t are produced with nut coke, silica, pelletizing consumes 7.73t/t, and nut coke consumes 1.40t/ T, silica consume 0t/t, phosphorous recovery 94%.Yellow phosphorus is produced compared with 22.5% grade lump ore, power consumption reduces 5700kwh/t, reduces 32.1%, phosphorus ore consumption reduces 3.75t/t, reduces by 32.7%, nut coke consumption reduces 0.71t/t, reduces by 33.6%.Yellow phosphorus unit 2889 yuan/t of cost reduction.Clinker yield drops to 5.3t/t from 12t/t, reduces by 55.84%, and tail gas (CO) is from 2993Nm³It reduces To 1991Nm³, 33.5% is reduced, corresponding CO₂Directly reduce 33.5%.

Embodiment 4

Use SiO₂Content 35%, P₂O₅The low-grade phosphate ore direct flotation mode that content is 22.5% obtains the special phosphorus ore of yellow phosphorus Powder.Iron containing compounds are removed when phosphorus ore is crushed.By the special ground phosphate rock of yellow phosphorus in 100~300 DEG C of dryings (control special phosphorus of yellow phosphorus Miberal powder drying after moisture content be 0.6%) after 3% binder is added.At the compacting balling-up for carrying out 14MPa pressure after stirring homogenizing Reason, screening obtains the special ground phosphate rock pelletizing of yellow phosphorus of 5mm~30mm sphere diameters, then the special ground phosphate rock pelletizing of yellow phosphorus is consolidated through consolidation machine After knot, secondary consolidation is carried out using furnace gas sensible heat in yellow phosphorus electric furnace, yellow phosphorus is made in final reaction.Wherein, into before yellow phosphorus electric furnace First time consolidation temperature be 650 DEG C.

In the present embodiment, it is generally by the moisture content of the special ground phosphate rock of yellow phosphorus after direct flotation mode first time enrichment 10%~12%, special ground phosphate rock moisture content≤0.6% of yellow phosphorus after drying.The special ground phosphate rock P of yellow phosphorus₂O₅Content be 28%, 200 80% or more mesh sieving rates, CO₂Content 1.64%.Ground phosphate rock pelletizing compression strength is 130kg/cm², tumbler index is 85%.Ground phosphate rock pelletizing quality obtained is：P₂O₅27.53%, CaO 34.5%, SiO₂27.0%, CO₂1.64%, Fe₂O₃0.55%.

Embodiment 5

Use P₂O₅The low-grade phosphate ore that content is 25%, CO₂Content 12%, organic matter 4%.It removes and contains when phosphorus ore is crushed Iron compound.With drying, flash calcining.It is added 8% and is modified raw phosphoric acid, the compacting of 19MPa pressure is carried out after stirring, infiltration homogenizing Balling-up is handled, and screening obtains the phosphorus ore pelletizing of 5mm~30mm sphere diameters.Through consolidating machine after phosphorus ore pelletizing is dried at 100~300 DEG C After consolidation, secondary consolidation is carried out using furnace gas sensible heat in yellow phosphorus electric furnace, yellow phosphorus is made in final reaction.Wherein, into yellow phosphorus electric furnace The first preceding secondary consolidation calcination temperature is 650 DEG C.

In the present embodiment, the phosphorus ore P after first time enrichment₂O₅Content is 27.78%, 200 80% or more mesh sieving rates, CO₂ Content is 0.Phosphorus ore pelletizing compression strength is 99kg/cm², tumbler index 88%, phosphorus ore pelletizing quality obtained is P₂O₅28.93%, CaO 36.06%, SiO₂26.32%, no CO₂, Fe₂O₃0.55%.

Yellow phosphorus, energy consumption of electric furnace 12777kwh/t are produced with nut coke, silica, pelletizing consumes 8.42t/t, and nut coke consumes 1.41t/ T, silica consume 0.13t/t, phosphorous recovery 94%.Yellow phosphorus is produced compared with 25% grade lump ore, power consumption reduces 5000kwh/t, reduces 28.1%, phosphorus ore consumption reduces 3.06t/t, reduces by 26.7%, nut coke consumption reduces 0.70t/t, reduces by 33.2%.Yellow phosphorus unit 2088 yuan/t of cost reduction.Clinker yield drops to 6.16t/t from 12t/t, reduces by 48.7%, and tail gas (CO) is from 2993Nm³It reduces To 2000Nm³, 33.2% is reduced, corresponding CO₂Directly reduce 33.2%.

Embodiment 6

Use P₂O₅The low-grade phosphate ore that content is 25%, CO₂Content 12%, organic matter 4%.It removes and contains when phosphorus ore is crushed Iron compound.With drying, flash calcining.3% binder is added, the compacting balling-up of 19MPa pressure is carried out after stirring, infiltration homogenizing Processing, screening obtain the phosphorus ore pelletizing of 5mm~30mm sphere diameters.Phosphorus ore pelletizing is consolidated after drying through consolidating machine at 100~300 DEG C Afterwards, secondary consolidation is carried out using furnace gas sensible heat in yellow phosphorus electric furnace, yellow phosphorus is made in final reaction.Wherein, into before yellow phosphorus electric furnace First secondary consolidation calcination temperature is 650 DEG C.

In the present embodiment, the phosphorus ore P after first time enrichment₂O₅Content is 28.41%, 200 80% or more mesh sieving rates, CO₂ Content is 0.Without secondary enrichment, phosphorus ore pelletizing compression strength is 99kg/cm², tumbler index 88%, phosphorus ore pelletizing product obtained Matter is P₂O₅28.41%, CaO 36.06%, SiO₂26.32%, no CO₂, Fe₂O₃0.55%.

Yellow phosphorus, energy consumption of electric furnace 13177kwh/t are produced with nut coke, silica, pelletizing consumes 8.42t/t, and nut coke consumes 1.41t/ T, silica consume 0.13t/t, phosphorous recovery 94%.Yellow phosphorus is produced compared with 25% grade lump ore, power consumption reduces 4600kwh/t, reduces 25.8%, phosphorus ore consumption reduces 3.06t/t, reduces by 26.7%, nut coke consumption reduces 0.70t/t, reduces by 33.2%.Yellow phosphorus unit 2088 yuan/t of cost reduction.Clinker yield drops to 6.16t/t from 12t/t, reduces by 48.7%, and tail gas (CO) is from 2993Nm³It reduces To 2000Nm³, 33.2% is reduced, corresponding CO₂Directly reduce 33.2%.

Embodiment 7

With the P for taking mining Silicon-rich measure₂O₅It is special that the low-grade phosphate ore reverse flotation mode that content is 22.5% obtains yellow phosphorus Ground phosphate rock.Iron containing compounds are removed when phosphorus ore is crushed.The compacting balling-up processing of 19MPa pressure is carried out, addition 4% is modified thick phosphorus Acid and silicate binder, while it being pressed into stove proportioning addition coke powder, screening obtains the phosphorus ore pelletizing of 5mm~30mm sphere diameters, by phosphorus Mine pelletizing carries out secondary consolidation, yellow phosphorus is made in final reaction after consolidation machine consolidation using furnace gas sensible heat in yellow phosphorus electric furnace.Its In, it is 650 DEG C into the first time consolidation temperature before yellow phosphorus electric furnace.

In the present embodiment, the special ground phosphate rock P of yellow phosphorus after first time enrichment₂O₅Content be 31.5%, moisture content 10%~ 12%, 200 80% or more mesh sieving rates, CO₂Content 2.68%.The special ground phosphate rock pelletizing compression strength of finished phosphorus is 87kg/ cm², tumbler index 86%, the special ground phosphate rock pelletizing quality of yellow phosphorus obtained is P₂O₅32.03%, CaO 42.24%, SiO₂18.10%, CO₂2.68%, Fe₂O₃0.65%.

Yellow phosphorus, energy consumption of electric furnace 12917kwh/t are produced with silica, pelletizing consumes 7.69t/t, and nut coke consumes 1.42t/t, silicon Stone consumes 1.26t/t, phosphorous recovery 93%.Yellow phosphorus is produced compared with 22.5% grade lump ore, power consumption reduces 4864kwh/t, reduces 27.4%, phosphorus ore consumption reduces 3.79t/t, reduces by 33%, nut coke consumption reduces 0.69t/t, reduces by 32.7%.Yellow phosphorus unit at 2933 yuan/t of this reduction.Clinker yield drops to 6.55t/t from 12t/t, reduces by 45.4%, and tail gas (CO) is from 2993Nm³It is reduced to 2014Nm³, 32.7% is reduced, corresponding CO₂Directly reduce 32.7%.

Embodiment 8

With the P for taking mining Silicon-rich measure₂O₅It is special that the low-grade phosphate ore reverse flotation mode that content is 22.5% obtains yellow phosphorus Ground phosphate rock.Iron containing compounds are removed when phosphorus ore is crushed.The compacting balling-up processing for carrying out 19MPa pressure, adds 4% binder, It is pressed into stove proportioning addition coke powder simultaneously, screening obtains the phosphorus ore pelletizing of 5mm~30mm sphere diameters, by phosphorus ore pelletizing through consolidating machine consolidation Afterwards, secondary consolidation is carried out using furnace gas sensible heat in yellow phosphorus electric furnace, yellow phosphorus is made in final reaction.Wherein, into before yellow phosphorus electric furnace First time consolidation temperature is 650 DEG C.

Embodiment 9

With the P for taking mining Silicon-rich measure₂O₅It is special that the low-grade phosphate ore reverse flotation mode that content is 22.5% obtains yellow phosphorus Ground phosphate rock.Iron containing compounds are removed when phosphorus ore is crushed.The compacting balling-up processing of 19MPa pressure is carried out, addition 4% is modified thick phosphorus Acid and silicate binder, while it being pressed into stove proportioning addition coke powder and silica flour, screening obtains the phosphorus ore ball of 5mm~30mm sphere diameters Group carries out secondary consolidation, Huang is made in final reaction by phosphorus ore pelletizing after consolidation machine consolidation using furnace gas sensible heat in yellow phosphorus electric furnace Phosphorus.Wherein, it is 650 DEG C into the first time consolidation temperature before yellow phosphorus electric furnace.

In the present embodiment, the special ground phosphate rock P of yellow phosphorus after first time enrichment₂O₅Content be 31.5%, moisture content 10%~ 12%, 200 80% or more mesh sieving rates, CO₂Content 2.68%.Ground phosphate rock pelletizing compression strength is 87kg/cm², tumbler index is 86%, the special ground phosphate rock pelletizing quality of yellow phosphorus obtained is P₂O₅32.03%, CaO 42.24%, SiO₂18.10%, CO₂ 2.68%, Fe₂O₃0.65%.

Pelletizing directly produces yellow phosphorus, energy consumption of electric furnace 12917kwh/t, and pelletizing consumes 7.69t/t, and nut coke consumes 1.42t/t, Silica consumes 1.26t/t, phosphorous recovery 93%.Yellow phosphorus is produced compared with 22.5% grade lump ore, power consumption reduces 4864kwh/t, reduces 27.4%, phosphorus ore consumption reduces 3.79t/t, reduces by 33%, nut coke consumption reduces 0.69t/t, reduces by 32.7%.Yellow phosphorus unit at 3089 yuan/t of this reduction.Clinker yield drops to 6.55t/t from 12t/t, reduces by 45.4%, and tail gas (CO) is from 2993Nm³It is reduced to 2014Nm³, 32.7% is reduced, corresponding CO₂Directly reduce 32.7%.

Embodiment 10

With the P for taking mining Silicon-rich measure₂O₅It is special that the low-grade phosphate ore reverse flotation mode that content is 22.5% obtains yellow phosphorus Ground phosphate rock.Iron containing compounds are removed when phosphorus ore is crushed.The compacting balling-up processing for carrying out 19MPa pressure, adds 4% binder, It is pressed into stove proportioning addition coke powder and silica flour simultaneously, screening obtains the phosphorus ore pelletizing of 5mm~30mm sphere diameters, by phosphorus ore pelletizing through consolidation After machine consolidation, secondary consolidation is carried out using furnace gas sensible heat in yellow phosphorus electric furnace, yellow phosphorus is made in final reaction.Wherein, into yellow phosphorus electricity The first time consolidation temperature of stokehold is 650 DEG C.

The consumption of the present invention and existing phosphorus production technique and expense compare, and are shown in Table 1.

Table 1

It should be noted that signified " the suitable silicon " of the present invention refers to silicon in the special ground phosphate rock of yellow phosphorus after enrichment is handled Reach moderate amount, meets neither excessively high only low this requirement.Determining for the moderate silicon content is needed according to specific The component of raw material, electric furnace operating parameter determine in preparation process.The present invention only illustrates technical concept, for specific Content control is not described, and those skilled in the art should be understood that.

It should be noted that above-mentioned specific embodiment is exemplary, those skilled in the art can disclose in the present invention Various solutions are found out under the inspiration of content, and these solutions also belong to disclosure of the invention range and fall into this hair Within bright protection domain.It will be understood by those skilled in the art that description of the invention and its attached drawing are illustrative and are not Constitute limitations on claims.Protection scope of the present invention is limited by claim and its equivalent.

Claims

1. a kind of method preparing yellow phosphorus using low-grade phosphate ore, which is characterized in that optional for different phosphorus ores in the mining stage It takes Silicon-rich or poor silicon measure with selecting and removes iron containing compounds in crushing stage to obtain the ground phosphate rock of suitable silicon, low iron, pass through The mode of phosphorus ore pelletizing after the mode and drying of dry, calcining or direct flotation or reverse flotation, consolidation balling-up carries out first respectively Secondary enrichment P₂O₅With second of enrichment P₂O₅,

Wherein, the method further includes that basis enters the operating parameters that stokehold raw material forms different adjustment yellow phosphorus electric furnaces, the operation The adjustment of parameter is to control slag acidity, carbon excess coefficient, clinker residual P with resistivity according to the activity of the carbon dust used₂O₅ Content and electric furnace secondary voltage,

The mud phosphorus residue of phosphorus production Main By product presses 1 with the phosphorus ore after first time enrichment:1~3 ratio mixing, addition change It is pressed into pelletizing after property raw phosphoric acid binder, the phosphorus ore pelletizing is dried by drying and consolidating machine at a temperature of 400 DEG C With the first secondary consolidation,

The raw material components of the modified raw phosphoric acid binder include raw phosphoric acid, inorganic binder, dispersant and are selected from silicate, sea One or more conditioning agents in afrodite and bentonite,

A concentration of the 28~35% of the raw phosphoric acid obtained, and in second of enrichment P₂O₅During raw phosphoric acid addition Amount is into the 3~14% of stove material total amount.

2. the method according to claim 1 for preparing yellow phosphorus using low-grade phosphate ore, which is characterized in that by for the first time The ground phosphate rock pelletizing that the ground phosphate rock of enrichment is pressed into carries out two secondary consolidation measures, wherein

Phosphorus ore pelletizing by first time enrichment carries out the first secondary consolidation before entering yellow phosphorus electric furnace by drying and consolidating machine, makes The surface for obtaining the phosphorus ore pelletizing forms stable lattice structure, and the phosphorus ore pelletizing Jing Guo first time enrichment is carrying out first Second of enrichment P is also carried out while consolidation under the action of high temperature₂O₅,

It is carried out second using the furnace gas sensible heat in stove when phosphorus ore pelletizing after the first secondary consolidation reacts in yellow phosphorus electric furnace Consolidation.

3. the method according to claim 1 for preparing yellow phosphorus using low-grade phosphate ore, which is characterized in that by drying, admittedly Second of enrichment P that the mode of phosphorus ore pelletizing after balling carries out₂O₅The step of be replaced by：It is modified thick by adding The mode of the special ground phosphate rock of yellow phosphorus after phosphoric acid binder to the first enrichment carries out second of enrichment P₂O₅。

4. the method according to claim 3 for preparing yellow phosphorus using low-grade phosphate ore, which is characterized in that rich twice to process The ground phosphate rock pelletizing that the ground phosphate rock of change is pressed into carries out two secondary consolidation measures, wherein

Phosphorus ore pelletizing by enrichment twice carries out the first secondary consolidation before entering yellow phosphorus electric furnace by drying and consolidating machine so that The surface of the phosphorus ore pelletizing forms stable lattice structure,

When phosphorus ore pelletizing after two secondary consolidation reacts in yellow phosphorus electric furnace second is carried out using the furnace gas sensible heat in stove admittedly Knot.

5. the method for preparing yellow phosphorus using low-grade phosphate ore according to one of preceding claims, which is characterized in that described Method further includes：Carbon dust and silica flour are added before ground phosphate rock is pressed into phosphorus ore pelletizing so that the carbon dust and the silica flour Phosphorus ore pelletizing is pressed into after being mixed with ground phosphate rock together.

6. the method according to claim 5 for preparing yellow phosphorus using low-grade phosphate ore, which is characterized in that the method is also wrapped It includes according to the operating parameters for entering stokehold raw material and forming different adjustment yellow phosphorus electric furnaces, the adjustment of the operating parameter is according to using The activity and resistivity of carbon dust remain P to control slag acidity, carbon excess coefficient, clinker₂O₅Content and electric furnace secondary voltage；

Wherein, carbon dust is coke, and the slag acidity is 0.78~0.82, and the carbon excess coefficient is -2~7%, the clinker Remain P₂O₅Content be 1.1~1.7%, the electric furnace secondary voltage be 360~390V；Or

Wherein, carbon dust is semi-coke, and the slag acidity is 0.80~0.84, and the carbon excess coefficient is 0~6%, the clinker Remain P₂O₅Content be 1.5~2.5%, the electric furnace secondary voltage be 370~400V；Or

Wherein, carbon dust is anthracite, and the slag acidity is 0.83~0.87, and the carbon excess coefficient is 0~5%, the clinker Remain P₂O₅Content be 2.0~3.0%, the electric furnace secondary voltage be 380~420V.

7. the method according to claim 5 for preparing yellow phosphorus using low-grade phosphate ore, which is characterized in that the phosphorus ore is high Carbonate, high organic type phosphorus ore carry out Silicon-rich measure when mining, and pass through yellow phosphoric tail gas or other fuel dryers, calcining Phosphorus ore removes CO therein₂First time enrichment P is realized with organic matter₂O₅；Or

The phosphorus ore is carbonate-type phosphorus ore, and when mining carries out Silicon-rich measure, and is realized by reverse flotation mode rich for the first time Change P₂O₅；Or

The phosphorus ore is silicate-type phosphorus ore, and when mining carries out poor silicon measure, and is removed by direct flotation mode more in phosphorus ore Remaining SiO₂Realize first time enrichment P₂O₅。

8. the method according to claim 5 for preparing yellow phosphorus using low-grade phosphate ore, which is characterized in that by rich for the first time Change P₂O₅The special ground phosphate rock of yellow phosphorus afterwards carries out second of enrichment P₂O₅The step of include：

Addition is one or more in the silicate, sepiolite and bentonit of harmful components in inorganic binder for controlling, In, harmful components are Na₂O and Al₂O₃；

Add dispersant；

9. the method according to claim 5 for preparing yellow phosphorus using low-grade phosphate ore, which is characterized in that the phosphorus ore pelletizing The pressure for applying 4~23MPa by ball press is pressed into the phosphorus ore pelletizing that grain size is 5~30mm, and the phosphorus ore pelletizing passes through Drying and consolidating machine be dried at a temperature of 180~1200 DEG C with the first secondary consolidation, and

It is optionally added carbon dust and silica flour when phosphorus ore pelletizing enters yellow phosphorus electric furnace, wherein the moisture of carbon dust and silica flour is 0 ~3%, the additive amount of carbon dust and silica flour is into the 0~20% of stove material total amount.

10. a kind of preparation process preparing yellow phosphorus using low-grade phosphate ore, which is characterized in that the preparation process includes：

It carries out broken to phosphorus ore and removes iron；

First time enrichment P is carried out by way of drying, calcining or reverse flotation or direct flotation₂O₅, obtain the special ground phosphate rock of yellow phosphorus；

Second of enrichment is carried out by the way that modified raw phosphoric acid binder is added into the special ground phosphate rock of yellow phosphorus after first time enrichment P₂O₅, and the special ground phosphate rock of yellow phosphorus is pressed into phosphorus ore pelletizing after the modified raw phosphoric acid binder infiltration, alternatively, pass through to The special ground phosphate rock of yellow phosphorus after first time enrichment is pressed into phosphorus ore pelletizing after binder infiltration, and passes through drying, consolidation Mode carry out second of enrichment；

It is dried and the first secondary consolidation before phosphorus ore pelletizing is entered yellow phosphorus electric furnace so that the surface of the phosphorus ore pelletizing is formed Stable lattice structure；Activity and resistivity according to the carbon dust used remain to adjust slag acidity, carbon excess coefficient, clinker P₂O₅Content and electric furnace secondary voltage, and the phosphorus ore pelletizing for being fed through yellow phosphorus electric furnace utilizes furnace gas sensible heat in stove to carry out Second secondary consolidation；

Continue to be used to prepare yellow phosphorus after mud phosphorus residue is mixed with the special ground phosphate rock of yellow phosphorus after first time enrichment so that mud phosphorus is residual Slag is recycled；Wherein,