CN115093253B - Method and device for preparing calcium magnesium phosphate fertilizer by smelting - Google Patents
Method and device for preparing calcium magnesium phosphate fertilizer by smelting Download PDFInfo
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- CN115093253B CN115093253B CN202210629605.1A CN202210629605A CN115093253B CN 115093253 B CN115093253 B CN 115093253B CN 202210629605 A CN202210629605 A CN 202210629605A CN 115093253 B CN115093253 B CN 115093253B
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- magnesium phosphate
- calcium magnesium
- phosphate fertilizer
- furnace
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- KMQAPZBMEMMKSS-UHFFFAOYSA-K calcium;magnesium;phosphate Chemical compound [Mg+2].[Ca+2].[O-]P([O-])([O-])=O KMQAPZBMEMMKSS-UHFFFAOYSA-K 0.000 title claims abstract description 243
- 238000003723 Smelting Methods 0.000 title claims abstract description 176
- 239000003337 fertilizer Substances 0.000 title claims abstract description 169
- 238000000034 method Methods 0.000 title claims abstract description 126
- 239000007921 spray Substances 0.000 claims description 90
- 239000000446 fuel Substances 0.000 claims description 82
- 238000007664 blowing Methods 0.000 claims description 80
- 239000000047 product Substances 0.000 claims description 76
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 75
- 239000001301 oxygen Substances 0.000 claims description 75
- 229910052760 oxygen Inorganic materials 0.000 claims description 75
- 239000000463 material Substances 0.000 claims description 67
- 239000011265 semifinished product Substances 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 53
- 239000003546 flue gas Substances 0.000 claims description 53
- 238000001035 drying Methods 0.000 claims description 50
- 239000000428 dust Substances 0.000 claims description 50
- 239000002918 waste heat Substances 0.000 claims description 48
- 238000002844 melting Methods 0.000 claims description 47
- 230000008018 melting Effects 0.000 claims description 47
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 43
- 238000002485 combustion reaction Methods 0.000 claims description 43
- 239000007789 gas Substances 0.000 claims description 43
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 43
- 239000011707 mineral Substances 0.000 claims description 43
- 229910052698 phosphorus Inorganic materials 0.000 claims description 42
- 239000011574 phosphorus Substances 0.000 claims description 42
- 239000000779 smoke Substances 0.000 claims description 41
- 238000011084 recovery Methods 0.000 claims description 38
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 37
- 238000005485 electric heating Methods 0.000 claims description 27
- 239000000395 magnesium oxide Substances 0.000 claims description 26
- 238000007599 discharging Methods 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 23
- 238000007873 sieving Methods 0.000 claims description 23
- 239000002893 slag Substances 0.000 claims description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000011777 magnesium Substances 0.000 claims description 21
- 229910052749 magnesium Inorganic materials 0.000 claims description 21
- 239000010703 silicon Substances 0.000 claims description 21
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 18
- 239000002686 phosphate fertilizer Substances 0.000 claims description 18
- 239000002006 petroleum coke Substances 0.000 claims description 17
- LHLROOPJPUYVKD-UHFFFAOYSA-N iron phosphanylidynenickel Chemical compound [Fe].[Ni]#P LHLROOPJPUYVKD-UHFFFAOYSA-N 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000003034 coal gas Substances 0.000 claims description 13
- 239000004449 solid propellant Substances 0.000 claims description 12
- 239000003915 liquefied petroleum gas Substances 0.000 claims description 11
- 239000002817 coal dust Substances 0.000 claims description 10
- 239000003345 natural gas Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 6
- 239000002028 Biomass Substances 0.000 claims description 5
- 238000007781 pre-processing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 238000003912 environmental pollution Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 52
- 230000008569 process Effects 0.000 description 46
- 235000010755 mineral Nutrition 0.000 description 41
- 239000002994 raw material Substances 0.000 description 38
- 238000010791 quenching Methods 0.000 description 33
- 230000000171 quenching effect Effects 0.000 description 33
- 229910019142 PO4 Inorganic materials 0.000 description 28
- 239000000377 silicon dioxide Substances 0.000 description 26
- 239000010452 phosphate Substances 0.000 description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 25
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 16
- 239000000155 melt Substances 0.000 description 14
- 239000002367 phosphate rock Substances 0.000 description 12
- 229910004298 SiO 2 Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 239000003245 coal Substances 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000000571 coke Substances 0.000 description 7
- 238000006115 defluorination reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000010309 melting process Methods 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000000746 purification Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229910004762 CaSiO Inorganic materials 0.000 description 3
- 229910004283 SiO 4 Inorganic materials 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000010459 dolomite Substances 0.000 description 3
- 229910000514 dolomite Inorganic materials 0.000 description 3
- 238000004134 energy conservation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000010450 olivine Substances 0.000 description 3
- 229910052609 olivine Inorganic materials 0.000 description 3
- 238000013021 overheating Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 241000255925 Diptera Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000270295 Serpentes Species 0.000 description 1
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B13/00—Fertilisers produced by pyrogenic processes from phosphatic materials
- C05B13/02—Fertilisers produced by pyrogenic processes from phosphatic materials from rock phosphates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The invention provides a method and a device for preparing a calcium magnesium phosphate fertilizer by smelting, which belong to the technical field of chemical industry. The device for preparing the calcium magnesium phosphate fertilizer by smelting has the characteristics of small environmental pollution, low production cost and high production efficiency.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a method and a device for preparing calcium magnesium phosphate fertilizer by smelting.
Background
The calcium magnesium phosphate fertilizer is an alkaline mineral fertilizer rich in phosphorus, calcium, magnesium, silicon and other nutrient elements, can supplement trace elements required by plants, improve acid soil, effectively reduce heavy metal pollution and improve crop nutrition and quality.
The production method of calcium magnesium phosphate fertilizer includes electric furnace method, blast furnace method and cyclone furnace method, and the phosphate ore and fluxing agent are melted at high temperature (above 1350 deg.C), then water-cooled under high pressure, dried and ground to obtain the finished product of calcium magnesium phosphate fertilizer. Electric furnace method is used abroad such as japan, korea, brazil, etc. Because the electric furnace does not use coke or coal as fuel, the method has no influence of fuel ash on ingredients, is simple to operate, and for the same grade of phosphorite, the content of phosphorus pentoxide in the product is higher than that of a blast furnace method and a cyclone furnace method. However, the electric furnace method cannot be adopted due to shortage of power supply in China, but a large number of idle iron-making blast furnaces can be modified to produce the calcium magnesium phosphate fertilizer, so that the investment is small and the effect is quick, and the blast furnace method is rapidly developed in China and becomes a main production method of the calcium magnesium phosphate fertilizer.
The method has the defects of low phosphorus conversion rate caused by waste of fine ore and difficult temperature control in the blast furnace method, and the problem of reduced content of effective phosphorus in the calcium magnesium phosphate fertilizer caused by reduction and volatilization of phosphorus. The prior art discloses a calcium magnesium phosphate fertilizer and a production method thereof (application number 200910042672.8), wherein ferrophosphorus and phosphate ore are mixed according to a proportion, the mixture is placed in a high-temperature open-hearth furnace, the temperature is raised to 1800-2200 ℃ to oxidize and burn phosphorus in the mixture, the product is discharged from the furnace and quenched, a semi-finished product of the calcium magnesium phosphate fertilizer is obtained, and finally the finished product is manufactured into a finished product of the calcium magnesium phosphate fertilizer. The phosphorus in the mixture is oxidized and combusted by direct blast to raise the temperature in the high-temperature open hearth furnace. Although the preparation of the calcium magnesium phosphate fertilizer is realized, the method still has the defects of complex steps, large water consumption and large energy consumption.
The prior art discloses a method for preparing calcium magnesium phosphate fertilizer by using phosphorite flotation tailings as raw materials through a cyclone furnace method (application number 200910218354.2), wherein the flotation tailings slurry is dried by a dryer and then screened into tailings powder with certain granularity; metering, mixing and crushing other raw phosphorite, coal, snake mosquito stone and silica which are blended and burned, and crushing the mixture to a certain granularity; mixing the powdery raw materials with air, and spraying the mixture into a cyclone furnace for high-temperature melting; and (3) quenching the melt with water, filtering, drying, crushing and sieving to obtain a finished product of the calcium magnesium phosphate fertilizer. Although the phosphorus content in the calcium magnesium phosphate fertilizer is improved, the problems of high cost, long process and high energy consumption still exist.
The prior art discloses a method for preparing calcium magnesium phosphate fertilizer by using phosphorus chemical tail gas (application number 201611163084.6), wherein phosphate ore is used as a main raw material, silica and serpentine are used as auxiliary materials, and the main raw materials are mixed and crushed; adding the crushed material into a melting tank in a kiln, burning phosphorus chemical tail gas at one side of the kiln, introducing flame and high-temperature hot gas generated by burning into the upper part of the melting tank, performing high-temperature melting on the crushed material in the melting tank, quenching the melt with water, filtering, drying, crushing and sieving to obtain a calcium magnesium phosphate fertilizer finished product. Although the tail gas discharged from yellow phosphorus production is used for replacing coke as a heat source, a heat exchange type kiln is used for replacing blast furnace production; the effect of saving energy is achieved, however, the tail gas is used as a heat source and has insufficient energy, so that the produced calcium magnesium phosphate fertilizer does not reach the standard.
Therefore, a device and a method for preparing the calcium magnesium phosphate fertilizer with high preparation efficiency are needed.
Disclosure of Invention
The invention aims to provide a method and a device for preparing calcium magnesium phosphate fertilizer by smelting, which are used for solving at least one problem in the prior art.
In order to achieve the above object, the invention provides a method for preparing calcium magnesium phosphate fertilizer by smelting, comprising the following steps:
Respectively preprocessing and mixing the phosphorus-containing minerals and the magnesium-containing silicon minerals to form a mixed material; wherein the standard of pretreatment is that the granularity is 1-5 cm, and the water content is less than or equal to 5wt%;
adding the mixed material into a molten pool of a smelting furnace, spraying fuel and oxygen-enriched air into the molten pool through a spray gun of the smelting furnace, and carrying out high-temperature melting on the mixed material through combustion of the fuel and the oxygen-enriched air to obtain a calcium magnesium phosphate fertilizer melt; wherein the smelting furnace is a side-blown smelting furnace or a top-blown smelting furnace, and the temperature of a molten pool is 1150-1500 ℃;
discharging the calcium magnesium phosphate melt to obtain a calcium magnesium phosphate semi-finished product;
and (3) draining, drying, crushing and sieving the calcium magnesium phosphate fertilizer semi-finished product to obtain the calcium magnesium phosphate fertilizer finished product.
Further, a preferred method comprises, when the smelting furnace is a top-blown smelting furnace, the lance is a top-blown lance, and in the step of injecting fuel and oxygen-enriched air into the molten pool through the top-blown lance of the top-blown smelting furnace, the temperature of the molten pool is 1350 to 1500 ℃, and the air excess coefficient in the top-blown smelting furnace is 1.0 to 1.1; the oxygen content of the oxygen-enriched air is 40-90% by volume.
Further, the preferred method includes, when the smelting furnace is a side-blown smelting furnace, the lance being a side-blown lance, in the step of injecting fuel and oxygen-enriched air into the molten pool through the side-blown lance of the side-blown smelting furnace, the temperature of the molten pool being 1350-1500 ℃, the fuel being one or more of natural gas, liquefied petroleum gas, biomass gas, hydrogen gas, or solid fuel particles, wherein the solid fuel particles are pulverized coal, pulverized coke, or petroleum coke; the granularity of the solid fuel particles is less than 100 mu m, and the volume content of oxygen in the oxygen-enriched air is 40% -90%.
Further, the preferred method includes, when the smelting furnace is a side-blown smelting furnace, the lance is a side-blown lance; in the step of injecting fuel and oxygen-enriched air into a molten pool through a side-blowing spray gun of a side-blowing smelting furnace, and carrying out high-temperature melting on a mixed material through combustion of the fuel and the oxygen-enriched air to obtain a calcium-magnesia phosphate fertilizer melt,
the mixed materials are melted at high temperature through the combustion of fuel and oxygen-enriched air, so as to obtain calcium magnesium phosphate liquid slag; obtaining liquid molten slag; wherein the temperature of the molten pool is 1150-1350 ℃;
and (3) feeding the liquid molten slag into an electric heating furnace, and fully melting at 1350-1500 ℃ to obtain a calcium magnesium phosphate fertilizer melt and a byproduct nickel phosphorus iron.
Further, a preferred method comprises, in the step of obtaining a calcium magnesia phosphate fertilizer melt by high temperature melting of the mixture by combustion of fuel and oxygen-enriched air, obtaining high temperature flue gas;
after the high-temperature flue gas is subjected to waste heat recovery, the recovered waste heat is utilized to dry the calcium magnesium phosphate fertilizer semi-finished product;
dedusting by using a dedusting device to obtain dedusted flue gas and smoke dust; and returning the smoke dust to the smelting furnace for smelting.
Further, the preferred method includes the top-blowing lance being movable up and down as the level of the bath changes.
The invention also protects a device for preparing the calcium magnesium phosphate fertilizer by smelting, which is used for the method for preparing the calcium magnesium phosphate fertilizer by smelting; comprises a pretreatment device, a top-blown smelting furnace, a water quenching device, a draining device, a drying device and a crushing device which are sequentially arranged;
the pretreatment device comprises a crushing device for respectively crushing the phosphorus-containing minerals and the magnesium-containing silicon minerals to the granularity of 1-5 cm and the water content of less than or equal to 5wt% and a batching device for mixing the crushed phosphorus-containing minerals and the crushed magnesium-containing silicon minerals to form a mixed material;
the top-blown smelting furnace comprises a furnace body and a top-blown spray gun arranged on the furnace body, wherein the furnace body comprises a feed inlet, a molten pool for carrying out high-temperature melting on a mixed material to obtain a calcium magnesium phosphate melt and a discharge outlet; the feeding port is connected with the batching device, a top-blowing spray gun jack is arranged on the top wall of the furnace body, and the top-blowing spray gun penetrates through the top-blowing spray gun jack and is positioned above the molten pool; the top-blowing spray gun is used for blowing fuel and oxygen-enriched air into the molten pool; the discharging hole is sequentially connected with the water quenching device, the draining device, the drying device and the crushing device;
the water quenching device is used for discharging the calcium magnesium phosphate melt to be quenched to obtain a calcium magnesium phosphate semi-finished product;
the draining device is used for draining the calcium magnesium phosphate fertilizer semi-finished product;
The drying device is used for drying the drained calcium magnesium phosphate fertilizer semi-finished product;
the crushing device is used for crushing and sieving the dried calcium magnesium phosphate semi-finished product to obtain a calcium magnesium phosphate finished product.
The invention also protects a device for preparing the calcium magnesium phosphate fertilizer by smelting, which is used for the method for preparing the calcium magnesium phosphate fertilizer by smelting; comprises a pretreatment device, a side-blown smelting furnace, a water quenching device, a draining device, a drying device and a crushing device which are sequentially arranged;
the pretreatment device comprises a crushing device for respectively crushing the phosphorus-containing minerals and the magnesium-containing silicon minerals to the granularity of 1-5 cm and the water content of less than or equal to 5wt% and a batching device for mixing the crushed phosphorus-containing minerals and the crushed magnesium-containing silicon minerals to form a mixed material;
the side-blown smelting furnace comprises a furnace body and a side-blown spray gun arranged on the furnace body, wherein the furnace body comprises a feed inlet, a molten pool for carrying out high-temperature melting on a mixed material to obtain a calcium magnesium phosphate melt and a discharge outlet; the feeding port is connected with the batching device, a side-blowing spray gun jack is arranged on the side wall of the furnace body, and the side-blowing spray gun penetrates through the side-blowing spray gun jack and is inserted into the molten pool; the side-blowing spray gun is used for spraying fuel and oxygen-enriched air into the molten pool; the discharging hole is sequentially connected with the water quenching device, the draining device, the drying device and the crushing device;
The water quenching device is used for discharging the calcium magnesium phosphate melt to be quenched to obtain a calcium magnesium phosphate semi-finished product;
the draining device is used for draining the calcium magnesium phosphate fertilizer semi-finished product;
the drying device is used for drying the drained calcium magnesium phosphate fertilizer semi-finished product;
the crushing device is used for crushing and sieving the dried calcium magnesium phosphate semi-finished product to obtain a calcium magnesium phosphate finished product.
The invention also protects a device for preparing the calcium magnesium phosphate fertilizer by smelting, which is used for the method for preparing the calcium magnesium phosphate fertilizer by smelting; comprises a pretreatment device, a side-blown smelting furnace, an electric heating furnace, a water quenching device, a draining device, a drying device and a crushing device which are sequentially arranged;
the pretreatment device comprises a crushing device for respectively crushing the phosphorus-containing minerals and the magnesium-containing silicon minerals to the granularity of 1-5 cm and the water content of less than or equal to 5wt% and a batching device for mixing the crushed phosphorus-containing minerals and the crushed magnesium-containing silicon minerals to form a mixed material;
the side-blown smelting furnace comprises a furnace body and a side-blown spray gun arranged on the furnace body, wherein the furnace body comprises a feed inlet, a molten pool for carrying out high-temperature melting on the mixed materials to obtain liquid molten slag and a discharge outlet; the feeding port is connected with the batching device, a side-blowing spray gun jack is arranged on the side wall of the furnace body, and the side-blowing spray gun penetrates through the side-blowing spray gun jack and is inserted into the molten pool; the side-blowing spray gun is used for spraying fuel and oxygen-enriched air into the molten pool;
The feed inlet of the electric heating furnace is communicated with the discharge outlet of the side-blown smelting furnace;
the discharge hole of the electric heating furnace is sequentially connected with the water quenching device, the draining device, the drying device and the crushing device;
the water quenching device is used for discharging the calcium magnesium phosphate melt to be quenched to obtain a calcium magnesium phosphate semi-finished product;
the draining device is used for draining the calcium magnesium phosphate fertilizer semi-finished product;
the drying device is used for drying the drained calcium magnesium phosphate fertilizer semi-finished product;
the crushing device is used for crushing and sieving the dried calcium magnesium phosphate semi-finished product to obtain a calcium magnesium phosphate finished product.
Further, the preferable structure is that the device also comprises a waste heat recovery device and a dust removal device, wherein the waste heat recovery device and the dust removal device are used for recovering waste heat of high-temperature flue gas obtained in the process of high-temperature melting of the mixed materials by fuel and oxygen-enriched air;
the heat output port of the waste heat recovery device is connected with the input port of the drying device;
the input end of the dust removing device is connected with the smoke output end of the waste heat recovery device; the dust removing device comprises a smoke output end and a smoke output end, and the smoke output end is connected with a feed inlet of the side-blown smelting furnace.
As described above, the method and the device for preparing the calcium magnesium phosphate fertilizer by smelting are characterized in that the mixed material of the phosphorus-containing minerals and the magnesium-silicon-containing minerals is added into a molten pool of a side-blown smelting furnace, oxygen-enriched air and fuel are sprayed into the molten pool by using a spray gun, the mixed material is smelted at a high temperature, the calcium magnesium phosphate fertilizer liquid slag is discharged from the furnace and quenched, and the finished product of the calcium magnesium phosphate fertilizer is obtained through draining, drying, crushing and sieving. The beneficial effects are as follows:
1) Compared with the existing blast furnace method, the method disclosed by the invention has the advantages that the use of coke is eliminated, the process flow is short, and the environmental pollution is reduced; the fuel has wide application range, the spray gun can use pulverized coal, carbon powder, oil and natural gas, and the combustion regulation ratio is large. When the top-blown smelting furnace is adopted, fuel and oxygen-enriched air are sprayed into a molten pool through a top-blown spray gun, and submerged flame directly heats the molten pool, so that the heat transfer efficiency is improved; the top-blowing spray gun can move up and down along with the change of the liquid level of the molten pool, so that the molten pool can be effectively heated, and the furnace opening time is shortened; the temperature and oxygen potential of the molten pool can be flexibly adjusted by adjusting the injection quantity of fuel and oxygen-enriched gas, so that the reduction volatilization of phosphorus is avoided, and the combustion product gas can disturb the molten pool in the process of escaping from the molten pool, so that the defluorination process is accelerated, and the technical effect of improving the content of available phosphorus in a finished calcium magnesium phosphate fertilizer product is achieved;
2) When the side-blown smelting furnace is adopted, fuel and oxygen-enriched air are sprayed into a molten pool through a side-blown spray gun, and submerged combustion flame directly contacts the molten pool, so that the heat transfer rate is improved, and the melting of materials is accelerated; the temperature and oxygen potential in the molten pool can be flexibly controlled, the reduction volatilization of phosphorus is avoided, and the technical effect of improving the content of available phosphorus in the finished calcium magnesium phosphate fertilizer is achieved;
3) The low-cost coal, natural gas, blast furnace gas and the like are used as fuels, and the materials are preliminarily melted by a side-blown smelting furnace, so that the melting can be carried out in an oxygen-enriched state, and the volatilization of phosphorus is reduced; meanwhile, the disturbance of the side-blown gas to the molten pool can promote the removal of fluorine-containing gas; the liquid molten slag obtained by pre-melting is sent into an electric heating furnace, heat is supplied by an electrode, the temperature is further increased for full melting, nickel-phosphorus iron can be obtained while a calcium magnesium phosphate fertilizer melt is prepared, recycling of the nickel-iron is realized, and further influence of nickel-iron impurities in a calcium magnesium phosphate fertilizer finished product on quality is reduced;
4) The device for preparing the calcium magnesium phosphate fertilizer by smelting has the characteristics of simple preparation, small environmental pollution, low production cost and high production efficiency, and is suitable for large-area popularization in the field of calcium magnesium phosphate fertilizer production.
To the accomplishment of the foregoing and related ends, one or more aspects of the invention comprise the features hereinafter fully described and particularly pointed out in the claims. The following description details certain exemplary aspects of the invention. These aspects are indicative, however, of but a few of the various ways in which the principles of the invention may be employed. Furthermore, the invention is intended to include all such aspects and their equivalents.
Drawings
Fig. 1 is a schematic diagram of a method for preparing a calcium magnesium phosphate fertilizer by top-blown smelting according to an embodiment of the invention.
Fig. 2 is a schematic structural view of an apparatus for preparing calcium magnesium phosphate by top-blown smelting according to an embodiment of the present invention.
Fig. 3 is a schematic diagram of a method for preparing a calcium magnesium phosphate fertilizer by side-blown smelting according to an embodiment of the invention.
Fig. 4 is a schematic structural view of an apparatus for preparing calcium magnesium phosphate by side-blown smelting according to an embodiment of the present invention.
Fig. 5 is a schematic diagram of a method for preparing a calcium magnesium phosphate fertilizer by two-step smelting according to an embodiment of the present invention.
Fig. 6 is a schematic structural view of an apparatus for preparing calcium magnesium phosphate by two-step smelting according to an embodiment of the present invention.
Detailed Description
It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. The specific techniques or conditions are not noted in the examples, and the reagents or apparatus used, or the manufacturer, may be purchased from a regular distributor, following the techniques or conditions described in the literature in the field, or following the product specifications.
It is to be understood that the terms "upper", "lower", "front", "bottom", "top", "side", "width", "inner", "outer", etc. indicate an orientation or positional relationship, are merely for convenience of describing the present invention and simplifying the description, rather than indicating or implying that the components or elements herein referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore should not be construed as limiting the invention.
Various embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Fig. 1 specifically illustrates the principle of the method for preparing the calcium magnesium phosphate fertilizer by top-blown smelting in the embodiment of the invention. Specifically, fig. 1 is a schematic diagram of a method for preparing a calcium magnesium phosphate fertilizer by top-blown smelting according to an embodiment of the invention.
As shown in fig. 1, the method for preparing the calcium magnesium phosphate fertilizer by top-blown smelting comprises the following steps: respectively preprocessing and mixing the phosphorus-containing minerals and the magnesium-containing silicon minerals to form a mixed material; wherein the standard of pretreatment is that the granularity is 1-5 cm, and the water content is less than or equal to 5wt%; wherein the phosphorus-containing mineral is phosphate ore and/or phosphate tailing; the magnesium-containing silicon mineral can be one or more of silica, serpentine, dolomite, and olivine.
Adding the mixed material into a molten pool of a top-blown smelting furnace, blowing fuel and oxygen-enriched air into the molten pool through a top-blown spray gun of the top-blown smelting furnace, and burning the fuel and the oxygen-enriched air to perform high-temperature melting on the mixed material to obtain a calcium-magnesia phosphate fertilizer melt; wherein the temperature of the molten pool is 1350-1500 ℃; the method comprises the steps of burning fuel and oxygen-enriched air to melt a mixed material at high temperature to obtain a calcium magnesium phosphate fertilizer melt, and obtaining high-temperature flue gas; and (3) carrying out waste heat recovery on the high-temperature flue gas, and drying the calcium magnesium phosphate fertilizer semi-finished product by utilizing the recovered waste heat. After the high-temperature flue gas is subjected to waste heat recovery, a dust removing device is utilized to remove dust to obtain dust-removed flue gas and smoke dust; and returning the smoke dust to the top-blown smelting furnace for smelting. Discharging the calcium magnesium phosphate melt to obtain a calcium magnesium phosphate semi-finished product; and (3) draining, drying, crushing and sieving the calcium magnesium phosphate fertilizer semi-finished product to obtain the calcium magnesium phosphate fertilizer finished product.
The fuel and the oxygen-enriched air are sprayed into a molten pool through a top-blowing spray gun, wherein the fuel comprises one or more of natural gas, liquefied petroleum gas, coal gas, biomass gas, hydrogen and other gas fuels or coal dust, coke powder, petroleum coke and other solid fuels; wherein, in order to avoid the volatilization of phosphorus caused by the reduction of phosphate ore in the smelting process; the air excess coefficient in the top-blown smelting furnace is controlled to be 1.0-1.1, so that the atmosphere of combustion products is oxidative, and the effective phosphorus content in the finished product of the calcium-magnesia phosphate fertilizer is further improved. The solid fuel particle size is less than 100 mu m; the volume content of oxygen in the oxygen-enriched air is 40% -90%; the fuel immersed combustion flame directly contacts the molten pool, so that the melting of the mixed materials can be quickened. In addition, siF is contained in the mixture during the melting process under the condition that silicon dioxide and combustion products contain steam along with the rise of furnace temperature 4 And HF is generated and volatilized.
2Ca 5 F(PO 4 ) 3 +SiO 2 ＝3Ca 3 (PO4) 2 +1/2Ca 2 SiO 4 +1/2SiF 4
2Ca 5 F(PO 4 ) 3 +SiO 2 +H 2 O＝3Ca 3 (PO 4 ) 2 +CaSiO 3 +2HF
The gas in the combustion products can disturb the molten pool and quicken the volatilization of fluoride, so compared with a blast furnace method and an electric furnace method for preparing the calcium magnesium phosphate fertilizer, the method has good defluorination conditions, thereby improving the quality of the calcium magnesium phosphate fertilizer finished product.
By the method, P in the finished product of the calcium magnesium phosphate fertilizer is obtained 2 O 5 12-20% of MgO, 8-18% of SiO 2 25-35% by mass and 25-40% by mass of CaO. The high-temperature flue gas is obtained in the smelting process, and enters a waste heat recovery device to recover heat, and the heat is utilized to be recoveredAnd the collected heat dries the calcium magnesium phosphate fertilizer semi-finished product, then the flue gas is dedusted by a dedusting device, the dedusted flue gas is treated by a purifying device, harmful gases such as fluoride in the flue gas are removed, the tail gas is discharged after reaching standards, and the smoke dust returns to a top-blown smelting furnace for smelting.
Fig. 2 specifically illustrates the structure of an apparatus for preparing calcium magnesium phosphate by top-blown smelting according to an embodiment of the present invention. Specifically, fig. 2 is a schematic structural diagram of an apparatus for preparing a calcium magnesium phosphate by top-blown smelting according to an embodiment of the present invention.
In another aspect, the invention provides a device for preparing calcium magnesium phosphate by top-blown smelting, which is shown in fig. 2, and comprises a pretreatment device, a top-blown smelting furnace, a water quenching device, a draining device, a drying device and a crushing device which are sequentially arranged; the pretreatment device comprises a crushing device for respectively crushing the phosphorus-containing minerals and the magnesium-containing silicon minerals to the granularity of 1-5 cm and the water content of less than or equal to 5wt% and a batching device for mixing the crushed phosphorus-containing minerals and the crushed magnesium-containing silicon minerals to form a mixed material; the top-blown smelting furnace is used for melting the raw materials to obtain the calcium magnesium phosphate fertilizer melt. The top-blown smelting furnace comprises a furnace body and a top-blown spray gun arranged on the furnace body, wherein the furnace body comprises a feed inlet, a molten pool for carrying out high-temperature melting on a mixed material to obtain a calcium magnesium phosphate melt and a discharge outlet; the feeding port is connected with the output port of the batching device, a top-blowing spray gun jack is arranged on the top wall of the furnace body, and the top-blowing spray gun penetrates through the top-blowing spray gun jack and is positioned above the molten pool; the top-blowing spray gun is used for blowing fuel and oxygen-enriched air into the molten pool; the discharging hole is sequentially connected with the water quenching device, the draining device, the drying device and the crushing device; wherein, the top-blowing spray gun is provided with a lifting mechanism which can move up and down along with the change of the liquid level of the molten pool.
It is to be noted that the top of furnace body is provided with the feed inlet, and the bottom is provided with the discharge gate. In order to further improve the heating efficiency in the molten pool, the number of top-blowing spray guns can be one or more, the top-blowing spray guns are vertically inserted into the melt from the top of the furnace body, and the insertion depth of the top-blowing spray guns can be adjusted in an up-and-down lifting manner through a lifting mechanism. The water quenching device is used for discharging the calcium magnesium phosphate melt to be quenched to obtain a calcium magnesium phosphate semi-finished product; the draining device is used for draining the calcium magnesium phosphate fertilizer semi-finished product; the drying device is used for drying the drained calcium magnesium phosphate fertilizer semi-finished product; the crushing device is used for crushing and sieving the dried calcium magnesium phosphate semi-finished product to obtain a calcium magnesium phosphate finished product.
In order to further improve the energy utilization efficiency of the device, the device also comprises a waste heat recovery device, wherein the waste heat recovery device is used for recovering waste heat of the obtained high-temperature flue gas in the process of carrying out high-temperature melting on the mixed materials by using fuel and oxygen-enriched air; the heat output port of the waste heat recovery device is connected with the input port of the drying device. The top of the top-blown smelting furnace is provided with a smoke outlet connected with the waste heat recovery device. The device also comprises a dust removing device, wherein the input end of the dust removing device is connected with the smoke output end of the waste heat recovery device; the dust removing device comprises a smoke output end and a smoke output end, and the smoke output end is connected with a feed inlet of the top-blown smelting furnace. In a specific implementation process, the dust removing device can comprise a dust removing device and a purifying device, and is used for treating high-temperature flue gas generated in the smelting process. Wherein, top-blown smelting furnace goes out the smoke outlet and links to each other with waste heat recovery device heat medium import, and waste heat recovery device heat medium export links to each other with dust collector, and dust collector's gaseous phase export links to each other with purifier. And then the smoke which is discharged and marked and returns to the top-blown smelting furnace is obtained.
Various embodiments of the method for preparing a calcium magnesia phosphate fertilizer by top-blown smelting according to the present invention will be described in detail.
Example 1
1. Raw material preparation and batching: the phosphate ore, the silica and the serpentine are respectively pretreated until the particle size is 1-5 cm and the water content is less than or equal to 5wt%. And determining the material proportion according to the components of the finished product of the calcium magnesium phosphate fertilizer, and mixing the phosphate rock, the silica and the serpentine to obtain a raw material for feeding into a furnace.
2. Top-blowing smelting process: adding a raw material into a top-blown smelting furnace from the furnace top through a belt, and blowing fuel and oxygen-enriched air with the oxygen volume content of 40% into a molten pool through a top-blown spray gun at the furnace top; wherein, the fuel comprises coal gas, hydrogen and petroleum coke; the granularity of the petroleum coke is less than 100 mu m; and (3) providing heat for a molten pool by utilizing heat released by combustion, controlling the air excess coefficient in a top-blown smelting furnace to be 1.0, controlling the temperature of the molten pool to be 1400-1500 ℃, inserting a furnace top spray gun into the molten pool to be 0.3 cm, and melting the materials at a high temperature to obtain the calcium-magnesia phosphate fertilizer melt.
3. And (3) a melt water quenching process: and discharging the calcium magnesium phosphate melt to be quenched to obtain a calcium magnesium phosphate semi-finished product.
4. Preparing a finished product of the calcium magnesium phosphate fertilizer: and (3) draining, drying, crushing and sieving the calcium magnesium phosphate fertilizer semi-finished product to obtain the calcium magnesium phosphate fertilizer finished product. The high-temperature flue gas is obtained in the melting process, the calcium magnesium phosphate semi-finished product can be dried by utilizing the high-temperature flue gas, and then the flue gas is subjected to dust collection and purification treatment, and the tail gas is discharged after reaching the standard.
Example 2
1. Raw material preparation and batching: the phosphate ore, the silica and the serpentine are respectively pretreated until the particle size is 1-5 cm and the water content is less than or equal to 5wt%. And determining the material proportion according to the components of the finished product of the calcium magnesium phosphate fertilizer, and mixing the phosphate rock, the silica and the serpentine to obtain a raw material for feeding into a furnace.
2. Top-blowing smelting process: adding a raw material into a top-blown smelting furnace from the furnace top through a belt, and blowing fuel and oxygen-enriched air with the oxygen volume content of 60% into a molten pool through a top-blown spray gun at the furnace top; wherein, the fuel comprises liquefied petroleum gas, coal gas, hydrogen, coal dust and petroleum coke; the granularity of the coal dust and the petroleum coke is less than 100 mu m; and (3) providing heat for a molten pool by utilizing heat released by combustion, controlling the air excess coefficient in a top-blown smelting furnace to be 1.1, controlling the temperature of the molten pool to be 1450-1500 ℃, inserting a furnace top spray gun into the molten pool to be 0.2 cm, and melting the materials at a high temperature to obtain the calcium-magnesia phosphate fertilizer melt.
3. And (3) a melt water quenching process: and discharging the calcium magnesium phosphate melt to be quenched to obtain a calcium magnesium phosphate semi-finished product.
4. Preparing a finished product of the calcium magnesium phosphate fertilizer: and (3) draining, drying, crushing and sieving the calcium magnesium phosphate fertilizer semi-finished product to obtain the calcium magnesium phosphate fertilizer finished product.
Example 3
1. Raw material preparation and batching: the phosphate ore, the silica and the serpentine are respectively pretreated until the particle size is 1-5 cm and the water content is less than or equal to 5wt%. And determining the material proportion according to the components of the finished product of the calcium magnesium phosphate fertilizer, and mixing the phosphate rock, the silica and the serpentine to obtain a raw material for feeding into a furnace.
2. Top-blowing smelting process: adding a raw material into a top-blown smelting furnace from the furnace top through a belt, and blowing fuel and oxygen-enriched air with the oxygen volume content of 90% into a molten pool through a top-blown spray gun at the furnace top; wherein, the fuel comprises liquefied petroleum gas, coal gas and coke powder; the granularity of the coke powder is less than 100 mu m; and the heat released by combustion is utilized to provide heat for a molten pool, the air excess coefficient in a top-blown smelting furnace is controlled to be 1.0, the temperature of the molten pool is 1350-1400 ℃, a furnace top spray gun is inserted into the molten pool to be 0.2 cm, and the calcium-magnesia phosphate fertilizer melt is obtained after the materials are melted at high temperature.
3. And (3) a melt water quenching process: and discharging the calcium magnesium phosphate melt to be quenched to obtain a calcium magnesium phosphate semi-finished product.
4. Preparing a finished product of the calcium magnesium phosphate fertilizer: and (3) draining, drying, crushing and sieving the calcium magnesium phosphate fertilizer semi-finished product to obtain the calcium magnesium phosphate fertilizer finished product.
In conclusion, the method and the device for preparing the calcium-magnesia phosphate fertilizer by top-blown smelting cancel the use of coke on one hand, have wide fuel selection range, can use pulverized coal, carbon powder, oil and natural gas as spray guns, and have large combustion regulation ratio; the process flow is short, and the environmental pollution is reduced; on the other hand, fuel and oxygen-enriched air are sprayed into a molten pool through a top-blowing spray gun, and the immersed flame directly heats the molten pool, so that the heat transfer efficiency is improved; during the process of escaping the combustion product gas from the molten pool, the combustion product gas can disturb the molten pool, so that the defluorination process is accelerated; the top-blowing spray gun can move up and down along with the change of the liquid level of the molten pool, so that the molten pool can be effectively heated, and the furnace opening time is shortened; and the temperature of the molten pool can be flexibly adjusted by adjusting the injection quantity of the fuel and the oxygen-enriched gas. The method has the technical effects of high cost performance of raw materials, little environmental pollution, energy conservation, strong market competitiveness and suitability for large-area popularization in the field of calcium magnesium phosphate fertilizer preparation.
Fig. 3 specifically illustrates the principle of the method for preparing the calcium magnesium phosphate fertilizer by side-blown smelting in the embodiment of the invention. Specifically, fig. 3 is a schematic diagram of a method for preparing a calcium magnesium phosphate fertilizer by side-blown smelting according to an embodiment of the invention.
As shown in fig. 3, the method for preparing the calcium magnesium phosphate fertilizer by side-blown smelting comprises the following steps: respectively preprocessing and mixing the phosphorus-containing minerals and the magnesium-containing silicon minerals to form a mixed material; wherein the standard of pretreatment is that the granularity is 1-5 cm, and the water content is less than or equal to 5wt%; wherein the phosphorus-containing mineral is phosphate ore and/or phosphate tailing; the magnesium-containing silicon mineral can be one or more of silica, serpentine, dolomite, and olivine.
Adding the mixed material into a molten pool of a side-blown smelting furnace, blowing fuel and oxygen-enriched air into the molten pool through a side-blown spray gun of the side-blown smelting furnace, and burning the fuel and the oxygen-enriched air to perform high-temperature melting on the mixed material to obtain a calcium-magnesia phosphate fertilizer melt; wherein the temperature of the molten pool is 1350-1500 ℃; the method comprises the steps of burning fuel and oxygen-enriched air to melt a mixed material at high temperature to obtain a calcium magnesium phosphate fertilizer melt, and obtaining high-temperature flue gas; and (3) carrying out waste heat recovery on the high-temperature flue gas, and drying the calcium magnesium phosphate fertilizer semi-finished product by utilizing the recovered waste heat. After the high-temperature flue gas is subjected to waste heat recovery, a dust removing device is utilized to remove dust to obtain dust-removed flue gas and smoke dust; and returning the smoke dust to the side-blown smelting furnace for smelting. Discharging the calcium magnesium phosphate melt to obtain a calcium magnesium phosphate semi-finished product; and (3) draining, drying, crushing and sieving the calcium magnesium phosphate fertilizer semi-finished product to obtain the calcium magnesium phosphate fertilizer finished product.
The fuel and the oxygen-enriched air are sprayed into a molten pool through a side-blowing spray gun, wherein the fuel comprises one or more of natural gas, liquefied petroleum gas, coal gas, biomass gas, hydrogen and other gas fuels or coal dust, coke powder, petroleum coke and other solid fuels; wherein, in order to avoid the volatilization of phosphorus caused by the reduction of phosphate ore in the smelting process; the air excess coefficient in the side-blown smelting furnace is controlled to be 1.0-1.1, so that the atmosphere of combustion products is oxidative, and the effective phosphorus content in the finished product of the calcium-magnesia phosphate fertilizer is further improved. The solid fuel particle size is less than 100 mu m; the volume content of oxygen in the oxygen-enriched air is 40% -90%; the fuel immersed combustion flame directly contacts the molten pool, so that the melting of the mixed materials can be quickened. In addition, the mixing material is along with the melting processThe furnace temperature is raised, under the condition that silicon dioxide and combustion products contain steam, siF is contained 4 And HF is generated and volatilized.
2Ca 5 F(PO 4 ) 3 +SiO 2 ＝3Ca 3 (PO4) 2 +1/2Ca 2 SiO 4 +1/2SiF 4
2Ca 5 F(PO 4 ) 3 +SiO 2 +H 2 O＝3Ca 3 (PO 4 ) 2 +CaSiO 3 +2HF
The gas in the combustion products can disturb the molten pool and quicken the volatilization of fluoride, so compared with a blast furnace method and an electric furnace method for preparing the calcium magnesium phosphate fertilizer, the method has good defluorination conditions, thereby improving the quality of the calcium magnesium phosphate fertilizer finished product.
By the method, P in the finished product of the calcium magnesium phosphate fertilizer is obtained 2 O 5 12-20% of MgO, 8-18% of SiO 2 25-35% by mass and 25-40% by mass of CaO. The high-temperature flue gas is obtained in the smelting process, the high-temperature flue gas enters a waste heat recovery device to recover heat, the recovered heat is utilized to dry the calcium magnesium phosphate fertilizer semi-finished product, then the flue gas is dedusted by a dedusting device, the dedusted flue gas is treated by a purifying device to remove harmful gases such as fluoride in the flue gas, the tail gas is discharged after reaching the standard, and the smoke dust returns to a side-blown smelting furnace to be smelted.
Fig. 4 specifically illustrates the structure of the apparatus for preparing calcium magnesium phosphate by side-blown smelting according to the embodiment of the present invention. Specifically, fig. 4 is a schematic structural diagram of an apparatus for preparing calcium magnesium phosphate by side-blown smelting according to an embodiment of the present invention.
In another aspect, the invention provides a device for preparing calcium magnesium phosphate by side-blown smelting, which is shown in fig. 4, and comprises a pretreatment device, a side-blown smelting furnace, a water quenching device, a draining device, a drying device and a crushing device which are sequentially arranged; the pretreatment device comprises a crushing device for respectively crushing the phosphorus-containing minerals and the magnesium-containing silicon minerals to the granularity of 1-5 cm and the water content of less than or equal to 5wt% and a batching device for mixing the crushed phosphorus-containing minerals and the crushed magnesium-containing silicon minerals to form a mixed material; the side-blown smelting furnace is used for melting the raw materials fed into the furnace to obtain the calcium magnesium phosphate fertilizer melt. The side-blown smelting furnace comprises a furnace body and a side-blown spray gun arranged on the furnace body, wherein the furnace body comprises a feed inlet, a molten pool for carrying out high-temperature melting on a mixed material to obtain a calcium magnesium phosphate melt and a discharge outlet; the feeding port is connected with the output port of the batching device, a side-blowing spray gun jack is arranged on the side wall of the furnace body, and the side-blowing spray gun penetrates through the side-blowing spray gun jack and is inserted into the molten pool; the side-blowing spray gun is used for spraying fuel and oxygen-enriched air into the molten pool; the discharge port is connected with the water quenching device, the draining device, the drying device and the crushing device in sequence.
It is to be noted that the top of furnace body is provided with the feed inlet, and the bottom is provided with the discharge gate. In order to further improve the heating efficiency in the molten pool, the number of the side-blowing spray guns can be more than two, and the side-blowing spray guns are inserted into the melt from the side wall of the furnace body. In order to further improve the melting efficiency, the side blowing spray guns can be symmetrically distributed by taking the center of the molten pool as the center of a circle. That is, a plurality of side-blowing lances extend into a plurality of angles of the molten pool to improve the combustion efficiency and further make the melting more uniform. The water quenching device is used for discharging the calcium magnesium phosphate melt to be quenched to obtain a calcium magnesium phosphate semi-finished product; the draining device is used for draining the calcium magnesium phosphate fertilizer semi-finished product; the drying device is used for drying the drained calcium magnesium phosphate fertilizer semi-finished product; the crushing device is used for crushing and sieving the dried calcium magnesium phosphate semi-finished product to obtain a calcium magnesium phosphate finished product.
In order to further improve the energy utilization efficiency of the device, the device also comprises a waste heat recovery device, wherein the waste heat recovery device is used for recovering waste heat of the obtained high-temperature flue gas in the process of carrying out high-temperature melting on the mixed materials by using fuel and oxygen-enriched air; the heat output port of the waste heat recovery device is connected with the input port of the drying device. The top of the side-blown smelting furnace is provided with a smoke outlet connected with the waste heat recovery device. The device also comprises a dust removing device, wherein the input end of the dust removing device is connected with the smoke output end of the waste heat recovery device; the dust removing device comprises a smoke output end and a smoke output end, and the smoke output end is connected with a feed inlet of the side-blown smelting furnace. In a specific implementation process, the dust removing device can comprise a dust removing device and a purifying device, and is used for treating high-temperature flue gas generated in the smelting process. The flue gas outlet of the side-blown smelting furnace is connected with the heat medium inlet of the waste heat recovery device, the heat medium outlet of the waste heat recovery device is connected with the dust removal device, and the gas phase outlet of the dust removal device is connected with the purification device. And then the smoke gas which is discharged and labeled and returns to the side-blown smelting furnace is obtained.
Various examples of the method for preparing a calcium magnesia phosphate fertilizer by side-blown smelting according to the present invention will be described in detail.
Example 4
1. Raw material preparation and batching: the phosphate ore, the silica and the serpentine are respectively pretreated until the particle size is 1-5 cm and the water content is less than or equal to 5wt%. And determining the material proportion according to the components of the finished product of the calcium magnesium phosphate fertilizer, and mixing the phosphate rock, the silica and the serpentine to obtain a raw material for feeding into a furnace.
2. The side-blowing smelting process comprises the following steps: adding a raw material into a side-blown smelting furnace from the top of the furnace through a belt, and blowing fuel and oxygen-enriched air with the oxygen volume content of 40% into a molten pool through two side-blown spray guns; wherein, the fuel comprises coal gas, hydrogen and petroleum coke; the granularity of the petroleum coke is less than 100 mu m; the heat released by combustion is utilized to provide heat for a molten pool, the air excess coefficient in a side-blown smelting furnace is controlled to be 1.0, the temperature of the molten pool is 1400-1500 ℃, side-blown spray guns are inserted into the molten pool from two sides, and the calcium-magnesia phosphate fertilizer melt is obtained after the materials are melted at high temperature.
3. And (3) a melt water quenching process: and discharging the calcium magnesium phosphate melt, and performing water quenching in water at a temperature lower than 40 ℃ to obtain a calcium magnesium phosphate semi-finished product.
4. Preparing a finished product of the calcium magnesium phosphate fertilizer: and (3) draining, drying, crushing and sieving the calcium magnesium phosphate fertilizer semi-finished product to obtain the calcium magnesium phosphate fertilizer finished product. The high-temperature flue gas is obtained in the melting process, the calcium magnesium phosphate semi-finished product can be dried by utilizing the high-temperature flue gas, and then the flue gas is subjected to dust collection and purification treatment, and the tail gas is discharged after reaching the standard.
Example 5
1. Raw material preparation and batching: the phosphate ore, the silica and the serpentine are respectively pretreated until the particle size is 1-5 cm and the water content is less than or equal to 5wt%. And determining the material proportion according to the components of the finished product of the calcium magnesium phosphate fertilizer, and mixing the phosphate rock, the silica and the serpentine to obtain a raw material for feeding into a furnace.
2. The side-blowing smelting process comprises the following steps: adding a raw material into a side-blown smelting furnace from the top of the furnace through a belt, and blowing fuel and oxygen-enriched air with the oxygen volume content of 60% into a molten pool through 4 side-blown spray guns; wherein, the fuel comprises liquefied petroleum gas, coal gas, hydrogen, coal dust and petroleum coke; the granularity of the coal dust and the petroleum coke is less than 100 mu m; the heat released by combustion is utilized to provide heat for a molten pool, the air excess coefficient in a side-blown smelting furnace is controlled to be 1.1, the temperature of the molten pool is 1450-1500 ℃, a side-blown spray gun is inserted into the molten pool, and the calcium-magnesia phosphate melt is obtained after the materials are melted at high temperature. Wherein, 4 side-blowing spray guns are distributed in a central symmetry way by taking the center of a molten pool as the center.
3. And (3) a melt water quenching process: and discharging the calcium magnesium phosphate melt to be quenched to obtain a calcium magnesium phosphate semi-finished product.
4. Preparing a finished product of the calcium magnesium phosphate fertilizer: and (3) draining, drying, crushing and sieving the calcium magnesium phosphate fertilizer semi-finished product to obtain the calcium magnesium phosphate fertilizer finished product.
Example 6
1. Raw material preparation and batching: the phosphate ore, the silica and the serpentine are respectively pretreated until the particle size is 1-5 cm and the water content is less than or equal to 5wt%. And determining the material proportion according to the components of the finished product of the calcium magnesium phosphate fertilizer, and mixing the phosphate rock, the silica and the serpentine to obtain a raw material for feeding into a furnace.
2. The side-blowing smelting process comprises the following steps: adding a raw material into a side-blown smelting furnace from the top of the furnace through a belt, and blowing fuel and oxygen-enriched air with the oxygen volume content of 90% into a molten pool through 8 side-blown spray guns; wherein, the fuel comprises liquefied petroleum gas, coal gas and coke powder; the granularity of the coke powder is less than 100 mu m; the heat released by combustion is utilized to provide heat for a molten pool, the air excess coefficient in a side-blown smelting furnace is controlled to be 1.0, the temperature of the molten pool is 1350-1400 ℃, a side-blown spray gun is inserted into the molten pool, and the material is melted at high temperature to obtain the calcium magnesium phosphate fertilizer melt. Wherein, 8 side-blowing spray guns are arranged in groups of every two, and 4 groups of side-blowing spray guns are symmetrically distributed in the center by taking the center of a molten pool as the center.
3. And (3) a melt water quenching process: and discharging the calcium magnesium phosphate melt to be quenched to obtain a calcium magnesium phosphate semi-finished product.
4. Preparing a finished product of the calcium magnesium phosphate fertilizer: and (3) draining, drying, crushing and sieving the calcium magnesium phosphate fertilizer semi-finished product to obtain the calcium magnesium phosphate fertilizer finished product.
In conclusion, the method and the device for preparing the calcium-magnesia phosphate fertilizer by side-blown smelting cancel the use of coke on one hand, have wide fuel selection range, can use pulverized coal, carbon powder, oil and natural gas as spray guns, and have large combustion regulation ratio; the process flow is short, and the environmental pollution is reduced; on the other hand, fuel and oxygen-enriched air are sprayed into a molten pool through a side-blowing spray gun, and the submerged flame directly heats the molten pool, so that the heat transfer efficiency is improved; during the process of escaping the combustion product gas from the molten pool, the combustion product gas can disturb the molten pool, so that the defluorination process is accelerated; the side-blowing spray gun can effectively heat the molten pool, so that the furnace opening time is shortened; and the temperature of the molten pool can be flexibly adjusted by adjusting the injection quantity of the fuel and the oxygen-enriched gas. The method has the technical effects of high cost performance of raw materials, little environmental pollution, energy conservation, strong market competitiveness and suitability for large-area popularization in the field of calcium magnesium phosphate fertilizer preparation.
Fig. 5 specifically illustrates the principle of the method for preparing the calcium magnesium phosphate fertilizer by two-step smelting according to the embodiment of the invention. Specifically, fig. 5 is a schematic diagram of a method for preparing a calcium magnesium phosphate fertilizer by two-step smelting according to an embodiment of the present invention.
As shown in fig. 5, the method for preparing the calcium magnesium phosphate fertilizer by two-step smelting comprises the following steps: respectively preprocessing and mixing the phosphorus-containing minerals and the magnesium-containing silicon minerals to form a mixed material; wherein the standard of pretreatment is that the granularity is 1-5 cm, and the water content is less than or equal to 5wt%; wherein the phosphorus-containing mineral is phosphate ore and/or phosphate tailing; the magnesium-containing silicon mineral can be one or more of silica, serpentine, dolomite, and olivine.
Adding the mixed material into a molten pool of a side-blown smelting furnace, blowing fuel and air into the molten pool through a side-blown spray gun of the side-blown smelting furnace, and burning the mixed material through the fuel and oxygen-enriched air to perform high-temperature melting to obtain calcium magnesium phosphate liquid slag and nickel phosphorus iron; the method comprises the steps of obtaining calcium magnesium phosphate liquid slag by burning fuel and air to melt a mixed material at high temperature, and obtaining high-temperature flue gas; and (3) carrying out waste heat recovery on the high-temperature flue gas, and drying the calcium magnesium phosphate fertilizer semi-finished product by utilizing the recovered waste heat. After the high-temperature flue gas is subjected to waste heat recovery, a dust removing device is utilized to remove dust to obtain dust-removed flue gas and smoke dust; and returning the smoke dust to the side-blown smelting furnace for smelting. Wherein the temperature of the molten pool is 1150-1350 ℃;
the calcium magnesium phosphate fertilizer liquid slag is sent into an electric heating furnace and is fully melted at the temperature of 1350-1500 ℃ to obtain calcium magnesium phosphate fertilizer melt and nickel phosphorus iron; specifically, the liquid slag of the calcium magnesium phosphate fertilizer is sent into an electric heating furnace through a hot rolling chute or a slag ladle, and is fully melted and overheated at 1350-1500 ℃ to obtain a calcium magnesium phosphate fertilizer melt and a byproduct nickel-phosphorus-iron; wherein, the calcium magnesium phosphate fertilizer melt is discharged from a discharge hole of the electric heating furnace, and the nickel phosphorus iron flows out from a tap hole; wherein, in the step of obtaining the calcium magnesium phosphate fertilizer melt by high-temperature melting in the electric heating furnace, high-temperature smoke is also generated; and (3) carrying out waste heat recovery on the high-temperature flue gas, and drying the calcium magnesium phosphate fertilizer semi-finished product by utilizing the recovered waste heat. After the high-temperature flue gas is subjected to waste heat recovery, a dust removing device is utilized to remove dust to obtain flue gas and smoke dust which meet emission standards; and returning the smoke dust to the side-blown smelting furnace for smelting.
Discharging the calcium magnesium phosphate melt to obtain a calcium magnesium phosphate semi-finished product; draining, drying, crushing and sieving the calcium magnesium phosphate fertilizer semi-finished product to obtain a calcium magnesium phosphate fertilizer finished product; nickel-phosphorus iron is processed into metallic nickel.
The fuel and the oxygen-enriched air are sprayed into a molten pool through a side-blowing spray gun, wherein the fuel comprises one or more of natural gas, liquefied petroleum gas, coal gas, biomass gas, hydrogen and other gas fuels or coal dust, coke powder, petroleum coke and other solid fuels; wherein, in order to avoid the volatilization of phosphorus caused by the reduction of phosphate ore in the smelting process; the air excess coefficient in the side-blown smelting furnace is controlled to be 1.0-1.1, so that the atmosphere of combustion products is oxidative, and the effective phosphorus content in the finished product of the calcium-magnesia phosphate fertilizer is further improved. The solid fuel particle size is less than 100 mu m; oxygen-enriched air oxygen gasThe product content is 40% -90%; the fuel immersed combustion flame directly contacts the molten pool, so that the melting of the mixed materials can be quickened. In addition, siF is contained in the mixture during the melting process under the condition that silicon dioxide and combustion products contain steam along with the rise of furnace temperature 4 And HF is generated and volatilized.
2Ca 5 F(PO 4 ) 3 +SiO 2 ＝3Ca 3 (PO4) 2 +1/2Ca 2 SiO 4 +1/2SiF 4
2Ca 5 F(PO 4 ) 3 +SiO 2 +H 2 O＝3Ca 3 (PO 4 ) 2 +CaSiO 3 +2HF
The gas in the combustion products can disturb the molten pool and quicken the volatilization of fluoride, so compared with a blast furnace method and an electric furnace method for preparing the calcium magnesium phosphate fertilizer, the method has good defluorination conditions, thereby improving the quality of the calcium magnesium phosphate fertilizer finished product.
That is, the mixture is first premelted through a side-blown converter at a temperature of 1150-1350 ℃. And then, fully melting the mixture at 1350-1500 ℃ through an electric heating furnace to obtain a calcium magnesium phosphate fertilizer melt. During the melting process, small amounts of iron oxide carried over by the phosphate ore and nickel oxide in the serpentine will be reduced by the electrode, and furthermore small amounts of phosphorus will be reduced by the electrode. The nickel and the reduced iron and the phosphorus form nickel-phosphorus iron which is sunk into the furnace bottom and can be discharged periodically to be used as a raw material for nickel smelting.
Fe 2 O 3 +3C＝2Fe+3CO
NiO+CO＝Ni+CO 2
Ca 3 (PO 4 ) 2 +5C+2SiO 2 ＝3CaSiO 3 +P 2 +5CO
By the method, P in the finished product of the calcium magnesium phosphate fertilizer is obtained 2 O 5 12-20% of MgO, 8-18% of SiO 2 25-35% by mass and 25-40% by mass of CaO. The high-temperature flue gas is obtained in the smelting process, and enters a waste heat recovery device to recover heat, and the recovered heat is utilized to recycle calcium and magnesiumAnd drying the phosphate fertilizer semi-finished product, dedusting the flue gas by a dedusting device, treating the dedusted flue gas by a purifying device, removing harmful gases such as fluoride in the flue gas, discharging tail gas up to the standard, and returning the flue gas to a side-blown smelting furnace for smelting.
Fig. 6 specifically illustrates the structure of an apparatus for smelting and preparing calcium magnesium phosphate according to an embodiment of the present invention. Specifically, fig. 6 is a schematic structural diagram of an apparatus for smelting and preparing calcium magnesium phosphate fertilizer according to an embodiment of the present invention.
In another aspect, the invention provides a device for preparing calcium magnesium phosphate by smelting in a two-step method, which is shown in fig. 6, and comprises a pretreatment device, a side-blown smelting furnace, an electric heating furnace, a water quenching device, a draining device, a drying device and a crushing device which are sequentially arranged; the pretreatment device comprises a crushing device for respectively crushing the phosphorus-containing minerals and the magnesium-containing silicon minerals to the granularity of 1-5 cm and the water content of less than or equal to 5wt% and a batching device for mixing the crushed phosphorus-containing minerals and the crushed magnesium-containing silicon minerals to form a mixed material; the side-blown smelting furnace is used for melting the raw materials into the furnace to obtain the calcium magnesium phosphate liquid slag. The side-blown smelting furnace comprises a furnace body and a side-blown spray gun arranged on the furnace body, wherein the furnace body comprises a feed inlet, a molten pool for carrying out high-temperature melting on a mixed material to obtain calcium magnesium phosphate liquid slag and a discharge outlet; the feeding port is connected with the output port of the batching device, a side-blowing spray gun jack is arranged on the side wall of the furnace body, and the side-blowing spray gun penetrates through the side-blowing spray gun jack and is inserted into the molten pool; the side-blowing spray gun is used for spraying fuel and air into the molten pool; the feeding hole of the electric heating furnace is connected with the discharging hole of the side-blown smelting furnace; the discharge hole of the electric heating furnace is sequentially connected with the water quenching device, the draining device, the drying device and the crushing device; it is to be noted that the top of furnace body is provided with the feed inlet, and the bottom is provided with the discharge gate. In order to further improve the heating efficiency in the molten pool, the number of the side-blowing spray guns can be more than two, and the side-blowing spray guns are inserted into the melt from the side wall of the furnace body. In order to further improve the melting efficiency, the side blowing spray guns can be symmetrically distributed by taking the center of the molten pool as the center of a circle. That is, a plurality of side-blowing lances extend into a plurality of angles of the molten pool to improve the combustion efficiency and further make the melting more uniform.
Specifically, the electric heating furnace comprises an electrode, an electric heating furnace feed inlet, an electric heating furnace discharge outlet, an iron outlet and an electric heating furnace smoke outlet; the discharge port of the side-blown smelting furnace is communicated with the feed port of the electric heating furnace through a chute or a slag ladle transferring device. The water quenching device is used for discharging the calcium magnesium phosphate melt to be quenched to obtain a calcium magnesium phosphate semi-finished product; the draining device is used for draining the calcium magnesium phosphate fertilizer semi-finished product; the drying device is used for drying the drained calcium magnesium phosphate fertilizer semi-finished product; the crushing device is used for crushing and sieving the dried calcium magnesium phosphate semi-finished product to obtain a calcium magnesium phosphate finished product.
In order to further improve the energy utilization efficiency of the device, the device also comprises a waste heat recovery device for recovering waste heat of high-temperature flue gas generated in the melting process; the heat medium inlet of the waste heat recovery device is connected with the smoke outlet of the side-blown smelting furnace and the smoke outlet of the electric heating furnace; and the heat output port of the waste heat recovery device is connected with the input port of the drying device. The top of the side-blown smelting furnace is provided with a smoke outlet connected with the waste heat recovery device. The device also comprises a dust removing device, wherein the input end of the dust removing device is connected with the smoke output end of the waste heat recovery device; the dust removing device comprises a smoke output end and a smoke output end, and the smoke output end is connected with a feed inlet of the side-blown smelting furnace. In a specific implementation process, the dust removing device can comprise a dust removing device and a purifying device, and is used for treating high-temperature flue gas generated in the smelting process. The flue gas outlet of the side-blown smelting furnace is connected with the heat medium inlet of the waste heat recovery device, the heat medium outlet of the waste heat recovery device is connected with the dust removal device, and the gas phase outlet of the dust removal device is connected with the purification device. And then the smoke gas which is discharged and labeled and returns to the side-blown smelting furnace is obtained.
Various embodiments of the method for preparing a calcium magnesia phosphate fertilizer by two-step smelting according to the present invention will be described in detail.
Example 7
1. Raw material preparation and batching: the phosphate ore, the silica and the serpentine are respectively pretreated until the particle size is 1-5 cm and the water content is less than or equal to 5wt%. And determining the material proportion according to the components of the finished product of the calcium magnesium phosphate fertilizer, and mixing the phosphate rock, the silica and the serpentine to obtain a raw material for feeding into a furnace.
2. Side-blowing pre-smelting process: adding a raw material into a side-blown smelting furnace from the top of the furnace through a belt, and blowing fuel and oxygen-enriched air with the oxygen volume content of 40% into a molten pool through two side-blown spray guns; wherein, the fuel comprises coal gas, hydrogen and petroleum coke; the granularity of the petroleum coke is less than 100 mu m; the heat released by combustion is utilized to provide heat for a molten pool, the air excess coefficient in a side-blown smelting furnace is controlled to be 1.0, the temperature of the molten pool is 1150-1350 ℃, a side-blown spray gun is inserted into the molten pool from two sides, and the material is melted at high temperature to obtain calcium magnesium phosphate liquid slag and nickel phosphorus iron.
3. Smelting in an electric heating furnace: feeding the calcium magnesium phosphate fertilizer liquid slag into an electric heating furnace, and fully melting and overheating at 1350-1500 ℃ to obtain a calcium magnesium phosphate fertilizer melt;
4. And (3) a melt water quenching process: and discharging the calcium magnesium phosphate melt, and performing water quenching in water at a temperature lower than 40 ℃ to obtain a calcium magnesium phosphate semi-finished product.
5. Preparing a finished product of the calcium magnesium phosphate fertilizer: and (3) draining, drying, crushing and sieving the calcium magnesium phosphate fertilizer semi-finished product to obtain the calcium magnesium phosphate fertilizer finished product. And casting and forming the byproduct nickel-phosphorus iron for further processing into metallic nickel. The high-temperature flue gas is obtained in the melting process, the calcium magnesium phosphate semi-finished product can be dried by utilizing the high-temperature flue gas, and then the flue gas is subjected to dust collection and purification treatment, and the tail gas is discharged after reaching the standard.
P in finished calcium magnesium phosphate fertilizer 2 O 5 19 mass percent of MgO, 13 mass percent of SiO) 2 28 mass percent and 37 mass percent of CaO.
Example 8
1. Raw material preparation and batching: the phosphate ore, the silica and the serpentine are respectively pretreated until the particle size is 1-5 cm and the water content is less than or equal to 5wt%. And determining the material proportion according to the components of the finished product of the calcium magnesium phosphate fertilizer, and mixing the phosphate rock, the silica and the serpentine to obtain a raw material for feeding into a furnace.
2. The side-blowing smelting process comprises the following steps: adding a raw material into a side-blown smelting furnace from the top of the furnace through a belt, and blowing fuel and oxygen-enriched air with the oxygen volume content of 60% into a molten pool through 4 side-blown spray guns; wherein, the fuel comprises liquefied petroleum gas, coal gas, hydrogen, coal dust and petroleum coke; the granularity of the coal dust and the petroleum coke is less than 100 mu m; the heat released by combustion is utilized to provide heat for a molten pool, the air excess coefficient in a side-blown smelting furnace is controlled to be 1.1, the temperature of the molten pool is 1450-1500 ℃, a side-blown spray gun is inserted into the molten pool, and the calcium-magnesia phosphate liquid slag and nickel-phosphorus iron are obtained after the materials are melted at high temperature. Wherein, 4 side-blowing spray guns are distributed in a central symmetry way by taking the center of a molten pool as the center.
3. Smelting in an electric heating furnace: feeding the calcium magnesium phosphate fertilizer liquid slag into an electric heating furnace, and fully melting and overheating at 1350-1500 ℃ to obtain a calcium magnesium phosphate fertilizer melt;
4. and (3) a melt water quenching process: and discharging the calcium magnesium phosphate melt, and performing water quenching in water at a temperature lower than 40 ℃ to obtain a calcium magnesium phosphate semi-finished product.
5. Preparing a finished product of the calcium magnesium phosphate fertilizer: and (3) draining, drying, crushing and sieving the calcium magnesium phosphate fertilizer semi-finished product to obtain the calcium magnesium phosphate fertilizer finished product. And casting and forming the byproduct nickel-phosphorus iron for further processing into metallic nickel. P in finished calcium magnesium phosphate fertilizer 2 O 5 13% by mass of MgO, 18% by mass of SiO 2 29% by mass and 38% by mass of CaO.
Example 9
1. Raw material preparation and batching: the phosphate ore, the silica and the serpentine are respectively pretreated until the particle size is 1-5 cm and the water content is less than or equal to 5wt%. And determining the material proportion according to the components of the finished product of the calcium magnesium phosphate fertilizer, and mixing the phosphate rock, the silica and the serpentine to obtain a raw material for feeding into a furnace.
2. The side-blowing smelting process comprises the following steps: adding a raw material into a side-blown smelting furnace from the top of the furnace through a belt, and blowing fuel and oxygen-enriched air with the oxygen volume content of 90% into a molten pool through 8 side-blown spray guns; wherein, the fuel comprises liquefied petroleum gas, coal gas and coke powder; the granularity of the coke powder is less than 100 mu m; the heat released by combustion is utilized to provide heat for a molten pool, the air excess coefficient in a side-blown smelting furnace is controlled to be 1.0, the temperature of the molten pool is 1350-1400 ℃, a side-blown spray gun is inserted into the molten pool, and the material is melted at high temperature to obtain calcium magnesium phosphate liquid slag and nickel phosphorus iron. Wherein, 8 side-blowing spray guns are arranged in groups of every two, and 4 groups of side-blowing spray guns are symmetrically distributed in the center by taking the center of a molten pool as the center.
3. Smelting in an electric heating furnace: feeding the calcium magnesium phosphate fertilizer liquid slag into an electric heating furnace, and fully melting and overheating at 1350-1500 ℃ to obtain a calcium magnesium phosphate fertilizer melt;
4. and (3) a melt water quenching process: and discharging the calcium magnesium phosphate melt, and performing water quenching in water at a temperature lower than 40 ℃ to obtain a calcium magnesium phosphate semi-finished product.
5. Preparing a finished product of the calcium magnesium phosphate fertilizer: and (3) draining, drying, crushing and sieving the calcium magnesium phosphate fertilizer semi-finished product to obtain the calcium magnesium phosphate fertilizer finished product. And casting and forming the byproduct nickel-phosphorus iron for further processing into metallic nickel. Wherein, P in the finished product of the calcium magnesium phosphate fertilizer 2 O 5 17% by mass of MgO, 17% by mass of SiO 2 29 mass percent and 35 mass percent of CaO.
The method and the device for preparing the calcium magnesium phosphate fertilizer by two-step smelting have the advantages that on one hand, coke is not used, the fuel selection range is wide, pulverized coal, carbon powder, oil and natural gas can be used for the spray gun, and the combustion regulation ratio is large; the process flow is short, and the environmental pollution is reduced; on the other hand, fuel and oxygen-enriched air are sprayed into a molten pool through a side-blowing spray gun, and the submerged flame directly heats the molten pool, so that the heat transfer efficiency is improved; during the process of escaping the combustion product gas from the molten pool, the combustion product gas can disturb the molten pool, so that the defluorination process is accelerated; the side-blowing spray gun can effectively heat the molten pool, so that the furnace opening time is shortened; the temperature of the molten pool can be flexibly adjusted by adjusting the injection quantity of the fuel and the oxygen-enriched gas. In addition, the preparation efficiency of the calcium magnesium phosphate fertilizer is further improved through the full melting of the side-blown smelting furnace and the melting combined electric heating furnace; the method has the technical effects of high cost performance of raw materials, little environmental pollution, energy conservation, strong market competitiveness and suitability for large-area popularization in the field of calcium magnesium phosphate fertilizer preparation.
In summary, the method for preparing the calcium magnesium phosphate fertilizer by smelting comprises a method for preparing the calcium magnesium phosphate fertilizer by top-blown smelting, a method for preparing the calcium magnesium phosphate fertilizer by side-blown smelting and a method for preparing the calcium magnesium phosphate fertilizer by two-step smelting; the method has the characteristics of small environmental pollution, low production cost and high production efficiency, and is suitable for large-area popularization in the field of calcium magnesium phosphate fertilizer production.
However, it will be appreciated by those skilled in the art that various modifications may be made to the method and apparatus for smelting calcium magnesia phosphate provided by the present invention described above without departing from the scope of the invention. Accordingly, the scope of the invention should be determined from the following claims.
Claims (2)
1. The method for preparing the calcium magnesium phosphate fertilizer by smelting is characterized by comprising the following steps of:
respectively preprocessing and mixing the phosphorus-containing minerals and the magnesium-containing silicon minerals to form a mixed material; wherein the standard of pretreatment is that the granularity is 1-5 cm, and the water content is less than or equal to 5wt%;
adding the mixed material into a molten pool of a smelting furnace, spraying fuel and oxygen-enriched air into the molten pool through a spray gun of the smelting furnace, and burning the fuel and the oxygen-enriched air to melt the mixed material at a high temperature to obtain a calcium magnesium phosphate fertilizer melt;
Discharging the calcium magnesium phosphate fertilizer melt to be quenched to obtain a calcium magnesium phosphate fertilizer semi-finished product;
draining, drying, crushing and sieving the calcium magnesium phosphate fertilizer semi-finished product to obtain a calcium magnesium phosphate fertilizer finished product;
the smelting furnace is a side-blown smelting furnace, and the spray gun is a side-blown spray gun; in the step of injecting fuel and oxygen-enriched air into a molten pool through a side-blowing spray gun of a side-blowing smelting furnace, and carrying out high-temperature melting on the mixed materials through combustion of the fuel and the oxygen-enriched air to obtain a calcium-magnesia phosphate fertilizer melt,
the mixed materials are melted at high temperature through the combustion of fuel and oxygen-enriched air, so as to obtain calcium magnesium phosphate fertilizer liquid molten slag; wherein the temperature of the molten pool is 1150-1350 ℃;
the liquid molten slag is sent into an electric heating furnace and is fully melted at the temperature of 1350-1500 ℃ to obtain a calcium magnesium phosphate fertilizer melt and a byproduct nickel phosphorus iron;
the fuel is one or more of natural gas, liquefied petroleum gas, coal gas, biomass gas, hydrogen gas or solid fuel particles, wherein the solid fuel particles are coal dust, coke powder or petroleum coke; the granularity of the solid fuel particles is smaller than 100 mu m, and the volume content of oxygen in the oxygen-enriched air is 40% -90%; the air excess coefficient in the side-blown smelting furnace is 1.0-1.1;
The fuel submerged combustion flame directly contacts the molten bath.
2. The method for preparing calcium magnesium phosphate fertilizer by smelting according to claim 1, wherein,
in the step of obtaining a calcium magnesium phosphate fertilizer melt by high-temperature melting of the mixed materials through combustion of the fuel and oxygen-enriched air, high-temperature flue gas is obtained;
after the high-temperature flue gas is subjected to waste heat recovery, the recovered waste heat is utilized to dry the calcium magnesium phosphate fertilizer semi-finished product;
dedusting by using a dedusting device to obtain dedusted flue gas and smoke dust; and returning the smoke dust to the smelting furnace for smelting.
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