CN105836722A - A method of directly using phosphogypsum decomposition gas for wet method phosphoric acid production - Google Patents
A method of directly using phosphogypsum decomposition gas for wet method phosphoric acid production Download PDFInfo
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- CN105836722A CN105836722A CN201610218410.2A CN201610218410A CN105836722A CN 105836722 A CN105836722 A CN 105836722A CN 201610218410 A CN201610218410 A CN 201610218410A CN 105836722 A CN105836722 A CN 105836722A
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- 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
- C01B25/223—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 only one form of calcium sulfate being formed
- C01B25/225—Dihydrate process
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Abstract
The invention discloses a method of directly using phosphogypsum decomposition gas for wet method phosphoric acid production, and belongs to the fields of phosphogypsum treatment and utilization. The method includes steps of subjecting phosphate ore to wet grinding to prepare phosphate ore slurry, and directly subjecting the slurry and SO2 decomposition gas generated by phosphogypsum decomposition to a gas-liquid-solid heterogeneous chemical reaction to obtain calcium sulfite solid and a phosphoric acid solution, wherein the calcium sulfite solid is oxidized into a mixed solution of calcium sulfate and phosphoric acid in a liquid phase and the mixed solution is fed into a wet method phosphoric acid production device to produce wet-method phosphoric acid. Through adoption of the method, treatment of the phosphogypsum decomposition gas is free of a traditional sulfuric acid production steps. The method simplifies devices, shortens the process, reduces device investment, reduces the production cost, achieves economical and full-circulation utilization of a sulfur resource in wet method phosphoric acid production, achieves objectives of clean production, environment protection, energy conservation, cost reduction, efficiency increasing, investment reduction, and other objectives increasing economic benefit of producers, and has significant economic benefit and social benefit.
Description
Technical field
The present invention relates to the resource reutilization field of ardealite, particularly relate to a kind of decomposing ardealite gas and be directly used in wet method
The method of phosphoric acid production.
Background technology
Ardealite is the primary solids refuse that high concentration phosphate fertilizer produces, and China's phosphorous chemical industry yield ranks first in the world,
About 15,000,000 tons of (P of China's Wet-process Phosphoric Acid Production in 20152O5%), by-product ardealite 80,000,000 tons, simultaneously need to consume sulphuric acid production
Measure 40,000,000 tons, occupy No. 1 in the world.
Ardealite is the huge industrial solid by-product being related under " population, grain " conditions of existence have to produce,
For the problem solving ardealite bulk deposition.Current processing method is typically with outdoor storing up, contained by ardealite
Calcium is not utilized with Sulphur ressource element, i.e. landed property, brings again environmental hazard.Ardealite chemolysis produces cement also
Co-producing sulfuric acid, is to solve phosphorous chemical industry solid waste to store up the optimal path recycled with Sulphur ressource, i.e. saves Sulphur ressource, make use of again
Calcium resource.But, as decomposing ardealite gas for the production of sulphuric acid, the investment of its sulfuric acid apparatus is big, and will through dedusting,
The a series of tediously long flow processs such as purification, catalyzed conversion, acid absorption can produce sulphuric acid with loaded down with trivial details operational approach, is unfavorable for phosphorus stone
The optimum cycle economic benefit of cream.
Inventor is at patent No. ZL94111776.6 (patent name: a kind of Production By Sulfuric Acid Process phosphoric acid and the side of solution containing phosphate
Method), the principle that in successful Application phosphorus ore, carbonate and calcium phosphate can react with the sulphuric acid in phosphoric acid by wet process and phosphoric acid, solve
The problem that the sulphuric acid of Wet-process Phosphoric Acid Production of having determined feed phosphate is high with lime consumption, significantly reduces sulphuric acid and Calx raw material
Consumption, and established production of feedgrade phosphate technology today with domestic original creation.Thereafter in patent No. ZL97107676.6,
(patent name: utilize the method that wet phosphate waste residue produces ammophos), economical solves feed phosphate defluorinate
Slag, as fertilizer ammonium phosphate and a production difficult problem for Chemical Mixed Fertilizer basis phosphorus source fertilizer, makes production of feedgrade phosphate enterprise obtain huge
Economic and social profit.As the production development of phosphate rock resource complete utilization, inventor is again in the patent No.
ZL201310437466.3 (patent name: a kind of Gypsum Fibrosum produces the production method of cement joint production sulphuric acid), the patent No.
ZL201410070462.0 (patent name: energy-saving and cost-reducing Gypsum Fibrosum produces the method for cement joint production sulphuric acid) and the patent No.
In the patents of invention such as ZL201410069087.8 (patent name: the method for the high silicon Phosphate Rock low silicon ardealite of acid by-product)
Directly or indirectly calcium constituent in phosphorus ore and element silicon are circulated economic processing or recycling.
Chinese patent application (CN10467728) " a kind of deviate from sulfuric acid tail gas the method for sulfur dioxide ", uses 20-
60% phosphate ore pulp by sulfur dioxide in " double-absorption " sulfuric-acid production tail gas by 800mg/m3Drop to 100mg/m3Hereinafter, two are absorbed
The phosphate ore pulp of sulfur oxide is for the raw material of phosphate reverse flotation de-magging operation.The method uses Calx abjection cigarette as existing steam power plant
Sulfur dioxide in gas is the same, is only that phosphate ore pulp replaces lime white absorb low content sulfur dioxide gas, and absorbs
The amount of sulfur dioxide is relatively fewer, and is only used for flotation of phosphate rock raw material；The circulation of the solution Wet-process Phosphoric Acid Production Sulphur ressource failed
The investment expensive with sulfuric acid apparatus and producing cost problem.
Although above-mentioned patent solves decomposition efficiency and the production problem of ardealite, or the discharge of sulfuric-acid production tail gas is asked
Topic；But, the chemical energy of decomposing ardealite gas is not the most fully utilized, and is also not up to optimal recycling economy
Means.Existing gas washing in SA production technology, by Gypsum Fibrosum decomposition gas SO2Through dedusting, pickling or water washing cleaning, then carry out gas phase catalysis
It is oxidized to SO3, obtain sulphuric acid by sulfuric acid absorption.Sulfur oxide gas as decomposing ardealite gas is used for traditional gas washing in SA production,
No matter use " one turn of one suction " or use twice multistage to convert and twice absorption " double-absorption ", because sulfuric acid apparatus is at phosphorus stone
Investment cost shared in the production process that cream decomposition gas recycles is huge, the 2/3 of gross investment to be reached, and phosphorus ore
The sour position chemical energy of alkali position chemical energy and decomposition gas does not obtain the utilization of science, and also result in decomposing ardealite gas can not be economical
The passive situation of the utilization of resources.
Along with raising day by day and the phosphorous chemical industry sustainable development generation technique requirement of environmental requirement, ardealite follows as resource
The wet method phosphorous chemical industry that ring utilizes produces, and the circulation of Sulphur ressource can be held in the urgent need to exploitation with the realistic problem discharged without ardealite
Continuous advanced production technology, meets human survival and produces needs, accomplishing the harmony of " Kingsoft Yin Shan and blue montains and green waters ".
Summary of the invention
The purpose of the present invention is that a kind of method providing decomposing ardealite gas to be directly used in Wet-process Phosphoric Acid Production, to solve
The problem utilizing ardealite that certainly prior art can't be most economical.
To achieve these goals, the technical solution used in the present invention is such that a kind of decomposing ardealite gas and directly uses
In the method for Wet-process Phosphoric Acid Production, comprise the following steps:
(1), phosphorus ore is prepared phosphate ore pulp B through wet grinding；
(2), preparing Gypsum Fibrosum decomposition gas S, described Gypsum Fibrosum decomposition gas S, for by ardealite, or the natural gypsum, or steam power plant takes off
Sulfur Gypsum Fibrosum, or titanium dioxide waste acid by sulfuric acid process processes Gypsum Fibrosum, or other industry by-product gypsum carries out reduction decomposition and produces；
(3), the phosphate ore pulp B of decomposition gas S step (1) gained of step (2) gained is directly carried out gas, liquid, solid three-phase
Mixed decomposition and absorption chemical reaction, obtain the phosphoric acid material pulp C of tail gas A and sulfur acid calcium；
(4) ardealite of step (3) gained is carried out reduction decomposition again and produces decomposition gas S, for step (3)
The present invention is by Gypsum Fibrosum decomposition gas S, and the phosphate ore pulp B directly prepared with phosphoric acid by wet process carries out gas, solid, liquid three-phase mixes
Chemolysis, the concerted reaction precipitating and absorbing, through repeatedly adverse current three-phase hybrid reaction, make phosphorite stope become phosphoric acid and sulfurous
Acid calcium, calcium sulfite is oxidised with air to calcium sulfate in liquid phase, it is thus achieved that phosphoric acid by wet process slip C；Gypsum Fibrosum decomposition gas S is completely converted into
Calcium sulfate, discharges the sulfur dioxide in tail gas A far below discharge standard；Decomposition gas is not reprocessed into sulphuric acid, eliminates production sulfur
The pilot process of acid, eliminates and produces the device of sulphuric acid and investment of production, scientific and reasonable make use of phosphorus ore and Gypsum Fibrosum decomposition gas institute
The chemical energy having, plays the innovation effect of " arrow three is carved "；
Wherein, the three-phase hybrid reaction principle of phosphate ore pulp B and Gypsum Fibrosum decomposition gas S is:
(1) the hybrid reaction slip that decomposing ardealite gas is directly sent here with adverse current carries out three-phase mixed decomposition reaction, and oxygen
The calcium sulfite of change nascent state:
SO2+Ca(H2PO4)2+3H2O=CaSO3·2H2O↓+2H3PO4 (1)
SO3+Ca(H2FPO4)2+3H2O=CaSO4·2H2O↓+2H3PO4 (2)
Ca5F(PO4)3+7H3PO4=5Ca (H2PO4)2+HF (3)
2CaSO3·2H2O+O2=2CaSO4·2H2O↓ (4)
(2) the hybrid reaction slip that above-mentioned (one) reacted tail gas and (three) adverse current are sent here carries out three-phase hybrid reaction,
And aoxidize the calcium sulfite of nascent state:
6SO2+2Ca5F(PO4)3+18H2O=6CaSO3·2H2O↓+3Ca(H2PO4)2+CaF2↓ (5)
6SO3+2Ca5F(PO4)3+18H2O=6CaSO4·2H2O↓+3Ca(H2PO4)2+CaF2↓ (6)
2CaSO3·2H2O+O2=2CaSO4·2H2O↓ (7)
(3) above-mentioned (two) reacted tail gas is directly and phosphate ore pulp carries out three-phase hybrid reaction, and in phosphorus ore, carbonate is by tail
The low concentration SO of gas2All absorb precipitation
SO2+CaCO3+2H2O=CaSO3·2H2O↓+CO2↑ (8)
SO2+MgCO3+2H2O=MgSO3·2H2O+CO2↑ (9)
SO3+CaCO3+2H2O=CaSO4·2H2O↓+CO2↑ (10)
SO3+MgCO3+2H2O=MgSO4·2H2O+CO2↑ (11)
That is:
One-level three-phase hybrid reaction: Gypsum Fibrosum decomposition gas S is the most molten with the dalcium biphosphate that two grades of three-phase hybrid reactions obtain
Liquid carries out three-phase hybrid reaction, generates calcium sulfate and phosphoric acid, and phosphoric acid reacts generation biphosphate again with the phosphorus ore reacted the most completely
Calcium, continues to carry out three-phase hybrid reaction with decomposition gas, re-precipitates calcium sulfate, reaction equation (1)-(4).
Two grades of three-phase hybrid reactions, at most of decomposition gas that first order reaction has been fallen by dalcium biphosphate reactive absorption precipitation
Tail gas and phosphorus ore in fluor-apatite carry out three-phase hybrid reaction, generate calcium sulfate and biphosphate calcium solution, reaction equation (5)-
(7)。
Three grades of three-phase hybrid reactions, the tail gas of the decomposition gas being almost removed in the second level is directly and phosphate ore pulp carries out three
Phase hybrid reaction, the carbonate in phosphorus ore and low concentration SO in tail gas2Reaction, produces sulfate reaction equation (8)-(11), plays
The effect of desulfurization.
The temperature that in the present invention, decomposing ardealite gas S exports out from the suspended preheater of calcining kiln is 300-400 DEG C,
It is 300-350 DEG C well, SO in gas2Volumetric concentration can not limit, 0-14%.The cycle stock of one-level three-phase mixing reactor
The solid mass ratio of serosity is 1.5-5, and reaction temperature is 75-100 DEG C, the P of phosphoric acid2O5Mass concentration is 20-40%, discharges tail gas A1
Temperature 100-125 DEG C；The cycle stock slurry liquid-solid ratio of two grades of three-phase mixing reactors is 4-50, preferably 8-12, and reaction temperature is
60-100 DEG C, get rid of tail gas A2 temperature 62-100 DEG C；The cycle stock slurry liquid-solid ratio of three grades of three-phase hybrid reactions is 5-60, preferably
20-25, reaction temperature is 50-85 DEG C, discharges tail gas A3 temperature 52-95 DEG C, SO in gas phase2Volumetric concentration low to 100PPM with
Under.Deliver to the washing cooling of phosphoric acid by wet process vent gas treatment operation from three grades of three-phase mixing reactors tail gas A3 out, reclaim wherein
F.
As preferred technical scheme: described gas, liquid, solid three-phase mixed decomposition and chemical reaction absorption plant are single
Level or plural serial stage device, or the integration apparatus assembled by multistage mixed decomposition reaction unit；The liquid of phosphate ore pulp: Gu than
At the scope of 1:1-5, preferably 1:2-3, temperature room temperature, fineness was 80-200 mesh；Decomposing ardealite gas enters three-phase mixing
The SO of reactor2Original concentration is unrestricted.
Technical scheme as further preferred: described gas, liquid, solid three-phase mixed decomposition and chemical reaction absorption plant
For plural serial stage device.
As preferred technical scheme: the excessive heat that the mixed decomposition described in step (3) and absorption chemical reaction produce
Remove through heat exchanger and reclaim.
As preferred technical scheme: in step (3), the calcium sulfite that mixed decomposition reaction produces, produce dress in reaction
Put middle addition air, be oxidized to calcium sulfate.
As preferred technical scheme: the mixed decomposition described in step (3) and absorption chemical reaction aoxidize the slip obtained
C, send Wet Phosphoric Acid Plant to produce and isolates phosphoric acid by wet process and ardealite.
Compared with prior art, it is an advantage of the current invention that: owing to Gypsum Fibrosum decomposition gas is directly used in Wet-process Phosphoric Acid Production, point
Vent one's spleen and be not reprocessed into sulphuric acid, eliminate the pilot process producing sulphuric acid, eliminate device and investment of production, the section producing sulphuric acid
Learning Appropriate application phosphorus ore and Gypsum Fibrosum decomposition gas soda acid chemistry potential energy, enormously simplify ardealite Sulphur ressource, to recycle production wet
The technological process of method phosphoric acid, reduces equipment and the device of all production sulphuric acid, and technique is simple, and production cost is low, has significantly
Technology and economic benefit.Simultaneously as three-phase hybrid reaction is for SO in decomposing ardealite gas2Concentration range no requirement (NR), relaxes
The operating condition of the gas processed of ardealite reduction decomposition.This method is also the SO of super low concentration2Recycling open one
New way, has reached the saving energy, has reduced production cost, improved production efficiency, reduced investment, increased and produce.
Accompanying drawing explanation
The schematic flow sheet of Fig. 1: the present invention
1, ball mill；2, phosphate ore pulp storage tank；3, phosphoric ore pulp pump；4, one-level three-phase mixing reactor；5, primary cycle pump；6、
Two grades of three-phase hybrid reaction absorbers；7, secondary cycle pump；8, three grades of three-phase mixing reactors；9, three grades of circulating pumps；10, phosphoric acid
Slip storage tank；11, phosphoric acid material pulp pump；12, heat-exchanger rig I；13, heat-exchanger rig II；14, heat-exchanger rig III；15, cyclone dust removal
Device；16-19 suspended preheater.
The inventive method is described further by detailed description of the invention below in conjunction with process chart and with specific embodiment.
Embodiment 1
Phosphorus ore 36219.6 kilograms and water being joined in grinding machine 1, make phosphate ore pulp B, its moisture is by mass percentage
70%, phosphate ore pulp B is placed in phosphate ore pulp storage tank 2 stand-by, the composition of described phosphorus ore is shown in Table 1-1:
Table 1-1: phosphorus ore composition table (mass percent)
| Composition | P2O5 | Fe2O3 | Al2O3 | CaO | MgO | CO2 | SO3 | F | A.I | H2O |
| Composition % | 30.87 | 2.23 | 0.84 | 42.46 | 0.38 | 0.72 | 0.15 | 2.2 | 19.66 | 1.35 |
From decomposing and calcining kiln out, after suspended preheater 16-19 heat exchange, gas temperature drops to decomposing ardealite gas S
320 DEG C, output decomposition gas 2530.52Kmol gas per hour, its composition is shown in Table 1-2.
Table 1-2, decomposition gas S form table
| Composition | CO2 | SO2 | N2 | O2 | H2O | Add up to |
| Volume % | 16.1 | 11.1 | 58.7 | 0.6 | 13.5 | 100 |
| Kmol | 497.41 | 280.89 | 1485.42 | 15.18 | 341.62 | 2530.52 |
This gas enters through temperature after heat exchanger apparatus I 12 cools and reaches 85 DEG C, and the heat changed is sent to heat energy and returned
Receive, then decomposition gas S enter the circular response slip sent into primary cycle pump 5 in one-level three-phase mixing reactor 4 carry out solid,
Liquid, gas three-phase mixed chemical react, the SO in decomposition gas S2CaSO is generated with calcium ion in liquid3And then under the effect of air
It is oxidized to CaSO4, the circulation slurry temperature of one-level three-phase mixing reactor 4 95 DEG C, its P2O5Concentration 38%, liquid-solid ratio is 3, with
Time in one-level three-phase mixing reactor 4, blast air 1230.30Kmol per hour；The least from one-level three-phase mixing reactor 4
Time discharge 175302.86 kilograms of phosphorus slip C1 and overflow to phosphoric acid material pulp storage tank 10, then send to wet method by phosphoric acid material pulp pump 11
After phosphoric acid plant is finely adjusted, slip sends to separation solid phase calcium sulfate, thus obtains finished product phosphoric acid 27952.48 kilograms, its P2O5
Concentration 38%.
The gas temperature 85 DEG C of tail gas A1 discharged from one-level three-phase hybrid reaction 4 device, gas composition is shown in Table 1-3:
Table 1-3, one-level three-phase mixing reactor are discharged gas tail gas A1 and are formed table
| Composition | CO2 | SO2 | N2 | O2 | H2O | F | Add up to |
| Volume % | 8.98 | 0.49 | 54.12 | 3.18 | 33.21 | 0.02 | 100 |
| Kmol | 407.71 | 22.47 | 2457.56 | 144.39 | 1508.12 | 0.84 | 4541.09 |
Two grades of three-phase mixing reactors 6, gas is entered from one-level three-phase mixing reactor gas 4541.09Kmol out
In SO2The circulation slip continuing to send into secondary cycle pump 7 reacts, and generates CaSO3, two grades of three-phase mixing reactor 6 temperature
Spending 95 DEG C, the heat that after reaction, slip is too much is removed with 13 heat-exchanger rigs II and reclaims heat, from two grades of three-phase mixing reactors 6
Phosphorus slip out 175647.63 kilograms overflows to first order three-phase mixing reactor 4, simultaneously 177647.48 kilograms of slips from
Three grades of three-phase mixing reactors 8 overflow to two grades of three-phase mixing reactors 6, from two grades of three-phase mixing reactors 6 tail gas out
A2 temperature 85 DEG C, gas composition is shown in Table 1-4.
Table 1-4, two grades of three-phase mixing reactors are got rid of gas tail gas A2 and are formed table
| Composition | CO2 | SO2 | N2 | O2 | H2O | F | Add up to |
| Volume % | 8.66 | 0.04 | 52.14 | 2.84 | 36.29 | 0.03 | 100 |
| Kmol | 408.01 | 1.8 | 2457.56 | 134.06 | 1710.35 | 1.26 | 4713.04 |
Three grades of three-phase mixing reactors 8 are entered from two grades of three-phase mixing reactors gas A2 4713.04Kmol out,
With the circulation slurry reaction sent into by three grades of circulating pumps 9, the SO in gas A22Generate CaSO3, heat too much in reaction slurry
Remove heat with 14 heat-exchanger rigs III and reclaim, the temperature of three grades of three-phase mixing reactors 8 95 DEG C, exclude slip
177647.48 kilograms overflow to two grades of three-phase mixing reactors 6, from phosphoric acid by wet process ardealite segregation apparatus dilture acid out
127348.74 kilograms join three grades of three-phase mixing reactors 8, and phosphate ore pulp addition is 51742 kilograms, from three grades of three-phase mixing
Reactor gas tail gas A3 temperature 85 DEG C out, gas composition is shown in Table 1-5；Send phosphoric acid by wet process exhaust system to process wherein to be fluorinated
Thing.
Table 1-5, go out the gas tail gas A3 composition table of the 3rd absorber
| Composition | CO2 | SO2 | N2 | O2 | H2O | F | Add up to |
| Volume % | 8.77 | 0.04 | 52.13 | 2.84 | 36.19 | 0.04 | 100 |
| Kmol | 413.34 | 1.80 | 2457.56 | 134.06 | 1706.27 | 1.68 | 4714.71 |
Embodiment 2
Phosphorus ore 21357.24 kilograms and water are joined in grinding machine 1, makes phosphate ore pulp, its moisture 70%, phosphate ore pulp is put
In phosphate ore pulp storage tank 2 stand-by, the composition of its phosphorus ore is shown in Table 2-1.
Table 2-1: phosphorus ore composition table (mass percent)
| Composition | P2O5 | Fe2O3 | Al2O3 | CaO | MgO | CO2 | SO3 | F | A.I | H2O |
| Composition % | 33.44 | 1.63 | 1.58 | 48.98 | 1.29 | 4.12 | 0.46 | 2.2 | 4.96 | 5.09 |
Decomposing ardealite calcining kiln decomposition gas S out, after suspended preheater 16-19 heat exchange, gas temperature drops to
330℃.Output 2106.7Kmol gas per hour, its composition is shown in Table 2-2.
Table 2-2, decomposition gas S form table
| Composition | CO2 | SO2 | N2 | O2 | H2O | Add up to |
| Volume % | 16 | 10 | 61.7 | 0.8 | 11.5 | 100 |
| Kmol | 337.07 | 210.67 | 1299.83 | 16.85 | 242.27 | 2106.7 |
After decomposition gas S is lowered the temperature by 12 heat-exchanger rigs I again, temperature reaches 86 DEG C, and reclaims its heat, and then decomposition gas S enters
It is anti-that the circular response slip that one-level three-phase mixing reactor 4 and primary cycle pump 5 are sent into carries out solid, liquid, gas three-phase mixed chemical
Should, the SO in decomposition gas S2CaSO is generated with calcium ion in liquid3And in three-phase mixing reactor 4, blast air simultaneously
1003.17Kmol, and then oxidation CaSO3Become CaSO4, the circulation slurry temperature of one-level three-phase mixing reactor 4 96 DEG C, its P2O5
Concentration is 40%, and liquid-solid ratio is 3；Phosphorus is overflowed to from one-level three-phase mixing reactor 4 83720.38 kilograms of phosphorus slip C1 out
Slip collecting tank, after sending Wet Phosphoric Acid Plant by adjusting, slip sends to separation solid phase calcium sulfate, thus obtains finished product phosphoric acid
16961.92 kilograms, its P2O5Concentration 40%.
From the temperature 86 DEG C of one-level three-phase mixing reactor tail gas A1 out, composition is shown in Table 2-3；
Table 2-3, one-level three-phase mixing reactor are discharged tail gas A1 and are formed table
| Composition | CO2 | SO2 | N2 | O2 | H2O | F | Add up to |
| Volume % | 8.53 | 0.53 | 52.78 | 3.35 | 34.80 | 0.02 | 100 |
| Kmol | 338.07 | 21.07 | 2092.33 | 132.72 | 1379.62 | 0.73 | 3964.54 |
Two grades of three-phase mixing reactors 6 are entered from one-level three-phase mixing reactor 4 expellant gas A13964.54Kmol,
SO in gas2The circulation slip continuing to send into secondary cycle pump 7 reacts, and generates CaSO3, two grades of three-phase hybrid reactions
Device 6 temperature 96 DEG C, the heat that after reaction, slip is too much is removed with 13 heat-exchanger rigs II and reclaims heat, anti-from two grades of three-phase mixing
Device 6 phosphorus slip out 105563.87 kilograms is answered to overflow to one-level three-phase mixing reactor 4, simultaneously 97487.01 kilograms of slips
Two grades of three-phase mixing reactors 6 are overflowed to, from two grades of three-phase mixing reactors 6 tail out from three grades of three-phase mixing reactors 8
Gas A2 temperature 86 DEG C, gas composition is shown in Table 2-4.
The tail gas A2 composition table that table 2-4, two grades of three-phase mixing reactors are discharged
| Composition | CO2 | SO2 | N2 | O2 | H2O | F | Add up to |
| Volume % | 8.42 | 0.05 | 51.98 | 3.06 | 36.46 | 0.03 | 100 |
| Kmol | 339.07 | 2.11 | 2092.33 | 123.24 | 1467.75 | 1.10 | 4025.6 |
Three grades of three-phase mixing reactors 8 are entered from two grades of three-phase mixing reactors gas A24025.6Kmol out, with
The circulation slurry reaction sent into by three grades of circulating pumps 9, the SO in gas A22Generate CaSO3, heat too much in reaction slurry is used
14 heat-exchanger rigs III are removed heat and reclaim, the temperature of three grades of three-phase mixing reactors 8 96 DEG C, exclude slip 97487.01 public
Jin overflows to two grades of three-phase mixing reactors 6；Add from phosphoric acid by wet process ardealite segregation apparatus dilture acid out 66438.15 kilograms
Entering to three grades of three-phase mixing reactors 8, phosphate ore pulp addition is 51742 kilograms, from three grades of three-phase mixing reactors tail out
Gas A3 temperature 85 DEG C, gas composition is shown in Table 1-5；Phosphoric acid by wet process exhaust system is sent to process wherein fluoride.
The tail gas A3 composition table that table 2-5, three grades of three-phase mixing reactors are discharged
| Composition | CO2 | SO2 | N2 | O2 | H2O | F | Add up to |
| Composition % | 8.51 | 0.01 | 52.51 | 3.07 | 35.87 | 0.04 | 100 |
| Kmol | 339.07 | 0.21 | 2092.33 | 122.29 | 1429.07 | 1.47 | 3984.77 |
Claims (10)
1. the method that a decomposing ardealite gas is directly used in Wet-process Phosphoric Acid Production, it is characterised in that comprise the following steps:
(1), phosphorus ore is prepared phosphate ore pulp B through wet grinding；
(2), Gypsum Fibrosum decomposition gas S, described Gypsum Fibrosum decomposition gas S are prepared, for by ardealite, or the natural gypsum, or steam power plant's desulfurization stone
Cream, or titanium dioxide waste acid by sulfuric acid process processes Gypsum Fibrosum, or other industry by-product gypsum carries out reduction decomposition and produces；
(3), the phosphate ore pulp B of decomposition gas S step (1) gained of step (2) gained is directly carried out gas, liquid, solid three-phase mixing
Decompose and absorb chemical reaction, obtaining the phosphoric acid material pulp C of tail gas A and sulfur acid calcium；
(4) ardealite of step (3) gained is carried out reduction decomposition again and produces decomposition gas S, for step (3).
The method that decomposing ardealite gas the most according to claim 1 is directly used in Wet-process Phosphoric Acid Production, it is characterised in that: step
Suddenly the liquid of (1) gained phosphate ore pulp B: Gu mass ratio is 1:(1-5)；The fineness of the particles of phosphate ore pulp B is 80-250 mesh.
The method that decomposing ardealite gas the most according to claim 2 is directly used in Wet-process Phosphoric Acid Production, it is characterised in that: step
Suddenly the liquid of (1) gained phosphate ore pulp B: Gu mass ratio is 1:(2.5-4).
The method that decomposing ardealite gas the most according to claim 1 is directly used in Wet-process Phosphoric Acid Production, it is characterised in that: institute
State SO in Gypsum Fibrosum decomposition gas S2Concentration expressed in percentage by volume is 0-14%.
The method that decomposing ardealite gas the most according to claim 4 is directly used in Wet-process Phosphoric Acid Production, it is characterised in that: institute
State SO in Gypsum Fibrosum decomposition gas S2Concentration expressed in percentage by volume is 5-11%.
The method that decomposing ardealite gas the most according to claim 1 is directly used in Wet-process Phosphoric Acid Production, it is characterised in that: institute
The gas, liquid, solid three-phase mixed decomposition stated and chemical reaction absorption plant are single-stage or plural serial stage device, or by multistage mixing
The integration apparatus that decomposition reaction apparatus assembles.
The method that decomposing ardealite gas the most according to claim 1 is directly used in Wet-process Phosphoric Acid Production, it is characterised in that: institute
The gas, liquid, solid three-phase mixed decomposition stated and chemical reaction absorption plant are plural serial stage device.
The method that decomposing ardealite gas the most according to claim 1 is directly used in Wet-process Phosphoric Acid Production, it is characterised in that: step
Suddenly the excessive heat that the mixed decomposition described in (3) and absorption chemical reaction produce is removed through heat exchanger and is reclaimed.
The method that decomposing ardealite gas the most according to claim 1 is directly used in Wet-process Phosphoric Acid Production, it is characterised in that: step
Suddenly in (3), the calcium sulfite that mixed decomposition reaction produces, in reaction process units, add air, be oxidized to calcium sulfate.
The method that decomposing ardealite gas the most according to claim 1 is directly used in Wet-process Phosphoric Acid Production, it is characterised in that:
Mixed decomposition described in step (3) and absorption chemical reaction aoxidize the slip C obtained, and send Wet Phosphoric Acid Plant to produce and isolate
Phosphoric acid by wet process and ardealite.
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| CN201610218410.2A CN105836722A (en) | 2016-04-08 | 2016-04-08 | A method of directly using phosphogypsum decomposition gas for wet method phosphoric acid production |
| PCT/CN2016/083255 WO2017173717A1 (en) | 2016-04-08 | 2016-05-25 | Method for directly using phosphogypsum decomposition gas in wet phosphoric acid production |
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Cited By (3)
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| CN106276831A (en) * | 2016-08-24 | 2017-01-04 | 湖北三宁化工股份有限公司 | One utilizes SO2gas and phosphate ore pulp reaction produce the method and device of phosphoric acid |
| CN112250051A (en) * | 2020-10-16 | 2021-01-22 | 昆明理工大学 | Method for absorbing phosphogypsum roasting smoke and co-producing phosphoric acid and cement clinker by phosphate rock slurry |
| CN112934906A (en) * | 2019-12-11 | 2021-06-11 | 西南科技大学 | Method for innocent treatment of phosphorus tailings and phosphogypsum by burning raw materials |
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| CN109912245B (en) * | 2019-04-26 | 2024-04-12 | 四川绵竹市盘龙矿物质有限责任公司 | Method and device for co-production of gypsum powder in sulfuric acid production |
| CN113860269B (en) * | 2021-10-25 | 2023-06-16 | 云南云天化环保科技有限公司 | Method and device for preparing sulfuric acid and mineral cotton fibers by phosphogypsum in segments |
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| CN112250051B (en) * | 2020-10-16 | 2023-08-22 | 昆明理工大学 | Method for co-producing phosphoric acid and cement clinker by absorbing phosphogypsum roasting smoke by phosphorite slurry |
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| WO2017173717A1 (en) | 2017-10-12 |
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