CN104446070A - Comprehensive utilization method of phosphorus gypsum - Google Patents
Comprehensive utilization method of phosphorus gypsum Download PDFInfo
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- CN104446070A CN104446070A CN201410720081.2A CN201410720081A CN104446070A CN 104446070 A CN104446070 A CN 104446070A CN 201410720081 A CN201410720081 A CN 201410720081A CN 104446070 A CN104446070 A CN 104446070A
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- phosphogypsum
- ash
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Abstract
The invention discloses a comprehensive utilization method of phosphorus gypsum. According to the comprehensive utilization method, by using the characteristic of high carbon content in ash from a coal-fired boiler, the ash is utilized as a reducing agent to reduce and decompose the phosphorus gypsum, so that high-concentration SO2 can be produced; meanwhile, the quality of calcium oxide is improved; no waste is generated in the process; coal resources are fully saved; meanwhile, high-quality raw material can be provided for cement; and the environment problem caused by stacking of waste residues such as phosphorus gypsum is solved. According to the method disclosed by the invention, by using the characteristic of high carbon content in ash from the coal-fired boiler, the ash is utilized as the reducing agent to reduce and decompose phosphorus gypsum; the volume percentage of the produced SO2 is 5%-15% and produced SO2 can be used as a qualified raw material gas for preparing sulfuric acid; the mass percentage of the produced CaO can be up to over 70%; the CaO can be used as a cement material; a new way is provided for reasonable utilization of phosphorus gypsum and the ash from the coal-fired boiler by the overall process; the problem of stacking of a lot of phosphorus gypsum is solved; the environment is protected; and waste is changed into treasures.
Description
Technical field
The invention belongs to environment protection and technical field of phosphorous chemical industry, relate to a kind of phosphogypsum method of comprehensive utilization utilizing coal firing boiler lime-ash to be aided with scum powder reducing and decomposing phosphogypsum Sulphuric acid jointly producing cement raw material and raw gas of sulfuric acid.
Background technology
Now, coal remains energy resource supply product main in China's daily life, and coal firing boiler is as daily heating only use, and use range is more extensive.Coal firing boiler lime-ash take coal as the block waste residue produced in the boiler combustion process of fuel, and the generation of coal firing boiler lime-ash is only less than mine tailing and coal gangue and occupies the 3rd.The chemical composition of coal firing boiler lime-ash is similar to flyash, but carbon content is usually high than flyash, and generally about 15%, calorific value is generally 3500 ~ 6000kJ/kg, have up to more than 8000kJ/kg.Coal firing boiler lime-ash makes steam cured products aggregate can improve product strength, reduces product unit weight, because its unit weight is comparatively light, also can make roofing heat insulating material and brickmaking fuel etc.
The scum that scum powder produces when being blast furnace ironmaking, through a kind of material that magnetic separation machining obtains.Iron level residual in scum powder is higher, generally can be used to the iron extracted wherein, also can be used as the generation that catalyzer promotes reaction.
Phosphogypsum is the industrial residue produced in Wet-process Phosphoric Acid Production process, and its main component is CaSO
42H
2o, often produces 1t (P usually
2o
5meter) phosphoric acid will produce the phosphogypsum of about 5t.At present along with the domestic continuous growth needed ammonium phosphate and high concentration phosphorus composite fertilizer, facilitate phosphoric acid by wet process industrial expansion, also create a large amount of phosphogypsum thus, annual newly-increased phosphogypsum is at 1,000 ten thousand more than t.
The applied research of China's phosphogypsum is started late, and is mainly used in the industries such as building materials, chemical industry, chemical fertilizer, agricultural at present.But owing to utilizing level comparatively underground, larger environmental pollution still taked by a considerable amount of phosphogypsum.Therefore, the utilization of resources of phosphogypsum has become the key that phosphate fertilizer industry realizes Sustainable development.Phosphogypsum can be consumed on a large scale, mainly by the CaSO in phosphogypsum with phosphogypsum phosphoric acid jointly producing cement
42H
2o reduction decomposition becomes calcium oxide as the raw material of manufacture of cement processed, the SO simultaneously removed
2for extracting sulfuric acid.
Be in CN1948131, disclose a kind of phosphogypsum and the processing method of sulphur in conjunction with Sulphuric acid jointly producing cement at publication number, specifically refer to the low concentration SO utilizing phosphogypsum acid making system to go out rotary kiln
2gas, this kiln gas through washing, purification, after drying, with the high density SO of sulphur-burning sulphuric acid system
2gas and vapor permeation, is made into the SO of 8 ~ 9%
2gas concentration, adopt advanced double conversion and double absorption relieving haperacidity flow process to make sulfuric acid, phosphogypsum burns till as cement clinker in rotary kiln simultaneously, makes cement through grinding batching.
Publication number be disclose in CN1724338 a kind of with the method for phosphoric acid cream for raw material production industrial sulphuric acid.It comprises following processing step: A. Boiling Combustion; C. the washing of furnace gas; D. dry furnace gas; E. first time transforms; G second time transforms; H. second time absorbs; I. vent gas treatment.Not only produce for industrial sulphuric acid and provide the raw material that need not spend, but also solve the difficult problem that the solid residue gypsum that produces in Wet-process Phosphoric Acid Production cannot process.
Be in CN775660, disclose a kind of production method utilizing phosphogypsum slag extracting sulfuric acid at publication number.Undertaken by the step of batching, reducing roasting, replacement(metathesis)reaction, absorption reaction, filter pressing cake and roasting sulphur successively by phosphogypsum slag, reclaim from phosphogypsum slag and extract sulphur ore resources, replacement sulfur iron ore is as the raw material producing sulfuric acid product.
There is shortcoming in above-mentioned method: (1) complex process, operation steps is many, long reaction time, substantially increases production cost.(2) SO in kiln gas
2concentration is too low, unfavorable to follow-up acid-making process, causes production cost too high.
Summary of the invention
The object of this invention is to provide a kind of phosphogypsum method of comprehensive utilization, the method utilizes the feature that in coal firing boiler lime-ash, carbon content is high, as reductive agent reduction decomposition phosphoric acid gypsum, and both can production high density SO
2, simultaneous oxidation calcium quality is improved.Process no waste produces, and fully saves coal resource, can provide high quality raw material for cement simultaneously, and the environmental problem that the stacking solving the waste residues such as phosphogypsum brings.
A kind of phosphogypsum method of comprehensive utilization of the present invention feature is: by thin for the scum grinding after coal firing boiler lime-ash, the ageing of phosphogypsum nature, coal firing boiler lime-ash, phosphogypsum are prepared burden in proportion, and add after appropriate scum powder is mixed as catalyzer, send into reduction decomposition stove, controlling furnace temperature is 650 DEG C ~ 1200 DEG C, carry out reduction decomposition, the main component CaSO in phosphogypsum
4react with the C in coal firing boiler lime-ash, reaction starts the SO in the flue gas of rear flue gas analyzing apparatus on-line continuous detection generation
2volume content, simultaneously with the generation of side reaction.Reaction times is 0.5 ~ 1 hour, treats not produce SO
2flue gas after, stop heating, the solid product after naturally cooling can making cement raw material.
Described carefully should to 60 order ~ 140 orders by the scum grinding after coal firing boiler lime-ash, the ageing of phosphogypsum nature.
Described coal firing boiler lime-ash, phosphogypsum being prepared burden in proportion refers to that in coal firing boiler lime-ash, the mole number of C is 0.5 ~ 1.5C/S with the ratio of the mole number of the S in phosphogypsum.
The described reduction decomposition time of carrying out is 0.5 hour.
Major advantage of the present invention has:
(1) take full advantage of the carbon reducing and decomposing phosphogypsum in coal firing boiler lime-ash, can stable high density SO be produced
2, for acid-making process provides qualified unstripped gas.
(2) utilize iron in scum powder as catalyzer, accelerate speed of reaction, reduce temperature of reaction, reduce energy consumption, reduce production cost.
(3) step is simple, easy and simple to handle, reduces production cost further.
(4) each component to greatest extent in digestibility and utilization coal firing boiler lime-ash, scum powder, phosphogypsum, and do not produce secondary pollution, for waste residue and phosphogypsum comprehensive utilization have found a new way, achieve energy-saving and emission-reduction.
Accompanying drawing explanation
Fig. 1 is the production technological process for the embodiment of the present invention of the present invention.
Embodiment
Illustrate content of the present invention further below in conjunction with embodiment, but protection scope of the present invention is not limited in these examples.
The present invention completes according to the following steps:
1, this raw material
Raw material in the present invention is coal firing boiler lime-ash, scum powder and phosphogypsum.The main chemical compositions of each raw material is in table 1.
The main chemical compositions of each raw material of table 1
2, after coal firing boiler lime-ash, the ageing of phosphogypsum nature and scum powder grinding carefully to 60 order ~ 100 order mix by a certain percentage and form.
3, coal firing boiler lime-ash, phosphogypsum are pressed 0.5 ~ 1.5C/S than the ratio of the mole number of C in raw material with the mole number of S) prepare burden, and add after appropriate scum powder is mixed as catalyzer, send into reduction decomposition stove, controlling furnace temperature is 650 DEG C ~ 1200 DEG C, carry out reduction decomposition 0.5 hour, the important component CaSO in phosphogypsum
2react (1) with the C in coal firing boiler lime-ash, reaction starts rear flue gas analyzing apparatus on-line continuous and detects SO in the flue gas generated
2volume content, simultaneously with the generation of side reaction (2) (3), the reaction times is 0.5 ~ 1 hour, treats not produce containing SO
2flue gas after, stop heating, the solid product after naturally cooling can making cement raw material.
In reduction decomposition process, the main reactional equation occurred is:
2CaSO
4+C→2CaO+2SO
2↑+CO
2(1)
CaSO
4+4c→CaS+4CO↑ (2)
3CaSO
4+CaS→4CaO+4S0
2↑ (3)
Method of the present invention utilizes the feature that coal firing boiler ash content carbon is high, as the SO of reductive agent reducing and decomposing phosphogypsum output
2volumn concentration is 5% ~ 15%, can be used as qualified Sulphuric acid unstripped gas, and the CaO mass percentage of output is more than 70% to the maximum, can be used as cement raw material.Meanwhile, reduce the decomposition reaction temperature of phosphogypsum, shorten calcination time, reduce energy consumption, reduce production cost.Said process no waste produces, and phosphogypsum rate of decomposition 650 DEG C ~ 1200 DEG C time reaches 80% ~ 95%, desulfurization degree 80% ~ 90%.Method of the present invention makes full use of a large amount of phosphogypsum of China and slag the like waste, improve and stable product in sulfur dioxide concentration, for follow-up relieving haperacidity provides qualified unstripped gas; Simultaneous oxidation calcium quality is higher, for providing favourable condition as cement raw material.Whole technique is that the Appropriate application of phosphogypsum and coal firing boiler lime-ash provides new approach, solves the problem that phosphogypsum is stored up in a large number, protection of the environment, turns waste into wealth.
Embodiment 1, heat reduction decomposing furnace, control temperature is at 650 DEG C, and after getting dry and that grind 60 order phosphogypsum 1000g, 60 object coal firing boiler lime-ash 50g, 60 object scum powder 5g Homogeneous phase mixing, send in decomposing furnace, reaction starts SO in rear detection flue gas
2concentration stops heating after producing without gas, after naturally cooling, takes out fixing product and carries out analytical calculation.Acquired results is: SO
2volumn concentration mean value is 6.12%, and the rate of decomposition of phosphogypsum is 82.21%, and desulfurization degree is 80.47%, and calcium oxide content is 46.78%.
Embodiment 2, heat reduction decomposing furnace, control temperature is at 800 DEG C, and after getting dry and that grind 100 order phosphogypsum 1000g, 100 object coal firing boiler lime-ash 80g, 100 object scum powder 6g Homogeneous phase mixing, send in decomposing furnace, reaction starts SO in rear detection flue gas
2concentration stops heating after producing without gas, after naturally cooling, takes out fixing product and carries out analytical calculation.Acquired results is: SO
2volumn concentration mean value is 8.39%, and the rate of decomposition of phosphogypsum is 85.24%, and desulfurization degree is 83.61%, and calcium oxide content is 51.45%.
Embodiment 3, heat reduction decomposing furnace, control temperature is at 1000 DEG C, and after getting dry and that grind 120 order phosphogypsum 1000g, 140 object coal firing boiler lime-ash 55g, 100 object scum powder 8g Homogeneous phase mixing, send in decomposing furnace, reaction starts SO in rear detection flue gas
2concentration stops heating after producing without gas, after naturally cooling, takes out fixing product and carries out analytical calculation.Acquired results is: SO
2volumn concentration mean value is 9.04%, and the rate of decomposition of phosphogypsum is 87.84%, and desulfurization degree is 85.90%, and calcium oxide content is 56.62%.
Embodiment 4, heat reduction decomposing furnace, control temperature is at 1100 DEG C, and after getting dry and that grind 140 order phosphogypsum 1000g, 150 object coal firing boiler lime-ash 60g, 120 object scum powder 8g Homogeneous phase mixing, send in decomposing furnace, reaction starts SO in rear detection flue gas
2concentration stops heating after producing without gas, after naturally cooling, takes out fixing product and carries out analytical calculation.Acquired results is: SO
2volumn concentration mean value is 10.65%, and the rate of decomposition of phosphogypsum is 91.57%, and desulfurization degree is 83.38%, and calcium oxide content is 70.83%.
Claims (3)
1. a phosphogypsum method of comprehensive utilization, it is characterized in that coal firing boiler lime-ash, thin with scum grinding after the ageing of phosphogypsum nature, by coal firing boiler lime-ash, phosphogypsum is prepared burden in proportion, and add appropriate scum powder as after catalyzer mixing, send into reduction decomposition stove, controlling furnace temperature is 650 DEG C ~ 1200 DEG C, carry out reduction decomposition, C in main component CaSO4 in phosphogypsum and coal firing boiler lime-ash reacts, reaction starts the SO2 volume content in the flue gas of rear flue gas analyzing apparatus on-line continuous detection generation, simultaneously with the generation of side reaction, reaction times is 0.5 ~ 1 hour, treat not produce containing SO
2flue gas after, stop heating, the solid product after naturally cooling can making cement raw material,
Described carefully should to 60 order ~ 140 orders by the scum grinding after coal firing boiler lime-ash, the ageing of phosphogypsum nature.
2. phosphogypsum method of comprehensive utilization according to claim 1, is characterized in that the described mole number of the C referred in coal firing boiler lime-ash of coal furnace lime-ash, phosphogypsum being prepared burden in proportion is 0.5 ~ 1.5C/S with the ratio of the mole number of the S in phosphogypsum.
3. phosphogypsum method of comprehensive utilization according to claim 1, is characterized in that the described reduction decomposition time of carrying out is 0.5 hour.
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| CN201410720081.2A CN104446070A (en) | 2014-12-02 | 2014-12-02 | Comprehensive utilization method of phosphorus gypsum |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106044772A (en) * | 2016-05-25 | 2016-10-26 | 刘松 | Comprehensive utilization method for waste gypsum and high-sulfur coal |
| CN106753565A (en) * | 2017-01-09 | 2017-05-31 | 昆明理工大学 | A kind of method that utilization ardealite prepares synthesis gas |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101549859A (en) * | 2009-05-21 | 2009-10-07 | 昆明理工大学 | Comprehensive utilization method of phosphogypsum and fag-end |
-
2014
- 2014-12-02 CN CN201410720081.2A patent/CN104446070A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101549859A (en) * | 2009-05-21 | 2009-10-07 | 昆明理工大学 | Comprehensive utilization method of phosphogypsum and fag-end |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106044772A (en) * | 2016-05-25 | 2016-10-26 | 刘松 | Comprehensive utilization method for waste gypsum and high-sulfur coal |
| CN106753565A (en) * | 2017-01-09 | 2017-05-31 | 昆明理工大学 | A kind of method that utilization ardealite prepares synthesis gas |
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Application publication date: 20150325 |