CN107226460A - The method that peroxophosphoric acid is produced using phosphorus calory burning concentration of dilute phosphoric acid - Google Patents
The method that peroxophosphoric acid is produced using phosphorus calory burning concentration of dilute phosphoric acid Download PDFInfo
- Publication number
- CN107226460A CN107226460A CN201610176619.7A CN201610176619A CN107226460A CN 107226460 A CN107226460 A CN 107226460A CN 201610176619 A CN201610176619 A CN 201610176619A CN 107226460 A CN107226460 A CN 107226460A
- Authority
- CN
- China
- Prior art keywords
- phosphoric acid
- phosphorus
- acid
- concentration
- peroxophosphoric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/055—Peroxyhydrates; Peroxyacids or salts thereof
- C01B15/16—Peroxyhydrates; Peroxyacids or salts thereof containing phosphorus
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
Abstract
The present invention relates to a kind of method that utilization phosphorus calory burning concentration of dilute phosphoric acid produces peroxophosphoric acid, for producing during peroxophosphoric acid, the combustion heat and the hydration heat of phosphorus combustion product phosphorus pentoxide generation hydration reaction that are not produced merely with phosphorus burning evaporate the aqueous solvent in phosphoric acid,diluted jointly；Also absorb phosphorus combustion product phosphorus pentoxide to increase solute using phosphoric acid,diluted；P4Both the heat source substance for being to provide heat is also the raw material for preparing peroxophosphoric acid, so that the inventive method is not only by P4Burn the P produced2O5As solute, also by P4The combustion heat and P2O5Hydration heat be used to evaporation of phosphoric acid in solvent H2O, with increase P2O5Solute and evaporation H2ω (P in the two-way lifting phosphoric acid of O solvents2O5) effect, finally give high-concentration phosphoric acid；As can be seen here, the inventive method realizes P during peroxophosphoric acid is prepared4The combustion heat and P2O5The efficient utilization of hydration heat, with significant energy-saving effect.
Description
Technical field
The invention belongs to phosphoric acid production technical field, and in particular to one kind utilizes phosphorus calory burning concentration of dilute phosphoric acid
Produce concentrated phosphoric acid or the method for peroxophosphoric acid.
Background technology
Generally press phosphoric acid (chemical expression H3PO4) or phosphoric acid solution in phosphorus pentoxide (chemical expression P2O5)
Mass concentration be ω (P2O5) different types of phosphoric acid is defined, concrete concept is as follows：ω(P2O5)<53%
For phosphoric acid,diluted (Thin-phosphoric acid simplicity TPA), ω (P2O5) >=53% is referred to as concentrated phosphoric acid
(Phosphoric acid simplicity PA), ω (P2O5) >=68% claims peroxophosphoric acid (Superphosphoric acid letters
Spell SPA), ω (P2O5) >=76.1% claims polyphosphoric acid (Polyphosphoric acid simplicity PPA), ω (P2O5)
>=83.4% claims super phosphoric acid (Ultraphosphoric acid simplicity UPA)；Phosphoric acid,diluted is concentrated to go water or dissolving
P2O5, can obtain the phosphoric acid of high concentration.
It is divided into by chemical structural formula difference：Orthophosphoric acid (Orthophosphoric acid) H3PO4, pyrophosphoric acid
(Pyrophosphoric acid)H4P2O7, tripolyphosphate (Tripolyphosphoric acid) H5P3O10、
Four polyphosphoric acids (Tetraphosphoric acid) H6P4O13, polyphosphoric acids (Polyphosphoric acid)
Hn+2PnO3n+1；The heated dehydration of orthophosphoric acid or and P2O5Hydration reaction, can obtain polyphosphoric acid.
The impurity in phosphoric acid is removed, corresponding ω (P are can obtain2O5) fertilizer grade, technical grade, feed grade, food
Level and electron-level phosphoric acid.Peroxophosphoric acid SPA is orthophosphoric acid H3PO4, pyrophosphoric acid H4P2O7, triphosphoric acid H5P3O10、
Four polyphosphoric acid H6P4O13, polyphosphoric acids Hn+2PnO3n+1Mixture, with ω (P2O5) rise, wherein many
Polyphosphoric acid ratio accordingly increases.
From rock phosphate in powder production phosphoric acid (chemical expression H3PO4) industrial method have three kinds：Phosphoric acid production method
1. phosphorus ore is melted in electric furnace, occurring reduction reaction with carbon discharges phosphorus (chemical expression P4) and carbon monoxide
The mixed gas of (chemical expression CO), condenses P therein4Steam is yellow phosphorus, and yellow phosphorus burning is absorbed with water
The phosphorus pentoxide of generation obtains the higher phosphoric acid of purity, as thermal phosphoric acid；Phosphoric acid production method 2. sulfuric acid
The raw phosphoric acid containing a large amount of impurity, as phosphoric acid by wet process are obtained Deng strong acid decomposing phosphate rock；Phosphoric acid production method is 3.
Phosphorus ore is heated under the anoxybiotic environment of rotary kiln or tunnel cave leading portion and the uniform compound of carbon dust discharges P4Steam
Vapour and CO, back segment burning P4Steam and CO, kiln absorb P therein in outer absorption tower with water2O5Obtain phosphorus
Acid, as kiln-process phosphoric acid.
Industrially generally using phosphoric acid production method, 1. 2. two methods produce phosphoric acid, phosphorus with phosphoric acid production method
Sour production method is 3. still in evolution.
During phosphorus production, the yellow phosphorus containing a large amount of impurity can be produced and be referred to as mud phosphorus.Mud phosphorus produces phosphoric acid
Process fall within the category of phosphoric acid production method 1..
At present, it is directly to produce high concentration phosphorus that 1. phosphoric acid production method, which produces thermal phosphoric acid by raw material of yellow phosphorus,
The main stream approach of acid；Phosphoric acid production method 1. in produced by raw material of mud phosphorus mud phosphoric acid, phosphoric acid production method
2. the kiln-process phosphoric acid that 3. phosphoric acid by wet process that produces, phosphoric acid production method produce is the phosphoric acid,diluted of low concentration.
Combustion heat 24548kJ/kgP is produced during using yellow phosphorus as the phosphorous acid production by BEP of raw material4, combustion product
P2O5Hydration heat 1327kJ/kgP2O5, the heat that subsidiary steam boiler is removed is deducted, is also added up to about
10000kJ/kgP2O5, signature coal 0.293kg/kgP2O5, generally mainly through plate type heat exchanger by recirculated cooling water
Removal system.
Because mud phosphorus burning production phosphoric acid plant does not attach steam boiler typically, calculate on year-on-year basis
12405kJ/kgP2O5, signature coal 0.4kg/kgP2O5, the heat of generation generally mainly removes by tubular heat exchanger
System and the high-temperature tail gas discharged through chimney are removed.
During phosphorus production, it can produce based on CO and contain P4、H2The gas of S and dust is referred to as
Phosphorus furnace exhaust gas, calorific value is 10450kJ/Nm3；To avoid P therein4And H2S compositions or its combustion product are damaged
Hinder heat transmission equipment or pollution is heated material, generally need alkali cleaning purification to remove P4And H2As clear after the impurity such as S
Clean thermal source；5000Nm3/ h phosphorus furnace exhaust gas purification processing facility invests about 3,600,000 yuan, and total integrated cost is about
0.4 yuan/Nm3。
The high-temperature kiln gas of phosphoric acid production method 3. is with CO and P4Combustion product carbon dioxide CO2、P2O5Steam
And nitrogen N2Based on, its temperature generally absorbs P therein at 500~900 DEG C in absorption tower2O5For phosphoric acid,
And the mode exchanged heat with recycled phosphoric acid and cooling water, the heat that high-temperature kiln gas brings absorption tower into is removed, due to logical
ω (P in normal kiln gas2O5)≤6%, the heat up to 10000kJ/kgP for causing kiln-process phosphoric acid to be taken out of2O5, folding
Mark coal 0.293kg/kgP2O5。
2. phosphoric acid production method obtains initial product ω (P2O5)≤40%, phosphoric acid by wet process is through indirect heating manner
It is concentrated to give ω (P2O5The fertilizer grade phosphoric acid,diluted of)≤53%；Further concentration can obtain high concentration commodity wet method
Phosphoric acid, by ω (P2O5) there is Three Estate 53%, 60%, 68%；By traditional technology method from ω (P2O5)
46% is concentrated into 68%, calorific requirement 4000kJ/kgP2O5, signature coal 0.133kg/kgP2O5。
Commodity phosphoric acid by wet process typically takes harmful influence liquid tank car to transport phosphoric acid, is limited by freight, high
Concentration phosphoric acid more likely turns into fertilizer grade commercial phosphoric acid.Compared to ω (P2O5) 46% phosphoric acid, ω (P2O5)
68% SPA can save 36.5 yuan/ton of P of overland transport expense2O5·100km。
Fertilizer grade SPA (N-P2O5-K2O=0-68-0) it is the maximum high concentration commercial phosphoric acid of market demand,
There is 1,600,000 tons of demand in the current U.S. every year, it is contemplated that Chinese demand is up to 3,000,000 over 3~5 years
More than ton/year.
SPA generally reacts with anhydrous ammonia, the neutral APP solution (10-34-0 and 11-37-0 etc.) of production,
Also it can be used to prepare suspension fertilizer.
Production SPA method has three kinds at present：1. recycled phosphoric acid absorbs yellow phosphorus burning generation to SPA production methods
P2O5Generate SPA；SPA production methods 2. P2O5It is dissolved in phosphoric acid,diluted and obtains SPA；SPA is produced
3. method directly or indirectly heats phosphoric acid,diluted using electric energy or hot-air, and SPA is obtained by the method for concentration.
SPA production methods be 1. mainly used to production industry or the high-purity SPA that uses of food additives phosphoric acid or
PPA, with advantage easy to operate, but there is also the larger shortcoming of cooling load；Restricted by cost, SPA
2. production method is suitable only for small lot, small-scale production；SPA production methods are 3. main using phosphoric acid by wet process as original
Material, has the advantages that raw material is easy to get, and for producing the SPA of fertilizer, but exists to evaporate in phosphoric acid,diluted
H2O needs to consume a large amount of heat energy, and due to high using impurity content in phosphoric acid by wet process, causes in enrichment facility
The shortcoming of the easy fouling in portion, product SPA poor fluidity at normal temperatures.
Using SPA production methods 3. by ω (P2O5) 46% phosphoric acid,diluted is concentrated into ω (P2O5) 68% SPA,
It is generally necessary to evaporate 0.703kgH2O/kgP2O5, heat 4000kJ/kgP2O5, signature coal 0.133kg mark coals
/kgP2O5；Such as using natural gas as thermal source, its heat energy expense is 0.224 yuan/kgP2O5；10t/h68%P2O5It is raw
The Wet Phosphoric Acid Concentration Plant of production capacity power need to make an investment of 50 million yuan.
The content of the invention
It is dense using phosphorus calory burning the invention provides one kind in order to solve the above mentioned problem of prior art presence
Contracting phosphoric acid,diluted produces concentrated phosphoric acid and the method for peroxophosphoric acid, when this method is used to produce peroxophosphoric acid, on the one hand utilizes
Phosphorus P4Burn the combustion heat and combustion product P produced2O5The hydration heat for carrying out hydration reaction generation evaporates dilute jointly
Phosphoric acid reclaimed water, i.e. evaporation solvent H2O；On the other hand combustion product phosphorus pentoxide also is absorbed using phosphoric acid,diluted,
That is increase solute P2O5；So that in the above method, P4Or P2O5Both the heat source substance for being to provide heat is also to use
In the raw material for preparing peroxophosphoric acid, realize to P4The combustion heat and P2O5Effective utilization of hydration heat, it is molten with evaporating
Agent H2O and increase solute P2O5Two-way lifting phosphoric acid in ω (P2O5) effect, final production obtains height
Concentration phosphoric acid.
The technical solution adopted in the present invention is：
A kind of method that utilization phosphorus calory burning concentration of dilute phosphoric acid produces peroxophosphoric acid, comprises the following steps：
(1) P will be contained4The phosphorus source of simple substance is fully burnt under aerobic conditions, obtains containing P2O5Height
Wet body；
(2) high-temperature gas described in step (1) is passed through in absorption cycle phosphoric acid to follow using the absorption
Cycli phosphate absorbs the P in the high-temperature gas2O5, obtain the first concentrated phosphoric acid and middle wet body；
(3) the middle wet body that step (2) is obtained is passed through vaporization cycle phosphoric acid to utilize the middle wet body
Evaporate the H in the vaporization cycle phosphoric acid2O, obtains the second concentrated phosphoric acid and cryogenic gas；
(4) step (2) first concentrated phosphoric acid and step (3) second concentrated phosphoric acid are merged, produced
Concentrated phosphoric acid finished product.
The general principle of the method for utilization phosphorus calory burning concentration of dilute phosphoric acid production peroxophosphoric acid of the present invention
For：By P4Burning generation P2O5During the heat that produces be used for evaporating phosphoric acid,diluted reclaimed water (formula 1 and formula 3),
And absorb P with phosphoric acid,diluted2O5(formula 2), evaporates the aqueous solvent in phosphoric acid,diluted and absorbs P2O5To increase phosphorus
Solute in acid solution is conducive to improving the concentration of phosphoric acid,diluted, it can be seen that, the above method makes P4It is burned
The P produced in journey2O5ω (the P improved in phosphoric acid,diluted are served with the heat of release2O5) effect.
P4Burning：P4+5O2→2P2O5+25488kJ (1)
P2O5Absorption：2P2O5+4H2O→4H3PO4+1327kJ (2)
H2O evaporation：H2O(l)→H2O(g)-2253kJ (3)
The characteristics of the inventive method：(1) phosphorus source P4Product P2O5For the composition of final products peroxophosphoric acid,
Make P4It is both that the heat source substance for being used to evaporation of phosphoric acid aqueous solvent also turns into the raw material of peroxophosphoric acid product preparation process；
(2) combustion product P2O5Heating evaporation phosphoric acid is directly used in by the hydration heat discharged in phosphoric acid absorption process
The heat energy of middle aqueous solvent, realizes the lossless utilization that reaction heat is hydrated in preparation process；(3) combustion air shape
Into high-temperature flue gas, be both the heat carrier during direct heat transfer, be also solvent H in air- extraction evaporation of phosphoric acid2O
Mass transfer carrier.
In step (1), phosphorus source is one or more of in yellow phosphorus, thick phosphorus, mud phosphorus, phosphorus furnace exhaust gas
Mixture.
Also contain heat source substance in phosphorus source, as the embodiment that can be selected, the heat source substance is
Any combustible that heat is provided, including gas, liquid or solid, such as CO, natural gas.
Mass fraction >=0.02% of phosphorous simple substance in phosphorus source.
In step (1), mass fraction >=0.08% containing phosphorus pentoxide in the high-temperature gas.
The temperature of the high-temperature gas is 250~1650 DEG C；The temperature of first concentrated phosphoric acid be 100~
600 DEG C, ω (P2O5) it is 53~76%.
In step (2), the temperature of the middle wet body is 90~1200 DEG C, the temperature of second concentrated phosphoric acid
Spend for 80~500 DEG C, ω (P2O5) it is 53~68%.
In step (2), the ω (P of the absorption cycle phosphoric acid2O5) concentration >=53%, it is also dense to described first
ω (P are supplemented in phosphoric acid2O5) concentration≤53% phosphoric acid,diluted, phosphoric acid,diluted can be the institute that is used in Chemical Manufacture
There are the phosphoric acid of low concentration, such as mud phosphoric acid, supernatant phosphoric acid by wet process, purification of wet process phosphoric acid, half water law wet method phosphorus
Acid；
In step (3), the ω (P of the vaporization cycle phosphoric acid2O5) concentration >=53%, it is also dense to described second
ω (P are supplemented in phosphoric acid2O5) concentration≤53% phosphoric acid,diluted, phosphoric acid,diluted can be the institute that is used in Chemical Manufacture
There are the phosphoric acid of low concentration, such as mud phosphoric acid, supernatant phosphoric acid by wet process, purification of wet process phosphoric acid, half water law wet method phosphorus
Acid.
In step (3), the temperature of the cryogenic gas is 40~290 DEG C, and ω is passed through to the cryogenic gas
(P2O5)≤45%, temperature are 40~90 DEG C of wash cycle phosphoric acid, to utilize the wash cycle phosphoric acid pair
The cryogenic gas carries out washing cooling.
In step (4), the ω (P of the concentrated phosphoric acid product2O5) it is 53~76%, it is dense by adjustment first
The mixed proportion of phosphoric acid and the second concentrated phosphoric acid, you can the concentrated phosphoric acid product of various concentrations is made, it can be seen that,
Finally obtained concentrated phosphoric acid product includes ω (P2O5) 53~68% concentrated phosphoric acid and ω (P2O5) 68%~76%
Peroxophosphoric acid.
Beneficial effects of the present invention are：
The method that utilization phosphorus calory burning concentration of dilute phosphoric acid of the present invention produces peroxophosphoric acid, for producing
During phosphoric acid, P is on the one hand utilized4The combustion heat and combustion product P2O5Hydration heat evaporate jointly in phosphoric acid,diluted
H2O, i.e. evaporation solvent H2O；On the other hand also P is absorbed using phosphoric acid,diluted4Combustion product P2O5, that is, increase
Solute P2O5；P4Both the heat source substance for being to provide heat is also the raw material for preparing peroxophosphoric acid, compared to existing
There is technology, solve and high-purity P is simply absorbed by water merely2O5Prepare thermal waste in peroxophosphoric acid product process
Seriously, or by using electric energy or natural gas it is that thermal source heating concentration of dilute phosphoric acid obtains peroxophosphoric acid product process
The problem of middle thermal energy consumption is big；The inventive method is by P4Burn the P produced2O5It is used as final products peroxophosphoric acid
It is synchronous by P during solute4The combustion heat and P4Combustion product P2O5Hydration heat be used to evaporation of phosphoric acid
In solvent H2O, by increasing P2O5Solute and evaporation H2ω (P in the two-way lifting phosphoric acid of O solvents2O5)
Measure, final production obtains the peroxophosphoric acid of high concentration；As can be seen here, the inventive method makes phosphoric acid production side
3. production process is merged the production process of method 1. and 3. with SPA production methods, with High-Efficiency Utilization of Phosphorus
Sour production method 1. and 3. produce heat energy and significantly save SPA production methods 3. must heat energy energy-saving effect；
With merge production method 1. and 3. with SPA production methods 3. in vent gas treatment process, reduce outer waste air,
CO2、P2O5The environment protecting of total amount；The existing apparatus of phosphoric acid production method 1. and 3. is set to possess SPA by transformation
The function of production method 3., with the low economic effect of production management process small investment, cost.
Brief description of the drawings
Fig. 1 is the work of the utilization phosphorus calory burning concentration of dilute phosphoric acid production peroxophosphoric acid described in the embodiment of the present invention 1
Skill flow chart；
Fig. 2 is the work of the utilization phosphorus calory burning concentration of dilute phosphoric acid production peroxophosphoric acid described in the embodiment of the present invention 2
Skill flow chart；
Fig. 3 is the work of the utilization phosphorus calory burning concentration of dilute phosphoric acid production peroxophosphoric acid described in the embodiment of the present invention 3
Skill flow chart；
Fig. 4 is the work of the utilization phosphorus calory burning concentration of dilute phosphoric acid production peroxophosphoric acid described in the embodiment of the present invention 4
Skill flow chart；
Fig. 5 is the work of the utilization phosphorus calory burning concentration of dilute phosphoric acid production peroxophosphoric acid described in the embodiment of the present invention 5
Skill flow chart；
Fig. 6 is the work of the utilization phosphorus calory burning concentration of dilute phosphoric acid production peroxophosphoric acid described in the embodiment of the present invention 6
Skill flow chart；
Fig. 7 is the work of the utilization phosphorus calory burning concentration of dilute phosphoric acid production peroxophosphoric acid described in the embodiment of the present invention 7
Skill flow chart；
Fig. 8 is the work of the utilization phosphorus calory burning concentration of dilute phosphoric acid production peroxophosphoric acid described in the embodiment of the present invention 8
Skill flow chart.
Embodiment
Explanation is further expalined to the present invention with reference to specific embodiment.
Embodiment 1
The present embodiment provides a kind of method that utilization phosphorus calory burning concentration of dilute phosphoric acid produces peroxophosphoric acid, technique stream
Journey is as shown in figure 1, comprise the following steps：
(1) with phosphorus stove (tail) gas (ω (P4) 0.436%, T=65 DEG C, ω (CO) 89%) as phosphorus source,
Fully burnt in hot-blast stove A1 under aerobic conditions, obtain the high-temperature gas (ω containing phosphorus pentoxide
(P2O5) 0.125%, T=1365 DEG C)；
(2) high-temperature gas described in step (1) is passed through in the B1 of absorption tower, using from circulation acid tank
F1 recycled phosphoric acid absorbs P in high-temperature gas2O5While, also using high-temperature gas by the water in recycled phosphoric acid
Divide and be evaporated, obtain product concentrated phosphoric acid (ω (P2O561.5%) and middle wet body (T=135 DEG C))；Will
Product concentrated phosphoric acid (ω (P2O5) 61.5%) drawn from circulation acid tank F1；Simultaneously constantly will be dilute by pump P
Phosphoric acid (purifying phosphoric acid in Fig. 1, ω (P2O5) 47.4%) add in recycled phosphoric acid；
(3) the middle wet body that step (2) is obtained is passed through scrubbing tower C1, in scrubbing tower C1 using come
Wash cycle acid (ω (P from washing acid storage tank G12O5) 1.5%, T=65 DEG C) to the middle wet body
Carry out after washing cooling, then as tail gas (ω (P after demister D1 demistings2O5) 62ppm, T=71 DEG C)
Arranged outside exhaust fan E1；The concentration of phosphorus pentoxide is by outer row's acid-bearing wastewater (ω (P in wash cycle acid2O5)
1.5%) amount adjustment.
Embodiment 2
The present embodiment provides a kind of method that utilization phosphorus calory burning concentration of dilute phosphoric acid produces peroxophosphoric acid, technique stream
Journey is as shown in Fig. 2 comprise the following steps：
(1) by the yellow phosphorus (ω (P in yellow phosphorus storage tank A24) 99.8%), introduce phosphorus burning through phosphorus supply equipment B2
Tower C2, is fully burnt under aerobic conditions, obtains containing five oxidations after exchanging heat through steam recovery apparatus M2
High-temperature gas (ω (the P of two phosphorus2O5) 25.36%, T=250 DEG C)；
(2) high-temperature gas described in step (1) is passed through to five oxidations two in absorption tower D2, high-temperature gas
Phosphorus is absorbed by the absorption cycle phosphoric acid from absorption cycle acid tank H2, obtains the first concentrated phosphoric acid (ω (P2O5)
69.6%, T=192 DEG C) and middle wet body (T=258 DEG C)；
(3) the middle wet body that step (2) is obtained is passed through evaporating column E2, middle wet evacuator body carrys out spontaneous evaporation
Water in circulating slot N2 vaporization cycle phosphoric acid, obtains the second concentrated phosphoric acid (ω (P2O5) 54%, T=95 DEG C)
With cryogenic gas (T=192 DEG C)；Second concentrated phosphoric acid is led into absorption tower D2 and the described first dense phosphorus
Acid, which merges, to be carried out after absorption cycle, produces ω (P2O5) 70.6% concentrated phosphoric acid product, feeding finished product phosphoric acid storage
Groove I2；
(4) cryogenic gas for obtaining step (3) cools through venturi F2 and demister K2 demistings
Turn into tail gas (ω (P afterwards2O5) 64ppm, T=54 DEG C) arranged outside exhaust fan J2.
Demister K2 collection liquid returns to vaporization cycle acid tank N2, phosphoric acid,diluted (ω (P2O5) 45.3%, T=41 DEG C)
Vaporization cycle acid tank N2 is continuously replenished from phosphoric acid,diluted storage tank G2；Vaporization cycle groove N2 vaporization cycle phosphorus
The temperature of acid is controlled by heat exchanger L2.
Embodiment 3
The present embodiment provides a kind of method that utilization phosphorus calory burning concentration of dilute phosphoric acid produces peroxophosphoric acid, technique stream
Journey is as shown in figure 3, comprise the following steps：
(1) by the yellow phosphorus (ω (P in yellow phosphorus storage tank A34) 99.8%), introduce horizontal phosphorus through phosphorus supply equipment B3
Combustion furnace C3, is fully burnt under aerobic conditions, obtains containing five after exchanging heat through steam recovery apparatus K3
Aoxidize the high-temperature gas (ω (P of two phosphorus2O5) 26.31%, T=760 DEG C)；
(2) high-temperature gas described in step (1) is passed through to five oxidations two in absorption tower D3, high-temperature gas
It is also described using high-temperature gas evaporation while phosphorus is absorbed by the recycled phosphoric acid from absorption cycle acid tank H3
H in recycled phosphoric acid2O, obtains concentrated phosphoric acid (ω (P2O5) 69.4%, T=138 DEG C, as peroxophosphoric acid) and
Cryogenic gas (T=173 DEG C)；The concentrated phosphoric acid self-loopa acid tank H3 draws feeding finished product acid storage tank I3；
(3) tail gas (ω is turned into after the cryogenic gas for obtaining step (2) cools through demister E3 demistings
(P2O5) 76ppm, T=74 DEG C) arranged outside exhaust fan F3.
Mud phosphoric acid (ω (P2O5) 52.8%) as phosphoric acid,diluted from phosphoric acid,diluted storage tank G3 through absorption cycle groove H3 not
Disconnected to add in recycle acid, the temperature of recycle acid is controlled by heat exchanger J3.
Embodiment 4
The present embodiment provides a kind of method that utilization phosphorus calory burning concentration of dilute phosphoric acid produces peroxophosphoric acid, technique stream
Journey is as shown in figure 4, comprise the following steps：
(1) by the mud phosphorus (ω (P in mud phosphorus storage tank A44) 40.4%, ω (solid content) 6.3%, ω (H2O)
54%) one-level phosphorus combustion furnace C4 and air mixed combustion, are introduced through phosphorus supply equipment B4, air-flow enters after burning
Two grades of phosphorus combustion furnace D4 carry out second-time burning under aerobic conditions, obtain the high-temperature gas containing phosphorus pentoxide
(ω(P2O5) 11.94%, T=1150 DEG C)；
(2) high-temperature gas described in step (1) is passed through to five oxidations two in absorption tower E4, high-temperature gas
Phosphorus is absorbed by the absorption cycle phosphoric acid from absorption cycle groove I4, obtains the first concentrated phosphoric acid (ω (P2O5)
69.45%, T=135 DEG C) and middle wet body (ω (P2O5) 1.24%, T=950 DEG C)；
(3) gas for obtaining step (2) is passed through evaporating column F4, and evaporation comes self evaporating circulation groove K4's
Water in vaporization cycle phosphoric acid, obtains the second concentrated phosphoric acid (ω (P2O5) 61.3%, T=120 DEG C) and low temperature
Gas (T=210 DEG C)；Second concentrated phosphoric acid is constantly led into absorption tower E4 and first concentrated phosphoric acid
Merge and carry out after absorption cycle, produce ω (P2O5) 70.6% concentrated phosphoric acid product, feeding finished product acid storage tank J4；
(4) cryogenic gas for obtaining step (3) is passed through scrubbing tower G4, sharp in scrubbing tower G4
With the wash cycle acid (ω (P from wash cycle groove N42O5) 11.2%, T=70.5 DEG C) to described low
Wet body is carried out after washing cooling, and gas turns into tail gas (ω (P after electrostatic precipitator H4 demistings2O5)80ppm)
Arranged outside exhaust fan M4, the phosphoric acid,diluted (ω (P collected in electrostatic precipitator H2O5) 1.2%, T=60.4 DEG C)
Other devices are delivered to use；The temperature of wash cycle acid is adjusted by heat exchanger L4.
Embodiment 5
The present embodiment provides a kind of method that utilization phosphorus calory burning concentration of dilute phosphoric acid produces peroxophosphoric acid, technique stream
Journey is as shown in figure 5, comprise the following steps：
(1) by the mud phosphorus (ω (P in mud phosphorus storage tank A54) 30.24%, ω (solid content) 36.38%, ω (H2O)
33.38%) revolution combustion furnace C5 and air mixed combustion, are introduced through phosphorus supply equipment B5, obtains containing five oxidations
High-temperature gas (ω (the P of two phosphorus2O5) 13.38%, T=750 DEG C)；
(2) high-temperature gas described in step (1) is passed through to five oxidations two in absorption tower D5, high-temperature gas
Phosphorus is absorbed by the absorption cycle phosphoric acid from absorption cycle groove E5, obtains the first concentrated phosphoric acid (ω (P2O5)
61.88%, T=125 DEG C) and middle wet body (ω (P2O5) 1.24%, T=150 DEG C)；
(3) the middle wet body that step (2) is obtained is passed through evaporating column F5, evaporation carrys out self evaporating circulation groove
Water in G5 vaporization cycle phosphoric acid, obtains the second concentrated phosphoric acid (ω (P2O5) 48.36%, T=86 DEG C) and
Cryogenic gas (T=90 DEG C)；Second concentrated phosphoric acid is led into absorption tower D5 to be merged into the first concentrated phosphoric acid
After row absorption cycle, ω (P are produced2O5) 68.36% concentrated phosphoric acid product, self-absorption circulating slot E5 extraction products
Packaging；
(4) cryogenic gas for obtaining step (3) is passed through demister H5 after pipeline spraying cooling,
Gas turns into tail gas (ω (P after electrostatic precipitator H5 demistings2O5) 80ppm) arranged outside exhaust fan I5,
Liquid is phosphoric acid,diluted (ω (P2O5) 1.2%, T=60.4 DEG C) deliver to vaporization cycle groove G5, vaporization cycle
The temperature of groove G5 circulation phosphoric acid,diluted is adjusted by heat exchanger J5.
Embodiment 6
The present embodiment provides a kind of method that utilization phosphorus calory burning concentration of dilute phosphoric acid produces peroxophosphoric acid, technique stream
Journey is as shown in fig. 6, comprise the following steps：
(1) coke (powder) and ground phosphate rock are entered back after comminutor A6 and dryer B6 processing shapings
Brickkiln C6, with air mixed combustion, obtains reacting gas after hot precipitator D6 dedustings, obtains containing five
Aoxidize the high-temperature gas (ω (P of two phosphorus2O5) 6.84%, T=710 DEG C)；
(2) High Temperature Gas described in step (1) is passed through to the phosphorus pentoxide in absorption tower E6, high-temperature gas
Absorbed by the absorption cycle phosphoric acid from absorption cycle groove I6, obtain the first concentrated phosphoric acid (ω (P2O5) 61.3%,
T=154 DEG C) and first in wet body (T=163 DEG C)；First concentrated phosphoric acid is led into vaporization cycle groove
N6；
(3) external high temperature gas is passed through evaporating column M6, the evaporation that evaporation carrys out self evaporating circulation groove N6 is followed
Water in cycli phosphate, obtains the second concentrated phosphoric acid (ω (P2O5) 69.3%, T=172 DEG C) and second in wet
Body (T=183 DEG C)；First concentrated phosphoric acid self evaporating circulation groove N6 obtained by step (2) is led into evaporating column
M6 and after merging and circulated with the second concentrated phosphoric acid obtained by step (3), produces ω (P2O5) 69.5% it is dense
Phosphoric acid product, the concentrated phosphoric acid product spontaneous evaporation tower M6 leads to finished product acid tank L6；
(4) by step (2) obtain first in wet body and by step (3) obtain second in wet body
Middle effect demister F6 demistings are first passed through, scrubbing tower G6 is entered back into and utilizes washing that wash cycle groove K6 is passed through
Wash recycle acid and carry out cooling washing, gas turns into tail gas (ω (P after demister H6 demistings2O5)80ppm)
Arranged outside exhaust fan O6, portion washes recycle acid (ω (P2O5) 6.3%, T=52 DEG C) deliver to absorption and follow
Annular groove E6；The temperature of wash cycle acid is adjusted by heat exchanger J6.
Embodiment 7
The present embodiment provides a kind of method that utilization phosphorus calory burning concentration of dilute phosphoric acid produces peroxophosphoric acid, technique stream
Journey is as shown in fig. 7, comprises following steps：
(1) by the mud phosphorus (ω (P in mud phosphorus storage tank A74) 50.4%, ω (solid content) 25.6%, ω (H2O)
24%), introduced through phosphorus supply equipment B7 and steam phosphorus stove C7, utilize phosphorus furnace exhaust gas (ω (P4) 0.936%, T=65 DEG C,
ω (CO)=89%) combustion heat heating that produces of burning steams mud phosphorus in phosphorus stove C7, the P that the evaporation of mud phosphorus is produced4
Steam is exported and air burning in phosphorus burner J7, with phosphorus furnace exhaust gas burning gases (ω (P2O5) 0.28%) close
And, obtain the high-temperature gas (ω (P containing phosphorus pentoxide2O5) for 16.14%, T=810 DEG C)；
(2) high-temperature gas described in step (1) is passed through absorption tower D7, in high-temperature gas vaporization cycle phosphorus
H in acid2While O, the phosphorus pentoxide in high-temperature gas is by the recycled phosphoric acid from phosphoric acid circulation groove H7
Absorb, concentrated phosphoric acid (ω (P2O5) 68.9%, T=180 DEG C, as peroxophosphoric acid) and cryogenic gas (T=163 DEG C)；
Peroxophosphoric acid product self-absorption circulating slot H7 draws feeding finished product acid storage tank I7；
(3) tail gas (ω (P are turned into after the cryogenic gas for obtaining step (2) cools through demister E7 demistings2O5)
68ppm, T=81 DEG C) arranged outside exhaust fan F7；
Phosphoric acid,diluted (ω (P2O5) 40.4%) be continuously replenished and follow through absorption cycle groove H7 from phosphoric acid,diluted storage tank G7
In naphthenic acid.
Embodiment 8
The present embodiment provides a kind of method that utilization phosphorus calory burning concentration of dilute phosphoric acid produces peroxophosphoric acid, technique stream
Journey is as shown in figure 8, comprise the following steps：
(1) by the yellow phosphorus (ω (P in yellow phosphorus storage tank A84) 99.8%), introduce phosphorus burning through phosphorus supply equipment B8
Hydrated tower C8, carries out after fully burning under aerobic conditions, obtains the high-temperature gas (ω containing phosphorus pentoxide
(P2O5) 25.36%, T=650 DEG C)；
(2) phosphorus pentoxide in step (1) high-temperature gas phosphorus burning hydrated tower C8 middle and lower parts by from
Absorption cycle acid tank H8 recycled phosphoric acid absorbs, while high-temperature gas evaporates H in the recycled phosphoric acid2O,
Obtain concentrated phosphoric acid (ω (P2O5) 61.6%, T=150 DEG C) and cryogenic gas (T=154 DEG C)；Concentrated phosphoric acid is certainly
Circulate acid tank H8 and draw feeding finished product concentrated phosphoric acid storage tank I8；
(3) cryogenic gas for obtaining step (2) through venturi D8 and demister E8 demistings cooling after into
For tail gas (ω (P2O5) 70ppm, T=54 DEG C) arranged outside exhaust fan F8；
Phosphoric acid,diluted (ω (P2O5) 25.3%) it is continuously replenished circulation through cyclic acid pump H8 from phosphoric acid,diluted storage tank G8
Acid tank N8；The temperature of recycle acid is controlled by heat exchanger J8.
The present invention is not limited to above-mentioned preferred forms, and anyone can draw it under the enlightenment of the present invention
His various forms of methods, however, make any change in its process or combination, it is every to be based on the application base
Present principles and with technical scheme identical or similar to the present application, all fall within protection scope of the present invention it
It is interior.
Claims (10)
1. a kind of method that utilization phosphorus calory burning concentration of dilute phosphoric acid produces peroxophosphoric acid, it is characterised in that bag
Include following steps：
(1) phosphorus source containing phosphorus simple substance is fully burnt under aerobic conditions, obtains containing P2O5Height
Wet body；
(2) high-temperature gas described in step (1) is passed through in absorption cycle phosphoric acid to follow using the absorption
Cycli phosphate absorbs the P in the high-temperature gas2O5, obtain the first concentrated phosphoric acid and middle wet body；
(3) the middle wet body that step (2) is obtained is passed through vaporization cycle phosphoric acid to utilize the middle wet body
Evaporate the H in the vaporization cycle phosphoric acid2O, obtains the second concentrated phosphoric acid and cryogenic gas；
(4) step (2) first concentrated phosphoric acid and step (3) second concentrated phosphoric acid are merged, produced
Concentrated phosphoric acid finished product.
2. the method that utilization phosphorus calory burning concentration of dilute phosphoric acid according to claim 1 produces peroxophosphoric acid,
Characterized in that, in step (1), phosphorus source is one kind in yellow phosphorus, thick phosphorus, mud phosphorus, phosphorus furnace exhaust gas
Or several mixtures.
3. the method that utilization phosphorus calory burning concentration of dilute phosphoric acid according to claim 2 produces peroxophosphoric acid,
Characterized in that, also containing heat source substance in phosphorus source.
4. the method that utilization phosphorus calory burning concentration of dilute phosphoric acid according to claim 3 produces peroxophosphoric acid,
Characterized in that, in phosphorus source phosphorous simple substance mass fraction >=0.02%.
5. the method that utilization phosphorus calory burning concentration of dilute phosphoric acid according to claim 1 produces peroxophosphoric acid,
Characterized in that, in step (1), mass fraction >=0.08% containing phosphorus pentoxide in the high-temperature gas.
6. the method that utilization phosphorus calory burning concentration of dilute phosphoric acid according to claim 1 produces peroxophosphoric acid,
Characterized in that, the temperature of the high-temperature gas is 250~1650 DEG C；The temperature of first concentrated phosphoric acid is
100-600 DEG C, ω (P2O5) it is 53~76%.
7. the method that utilization phosphorus calory burning concentration of dilute phosphoric acid according to claim 1 produces peroxophosphoric acid,
Characterized in that, in step (2), the temperature of the middle wet body is 90~1200 DEG C, and described second is dense
The temperature of phosphoric acid is 80~500 DEG C, ω (P2O5) it is 53~68%.
8. the method that utilization phosphorus calory burning concentration of dilute phosphoric acid according to claim 1 produces peroxophosphoric acid,
Characterized in that, in step (2), the ω (P of the absorption cycle phosphoric acid2O5) concentration >=53%, also to institute
State and ω (P are supplemented in absorption cycle phosphoric acid2O5) concentration≤53% phosphoric acid,diluted；
In step (3), the ω (P of the vaporization cycle phosphoric acid2O5) concentration >=53%, also followed to the evaporation
ω (P are supplemented in cycli phosphate2O5) concentration≤53% phosphoric acid,diluted.
9. the method that utilization phosphorus calory burning concentration of dilute phosphoric acid according to claim 1 produces peroxophosphoric acid,
Characterized in that, in step (3), the temperature of the cryogenic gas is 40~290 DEG C, to the low temperature gas
Body is passed through ω (P2O5)≤50%, temperature are 40~90 DEG C of wash cycle phosphoric acid, to be followed using the washing
Cycli phosphate carries out washing cooling to the cryogenic gas.
10. utilization phosphorus calory burning concentration of dilute phosphoric acid according to claim 1 produces the side of peroxophosphoric acid
Method, it is characterised in that in step (4), the ω (P of the high concentration phosphorus acid product of taking-up2O5) it is 53~76%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610176619.7A CN107226460A (en) | 2016-03-25 | 2016-03-25 | The method that peroxophosphoric acid is produced using phosphorus calory burning concentration of dilute phosphoric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610176619.7A CN107226460A (en) | 2016-03-25 | 2016-03-25 | The method that peroxophosphoric acid is produced using phosphorus calory burning concentration of dilute phosphoric acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107226460A true CN107226460A (en) | 2017-10-03 |
Family
ID=59931942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610176619.7A Pending CN107226460A (en) | 2016-03-25 | 2016-03-25 | The method that peroxophosphoric acid is produced using phosphorus calory burning concentration of dilute phosphoric acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107226460A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB245430A (en) * | 1924-12-30 | 1926-04-15 | Griesheim Elektron Chem Fab | Process for the production of phosphoric acid anhydride |
| GB965728A (en) * | 1961-08-05 | 1964-08-06 | Knapsack Ag | Method and apparatus for producing phosphoric acids |
| US3507614A (en) * | 1966-03-14 | 1970-04-21 | Tennessee Valley Authority | Process for production of phosphoric acid |
| SU1310336A1 (en) * | 1985-01-30 | 1987-05-15 | Ленинградский Государственный Научно-Исследовательский И Проектный Институт Основной Химической Промышленности | Method for producing phosphoric acid |
| CN1579930A (en) * | 2003-08-08 | 2005-02-16 | 四川川恒化工有限责任公司 | New method for concentrating and purifying wet phosphoric acid by humid heat joint |
| CN101531352A (en) * | 2009-04-22 | 2009-09-16 | 瓮福（集团）有限责任公司 | Method for using phosphoric oxide to concentrate diluted phosphoric acid to prepare crystal polyphosphoric acid |
| CN101531354A (en) * | 2009-04-22 | 2009-09-16 | 瓮福（集团）有限责任公司 | Method for using phosphoric oxide to concentrate diluted phosphoric acid to prepare polyphosphoric acid |
| CN103449390A (en) * | 2013-08-30 | 2013-12-18 | 常州大学 | Hot-process phosphoric acid waste-heat utilization device with radiative and convective heat exchange surface |
-
2016
- 2016-03-25 CN CN201610176619.7A patent/CN107226460A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB245430A (en) * | 1924-12-30 | 1926-04-15 | Griesheim Elektron Chem Fab | Process for the production of phosphoric acid anhydride |
| GB965728A (en) * | 1961-08-05 | 1964-08-06 | Knapsack Ag | Method and apparatus for producing phosphoric acids |
| US3507614A (en) * | 1966-03-14 | 1970-04-21 | Tennessee Valley Authority | Process for production of phosphoric acid |
| SU1310336A1 (en) * | 1985-01-30 | 1987-05-15 | Ленинградский Государственный Научно-Исследовательский И Проектный Институт Основной Химической Промышленности | Method for producing phosphoric acid |
| CN1579930A (en) * | 2003-08-08 | 2005-02-16 | 四川川恒化工有限责任公司 | New method for concentrating and purifying wet phosphoric acid by humid heat joint |
| CN101531352A (en) * | 2009-04-22 | 2009-09-16 | 瓮福（集团）有限责任公司 | Method for using phosphoric oxide to concentrate diluted phosphoric acid to prepare crystal polyphosphoric acid |
| CN101531354A (en) * | 2009-04-22 | 2009-09-16 | 瓮福（集团）有限责任公司 | Method for using phosphoric oxide to concentrate diluted phosphoric acid to prepare polyphosphoric acid |
| CN103449390A (en) * | 2013-08-30 | 2013-12-18 | 常州大学 | Hot-process phosphoric acid waste-heat utilization device with radiative and convective heat exchange surface |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101913573B (en) | Method for producing sulfuric acid and iron oxide red | |
| WO2014194570A1 (en) | Phosphorus absorption by hydration and fluorine recovery for smoke exiting kiln in kiln process for production of phosphoric acid | |
| CN103818890B (en) | A kind of production method of high-quality polyphosphoric acids | |
| CN101177264A (en) | Method for combined production of activative carbon, white carbon black and soda by employing biomass power plant waste | |
| US20160152474A1 (en) | Apparatus for preparing phosphoric acid from fume exiting the kiln in a kiln phosphoric acid process | |
| WO2016086826A1 (en) | Improved device for preparing phosphoric acid from kiln egression flue gas of phosphoric acid process of kiln method, and phosphoric acid preparing process | |
| WO2014194564A1 (en) | Device and process for fluorine recovery from smoke after phosphorus absorption by hydration in kiln process for production of phosphoric acid | |
| CN104986934A (en) | Continuous thermal decomposition method and apparatus for sludge | |
| CN102367169A (en) | Method for preparation of sulfuric acid and combined production of fine flour iron through calcination of coal-derived pyrite in presence of oxygen-rich air | |
| WO2015101361A1 (en) | Method of producing nanoscale white carbon black by using furnace flue gas directly to carbonize water glass | |
| CN104528674B (en) | A kind of method of large-scale production high-purity phosphorus pentoxide | |
| CN112142350A (en) | Phosphogypsum desulfurization and calcination treatment system and treatment method | |
| CN213865977U (en) | Ardealite desulfurization calcination processing system | |
| CN109279921B (en) | Method for producing calcium superphosphate by using industrial waste mixed acid | |
| CN103466576A (en) | Method for production of phosphoric acid and coproduction of alkaline fertilizer from phosphate ore and potash feldspar | |
| CN102674473A (en) | Process for preparing ferric oxide red by adopting iron vitriol | |
| CN201191145Y (en) | Waste heat utilization apparatus for pyrite slag | |
| CN102556988A (en) | Ultra-pure white phosphorus ordinary-pressure conversion method | |
| CN107226460A (en) | The method that peroxophosphoric acid is produced using phosphorus calory burning concentration of dilute phosphoric acid | |
| CN202430008U (en) | Device for phosphorus pentoxide production and thermal energy recovery | |
| CN111071996A (en) | Method for preparing sulfuric acid | |
| CN101382395B (en) | Heat energy recovering and purifying method for high-temperature kiln gas | |
| CN110745798A (en) | Method and device for removing carbon dioxide in phosphate ore by calcining CO-containing industrial tail gas | |
| CN203558850U (en) | Sulfur-containing waste liquid dry method acid making system | |
| CN206384846U (en) | The system for handling phosphorus ore |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Ma Zhongming Inventor after: Yang Jiashun Inventor after: Zhang Hui Inventor after: Li Hui Inventor after: Zhou Qiongbo Inventor after: Fang Zhukun Inventor after: Wang Hui Inventor after: Yang Jizhou Inventor after: Zhong Qisheng Inventor before: Ma Zhongming |
|
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20180725 Address after: 650607 Yue Shan middle road, Kunyang Town, Jinning County, Kunming, Yunnan, China Applicant after: Yunnan Linhua Group Corp., Ltd. Applicant after: Yunnan paibo Technology Co. Ltd. Address before: 650000 Yunnan science and Technology Park, Kunming, 94, No. 1, 4 unit, 2 level 4, tobacco science and technology park. Applicant before: Yunnan paibo Technology Co. Ltd. |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171003 |