CN110510590A - A kind of the Wet-process Phosphoric Acid Production system and technique of stability and high efficiency - Google Patents
A kind of the Wet-process Phosphoric Acid Production system and technique of stability and high efficiency Download PDFInfo
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- CN110510590A CN110510590A CN201910949900.3A CN201910949900A CN110510590A CN 110510590 A CN110510590 A CN 110510590A CN 201910949900 A CN201910949900 A CN 201910949900A CN 110510590 A CN110510590 A CN 110510590A
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- phosphoric acid
- reaction
- water
- outlet
- half water
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 289
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 144
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 210
- 238000006243 chemical reaction Methods 0.000 claims abstract description 149
- 239000007789 gas Substances 0.000 claims abstract description 81
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 22
- 238000004064 recycling Methods 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 17
- 238000012805 post-processing Methods 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 111
- 238000010521 absorption reaction Methods 0.000 claims description 31
- 238000001914 filtration Methods 0.000 claims description 31
- 238000002425 crystallisation Methods 0.000 claims description 27
- 230000008025 crystallization Effects 0.000 claims description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 26
- 229910052698 phosphorus Inorganic materials 0.000 claims description 26
- 239000011574 phosphorus Substances 0.000 claims description 26
- 238000003860 storage Methods 0.000 claims description 18
- 230000007246 mechanism Effects 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 15
- CKRORYDHXIRZCH-UHFFFAOYSA-N phosphoric acid;dihydrate Chemical compound O.O.OP(O)(O)=O CKRORYDHXIRZCH-UHFFFAOYSA-N 0.000 claims description 15
- 238000010079 rubber tapping Methods 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 10
- 238000009156 water cure Methods 0.000 claims description 10
- 239000012141 concentrate Substances 0.000 claims description 9
- 239000012495 reaction gas Substances 0.000 claims description 9
- 229910052602 gypsum Inorganic materials 0.000 claims description 8
- 239000010440 gypsum Substances 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 2
- 239000006071 cream Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 9
- 238000005406 washing Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000002918 waste heat Substances 0.000 abstract description 2
- 239000002920 hazardous waste Substances 0.000 abstract 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 12
- 239000002367 phosphate rock Substances 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229910052925 anhydrite Inorganic materials 0.000 description 4
- 235000011132 calcium sulphate Nutrition 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 238000005188 flotation Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 3
- 239000005696 Diammonium phosphate Substances 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 235000019838 diammonium phosphate Nutrition 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 235000019700 dicalcium phosphate Nutrition 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910003638 H2SiF6 Inorganic materials 0.000 description 1
- 229910004014 SiF4 Inorganic materials 0.000 description 1
- JLFVIEQMRKMAIT-UHFFFAOYSA-N ac1l9mnz Chemical compound O.O.O JLFVIEQMRKMAIT-UHFFFAOYSA-N 0.000 description 1
- QLULGSLAHXLKSR-UHFFFAOYSA-N azane;phosphane Chemical compound N.P QLULGSLAHXLKSR-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
- C01B25/222—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with sulfuric acid, a mixture of acids mainly consisting of sulfuric acid or a mixture of compounds forming it in situ, e.g. a mixture of sulfur dioxide, water and oxygen
- C01B25/228—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with sulfuric acid, a mixture of acids mainly consisting of sulfuric acid or a mixture of compounds forming it in situ, e.g. a mixture of sulfur dioxide, water and oxygen one form of calcium sulfate being formed and then converted to another form
- C01B25/229—Hemihydrate-dihydrate process
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Abstract
The invention discloses a kind of Wet-process Phosphoric Acid Production systems of stability and high efficiency, including pre-reaction module, half water reaction module, two water reaction modules, phosphoric acid post-processing module, gas treatment recycling module and steam-heating system, steam-heating system is pre-reaction module and half water reaction module heat supply, material sufficiently reacts after the pre-reaction module, half water reaction module, two water reaction modules, generate product phosphoric acid and ardealite, phosphoric acid is sent into phosphoric acid post-processing module and is handled, and the gas for reacting generation is handled through gas treatment recycling module to recycle fluosilicic acid.Compared with the prior art, the beneficial effects of the present invention are: reaction homogeneity is higher, reaction controlling is more simple, system driving rate is high, and the product, byproduct and waste heat of gas washing in SA production chain output are taken full advantage of, entire production system and process economy are good, no hazardous waste products.
Description
Technical field
The invention belongs to phosphoric acid production technical fields, and in particular to one kind half water-dihydrate wet phosphoric acid production system and work
Skill.
Background technique
Wet Processes of Phosphoric Acid mainly manufactures phosphoric acid with sulfuric acid decomposition phosphorus ore.It is reacted with sulfuric acid with phosphorus ore, generates calcium sulfate
Crystallization and phosphoric acid solution, then solid-liquor separation is carried out, obtain phosphoric acid.The production of phosphoric acid is the crystal of calcium sulfate high-quality around acquirement
(gypsum) and carry out, under different reaction temperatures and phosphoric acid concentration, crystal of calcium sulfate produces calcium sulphate dihydrate
(CaSO4·2H2O), half-H 2 O calcium sulphate (CaSO4·1/2H2) and dead plaster (CaSO O4).Thus, the production of phosphoric acid by wet process
Technique divides into two water laws, half water law and therefrom without techniques such as water laws.
No matter any technique, have its advantage and disadvantage.Although two water laws in whole world phosphoric acid production technique predominantly
Position, simple production process, but the phosphoric acid concentration obtained after the filtering of its reactant is low, with P2O5Meter parts by weight only have 26-30%,
The needs that phosphorus ammonium or calcium hydrogen phosphate fodder produce, and the impurity such as Al contained in acid and F are just able to satisfy after having to pass through concentration
More, decontamination process is complicated.
Half wet technology process is short, and investment is low, can directly obtain with P2O5The phosphoric acid for counting parts by weight 42-45%, is not required to dense
Contracting can be directly used for the production of Diammonium phosphate (DAP) or calcium hydrogen phosphate fodder, so energy consumption and lower production costs；Grain can be used
Thicker mine is spent, the energy consumption of ore grinding, SO in product acid are saved3, the impurity such as Al and F it is low, sour quality is high；But its filtration system is easy
Fouling, cleaning cycle is short, and operating rate is low, and production process reaction temperature is high, and control difficulty is big, P in ardealite2O5Content is high, unfavorable
In comprehensive utilization.
Advantage and disadvantage based on two water laws Yu half water law, Publication No. CN 105036101 A's and 105384157 A of CN is special
The advantages of sharp document individually discloses a kind of-two water law phosphoric acid process of half water, combines half water law and two water laws, in phosphorus ore
P2O5The rate of recovery is higher, but it still has deficiency: phosphorus ore does not pre-process in the former technical process, and two kinds of techniques are half
Water reacts workshop section and controls without temperature, and the reaction that half water reaction workshop section's phosphorus ore actually occurs is indefinite, and half water reaction workshop section easily occurs
Fouling, cleaning cycle is short, influences driving rate, further, since the influence of phosphorus ore quality comparison, needs repeatedly to adjust sulfuric acid in reaction
Concentration, so that control is very inconvenient.
In addition, phosphoric acid production technique is based on sulfuric acid, in chemical industrial park, each production chain can all be generated largely
Byproduct and waste heat comprehensively consider each item production chain in entire garden, the product for producing chain or byproduct are made full use of, favorably
In reducing byproduct for treatment cost and cost of material, meets the requirement of Green Chemistry and sustainable development, advantageously reduce buying
And transportation cost, improve comprehensive benefit.
Summary of the invention
In view of this, one of the objects of the present invention is to provide a kind of Wet-process Phosphoric Acid Production systems of stability and high efficiency.
Its technical solution is as follows:
A kind of Wet-process Phosphoric Acid Production system of stability and high efficiency, it is critical that including pre-reaction module, half water reaction mould
Block, two water reaction modules, phosphoric acid post-processing module, gas treatment recycling module and steam-heating system；
The discharge port of the pre-reaction module is connected with the feed inlet of the half water reaction module, the half water reaction module
Further respectively have half water reaction gas outlet, the outlet of half water phosphoric acid and the outlet of half water recrement, the half water recrement outlet and described two
The feed inlet of water reaction module is connected, and the two water reaction module further respectively has phosphate dihydrate outlet and ardealite outlet；
The feed inlet of the feed inlet of the half water reaction module and the two water reaction module is connected separately with concentrated sulfuric acid confession
Answer device；
Half water reaction gas outlet is connected with the air inlet of the gas treatment recycling module；
The half water phosphoric acid outlet and the phosphate dihydrate export the feed inlet phase with the phosphoric acid post-processing module respectively
Even；
The steam-heating system is the pre-reaction module and the half water reaction module heat supply.
As optimal technical scheme, above-mentioned phosphoric acid production system further includes sulfuric acid afterheat steam device, which steams
The hot steam outlet of vapour device is connected to the hot air intake of the steam-heating system.
As optimal technical scheme, above-mentioned half water reaction module includes according to the sequentially connected half water reaction knot of flow direction of material
Brilliant slot, flash cooler, half water cure slot and half water filtering device, the feed inlet of the half water crystallization reaction tank form described half
The feed inlet of water reaction module, the flash cooler are equipped with half water and react gas outlet, and the half water cure slot goes out
Material mouth is connected with the feed inlet of half water filtering device；
Half water filtering device is also respectively provided with the half water phosphoric acid outlet and half water recrement outlet.
As optimal technical scheme, above-mentioned two water reaction module includes according to the sequentially connected two water reaction of flow direction of material
Slot, two water crystallization slots, two water filtering devices；
The feed inlet of the two water reactive tank forms the feed inlet of the two water reaction module；
Two water filtering device is respectively arranged with the phosphate dihydrate outlet and ardealite outlet.
As optimal technical scheme, it includes spray-absorption device, fluosilicic acid slot and purification that above-mentioned gas, which handles recycling module,
Gas tapping equipment；
Half water reaction gas outlet is connected with the air inlet of the spray-absorption device；
The offgas outlet of the spray-absorption device is connected with the purified gas tapping equipment, the spray-absorption device
Liquid outlet is connected with the fluosilicic acid slot.
As optimal technical scheme, above-mentioned phosphoric acid post-processing module includes concentrated phosphoric acid dashpot, phosphoric acid,diluted dashpot, first
Enrichment facility, the second enrichment facility, the first concentrated phosphoric acid storage tank, the second concentrated phosphoric acid storage tank；
Half water phosphoric acid outlet is connected with the feed inlet of the concentrated phosphoric acid dashpot, the phosphate dihydrate export with it is described
The feed inlet of phosphoric acid,diluted dashpot is connected, the feed inlet phase of the discharge port of the phosphoric acid,diluted dashpot and first enrichment facility
Even, the discharge port of first enrichment facility is connected with the feed inlet of the concentrated phosphoric acid dashpot；
The discharge port of the concentrated phosphoric acid dashpot respectively with the first concentrated phosphoric acid storage tank and second enrichment facility
Feed inlet is connected, and the discharge port of second enrichment facility is connected with the second concentrated phosphoric acid storage tank；
First enrichment facility is additionally provided with first gas outlet, and second enrichment facility is additionally provided with second gas
Outlet；
The gas treatment recycling module further includes water absorption plant, and the first gas outlet and the second gas go out
Mouth is connected with the air inlet of the water absorption plant, the offgas outlet of the water absorption plant and the purified gas tapping equipment
It is connected, the liquid outlet of the water absorption plant is connected with the fluosilicic acid slot.
As optimal technical scheme, above-mentioned pre-reaction module includes anterior reactor and pre-reaction digester, the pre-reaction
The discharge port of slot is connected with the feed inlet of the pre-reaction digester；
The feed inlet of the anterior reactor is connected separately with phosphorus ore pretreatment unit and dilute sulfuric acid feeding mechanism；
The dilute sulfuric acid feeding mechanism is connected with sulfuric acid tail gas processing unit, which is equipped with dilute sulfuric acid
Outlet, dilute sulfuric acid outlet are connected with the dilute sulfuric acid feeding mechanism.
As optimal technical scheme, above-mentioned steam-heating system includes hot steam inlet pipe, heating endless tube and remaining vapour discharge pipe；
The inlet end of the hot steam inlet pipe forms the hot air intake of the steam-heating system, the hot steam inlet pipe
Outlet side is connect with the inlet end of the heating endless tube, and the outlet side of the heating endless tube is connect with the remaining vapour discharge pipe；
The outer wall of the anterior reactor, pre-reaction digester and the half water crystallization reaction tank adds described in being respectively surrounded with one section
Hot endless tube, all heating endless tubes are connected separately with the same hot steam inlet pipe, the outlet side of all heating endless tubes
It is connected separately with same remaining vapour discharge pipe.
The second object of the present invention is to provide a kind of wet method phosphoric acid manufacture process.
A kind of wet method phosphoric acid manufacture process, key are to sequentially include the following steps:
(1) phosphorus ore pre-reaction: is sent into the concentrate slurry that the phosphorus ore pretreatment unit is handled, P in the concentrate slurry2O5
Weight content is 32%, and the dilute sulfuric acid that the concentrate slurry and the dilute sulfuric acid feeding mechanism generate is each led into the pre-reaction
Slot enters the pre-reaction digester after reacting at 94-98 DEG C, and slaking reaction 120min obtains pre-reaction material；
The reaction of (2) half water: the pre-reaction material enters the half water crystallization reaction tank, and to the half water crystallization reaction tank
In be passed through the excessive concentrated sulfuric acid, be sufficiently stirred carry out half water reaction, reaction temperature be 88-93 DEG C, then reaction mass be sent into described in
Flash cooler is cooled down, and the gas of generation is passed through the gas treatment recycling module, and material after cooling is sent into described half
Water cure slot is cured, and material is filtered through half water filtering device after the completion of curing, and filtrate exports from the half water phosphoric acid
It is discharged into the concentrated phosphoric acid dashpot, filter residue is to contain P2O5Semi-hydrated gypsum, filter residue from the half water recrement outlet be sent into described two
Water reactive tank；
The reaction of (3) two water: bis- water reactive tank of Xiang Suoshu is passed through the concentrated sulfuric acid and carries out two water reactions, and reaction mass subsequently enters institute
Two water crystallization slots are stated the reaction was continued crystallization, subsequently enters two water filtering device and be filtered, filtrate is phosphoric acid,diluted, described dilute
Phosphoric acid is discharged into the phosphoric acid,diluted dashpot through phosphate dihydrate outlet, and filter residue is exported from the ardealite and is discharged.
As optimal technical scheme, above-mentioned wet method phosphoric acid manufacture process is further comprised the steps of:
(4) Phosphoric Acid Concentration is handled: the phosphoric acid,diluted in the phosphoric acid,diluted dashpot is carried out the through first enrichment facility
One concentration obtains parts by weight and is 42% phosphoric acid, and is passed through the first concentrated phosphoric acid storage tank, the gas that first concentration generates
Body is passed through the water absorption plant, and absorbing liquid is fluosilicic acid, and tail gas is discharged from the purified gas tapping equipment；
Phosphoric acid in the first concentrated phosphoric acid storage tank carries out the second concentration through second enrichment facility, obtains parts by weight
For 52% or more concentrated phosphoric acid, the gas that second concentration generates is also passed into the water absorption plant, and absorbing liquid is fluosilicic acid,
Tail gas is discharged from the purified gas tapping equipment.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of production system；
Fig. 2 is the schematic diagram of steam-heating system；
Fig. 3 is process flow diagram.
Specific embodiment
The invention will be further described with attached drawing with reference to embodiments.
As shown in Figure 1, a kind of Wet-process Phosphoric Acid Production system of stability and high efficiency, including pre-reaction module 1, half water reaction module
2, two water reaction modules 3, phosphoric acid post-processing module 4, gas treatment recycling module 5.
The discharge port of the pre-reaction module 1 is connected with the feed inlet of the half water reaction module 2, and half water reacts mould
Block 2 further respectively has half water reaction gas outlet, the outlet of half water phosphoric acid and the outlet of half water recrement, half water recrement outlet with it is described
The feed inlet of two water reaction modules 3 is connected, and the two water reaction module 3 further respectively has phosphate dihydrate outlet and ardealite goes out
Mouthful.
The feed inlet of the feed inlet of the half water reaction module 2 and the two water reaction module 3 is connected separately with the concentrated sulfuric acid
Feeding mechanism 7.
Half water reaction gas outlet is connected with the air inlet of the gas treatment recycling module 5.The half water phosphoric acid goes out
Mouth and phosphate dihydrate outlet are connected with the feed inlet of the phosphoric acid post-processing module 4 respectively.
The phosphoric acid production system is additionally provided with steam-heating system 6, which is the pre-reaction module
1 and half water reaction module, 2 heat supply.
Specifically, the pre-reaction module 1 includes anterior reactor 11 and pre-reaction digester 12.The anterior reactor 11
Feed inlet is connected separately with phosphorus ore pretreatment unit 13 and dilute sulfuric acid feeding mechanism 14.The phosphorus ore pretreatment unit 13 includes ball
Grinding machine and phosphate rock floating machine, wherein for rock phosphate in powder to be crushed ore pulp is made, then be passed through the phosphate rock floating machine, institute in ball mill
Phosphate rock floating machine is stated to be concentrated for flotation.The dilute sulfuric acid feeding mechanism 14 is connected with sulfuric acid tail gas processing unit 9, the sulfuric acid tail
Flash Gas Compression Skid System 9 is exported equipped with dilute sulfuric acid, and dilute sulfuric acid outlet is connected with the dilute sulfuric acid feeding mechanism 14.
The discharge port of the anterior reactor 11 is connected with the feed inlet of the pre-reaction digester 12, the pre-reaction curing
The discharge port of slot 12 forms the discharge port of the pre-reaction module 1.
The half water reaction module 2 includes according to the sequentially connected half water crystallization reaction tank 21 of flow direction of material, flash cooled
Device 22, half water cure slot 23 and half water filtering device 24, it is anti-that the feed inlet of the half water crystallization reaction tank 21 forms half water
Answer the feed inlet of module 2, be additionally provided with the outer escape orifice of gas on the half water crystallization reaction tank 21, the outer escape orifice of the gas with it is described
The feed inlet of flash cooler 22 is connected, and the flash cooler 22 is equipped with half water and reacts gas outlet, and half water is ripe
The discharge port for changing slot 23 is connected with the feed inlet of half water filtering device 24.Half water filtering device 24 is also respectively provided with
The half water phosphoric acid outlet and half water recrement outlet.
The two water reaction module 3 include according to the sequentially connected two water reactive tank 31 of flow direction of material, two water crystallization slots 32,
Two water filtering devices 33；
The feed inlet of the two water reactive tank 31 forms the feed inlet of the two water reaction module 3；
Two water filtering device 33 is respectively arranged with the phosphate dihydrate outlet and ardealite outlet.
The two water reaction module 3 further includes ardealite slot 34, and the feed inlet of the ardealite slot 34 goes out with the ardealite
Mouth is connected；
The ardealite slot 34 is additionally provided with backwater outlet, the charging of the backwater outlet and half water filtering device 22
The feed inlet of mouth or/and two water filtering device 33 is connected.
The phosphoric acid post-processing module 4 include concentrated phosphoric acid dashpot 41, phosphoric acid,diluted dashpot 42, the first enrichment facility 43,
Second enrichment facility 44, the first concentrated phosphoric acid storage tank 45, the second concentrated phosphoric acid storage tank 46.The feed inlet of the phosphoric acid post-processing module 4
There are two, the feed inlet of the feed inlet of the respectively described concentrated phosphoric acid dashpot 41 and the phosphoric acid,diluted dashpot 42.It is described
The outlet of half water phosphoric acid is connected with the feed inlet of the concentrated phosphoric acid dashpot 41, and the phosphate dihydrate outlet is buffered with the phosphoric acid,diluted
The feed inlet of slot 42 is connected, and the discharge port of the phosphoric acid,diluted dashpot 42 is connected with the feed inlet of first enrichment facility 43,
The discharge port of first enrichment facility 43 is connected with the feed inlet of the concentrated phosphoric acid dashpot 41.
The discharge port of the concentrated phosphoric acid dashpot 41 is filled with the first concentrated phosphoric acid storage tank 45 and second concentration respectively
The feed inlet set is connected, and the discharge port of second enrichment facility is connected with the second concentrated phosphoric acid storage tank 46.
The gas treatment recycling module 5 includes spray-absorption device 51, fluosilicic acid slot 52 and purified gas tapping equipment 53.
Half water reaction gas outlet is connected with the air inlet of the spray-absorption device 51.The spray-absorption device 51 includes three-level
Concatenated spray absorber, the offgas outlet of the spray-absorption device 51 is connected with the purified gas tapping equipment 53, described
The liquid outlet of spray-absorption device 51 is connected with the fluosilicic acid slot 52.The spray absorber can be Venturi scrubbing
Device.
The gas treatment recycling module 5 further includes water absorption plant 54.First enrichment facility 43 is additionally provided with
One gas vent, second enrichment facility 44 are additionally provided with second gas outlet.The first gas outlet and described second
Gas vent is connected with the air inlet of the water absorption plant 54, the offgas outlet of the water absorption plant 54 and the purification
Gas tapping equipment 53 is connected, and the liquid outlet of the water absorption plant 54 is connected with the fluosilicic acid slot 52.
The steam-heating system 6 is connected with sulfuric acid afterheat steam device 8, the hot steam of the sulfuric acid afterheat steam device 8
Outlet is connected to the hot air intake of the steam-heating system 6.The steam-heating system 6 includes hot steam inlet pipe, heating ring
Pipe and remaining vapour discharge pipe.The inlet end of the hot steam inlet pipe forms the hot air intake of the steam-heating system 6, and the heat is steamed
The outlet side of vapour inlet pipe is connect with the inlet end of the heating endless tube, the outlet side of the heating endless tube and the remaining vapour discharge pipe
Connection.
The outer wall of the anterior reactor 11, pre-reaction digester 12 and the half water crystallization reaction tank 21 is respectively surrounded with one section
The heating endless tube, all heating endless tubes are connected separately with the same hot steam inlet pipe, all heating endless tubes
Outlet side is connected separately with same remaining vapour discharge pipe.
The concentrated sulfuric acid feeding mechanism 7 and dilute sulfuric acid feeding mechanism 14 are connect with the sulfuric acid production system of same garden.
The sulfuric acid production system includes the sulfuric acid afterheat steam device 8 and exhaust gas processing device, the sulfuric acid afterheat steam device 8
Hot steam is sent into the steam-heating system 6；The dilute sulfuric acid that the exhaust gas processing device generates is delivered to the concentrated sulfuric acid and supplies
Answer device 7.The concentrated sulfuric acid of the sulfuric acid production system production is transported to the concentrated sulfuric acid feeding mechanism 7.
In this system, connected on demand with pipeline between each device between each module, in each module, when necessary arranging thing
Material pump.Wherein, it is provided with insulation jacket outside the slurry conveying pipeline between the half water cure slot 23 and half water filtering device 24,
Pipeline is heated, heat loss is avoided, prevents semi-hydrated gypsum fouling in pipeline.Half water filtering device 24 and concentrated phosphoric acid are slow
It is also equipped with insulation jacket outside finished acid pipeline between jet-bedding 41, prevents semi-hydrated gypsum a small amount of in cooling post mother liquor in pipeline
Interior fouling.
Half water filtering device 24 and two water filtering devices 33 are rotary-disc vacuum filter.The first concentration dress
Set 43 and second enrichment facility 44 be respectively evaporator.
The anterior reactor 11, pre-reaction digester 12, half water crystallization reaction tank 21, half water cure slot 23, the reaction of two water
In slot 31, two water crystallization slots 32 include groove body, the cell wall of the groove body include the armored concrete set gradually from outside to inside,
Rubber lining impervious barrier and carbon brick layer are respectively equipped with two-layer equation blender in the groove body.The stirring of the two-layer equation blender
Paddle includes upper blade group and lower layer's blade group.The upper blade group and lower layer's blade group are to count liquid in the intracorporal position of liquid
Position height is h, and to guarantee mixing effect, then height of the upper blade group apart from slot bottom is h1=0.7h, lower layer's paddle
Height of the leaf group apart from slot bottom is h1=0.3h.The outer end of the upper blade group and lower layer's blade group is apart from groove body inner sidewall
Distance is less than 20cm.Agitating paddle selects 904L or comparable material to be made.By the optimization design of the two-layer equation blender, make
It obtains material in reaction process to be sufficiently stirred, improves driving rate.Before this, the normal driving time of reaction unit about three
Month, it then needs to overhaul three days, the time of driving normal at present is six to eight months, and maintenance rate reduces, and greatly improves production
Rate and economic benefit.
Technical process based on above-mentioned phosphoric acid production system are as follows:
(1) pre-reaction: rock phosphate in powder is sent into the phosphorus ore pretreatment unit 13 and is pre-processed.The pretreatment includes making
With ball mill ball mill crushing rock phosphate in powder, ore pulp is made after rich phosphorus ore is broken, for phosphorous low mine, is passed through the phosphorus ore again after broken
Flotation device flotation.Concentrate slurry is obtained by pretreatment, P in the concentrate slurry2O5Weight content be not less than 32%, by the concentrate slurry with
And the dilute sulfuric acid that the dilute sulfuric acid feeding mechanism 14 generates each leads into the anterior reactor 11, and at 94-98 DEG C, preferably 95 DEG C
Under the conditions of react, then continuously enter the pre-reaction digester 12, slaking reaction 60min or so obtains pre-reaction material；
The amount for the dilute sulfuric acid being wherein passed through sufficiently reacts the amount of the sulfuric acid that need to be consumed less than phosphorus ore, due to sulfuric acid amount not
Following three chemical reactions occur for foot:
Ca3(PO4)2+H2SO4=2CaHPO4+CaSO4 (1)
Ca3(PO4)2+2H2SO4=Ca (H2PO4)2+2CaSO4 (2)
Ca3(PO4)2+3H2SO4=2H3PO4+3CaSO4 (3)
The reaction of (2) half water: the pre-reaction material enters the half water crystallization reaction tank 21, and to the half water reactive crystallization
It is passed through the excessive concentrated sulfuric acid in slot 21, is sufficiently stirred and carries out half water reaction, reacts 60-120 min, reaction temperature is 88-93 DEG C, excellent
95 DEG C are selected as, then reaction mass is sent into the flash cooler 22 and is cooled down, and the gas of generation is passed through the gas treatment
Recycling module 5, material after cooling are sent into the half water cure slot 23 and are cured, and material is through the half water mistake after the completion of curing
It filters device 22 to filter, the phosphoric acid that filtrate is 42% or more, filtrate is discharged into the concentrated phosphoric acid dashpot from half water phosphoric acid outlet
41, filter residue is to contain P2O5Semi-hydrated gypsum, filter residue is sent into the two water reactive tank 31 from half water recrement outlet；
Since phosphorus ore contains Multiple components, after comprehensively considering various composition, reaction expression are as follows:
5Ca3F(PO4)3+5H2SO4+H2O→5(CaSO4·1/2H2O)+H3PO4+HF↑ (4)
In reaction process and during flash cooled, it may appear that HF and SiF4Gas evolution, into efficient Venturi scrubbing
Device, washed liquid spray washing make HF and SiF in tail gas4Reaction generates H2SiF6It is only absorbed by the water, obtains fluosilicic acid, have very high
Economic value.The half water stage of reaction, most of phosphorus ore are reacted, and a small amount of P is mingled in semi-hydrated gypsum2O5, go successively to two
Water reaction workshop section is reacted.
The reaction of (3) two water: bis- water reactive tank 31 of Xiang Suoshu is passed through the concentrated sulfuric acid and carries out two water reactions, and reaction is under normal temperature conditions
It carries out, reaction mass subsequently enters the two water crystallizations slot 32 the reaction was continued crystallization, subsequently enters two water filtering device 33
It is filtered, filtrate is with P2O5The phosphoric acid,diluted that parts by weight are 26~30% is counted, the phosphoric acid,diluted is exported through the phosphate dihydrate
It is discharged into the phosphoric acid,diluted dashpot 42, filter residue is discharged to ardealite slot 34 from ardealite outlet, the ardealite slot 34
Return water is discharged from the backwater outlet, and the return water is used for half water filtering device 22 or/and two water filtering device 33
Filtration and washing water, can also be added in ball mill；
The reaction expression of two water reaction are as follows:
5(CaSO4·1/2H2O)+5H2SO4→5(CaSO4·2H2O)+3H3PO4 (5)
(4) Phosphoric Acid Concentration handle: by the phosphoric acid,diluted in the phosphoric acid,diluted dashpot 42 through first enrichment facility 43 into
Row first is concentrated, and obtains parts by weight and is 42% phosphoric acid, and is passed through the first concentrated phosphoric acid storage tank 45, and first concentration produces
Raw gas is passed through the water absorption plant 55, and absorbing liquid is fluosilicic acid, and tail gas is discharged from the purified gas tapping equipment 54；
Phosphoric acid in the first concentrated phosphoric acid storage tank 45 carries out the second concentration through second enrichment facility 44, obtains weight
The concentrated phosphoric acid that number is 52% or more, the gas that second concentration generates are also passed into the water absorption plant 55, and absorbing liquid is
Fluosilicic acid, tail gas are discharged from the purified gas tapping equipment 54.
Calculate through detection, P in phosphorus ore2O5In the half water conservancy project section rate of recovery up to 93% or more, in two water conservancy project section recyclings 6%, always
The rate of recovery is up to 99%.It is recycled by the escaping gas to reaction process and concentration process generation, F element in phosphorus ore
The rate of recovery reach 96% or more.
Compared with prior art, beneficial effects of the present invention:
(1) it is pre-processed by front end phosphorus ore and the subsequent good control to reaction temperature, ensure that Ban Shui and two water two
It walks stable production process to carry out, does not change with phosphate rock quality, compared with the prior art, reacted between different batches in each reactive tank
Homogeneity is higher；
(2) it is not required to repeatedly adjust sulfuric acid concentration in reaction system in reaction process, reaction controlling is more simple；
The rational design of agitating device in (3) half water reactive tanks is reduced so that material is sufficiently stirred in reaction process
Scale deposition reacts more abundant, extends cleaning cycle, improves driving rate；
(4) concentrated sulfuric acid of gas washing in SA production chain output in same garden is taken full advantage of, transportation cost is reduced；Also, half
During the pretreatment (acidification) of water law ore pulp, using the dilute sulfuric acid that the tail gas of processing gas washing in SA production obtains, it is raw to save sulfuric acid
Process and equipment that chain post-processes dilute sulfuric acid are produced, reduces cost, while it being made to get utilization；
(5) a large amount of steam heats that gas washing in SA production chain generates in the same garden of company are taken full advantage of, phosphoric acid production has been saved
The energy consumption of chain: the phosphoric acid of half water section production 42%~45%, average 1m3Phosphoric acid consume 0.35~0.4m3Steam
(150 to 200 DEG C) are concentrated to 42%~45% phosphoric acid, steam consumption with the phosphoric acid,diluted of two water laws production 20%~26% again
Reduce about 50%；
(6) the advantages of combining half water law and two two kinds of technique of water law, can not only produce dense high-end phosphoric acid,
It can be with remanufacture low side phosphoric acid, for different subsequent productions；
(7) P element conversion is high in phosphorus ore, P in dihydrate gypsum2O5Less residue is conducive to subsequent industrial application；
(8) sufficiently the production tail gas of washing recycling each process, the available higher fluosilicic acid of economic value, purified gas reach
To discharge standard.
Finally, it should be noted that foregoing description is only the preferred embodiment of the present invention, the ordinary skill people of this field
Member under the inspiration of the present invention, without prejudice to the purpose of the present invention and the claims, can make multiple similar tables
Show, such transformation is fallen within the scope of protection of the present invention.
Claims (10)
1. a kind of Wet-process Phosphoric Acid Production system of stability and high efficiency, it is characterised in that: react mould including pre-reaction module (1), half water
Block (2), two water reaction modules (3), phosphoric acid post-processing module (4), gas treatment recycling module (5) and steam-heating system (6)；
The discharge port of the pre-reaction module (1) is connected with the feed inlet of the half water reaction module (2), and half water reacts mould
Block (2) further respectively has half water reaction gas outlet, the outlet of half water phosphoric acid and the outlet of half water recrement, the half water recrement outlet and institute
The feed inlet for stating two water reaction modules (3) is connected, and the two water reaction module (3) further respectively has phosphate dihydrate outlet and phosphorus stone
Cream outlet；
The feed inlet of the half water reaction module (2) and the feed inlet of the two water reaction module (3) are connected separately with the concentrated sulfuric acid
Feeding mechanism (7)；
Half water reaction gas outlet is connected with the air inlet of the gas treatment recycling module (5)；
The half water phosphoric acid outlet and the phosphate dihydrate export the feed inlet phase with the phosphoric acid post-processing module (4) respectively
Even；
The steam-heating system (6) is the pre-reaction module (1) and half water reaction module (2) heat supply.
2. a kind of Wet-process Phosphoric Acid Production system of stability and high efficiency according to claim 1, it is characterised in that: further include sulfuric acid
The hot steam outlet of afterheat steam device (8), the sulfuric acid afterheat steam device (8) is connected to the steam-heating system (6)
Hot air intake.
3. a kind of Wet-process Phosphoric Acid Production system of stability and high efficiency according to claim 2, it is characterised in that: half water is anti-
Answering module (2) includes according to the sequentially connected half water crystallization reaction tank (21) of flow direction of material, flash cooler (22), half water cure
The feed inlet of slot (23) and half water filtering device (24), the half water crystallization reaction tank (21) forms the half water reaction module
(2) feed inlet, the flash cooler (22) are equipped with half water and react gas outlet, and the half water cure slot (23) goes out
Material mouth is connected with the feed inlet of half water filtering device (24)；
Half water filtering device (24) is also respectively provided with the half water phosphoric acid outlet and half water recrement outlet.
4. a kind of Wet-process Phosphoric Acid Production system of stability and high efficiency according to claim 3, it is characterised in that: two water is anti-
Answering module (3) includes according to the sequentially connected two water reactive tank (31) of flow direction of material, two water crystallization slots (32), two water filtering devices
(33)；
The feed inlet of the two water reactive tank (31) forms the feed inlet of the two water reaction module (3)；
Two water filtering device (33) is respectively arranged with the phosphate dihydrate outlet and ardealite outlet.
5. a kind of Wet-process Phosphoric Acid Production system of stability and high efficiency according to claim 4, it is characterised in that: at the gas
Managing recycling module (5) includes spray-absorption device (51), fluosilicic acid slot (52) and purified gas tapping equipment (53)；
Half water reaction gas outlet is connected with the air inlet of the spray-absorption device (51)；
The offgas outlet of the spray-absorption device (51) is connected with the purified gas tapping equipment (53), the spray-absorption dress
The liquid outlet for setting (51) is connected with the fluosilicic acid slot (52).
6. a kind of Wet-process Phosphoric Acid Production system of stability and high efficiency according to claim 5, it is characterised in that: after the phosphoric acid
Processing module (4) includes concentrated phosphoric acid dashpot (41), phosphoric acid,diluted dashpot (42), the first enrichment facility (43), the second concentration dress
Set (44), the first concentrated phosphoric acid storage tank (45), the second concentrated phosphoric acid storage tank (46)；
Half water phosphoric acid outlet is connected with the feed inlet of the concentrated phosphoric acid dashpot (41), the phosphate dihydrate export with it is described
The feed inlet of phosphoric acid,diluted dashpot (42) is connected, the discharge port and first enrichment facility of the phosphoric acid,diluted dashpot (42)
(43) feed inlet is connected, the feed inlet phase of the discharge port of first enrichment facility (43) and the concentrated phosphoric acid dashpot (41)
Even；
The discharge port of the concentrated phosphoric acid dashpot (41) is filled with the first concentrated phosphoric acid storage tank (45) and second concentration respectively
The feed inlet for setting (44) is connected, the discharge port of second enrichment facility (44) and the second concentrated phosphoric acid storage tank (46) phase
Even；
First enrichment facility (43) is additionally provided with first gas outlet, and second enrichment facility (44) is additionally provided with second
Gas vent；
The gas treatment recycling module (5) further includes water absorption plant (54), the first gas outlet and second gas
Body outlet is connected with the air inlet of the water absorption plant (54), the offgas outlet of the water absorption plant (54) and it is described only
Change gas tapping equipment (53) to be connected, the liquid outlet of the water absorption plant (54) is connected with the fluosilicic acid slot (52).
7. a kind of Wet-process Phosphoric Acid Production system of stability and high efficiency according to claim 6, it is characterised in that: the pre-reaction
Module (1) includes anterior reactor (11) and pre-reaction digester (12), the discharge port of the anterior reactor (11) and described pre- anti-
The feed inlet of digester (12) is answered to be connected；
The feed inlet of the anterior reactor (11) is connected separately with phosphorus ore pretreatment unit (13) and dilute sulfuric acid feeding mechanism (14)；
The dilute sulfuric acid feeding mechanism (14) is connected with sulfuric acid tail gas processing unit (9), which is equipped with
Dilute sulfuric acid outlet, dilute sulfuric acid outlet are connected with the dilute sulfuric acid feeding mechanism (14).
8. a kind of Wet-process Phosphoric Acid Production system of stability and high efficiency according to claim 7, it is characterised in that: the steam adds
Hot systems (6) include hot steam inlet pipe, heating endless tube and remaining vapour discharge pipe；
The inlet end of the hot steam inlet pipe forms the hot air intake of the steam-heating system (6), the hot steam inlet pipe
Outlet side is connect with the inlet end of the heating endless tube, and the outlet side of the heating endless tube is connect with the remaining vapour discharge pipe；
The outer wall of the anterior reactor (11), pre-reaction digester (12) and the half water crystallization reaction tank (21) is respectively surrounded with one
Duan Suoshu heats endless tube, and all heating endless tubes are connected separately with the same hot steam inlet pipe, all heating endless tubes
Outlet side be connected separately with same remaining vapour discharge pipe.
9. a kind of wet method phosphoric acid manufacture process based on system described in claim 7, it is characterised in that sequentially include the following steps:
(1) pre-reaction: phosphorus ore is sent into the phosphorus ore pretreatment unit (13) and handles obtained concentrate slurry, P in the concentrate slurry2O5
Weight content is 32%, the dilute sulfuric acid that the concentrate slurry and the dilute sulfuric acid feeding mechanism (14) generate is each led into described pre-
Reactive tank (11), enters the pre-reaction digester (12) after reacting at 94-98 DEG C, slaking reaction 120min is obtained pre- anti-
It should expect；
The reaction of (2) half water: the pre-reaction material enters the half water crystallization reaction tank (21), and to the half water crystallization reaction tank
(21) it is passed through the excessive concentrated sulfuric acid in, is sufficiently stirred and carries out half water reaction, reaction temperature is 88-93 DEG C, and then reaction mass is sent into
The flash cooler (22) is cooled down, and the gas of generation is passed through the gas treatment recycling module (5), material after cooling
It is sent into the half water cure slot (23) to be cured, material is filtered through half water filtering device (22) after the completion of curing, filtrate
It is discharged into the concentrated phosphoric acid dashpot (41) from half water phosphoric acid outlet, filter residue is to contain P2O5Semi-hydrated gypsum, filter residue is from described
The two water reactive tank (31) is sent into the outlet of half water recrement；
The reaction of (3) two water: bis- water reactive tank (31) of Xiang Suoshu is passed through the concentrated sulfuric acid and carries out two water reactions, and reaction mass subsequently enters institute
Two water crystallization slots (32) are stated the reaction was continued crystallization, subsequently enters two water filtering device (33) and be filtered, filtrate is dilute phosphorus
Acid, the phosphoric acid,diluted are discharged into the phosphoric acid,diluted dashpot (42) through phosphate dihydrate outlet, and filter residue is exported from the ardealite
Discharge.
10. wet method phosphoric acid manufacture process according to claim 9, it is characterised in that further comprise the steps of:
(4) Phosphoric Acid Concentration handle: by the phosphoric acid,diluted in the phosphoric acid,diluted dashpot (42) through first enrichment facility (43) into
Row first is concentrated, and obtains parts by weight and is 42% phosphoric acid, and is passed through the first concentrated phosphoric acid storage tank (45), first concentration
The gas of generation is passed through the water absorption plant (54), and absorbing liquid is fluosilicic acid, and tail gas is from the purified gas tapping equipment (53)
Discharge；
Phosphoric acid in the first concentrated phosphoric acid storage tank (45) carries out the second concentration through second enrichment facility (44), obtains weight
The concentrated phosphoric acid that number is 52% or more, the gas that second concentration generates are also passed into the water absorption plant (54), absorbing liquid
For fluosilicic acid, tail gas is discharged from the purified gas tapping equipment (53).
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|---|---|---|---|---|
| CN1421385A (en) * | 2002-12-25 | 2003-06-04 | 云南红磷化工有限责任公司 | Production process of semiwater-diaquo phosphoric acid |
| CN1843901A (en) * | 2006-04-27 | 2006-10-11 | 中国石化集团南京设计院 | Wet-process two-stage phosphoric acid concentration method |
| CN101830656A (en) * | 2010-04-27 | 2010-09-15 | 山东鲁北企业集团总公司 | Method for realizing energy-saving emission-reducing low-carbon circular economy by utilizing chemical energy instead of heat energy |
| US20180257938A1 (en) * | 2015-09-18 | 2018-09-13 | Kingenta Ecological Engineering Group Co., Ltd. | Method for producing phosphoric acid and by-producing alpha-hemihydrate gypsum by wet-process |
-
2019
- 2019-10-08 CN CN201910949900.3A patent/CN110510590A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1421385A (en) * | 2002-12-25 | 2003-06-04 | 云南红磷化工有限责任公司 | Production process of semiwater-diaquo phosphoric acid |
| CN1843901A (en) * | 2006-04-27 | 2006-10-11 | 中国石化集团南京设计院 | Wet-process two-stage phosphoric acid concentration method |
| CN101830656A (en) * | 2010-04-27 | 2010-09-15 | 山东鲁北企业集团总公司 | Method for realizing energy-saving emission-reducing low-carbon circular economy by utilizing chemical energy instead of heat energy |
| US20180257938A1 (en) * | 2015-09-18 | 2018-09-13 | Kingenta Ecological Engineering Group Co., Ltd. | Method for producing phosphoric acid and by-producing alpha-hemihydrate gypsum by wet-process |
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