WO2014194571A1 - 适用于窑法磷酸工艺的原料预处理方法和原料预处理工艺系统 - Google Patents

适用于窑法磷酸工艺的原料预处理方法和原料预处理工艺系统 Download PDF

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Publication number
WO2014194571A1
WO2014194571A1 PCT/CN2013/081232 CN2013081232W WO2014194571A1 WO 2014194571 A1 WO2014194571 A1 WO 2014194571A1 CN 2013081232 W CN2013081232 W CN 2013081232W WO 2014194571 A1 WO2014194571 A1 WO 2014194571A1
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Prior art keywords
equipment
silica
powder
pretreatment
raw material
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PCT/CN2013/081232
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English (en)
French (fr)
Inventor
侯拥和
吴鋆
刘诗华
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四川玖长科技有限公司
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Application filed by 四川玖长科技有限公司 filed Critical 四川玖长科技有限公司
Priority to RU2015144554A priority Critical patent/RU2637909C2/ru
Publication of WO2014194571A1 publication Critical patent/WO2014194571A1/zh
Priority to US14/958,899 priority patent/US10744512B2/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
    • B02C23/18—Adding fluid, other than for crushing or disintegrating by fluid energy
    • B02C23/38—Adding fluid, other than for crushing or disintegrating by fluid energy in apparatus having multiple crushing or disintegrating zones
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/18—Phosphoric acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/18—Phosphoric acid
    • C01B25/20—Preparation from elemental phosphorus or phosphoric anhydride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C21/00—Disintegrating plant with or without drying of the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
    • B02C23/08—Separating or sorting of material, associated with crushing or disintegrating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
    • B02C23/18—Adding fluid, other than for crushing or disintegrating by fluid energy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/18—Phosphoric acid
    • C01B25/185—Preparation neither from elemental phosphorus or phosphoric anhydride nor by reacting phosphate-containing material with an acid, e.g. by reacting phosphate-containing material with an ion-exchange resin or an acid salt used alone

Definitions

  • the invention relates to a raw material pretreatment method and equipment in a phosphoric acid production process, in particular to a raw material pretreatment method and a pretreatment process system in a kiln process phosphoric acid process (KPA).
  • KPA kiln process phosphoric acid process
  • wet process phosphoric acid that is, the phosphate ore is decomposed by sulfuric acid to obtain dilute phosphoric acid and solid waste residue (referred to as phosphogypsum) mainly composed of CaS0 4 ⁇ ⁇ 3 ⁇ 40, and the dilute phosphoric acid is concentrated to obtain wet-process phosphoric acid containing about 54% of phosphoric acid.
  • the main disadvantages of this process are as follows: First, a large amount of sulfuric acid is consumed; second, the waste slag phosphogypsum cannot be effectively utilized, and the entrained sulfuric acid, phosphoric acid and soluble fluoride are all dissolved in water, and are naturally washed by rainwater, which is easy to wash. Serious pollution to the environment; Third, the product phosphoric acid has a high impurity content, generally only used to produce fertilizer; Fourth, in order to ensure the economical efficiency of the product, high-grade phosphate rock must be used.
  • the method is to finely grind phosphate rock, silica and carbonaceous reducing agent (coke powder or pulverized coal) to 50% ⁇ 85%-325 mesh, add 1% bentonite ball, and dry preheat through chain dryer.
  • the pellets in the kiln reduction to control the maximum temperature of the solids is 1400 ° C ⁇ 1500 ° C, to adjust the pellet Ca0 / Si0 2 molar ratio of 0. 26 ⁇ 0.
  • the melting point of the pellet is higher than the carbothermal reduction temperature of the phosphate ore in the pellet, and the phosphorus is volatilized from the pellet in the form of phosphorus vapor, and then The central space of the kiln is oxidized into phosphorus pentoxide by the ventilating air, and the heat released by the oxidation is in turn supplied to the reduction reaction, and finally the kiln gas containing phosphorus pentoxide is hydrated and absorbed to obtain phosphoric acid.
  • the above-mentioned kiln phosphoric acid process idea shows a good industrial application prospect, because the principle is to use the carbothermal reduction of phosphate rock to form a gas, transfer the phosphorus in the phosphate ore to the gas phase of the rotary kiln, and utilize the gas.
  • the principle of solid separation makes the phosphorus and the remaining solid matter in the pellets separate well.
  • the P 4 gas transferred to the gas phase of the rotary kiln can react with the oxygen in the gas phase of the rotary kiln to generate P 2 0 5 , which is released.
  • the rotary kiln maintains the carbon-thermal reduction temperature of the phosphate rock, the primary energy source is used, and the combustible material produced by the carbothermal reduction of the phosphate rock and the CO can be subjected to a combustion exothermic reaction inside the rotary kiln, and is supplemented and supplied to maintain the carbon heat of the phosphate rock in the rotary kiln.
  • the energy required to reduce the temperature which is significantly reduced compared to the traditional thermal process phosphoric acid process.
  • Rotary kiln is the equipment whose kiln body runs at a certain speed (0.5 r/mir! ⁇ 3r/min). It has the advantage of continuously mechanically turning and mixing the solid materials sent into the kiln to ensure the solid materials in the kiln. The uniformity of heat is everywhere, but in turn the solid material in the kiln is also subject to the mechanical friction of the material movement. If the material strength is less than the mechanical friction, it will be easily destroyed.
  • the basic principle of the KPA process proposed by the US 0RC company is to finely grind phosphate rock, silica and carbonaceous reducing agent (coke powder or pulverized coal) to 50% ⁇ 85%-325 mesh to make pellets.
  • the material pellets used in the process are equipped with a reducing agent carbon, and the carbon undergoes a rapid oxidation reaction with oxygen in the air at a temperature of more than 350 ° C to be converted into C0 2 , if a conventional metallurgical industrial pellet is used on the grate machine.
  • high temperature consolidation 900 °C
  • the reduced carbon in the pellets is completely oxidized, and the reducing agent is lost in the rotary kiln pellets.
  • the pellets entering the kiln will be pulverized in large quantities due to the mechanical friction that can not withstand the movement of the ball in the rotary kiln.
  • Phosphate powder, silica powder and carbonaceous reducing agent which form pellets after pulverization will be separated, and the phosphate rock powder which is pulverized cannot be reduced due to intimate contact with the carbonaceous reducing agent. More seriously, once the phosphate rock is separated from the silica powder, its melting point will be drastically reduced to below 1250 °C.
  • This powdered phosphate rock passes through the high temperature reduction zone of the rotary kiln (the temperature of the layer is about 1300 °C). , all will change from the solid phase to the liquid phase, and then adhere to the rotary kiln lining to form the high temperature ring of the rotary kiln, hinder the normal movement of the material in the rotary kiln, and join Most of the material of the rotary kiln overflows from the rotary kiln at the feed end of the rotary kiln, and the high temperature reduction of phosphorus cannot be achieved, resulting in process failure. It can be seen that due to the inherent defects of the raw materials entering the kiln, the above-mentioned KPA technology has not been used for any industrialization, scale or commercial application.
  • the solid material zone in the lower part of the rotary kiln belongs to the reduction zone, and the upper part of the zone is the gas flow zone of the rotary kiln, which belongs to the oxidation zone, the feed ball.
  • the group is added from the end of the rotary kiln, and is discharged from the kiln head area of the rotary kiln by its own gravity and the frictional force of the rotary kiln.
  • the burner for burning the rotary kiln is installed in the rotary kiln head, and the combustion fumes generated by the kiln are
  • the tail fan is taken out, and the micro-negative pressure is maintained in the rotary kiln, and the air flow is opposite to the moving direction of the material. Since there is no mechanical isolation zone in the reduction zone (solid layer zone) of the rotary kiln and the oxidation zone (the gas flow zone above the solid layer of the rotary kiln), the ball exposed on the surface of the solid zone zone will be in the gas stream with the oxidation zone.
  • the white shell of 5 the thickness of the shell is generally 300 ⁇ m ⁇ 1000 ⁇ m, and the content of P 2 0 5 in the shell layer can be as high as 30% or more; this will cause the transfer ball to P 2 0 5 in the gas phase to not exceed 60%. , resulting in a yield of phosphate in P 205 is low,
  • the waste of mineral resources and the significant increase in the cost of phosphoric acid production have caused the above-mentioned KPA process to lose its commercial application and industrial promotion value.
  • Some researchers hope to isolate the reduction zone in the rotary kiln through the volatilized gas in the layer. Oxidation zones, but industrial tests conducted in rotary kiln with an inner diameter of 2 m have shown that the presence of P 2 0 5 -rich white shell on the pellet surface is still unavoidable.
  • phosphoric acid is produced according to the KPA process proposed by 0RC, which is still very difficult in large-scale industrial applications and practices.
  • Joseph A. Megy has proposed some improved technical methods for the KPA process (see US Pat. No. 7,910,080 B), which is to set the stop at the discharge end of the kiln head of the rotary kiln cylinder while maintaining the basic KPA process.
  • the material ring is used to increase the solid material filling rate of the rotary kiln.
  • by increasing the diameter of the rotary kiln to reduce the surface area-volume ratio of the material layer in the rotary kiln the probability of the material layer being exposed on the surface of the solid material layer is reduced.
  • the process also adds a portion of petroleum coke to the material entering the rotary kiln, in order to utilize the reducing gas generated by the volatilization of the volatiles in the petroleum coke to cover between the material layer and the oxidation zone of the rotary kiln.
  • the material pellets to be used are double-layer composite structure, and the inner layer is made of phosphate rock, silica (or lime, limestone, etc.) and carbonaceous reducing agent after being ground and mixed.
  • the outer layer is a layer of solid fuel containing more than 20% carbon on the inner layer pellet. The inner and outer layers of the pellet are added with a binder, and the pellet is dried and consolidated.
  • Pellet inner Ca0 / Si0 2 molar ratio may be less than 0.6 or greater than 6.5, the carbonaceous reducing agent is a reducing 1 ⁇ 3 times the theoretical amount of phosphate rock, the solid fuel pellet with an outer layer of the inner layer can amount
  • the mass of the pellet is 5% to 25%;
  • the binder added to the pellet and the outer layer may be asphalt, sodium humate, ammonium humate, water glass, sulfite pulp waste liquid, syrup, lignosulfonate 2% ⁇ 15% ( ⁇ ) ⁇
  • the pellet can be dried and consolidated, the consolidation temperature is 80 ° C ⁇ 600 ° C, and the consolidation time is 3 min ⁇ 120 min.
  • the above method proposed by the method uses a high temperature resistant wrapping material containing solid carbon on the pellet, and a binder is added during the wrapping so that the outer covering can adhere well to the inner pellet.
  • the double-layer composite pellets are dried and consolidated and sent to the rotary kiln.
  • the high temperature zone of the rotary kiln 300 ° C ⁇ 140 (about TC) can achieve the carbothermal reduction of phosphate ore.
  • the surface of the sphere is artificially coated with a coating layer containing a solid reducing agent (carbonaceous material), which can align its inner layer pellets with the gas oxidization zone containing 0 2 and P 2 0 5 in the upper part of the rotary kiln layer. Effective physical isolation.
  • the carbon in the coating layer can undergo a limited oxidation reaction with 0 2 in the oxidation zone (due to the time when the material ball is exposed on the surface of the rotary kiln layer in the industrial large rotary kiln) Shorter, less complete reaction, so that 0 2 can not be transferred to the inner pellet, ensuring that the reducing agent carbon in the inner pellet is not oxidized by the oxygen in the rotary kiln gas flow, so that P 2 0 5 in the phosphate rock the reduction process can be performed completely realized process P 2 0 5 in phosphate Reduction rate.
  • an upper kiln gas stream in the oxidation zone layers P 2 0 5 can not react with the carbon composite pellet surface layer and wrapping, thus preventing the formation of a phosphate or metaphosphate on the composite pellets
  • the salt compound eliminates the formation of P 2 0 5 white shell on the original KPA process sphere, ensuring that the process can obtain a higher P 2 O 5 yield.
  • the method is replaced by solid fuel or Partially replaced Gas or liquid fuel, which further reduces the production cost of phosphoric acid.
  • the technical problem to be solved by the invention is to overcome the deficiencies of the prior art, and provide a raw material pretreatment process suitable for the kiln process phosphoric acid process, which has the advantages of reasonable structure optimization, low cost, low energy consumption, and stable operation of the subsequent kiln process phosphoric acid process.
  • System and pre-processing methods are provided.
  • the technical solution proposed by the present invention is a raw material pretreatment process system suitable for a kiln process phosphoric acid process, the pretreatment process system comprising mutually independent carbonaceous reductant pretreatment systems, phosphate ore pretreatment a treatment system and a silica pretreatment system, the carbonaceous reductant pretreatment system, the phosphate ore pretreatment system, and the outlet of the silica pretreatment system are each connected to an inner ball mixing device by the first conveying device, the carbonaceous material
  • the reducing agent pretreatment system and the outlet of the silica pretreatment system are further connected to a casing material mixing device through the second conveying device; the carbonaceous reducing agent pretreatment system is mainly composed of a single-stage crushing device and a carbonaceous reducing agent connected in sequence.
  • the intermediate silo, the grinding equipment, the carbonaceous reducing agent powder storage silo and the dosing device; the phosphate ore pretreatment system mainly comprises a single-stage crushing device, a phosphate ore intermediate silo, a grinding device, The homogenization library and the dosing device are composed; the silica pretreatment system is mainly composed of a single-stage crushing device, a silica intermediate silo, and Mining equipment, storage silos and silica powder dosing device, or of two successively connected to a closed circuit crushing device, the intermediate silo silica, grinding equipment, silica powder and the dosing device consisting of storage silos.
  • the single-stage crushing device adopts a hammer crusher or a counter-break type a crusher, or a combined crusher synthesized by a hammer crusher and a counter crushing unit;
  • the two-stage one closed-circuit crushing device is mainly composed of a jaw crusher, a screen crusher and a cone crusher which are sequentially connected, and the cone is broken.
  • the discharge port of the machine is cyclically connected to the inlet of the screening machine.
  • the grinding device in the carbonaceous reductant pretreatment system adopts a vertical mill or a wind sweep coal mill, and the grinding device is connected to the powder through a powder collecting and conveying device.
  • Carbonaceous reducing agent powder storage bin preferably, Carbonaceous reducing agent powder storage bin.
  • the grinding equipment in the phosphate ore pretreatment system adopts a vertical mill or a wind sweep ball mill, and the grinding equipment is connected to the above by a powder collecting and conveying device.
  • Chemical library preferably, Chemical library.
  • the grinding equipment in the silica pretreatment system adopts a ball mill and/or a high pressure roller press, and the grinding equipment is connected to the silica powder through a powder collecting and conveying device. Storage bin.
  • the grinding equipment is equipped with a hot air furnace which supplies hot air to the grinding process.
  • the powder collecting and conveying device comprises a cyclone collecting device, a bag collecting device and a fan connected in sequence.
  • the present invention also provides a raw material pretreatment method suitable for a kiln process phosphoric acid process, wherein the raw material pretreatment method uses the above raw material pretreatment process system, and the raw material pretreatment method comprises the following steps : pretreating the raw carbonaceous reducing agent, phosphate rock and silica with the carbonaceous reducing agent pretreatment system, the phosphate ore pretreatment system and the silica pretreatment system, and pretreating the carbonaceous reducing agent and phosphate rock
  • the stone and the silica are sent to the inner ball mixing device for mixing and spherizing, and the pretreated carbonaceous reducing agent and the silica are additionally sent to the outer shell mixing device for mixing;
  • the process of the carbonaceous reductant pretreatment system comprises: first crushing the carbonaceous reducing agent by using the single-stage crushing device to a particle size of 30 or less (preferably 6 let ⁇ 30 let), and then crushing the crushed stone
  • the material is sent to the carbonaceous reductant intermediate silo, and the carbonaceous reductant intermediate silo is sent to the grinding equipment for grinding by the metering feeding device, and the grinding equipment is used to grind the feed to the process requirement.
  • the particle size generally -100 mesh or more, preferably -200 mesh to -325 mesh
  • the combined dust collector or the bag collecting device alone
  • the hot air is continuously supplemented by the configured hot blast stove to dry the entrained moisture in the powder;
  • the process of the phosphate ore pretreatment system comprises: firstly crushing the phosphate rock with the single-stage crushing device to a particle size of 30 mm or less (preferably 6 mm to 30 mm), and then sending the crushed crushed stone to the phosphate rock.
  • the stone intermediate silo, the phosphate ore intermediate silo sends the crushed stone to the grinding equipment through the metering feeding device for grinding, and the grinding equipment grinds the feed to the required particle size (generally -100)
  • the combined dust collector or the bag collecting device alone
  • the bag collecting device collects the powder and transports it to the homogenizing library.
  • the process of the silica pretreatment system comprises: firstly crushing the silica into the single-stage crushing device or the two-stage one closed-circuit crushing device to a particle size of 30 mm or less (preferably 6 mm to 30 mm), and then sending the crushed crushed stone material.
  • the silica intermediate silo is sent to the grinding equipment for grinding by the metering feeding device, and the grinding equipment grinds the feed to the required particle size (generally -100 mesh) Above, preferably -100 mesh to -200 mesh), the combined dust collector consisting of the cyclone collecting device and the bag collecting device collects the powder and transports it to the silica powder storage bin;
  • the configured hot blast stove continuously replenishes the hot air to dry the moisture entrained in the powder.
  • the homogenization library is a gap homogenization library or a continuous homogenization library, and the homogenization library uses compressed air to stir and homogenize the powder in the library. And the homogenization value is greater than or equal to 4.
  • the raw material pretreatment in the present invention is an optimized and improved high crushing ratio crushing device, which not only can significantly reduce the crushing energy consumption, but also can reduce the crushing equipment investment and Process cost;
  • the crushing of silica is preferably carried out by a high-strength counter-attack type of one-stage crushing or a two-stage closed-circuit crushing method consisting of a jaw crusher-vibrating screen-cone crushing, Effectively improve the crushing efficiency of silica;
  • each main raw material is equipped with independent crushing equipment and grinding equipment, respectively, by separately crushing, separately grinding and milling, and then According to the process regulations
  • the Ca0/Si0 2 molar ratio and the reducing agent dosage can ensure the stability of the raw material formulation to a large extent, prevent the raw material ratio from fluctuating greatly, and the melting point of the subsequently prepared composite pellets can be kept consistent.
  • the homogenization of the phosphate rock powder is carried out by a gas flow homogenization method, which is advantageous for further ensuring the stability of the chemical composition of the process phosphate ore and making industrialized stable production possible.
  • FIG. 1 is a schematic view showing the process flow of a raw material pretreatment process using the raw material pretreatment process system of the present invention in a specific embodiment of the present invention.
  • the pretreatment process system includes mutually independent carbonaceous reductant pretreatment system, phosphate ore pretreatment system and silica pretreatment system, carbonaceous Reductant pretreatment system
  • the outlets of the phosphate ore pretreatment system and the silica pretreatment system are connected to an inner ball mixing device through the first conveying device, and the carbonaceous reducing agent pretreatment system and the outlet of the silica pretreatment system are passed through the second conveying device. Both are connected to a shell material mixing device.
  • coal material (coke powder or petroleum coke) is used as the carbonaceous reducing agent
  • the carbonaceous reducing agent pretreatment system of the embodiment mainly comprises a single-stage crushing device, a coal material intermediate silo, and a grinding device which are sequentially connected.
  • the pulverized coal storage bin and the dosing device are composed;
  • the phosphate ore pretreatment system in the embodiment is mainly composed of a single-stage crushing device, a phosphate ore intermediate silo, a grinding device, a homogenizing library and a dosing device connected in sequence.
  • the silica pretreatment system in this embodiment is mainly composed of two sections, a closed circuit crushing device, a silica intermediate silo, a grinding equipment, a silica powder storage silo and a dosing device.
  • the single-stage crushing equipment used in the carbonaceous reductant pretreatment system and the phosphate ore pretreatment system adopts a hammer crusher
  • the two-stage one closed-circuit crushing equipment used in the silica pretreatment system is mainly composed of
  • the jaw crusher, the sieving machine and the cone crusher are connected in sequence, and the discharge port of the cone crusher is cyclically connected to the inlet of the screening machine.
  • the grinding device of the carbonaceous reducing agent pretreatment system and the phosphate ore pretreatment system adopts vertical grinding
  • the grinding equipment in the silica pretreatment system adopts a ball mill and/or a high pressure roller press, and each grinding device They are connected to the pulverized coal storage silo, the homogenization storage tank and the silica powder storage silo through their respective powder collection and conveying devices.
  • Each grinding equipment is equipped with a hot blast stove that supplies hot air to the grinding process.
  • each of the powder collecting and conveying devices comprises a cyclone collecting device, a bag collecting device and a fan which are sequentially connected, and the air outlets of the respective fans are connected to the hot air furnace corresponding to each pretreatment system or directly discharged.
  • the silica is pretreated by the above-mentioned carbonaceous reducing agent pretreatment system, the phosphate ore pretreatment system and the silica pretreatment system, and the pretreated pulverized coal, phosphate rock powder and silica powder are fed into the inner ball mixing device for mixing. After the ball is formed, the pre-treated coal powder and the silica powder are further sent to the outer shell mixing device for mixing; the raw material pretreatment method specifically comprises the following steps:
  • Coal material pretreatment The -200mm coal material (coke powder or petroleum coke) is firstly crushed to a particle size of 12mm or less by single-stage hammer crushing method (also available in counter-attack or hammer-counter-type combination crushing).
  • the crushed crushed stone is sent to the intermediate silo of the coal material, and the intermediate silo of the coal material is sent to the vertical roller mill through the metering feeding device (ie, the vertical mill, and the wind sweeping coal mill can also be used) Grinding, the load of the mill can be stabilized by the metering feeding device; after the vertical mill grinds the feed to -100 mesh to -325 mesh, the combination of the cyclone collecting device and the bag collecting device
  • the dust collector collects the powder (can also be collected by a high-concentration bag filter) and transports it to the pulverized coal storage bin; during the grinding process, the hot air is continuously replenished through the configured hot blast stove to dry the powder according to the moisture content of the raw material.
  • the moisture entrained in the middle; the pretreatment process of the entire coal material has a higher crushing ratio, which can save energy consumption and reduce investment and process costs;
  • Phosphate ore pretreatment The -200mm phosphate rock is firstly subjected to single-stage hammer crushing (reverse type or hammer can also be used) - Counter-attack combination crushing) is crushed to a particle size below 12mm, and then the crushed crushed stone is sent to the phosphate ore intermediate silo, and the phosphate ore intermediate silo is sent to the vertical by the metering feeding device Grinding (also using a wind sweep ball mill) for grinding, the mill load can be stabilized by the metering feeding device; after the vertical mill grinds the feed to -100 mesh ⁇ -200 mesh, the cyclone collecting device and The combined dust collector consisting of bag collecting equipment collects the powder (can also be collected by a high-concentration bag filter) and transports it to the homogenization tank; during the grinding process, the hot air is continuously replenished by the configured hot blast stove so that The moisture contained in the dry powder according to the moisture content of the raw material; the pretreatment process of the whole phosphate rock has
  • Silica pretreatment The silica of -200mm is firstly used in two-stage closed-circuit crushing equipment (also can be used in single-stage impact crushing equipment or counter-shock-hammer combined crushing method) to crush to a particle size of 12mm or less, and then crushed.
  • the crushed stone is sent to the silt intermediate silo, and the silica intermediate silo is sent to the high-pressure roller press by means of the metering and feeding device (also can be combined by high-pressure rolling and ball milling), and the feeding is carried out.
  • the equipment can stabilize the load of the mill; after the grinding equipment grinds the feed to -100 mesh to -200 mesh, the powder collector is collected by the combined dust collector consisting of the cyclone collecting device and the bag collecting device, and is transported.
  • the hot air is continuously replenished through the configured hot blast stove during the grinding process, so that the moisture entrained in the powder is dried according to the moisture content of the raw material;
  • the chemical library can also use a continuous homogenization library, and its homogenization value is greater than 4; the homogenization library itself serves as a storage bin for phosphate rock powder.

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  • Organic Chemistry (AREA)
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Abstract

本发明公开了一种适用于窑法磷酸工艺的原料预处理工艺系统，包括相互独立的碳质还原剂、磷矿石和硅石预处理系统，各预处理系统的出口通过输送设备均连接至内球料混合装置，碳质还原剂和硅石预处理系统的出口另通过输送设备均连接至外壳料混合装置；各预处理系统主要由依次相连的单段破碎设备、中间料仓、磨矿设备、储料仓和配料装置组成。本发明还公开了一种适用于窑法磷酸工艺的原料预处理方法，即将碳质还原剂、磷矿石和硅石分别用各自的预处理系统进行预处理，然后送入内球料混合装置进行造球，预处理后的碳质还原剂和硅石另送入外壳料混合装置进行混合。本发明具有结构优化合理、成本低、能耗小、能保证窑法磷酸工艺稳定运行等显著优势。

Description

适用于窑法磷酸工艺的原料预处理方法和原料预处理工艺系统
【技术领域】
本发明涉及一种制磷酸工艺中的原料预处理方法及设备， 尤其涉及一种窑法磷酸工艺 (KPA) 中的原料预处理方法及预处理工艺系统。
【背景技术】
目前世界上工业生产磷酸的方法主要有两种。 （1 ) 湿法制磷酸： 即利用硫酸分解磷矿石 得到稀磷酸和以 CaS04 · η¾0为主体的固体废渣（简称磷石膏），将稀磷酸浓缩得到含磷酸 54% 左右的湿法磷酸。 这种工艺的主要缺点： 一是要耗用大量的硫酸； 二是废渣磷石膏无法得到 有效的利用， 其中夹带的硫酸、 磷酸和可溶性氟化物均溶于水， 自然堆放后被雨水冲刷， 容 易对环境造成严重污染； 三是产品磷酸的杂质含量较高， 一般只用于生产肥料； 四是为保证 产品的经济性， 必须使用高品位磷矿。 （2 ) 热法制磷酸： 即首先将磷矿石、 硅石、 碳质固体 还原剂置于一台矿热电炉中， 用电短路形成电弧的能量， 将炉内温度加热到 1300°C以上， 将 磷矿石中的磷以 形式还原出来， 同时碳质固体还原剂被转化为 C0， 将排出矿热炉的 和 CO为主的气体用水洗涤降温， P4被冷却成固体与气相分离， 得到产品黄磷， 含 CO的废气在烟 囱出口点火燃烧后排入大气； 将得到的 加热到 80°C左右， 使其变为液相， 将其在水化塔中 与通入的空气发生氧化燃烧反应， 得到磷酸酐 P205， 再用水吸收得到磷酸。 热法制磷酸的主 要缺点： 一是要耗费大量的电能； 二是排出矿热炉后分离了 的气体还夹带有大量的氟化物 (以 SiF^P HF存在） 和少量未沉淀的气体 P4， 这将对大气环境造成严重污染； 三是含大量 CO的气体直接燃烧排空， 能源浪费很大； 四是为了保证生产的经济性， 同样需要使用高品位 磷矿石。
为了克服电能紧张、 硫铁矿资源不足和高品位磷矿石逐年减少对磷酸生产的影响， 八十 年代初美国 Occidental Research Corporation ( 0RC) 提出采用 KPA法， 即用回转窑生产 磷酸的方法（简称窑法磷酸工艺） （参见 Frederic Ledar and Won C. Park等， New Process for Technical-Grade Phosphoric Acid, Ind. Eng. Chem. Process Des. Devl985, 24, 688-697)， 并进行了 0. 84m (内） X 9. 14m回转窑中试装置的中间试验 （参见 US4389384号美国专利文 献）。 该方法是将磷矿石、 硅石和碳质还原剂（焦粉或煤粉）细磨到 50%〜85%— 325目， 配加 1%的膨润土造球， 经链式干燥机干燥预热后送入窑头燃烧天然气的回转窑中， 球团在窑内还 原， 控制最高固体温度为 1400°C〜1500°C， 调整球团 Ca0/Si02摩尔比为 0. 26〜0. 55， 使球团 熔点高于球团中磷矿石的碳热还原温度， 磷以磷蒸气的形式从球团中还原挥发出来， 然后在 窑的中部空间被通入的空气氧化成五氧化二磷， 氧化放出来的热反过来又供给还原反应， 最 后将含有五氧化二磷的窑气水化吸收即制得磷酸。
上述的窑法磷酸工艺思路显示了一种良好的工业应用前景， 因其原理是利用磷矿的碳热 还原形成 气体， 将磷矿石中的磷转移到回转窑的气相当中， 并利用气固分离原理使磷与料 球中的其余固体物质很好的进行分离， 转移到回转窑气相中的 P4气体可与回转窑气相中的氧 发生氧化放热反应生成 P205， 放出的热则供给料球中磷矿石的碳热还原 （吸热反应）， 最后将 出回转窑的含 P205的窑气水化吸收， 可获得洁净度远高于湿法磷酸的工业磷酸。 由于回转窑 维持磷矿碳热还原温度使用的是初级能源，同时磷矿碳热还原产生的可燃物质 与 CO在回转 窑内部即可进行燃烧放热反应， 补充提供给维持回转窑磷矿碳热还原温度所需能量， 这与传 统的热法制磷酸工艺相比， 其能耗得到大幅度降低。
然而， 我们的研究表明， 上述的窑法磷酸工艺在规模化的工业应用及实践中很难实现， 其主要缺陷在于：
1、 回转窑是窑体以一定速度（0. 5r/mir！〜 3r/min )运转的设备， 其优点是可以连续对送 入窑内的固体物料进行机械翻转、 混合， 保证窑内固体物料各处受热的均匀性， 但反过来窑 内固体物料亦须承受物料运动的机械摩擦力， 如果物料强度小于受到的机械摩擦力将很容易 被破坏。 美国 0RC公司提出的 KPA工艺基本原理是将磷矿石、 硅石和碳质还原剂 （焦粉或煤 粉） 细磨到 50%〜85%— 325 目后制成球团， 这三种物质必须紧密地共聚一体， 才能在混合物 中 Ca0/Si02摩尔比为 0. 26〜0. 55 的条件下， 实现混合物料在磷矿石的碳热还原温度下不熔 化， 同时， 磷矿的碳还原才能得以顺利进行。 但工艺使用的物料球团中配入了还原剂碳， 碳 在大于 350 °C温度下会与空气中的氧发生快速的氧化反应转变成 C02， 如果采用传统冶金工业 球团在链篦机上高温固结的方法 （ 900 °C )， 则球团中的还原碳会被全部氧化， 入回转窑球 团则流失了还原剂， 磷的碳热还原反应自然也无法进行， 导致工艺失败。 如果仅通过添加膨 润土作球团粘结剂在 300 °C以下进行干燥脱水， 则球团抗压强度仅为 10KN/个球左右， 落下强 度 1次 /米； 因为膨润土的作用机理主要是利用其物质结构中的层间水来调节球团干燥过程 中的水分释放速率， 提高球团在干燥过程中的爆裂温度， 其本身对提高球团强度并无显著作 用。 将这种球团送入回转窑后、 且在回转窑温度值达到 900 °C温度前， 由于承受不住回转窑 内料球运动所受到的机械摩擦力， 入窑的球团将大量粉化， 粉化后组成球团的磷矿粉、 硅石 粉和碳质还原剂等将分离， 粉化后的磷矿粉由于不能与碳质还原剂紧密接触， 将导致磷不能 被还原。 更为严重的是， 磷矿粉一旦与硅石粉分开， 其熔点将急剧降低到 1250 °C以下， 这种 粉状磷矿通过回转窑的高温还原区 （料层温度为 1300 °C左右） 时， 将全部由固相变成液相， 进而粘附在回转窑窑衬上形成回转窑的高温结圈， 阻碍物料在回转窑内的正常运动， 使加入 回转窑的大部分物料从回转窑加料端溢出回转窑， 无法实现磷的高温还原， 导致工艺失败。 可见， 由于入窑原料存在固有缺陷， 至今未见上述的 KPA技术进行过任何工业化、 规模化或 商业化的应用。
2、对于上述配碳磷矿球团的 KPA工艺而言， 在回转窑内料层下部的固体料层区属于还原 带， 料层上部则是回转窑的气流区， 属于氧化带， 进料球团从回转窑窑尾加入， 依靠其自身 重力和回转窑旋转的摩擦力从回转窑的窑头区排出， 回转窑燃烧燃料的烧嘴安装在回转窑窑 头， 产生的燃烧烟气则由窑尾的风机引出， 回转窑内维持微负压， 气流与物料的运动方向相 反。 由于在回转窑的还原带 （固体料层区） 和氧化带 （回转窑固体料层上部的气流区） 无机 械隔离区， 因此， 暴露在固体料层区表面的料球将与氧化带气流中的 、 （¾发生对流传质； 这一方面会使料球中的还原剂碳在料球被气流传热加热到磷矿石碳还原温度前被部分氧化 掉， 致使料球在回转窑还原带由于碳质还原剂的缺乏， 而得不到充分还原； 更为严重的是， 在回转窑高温区暴露于料层表面的料球， 会与窑气中已经还原生成的 P205发生进一步的化学 反应， 生成偏磷酸钙、 磷酸钙及其他的偏磷酸盐或磷酸盐， 进而导致已被还原到气相中的磷 又重新返回料球，并在料球表面形成一层富含 P205的白壳，壳层厚度一般在 300 μ m〜1000 μ m， 壳层中 P205含量可高达 30%以上； 这样会致使料球转移到气相中的 P205不超过 60%， 造成磷矿 中 P205的收率偏低， 进而造成矿产资源的浪费及磷酸生产成本的大幅度上升， 使上述的 KPA 工艺丧失商业应用和工业推广价值。 有研究人员寄望通过料层中挥发出的气体来隔离回转窑 中的还原带与氧化带， 但在内径 2m的回转窑中进行的工业试验表明， 球团表面出现富含 P205 的白壳现象仍是不可避免的。
鉴于上述提及的技术缺陷， 按照 0RC公司所提出的 KPA工艺来生产磷酸， 这在规模化的 工业应用及实践中还存在很大困难。
Joseph A. Megy对 KPA工艺提出过一些改进的技术方法 （参见 US7910080B号美国专利文 献）， 即在维持 KPA基本工艺方法不变的前提下， 通过在回转窑筒体的窑头泄料端设置挡料圈 以提高回转窑的固体物料填充率， 与此同时， 通过增大回转窑的直径以减少回转窑内料层的 表面积-体积比， 降低料层物料暴露在固体料层表面的几率， 以缩短料球中还原剂碳被回转窑 窑气中的 氧化的时间， 减少料球到达回转窑还原带前的还原剂碳的烧损， 同时减少回转窑 高温区中料球表面磷酸盐或偏磷酸盐的生成。 另外， 该工艺还通过在入回转窑的物料中加入 部分石油焦， 以希望利用石油焦中挥发分受热挥发产生的还原性气体， 使其覆盖在料层与回 转窑气流氧化区之间， 以进一步阻止回转窑气流中 、 P205与料球反应的几率， 以保证工艺的 正常进行。 然而， 提高回转窑的填充率将使料球在回转窑内承受更大的机械摩擦力， 进而将 造成料球在回转窑内更大比例的粉化， 形成更多的小于磷矿碳热还原温度的低熔点物质， 使 回转窑高温结圈更加迅速和严重， 从而更早造成工艺的失败。 而添加少量的石油焦产生的挥 发分不足以产生足够的气体， 难以在回转窑固体料层与回转窑内气流区之间形成有效的隔离 层， 若加入量过大， 则出回转窑物料中将夹带有大量的燃料， 这会导致在后续工艺的渣球冷 却机中， 剩余燃料将与冷却渣球的空气相遇并迅速燃烧， 燃烧放出的大量热量不仅增加了出 回转窑高温渣球冷却的难度， 而且又大大提高了工艺的生产成本， 使工艺的商业化、 规模化 运用变得不可实现。
鉴于上述问题， 我们经过反复研究， 曾提出过一种克服上述问题的解决方案 （参见 CN1026403C, CN1040199C 号中国专利文献）， 即采用一种双层复合球团直接还原磷矿石生产 磷酸的工艺， 具体技术解决方案是： 先将磷矿石与配入物料制成球团， 在回转窑内， 球团中 的 P205被还原成磷蒸气并挥发， 在料层上方， 磷蒸气被引入炉内的空气氧化成 P205气体， 然 后在水化装置中被吸收制得磷酸。 该技术方案的最大特点在于： 配入的物料球团采用双层复 合结构， 其内层是由磷矿石、 硅石 （或石灰、 石灰石等） 和碳质还原剂经磨碎、 混匀后造球 而成， 其外层是在内层球团上再裹上一层含碳量大于 20%的固体燃料， 球团的内、 外层配料 时添加粘结剂， 球团采用干燥固结。 球团内层 Ca0/Si02摩尔比可以小于 0. 6或大于 6. 5， 碳 质还原剂为还原磷矿石理论量的 1〜3倍，球团外层固体燃料配量可以为内层球团质量的 5%〜 25%； 球团内、 外层添加的粘结剂可以是沥青、 腐植酸钠、 腐植酸铵、 水玻璃、 亚硫酸盐纸浆 废液、糖浆、木质素磺酸盐中的一种或多种的组合，其添加量为被添加物料重量的 0. 2%〜15% (干基）。 该球团可以采用干燥固结， 固结温度为 80°C〜600°C， 固结时间为 3min〜120min。
我们提出的上述方法采用在球团上裹一层含固体碳的耐高温包裹料，包裹时添加粘结剂， 以使外层包裹料能良好地附着在内层球团上。 将这种双层复合球团经干燥固结后送入回转窑 中， 在回转窑高温带 （1300°C〜140(TC左右） 可以很好地实现磷矿石的碳热还原。 由于在料 球表面人为包覆了一层含固体还原剂 （碳质物料） 的包裹层， 该包裹层可将其内层球团与回 转窑料层上部的含 02和 P205的气流氧化区进行有效地物理隔离。 当这种复合球团在回转窑固 体料层中随回转窑的旋转运动上升到回转窑固体料层表面， 并与回转窑固体料层上部的含 02 和 P205的气流氧化区接触发生对流传质时， 包裹层中的碳便可与氧化区中的 02发生有限的氧 化反应 （因在工业大型回转窑中料球暴露在回转窑料层表面的时间较短， 反应不完全）， 使 02不能传递到内层球团， 保证了内层球团中的还原剂碳不被回转窑气流中的氧所氧化， 使磷 矿石中 P205的还原过程能进行彻底， 实现了工艺过程中磷矿 P205的高还原率。 另一方面， 回 转窑料层上部气流氧化区中的 P205也不可能与复合球团表层包裹层中的碳反应， 因而阻止了 在复合球团上形成磷酸盐或偏磷酸盐化合物， 消除了原有 KPA工艺料球上富含 P205白壳的生 成， 确保了工艺可获得较高的 P2O5收率。 与此同时， 该方法中以固体燃料取代或部分取代了 气体或液体燃料， 这可进一步降低磷酸的生产成本。
此外， 我们提出的上述方法中在造球时还加入了有机粘结剂， 这可使复合球团在干燥脱 水后 （低于球团中碳氧化温度）， 仍可以达到 200kN/个球以上的抗压强度和 10次 /米以上的 落下强度， 因此， 该复合球团可以抵抗在回转窑内受到的机械摩擦力而不被粉碎， 克服了原 有 KPA工艺存在的球团强度差等缺陷， 也克服了球团中碳在回转窑预热带过早氧化的现象， 使复合球团在窑内不出现粉化， 进而避免了粉料造成的回转窑高温结圈致使工艺失败， 保证 了工艺能在设定的条件下顺利进行。
然而， 在我们后续的研究过程中， 又发现了一系列新的技术问题， 这其中就有部分技术 问题体现在原料的预处理阶段。 首先， 原料预处理阶段选用的预处理设备及由此组合成的预 处理工艺系统还不够合理和科学， 这导致原料预处理阶段的工艺成本和能耗还相对较高； 更 为突出的技术问题是， 送入回转窑的原料成分波动较大， 原料的混合不够均匀， 这导致复合 球团中 Ca0/Si02的摩尔比波动较大， 这又进一步加重了回转窑内粉料的高温结圈问题， 使得 工艺失败的风险进一步增加。
因此， 为了使现有的窑法磷酸工艺的生产成本和能耗进一步降低以便于进行工业化、 商 业化的推广应用， 为了能更稳定地进行长周期生产， 在原料准备、 原料制粉的原料预处理阶 段还亟待本领域技术人员进行继续的改进和完善。
【发明内容】
本发明要解决的技术问题是克服现有技术的不足， 提供一种结构优化合理、 成本低、 能 耗小、 能保证后续窑法磷酸工艺稳定运行的适用于窑法磷酸工艺的原料预处理工艺系统及预 处理方法。
为解决上述技术问题， 本发明提出的技术方案为一种适用于窑法磷酸工艺的原料预处理 工艺系统， 所述预处理工艺系统包括相互独立的碳质还原剂预处理系统、 磷矿石预处理系统 和硅石预处理系统， 所述碳质还原剂预处理系统、 磷矿石预处理系统和硅石预处理系统的出 口通过第一输送设备均连接至一内球料混合装置， 所述碳质还原剂预处理系统和硅石预处理 系统的出口另通过第二输送设备均连接至一外壳料混合装置； 所述碳质还原剂预处理系统主 要由依次相连的单段破碎设备、 碳质还原剂中间料仓、 磨矿设备、 碳质还原剂粉储料仓和配 料装置组成； 所述磷矿石预处理系统主要由依次相连的单段破碎设备、 磷矿石中间料仓、 磨 矿设备、 均化库和和配料装置组成； 所述硅石预处理系统主要由依次相连的单段破碎设备、 硅石中间料仓、 磨矿设备、 硅石粉储料仓和配料装置组成， 或者由依次相连的两段一闭路破 碎设备、 硅石中间料仓、 磨矿设备、 硅石粉储料仓和配料装置组成。
上述的原料预处理工艺系统中， 优选的， 所述单段破碎设备采用锤式破碎机或反击式破 碎机， 或者采用锤式破碎机和反击式破碎机组合成的联合式破碎机； 所述两段一闭路破碎设 备主要由依次相连的颚式破碎机、 筛分机和圆锥破碎机组成， 且圆锥破碎机的出料口循环连 接至筛分机的进料口。
上述的原料预处理工艺系统中， 优选的， 所述碳质还原剂预处理系统中的磨矿设备采用 立式磨或风扫煤磨， 该磨矿设备通过粉料收集输送装置连接至所述的碳质还原剂粉储料仓。
上述的原料预处理工艺系统中， 优选的， 所述磷矿石预处理系统中的磨矿设备采用立式 磨或风扫球磨， 该磨矿设备通过粉料收集输送装置连接至所述的均化库。
上述的原料预处理工艺系统中， 优选的， 所述硅石预处理系统中的磨矿设备采用球磨机 和 /或高压辊压机， 该磨矿设备通过粉料收集输送装置连接至所述的硅石粉储料仓。
上述的原料预处理工艺系统中， 优选的， 所述磨矿设备配备有向粉磨过程补送热风的热 风炉。
上述的原料预处理工艺系统中， 优选的， 所述粉料收集输送装置包括依次相连的旋风收 粉设备、 布袋收粉设备和风机。
作为一个总的技术构思， 本发明还提供一种适用于窑法磷酸工艺的原料预处理方法， 所 述原料预处理方法用到上述的原料预处理工艺系统， 所述原料预处理方法包括以下步骤： 将 原料碳质还原剂、 磷矿石和硅石分别用所述碳质还原剂预处理系统、 磷矿石预处理系统和硅 石预处理系统进行预处理， 预处理后的碳质还原剂、 磷矿石和硅石送入内球料混合装置进行 混合造球， 预处理后的碳质还原剂和硅石另送入外壳料混合装置进行混合；
所述碳质还原剂预处理系统的工艺过程包括： 将碳质还原剂先采用所述单段破碎设备破 碎至粒度在 30讓以下 （优选 6讓〜30讓）， 然后将破碎后的碎石料送至碳质还原剂中间料仓， 碳质还原剂中间料仓通过计量给料设备将碎石料送至所述磨矿设备进行粉磨， 待磨矿设备将 进料粉磨至工艺要求的粒度 （一般为 -100 目以上， 优选 -200 目〜 -325 目） 后， 由旋风收粉 设备和布袋收粉设备组成的组合式收尘器 （或单独用布袋收粉设备） 收集粉料， 并输送至碳 质还原剂粉储料仓； 所述粉磨过程中通过配置的热风炉不断补充热风以干燥粉料中夹带的水 分；
所述磷矿石预处理系统的工艺过程包括： 将磷矿石先采用所述单段破碎设备破碎至粒度 在 30mm以下 （优选 6mm〜30mm)， 然后将破碎后的碎石料送至磷矿石中间料仓， 磷矿石中间 料仓通过计量给料设备将碎石料送至所述磨矿设备进行粉磨， 待磨矿设备将进料粉磨至工艺 要求的粒度 （一般为 -100 目以上， 优选 -100 目〜 -200 目） 后， 由旋风收粉设备和布袋收粉 设备组成的组合式收尘器 （或单独用布袋收粉设备） 收集粉料， 并输送至均化库； 所述粉磨 过程中通过配置的热风炉不断补充热风以干燥粉料中夹带的水分； 所述硅石预处理系统的工艺过程包括： 将硅石先采用所述单段破碎设备或两段一闭路破 碎设备破碎至粒度在 30mm以下 （优选 6mm〜30mm)， 然后将破碎后的碎石料送至硅石中间料 仓， 硅石中间料仓通过计量给料设备将碎石料送至所述磨矿设备进行粉磨， 待磨矿设备将进 料粉磨至工艺要求的粒度 （一般为 -100 目以上， 优选 -100 目〜 -200 目） 后， 由旋风收粉设 备和布袋收粉设备组成的组合式收尘器收集粉料， 并输送至硅石粉储料仓； 所述粉磨过程中 通过配置的热风炉不断补充热风以干燥粉料中夹带的水分。
上述的适用于窑法磷酸工艺的原料预处理方法， 优选的， 所述均化库为间隙均化库或连 续均化库， 所述均化库采用压缩空气对库内粉料进行搅拌均化， 且均化值大于或等于 4。
与现有技术相比， 本发明的优点在于：
( 1 )与传统的多段破碎工艺相比， 本发明中原料预处理采用的均是经过优化改进后的高 破碎比的破碎设备， 其不仅能显著降低破碎能耗， 而且可降低破碎设备投资和工艺成本； 考 虑到硅石的硬度等特性， 本发明中对硅石的破碎优选采用了高强度的反击式一段破碎或由鄂 式破碎机-振动筛 -圆锥破碎组成的二段一闭路破碎方法， 同样有效提高了硅石的破碎效率；
( 2 )相比传统工艺中基于常规思路采用的多原料混磨方式， 本发明中对每一种主要原料 均配备独立的破碎设备和磨矿设备， 通过单独破碎、 分别磨矿制粉， 然后按照工艺规定的
Ca0/Si02摩尔比和还原剂用量配料， 可以在很大程度上保证原料配方的稳定性， 防止原料的 配比出现较大波动， 后续制成的复合球团的熔点能保持一致， 解决了由于原料成分波动造成 后续工序中复合球团在回转窑内结圈的技术难题；
( 3 )在本发明优选的技术方案中， 通过采用磨矿设备配备热风炉的方式， 省去了各种矿 石及原料的干燥工序， 工艺流程更为简化， 同时磨矿能耗降低达 20%以上；
( 4)在本发明优选的技术方案中， 磷矿石粉均化采用气流均化方法， 有利于进一步保证 工艺磷矿石化学成分的稳定， 使工业化稳定生产成为可能。
【附图说明】
图 1为本发明具体实施方式中采用本发明原料预处理工艺系统进行原料预处理的工艺流 程原理图。
【具体实施方式】
以下结合说明书附图和具体优选的实施例对本发明作进一步描述， 但并不因此而限制本 发明的保护范围。
实施例：
一种如图 1所示适用于窑法磷酸工艺的原料预处理工艺系统， 预处理工艺系统包括相互 独立的碳质还原剂预处理系统、 磷矿石预处理系统和硅石预处理系统， 碳质还原剂预处理系 统、 磷矿石预处理系统和硅石预处理系统的出口通过第一输送设备均连接至一内球料混合装 置， 碳质还原剂预处理系统和硅石预处理系统的出口另通过第二输送设备均连接至一外壳料 混合装置。
本实施例中采用煤料 （焦粉或石油焦） 作为碳质还原剂， 本实施例的碳质还原剂预处理 系统主要由依次相连的单段破碎设备、 煤料中间料仓、 磨矿设备、 煤粉储料仓和配料装置组 成； 本实施例中的磷矿石预处理系统主要由依次相连的单段破碎设备、 磷矿石中间料仓、 磨 矿设备、 均化库和和配料装置组成； 本实施例中的硅石预处理系统主要由依次相连的两段一 闭路破碎设备、 硅石中间料仓、 磨矿设备、 硅石粉储料仓和配料装置组成。
本实施例中， 碳质还原剂预处理系统和磷矿石预处理系统中用到的单段破碎设备均采用 锤式破碎机，硅石预处理系统中采用的两段一闭路破碎设备则主要由依次相连的颚式破碎机、 筛分机和圆锥破碎机组成， 且圆锥破碎机的出料口循环连接至筛分机的进料口。
本实施例中， 碳质还原剂预处理系统、 磷矿石预处理系统的磨矿设备采用立磨， 硅石预 处理系统中的磨矿设备采用球磨机和 /或高压辊压机，各磨矿设备分别通过各自的粉料收集输 送装置连接至煤粉储料仓、 均化库和硅石粉储料仓。 各磨矿设备配备有向粉磨过程补送热风 的热风炉。
本实施例中， 各粉料收集输送装置均包括依次相连的旋风收粉设备、 布袋收粉设备和风 机， 各风机的出风口连接至各预处理系统对应的热风炉或直接外排。
一种如图 1所示本发明的适用于窑法磷酸工艺的原料预处理方法， 该原料预处理方法用 到上述本实施例的原料预处理工艺系统， 其主要是将原料煤、 磷矿石和硅石分别用上述的碳 质还原剂预处理系统、 磷矿石预处理系统和硅石预处理系统进行预处理， 预处理后的煤粉、 磷矿石粉和硅石粉送入内球料混合装置进行混合造球， 预处理后的煤粉和硅石粉另送入外壳 料混合装置进行混合； 该原料预处理方法具体包括以下步骤：
1. 煤料预处理： 将 -200mm 的煤料 （焦粉或石油焦） 先采用单段锤式破碎方式 （也可采 用反击式或锤式 -反击式组合破碎） 破碎至粒度在 12mm以下， 然后将破碎后的碎石料送至煤 料中间料仓， 煤料中间料仓通过计量给料设备将碎石料送至立式辊磨 （即立式磨， 也可采用 风扫煤磨） 进行粉磨， 通过计量给料设备可以稳定磨机的负荷； 待立式磨将进料粉磨至 -100 目〜 -325目后， 由旋风收粉设备和布袋收粉设备组成的组合式收尘器收集粉料 （也可单独由 高浓度布袋收尘器进行收集）， 并输送至煤粉储料仓； 粉磨过程中通过配置的热风炉不断补充 热风， 以便根据原料含水量干燥粉料中夹带的水分； 整个煤料的预处理过程具有较高的破碎 比， 能够节省破碎能耗、 降低投资和工艺成本；
2. 磷矿石预处理： 将 -200mm 的磷矿石先采用单段锤式破碎方式 （也可采用反击式或锤 式 -反击式组合破碎）破碎至粒度在 12mm以下， 然后将破碎后的碎石料送至磷矿石中间料仓， 磷矿石中间料仓通过计量给料设备将碎石料送至立式磨 （也可采用风扫球磨） 进行粉磨， 通 过计量给料设备可以稳定磨机的负荷； 待立式磨将进料粉磨至 -100目〜 -200目后， 由旋风收 粉设备和布袋收粉设备组成的组合式收尘器收集粉料 （也可单独由高浓度布袋收尘器进行收 集）， 并输送至均化库； 粉磨过程中通过配置的热风炉不断补充热风， 以便根据原料含水量干 燥粉料中夹带的水分； 整个磷矿石的预处理过程具有较高的破碎比， 可以进一步节省破碎能 耗和降低投资；
3. 硅石预处理： 将 -200mm 的硅石先采用两段一闭路破碎设备 （也可采用单段反击式破 碎设备或反击式-锤式联合破碎方式） 破碎至粒度在 12mm以下， 然后将破碎后的碎石料送至 硅石中间料仓， 硅石中间料仓通过计量给料设备将碎石料送至高压辊压机 （也可采用高压辊 压联合球磨的方式） 进行粉磨， 通过计量给料设备可以稳定磨机的负荷； 待磨矿设备将进料 粉磨至 -100目〜 -200目后， 由旋风收粉设备和布袋收粉设备组成的组合式收尘器收集粉料， 并输送至硅石粉储料仓； 粉磨过程中通过配置的热风炉不断补充热风， 以便根据原料含水量 干燥粉料中夹带的水分；
4. 由输运设备送入煤粉储料仓中的煤粉， 同时作为后续窑法磷酸工艺内球料和外壳料的 原料； 由输运设备送入硅石粉储料仓中的硅石粉， 也同时作为后续窑法磷酸工艺内球料和外 壳料的原料； 由输送设备送入均化库的磷矿石粉， 通过采用压缩空气对库内的磷矿石粉进行 搅拌均化， 可以用间隙均化库， 也可以用连续均化库， 其均化值大于 4即可； 均化库本身又 作为磷矿石粉的储料仓。
通过采用上述的预处理工艺系统和工艺方法， 完成了对窑法磷酸工艺原料的预处理。

Claims

权 利 要 求
1、 一种适用于窑法磷酸工艺的原料预处理工艺系统， 其特征在于： 所述预处理工艺 系统包括相互独立的碳质还原剂预处理系统、 磷矿石预处理系统和硅石预处理系统， 所述 碳质还原剂预处理系统、 磷矿石预处理系统和硅石预处理系统的出口通过第一输送设备均 连接至一内球料混合装置， 所述碳质还原剂预处理系统和硅石预处理系统的出口另通过第 二输送设备均连接至一外壳料混合装置； 所述碳质还原剂预处理系统主要由依次相连的单 段破碎设备、 碳质还原剂中间料仓、 磨矿设备、 碳质还原剂粉储料仓和配料装置组成； 所 述磷矿石预处理系统主要由依次相连的单段破碎设备、 磷矿石中间料仓、 磨矿设备、 均化 库和和配料装置组成； 所述硅石预处理系统主要由依次相连的单段破碎设备、 硅石中间料 仓、 磨矿设备、 硅石粉储料仓和配料装置组成， 或者由依次相连的两段一闭路破碎设备、 硅石中间料仓、 磨矿设备、 硅石粉储料仓和配料装置组成。
2、 根据权利要求 1 所述的原料预处理工艺系统， 其特征在于： 所述单段破碎设备采 用锤式破碎机或反击式破碎机， 或者采用锤式破碎机和反击式破碎机组合成的联合式破碎 机； 所述两段一闭路破碎设备主要由依次相连的颚式破碎机、 筛分机和圆锥破碎机组成， 且圆锥破碎机的出料口循环连接至筛分机的进料口。
3、 根据权利要求 2所述的原料预处理工艺系统， 其特征在于： 所述碳质还原剂预处 理系统中的磨矿设备采用立式磨或风扫煤磨， 该磨矿设备通过粉料收集输送装置连接至所 述的碳质还原剂粉储料仓。
4、 根据权利要求 2所述的原料预处理工艺系统， 其特征在于： 所述磷矿石预处理系 统中的磨矿设备采用立式磨或风扫球磨， 该磨矿设备通过粉料收集输送装置连接至所述的 均化库。
5、 根据权利要求 2所述的原料预处理工艺系统， 其特征在于： 所述硅石预处理系统 中的磨矿设备采用球磨机和 /或高压辊压机，该磨矿设备通过粉料收集输送装置连接至所述 的硅石粉储料仓。
6、 根据权利要求 3、 4或 5所述的原料预处理工艺系统， 其特征在于： 所述磨矿设备 配备有向粉磨过程补送热风的热风炉。
7、 根据权利要求 6所述的原料预处理工艺系统， 其特征在于： 所述粉料收集输送装 置包括依次相连的旋风收粉设备、 布袋收粉设备和风机。
8、 一种适用于窑法磷酸工艺的原料预处理方法， 所述原料预处理方法用到权利要求 1〜7中任一项所述的原料预处理工艺系统， 所述原料预处理方法包括以下步骤： 将原料碳 质还原剂、 磷矿石和硅石分别用所述碳质还原剂预处理系统、 磷矿石预处理系统和硅石预 处理系统进行预处理， 预处理后的碳质还原剂、 磷矿石和硅石送入内球料混合装置进行混 合造球， 预处理后的碳质还原剂和硅石另送入外壳料混合装置进行混合；
所述碳质还原剂预处理系统的工艺过程包括： 将碳质还原剂先采用所述单段破碎设备 破碎至粒度在 30mm以下， 然后将破碎后的碎石料送至碳质还原剂中间料仓， 碳质还原剂 中间料仓通过计量给料设备将碎石料送至所述磨矿设备进行粉磨， 待磨矿设备将进料粉磨 至工艺要求的粒度后， 由旋风收粉设备和布袋收粉设备组成的组合式收尘器收集粉料， 并 输送至碳质还原剂粉储料仓； 所述粉磨过程中通过配置的热风炉不断补充热风以干燥粉料 中夹带的水分；
所述磷矿石预处理系统的工艺过程包括： 将磷矿石先采用所述单段破碎设备破碎至粒 度在 30mm以下， 然后将破碎后的碎石料送至磷矿石中间料仓， 磷矿石中间料仓通过计量 给料设备将碎石料送至所述磨矿设备进行粉磨， 待磨矿设备将进料粉磨至工艺要求的粒度 后， 由旋风收粉设备和布袋收粉设备组成的组合式收尘器收集粉料， 并输送至均化库； 所 述粉磨过程中通过配置的热风炉不断补充热风以干燥粉料中夹带的水分；
所述硅石预处理系统的工艺过程包括： 将硅石先采用所述单段破碎设备或两段一闭路 破碎设备破碎至粒度在 30mm以下， 然后将破碎后的碎石料送至硅石中间料仓， 硅石中间 料仓通过计量给料设备将碎石料送至所述磨矿设备进行粉磨， 待磨矿设备将进料粉磨至工 艺要求的粒度后， 由旋风收粉设备和布袋收粉设备组成的组合式收尘器收集粉料， 并输送 至硅石粉储料仓； 所述粉磨过程中通过配置的热风炉不断补充热风以干燥粉料中夹带的水 分。
9、 根据权利要求 8 所述的适用于窑法磷酸工艺的原料预处理方法， 其特征在于： 所 述均化库为间隙均化库或连续均化库， 所述均化库采用压缩空气对库内粉料进行搅拌均 化， 且均化值大于或等于 4。
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