CN101186281B - Method for reducing phosphogypsum decomposition temperature in process of preparing sulfuric acid from phosphogypsum - Google Patents
Method for reducing phosphogypsum decomposition temperature in process of preparing sulfuric acid from phosphogypsum Download PDFInfo
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- CN101186281B CN101186281B CN200710066431A CN200710066431A CN101186281B CN 101186281 B CN101186281 B CN 101186281B CN 200710066431 A CN200710066431 A CN 200710066431A CN 200710066431 A CN200710066431 A CN 200710066431A CN 101186281 B CN101186281 B CN 101186281B
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- phosphogypsum
- coal
- sulfuric acid
- decomposition temperature
- composite catalyst
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Abstract
The invention relates to a method for reducing the decomposition temperature of phosphogypsum in the process of using the phosphogypsum to prepare sulfuric acid, which belongs to the technical field of phosphorus chemical preparation. In the process of using the phosphogypsum to prepare the sulfuric acid and cement clinker and under the premise of using coal as reducer and by adding compound catalyst, the decomposition temperature of the phosphogypsum can be reduced to be 700-750 DEG C, which is 250-300 DEG C lower. The method reduces the energy consumption and cost for treating solid waste, meanwhile, the calcium compounds and sulfur dioxide are mainly produced. The sulfur dioxide can be directly used for preparing acid raw gas and the compounds can be directly used as excellent cement clinker.
Description
One, technical field: the present invention relates to a kind of method that in phosphogypsum system producing sulfuric acid and jointly cement clinker process, reduces ardealite decomposition temperature, belong to the phosphorous chemical industry preparing technical field.
Two, background technology: the multiple fertilizer of phosphorus is the important foundation that ensures national food safety, phosphogypsum then is the multiple fertile inevitable outcome of producing of phosphorus, the quantity discharged of whole world phosphogypsum surpasses 2.8 hundred million t, the quantity discharged of the annual phosphogypsum of China surpasses 2,200 ten thousand t, but the utilization ratio of phosphogypsum does not surpass 10%, and the treatment and disposal of phosphogypsum and comprehensive utilization have become a global difficult problem.The stacking of phosphogypsum not only takies a large amount of soils, contaminate environment, but also bring very big economical load to manufacturing enterprise, comprehensive utilization of phosphogypsum has become the multiple fertile industry of restriction phosphorus and has realized one of key factor of Sustainable development, also is the important factor that guarantees China's grain security.
Wherein topmost direction of utilizing of phosphogypsum is a phosphogypsum system producing sulfuric acid and jointly grog, though known technology comparative maturity with coke reduction phosphogypsum system producing sulfuric acid and jointly cement clinker, but exist energy consumption too high, cause the cost height, infeasible economically, and the reactor content is perishable, caking, and reaction such as is not easy to carry out continuously at shortcoming.China utilizes phosphogypsum to produce the vitriolic ratio to be less than 2% of gas washing in SA production total amount.
The starting temperature of main component calcium sulfate generation decomposition reaction is 1650 ℃～1700 ℃ in the phosphogypsum, if use the coke reducing and decomposing phosphogypsum separately, the starting temperature that reacts is 850 ℃～900 ℃, if use reducing and decomposing phosphogypsum by carbon monoxide separately, the starting temperature that reacts is 950 ℃～1000 ℃, in the actual production rate of decomposition of phosphogypsum and desulfurization degree reach industrial reaction required require the time (the phosphogypsum rate of decomposition is 97%～99%, the phosphogypsum desulfurization degree is 96%～98%), the required optimum temps that reacts is 1000 ℃～1200 ℃, so the energy consumption that needs is higher.
Disclosing a kind of in publication number is the Chinese patent application of CN1724338A is the production method of the industrial sulphuric acid of raw material with phosphoric acid by wet process solid residue-phosphogypsum, and it comprises following processing step: the A. Boiling Combustion; B. dedusting cooling; C. the washing of furnace gas; D. dry furnace gas; E. transform for the first time; F. absorb for the first time; G. transform for the second time; H. absorb for the second time.Finish calcining but in the Boiling Combustion of the first step technology, phosphogypsum and the burning reduction carbon that accounts for phosphogypsum weight 20% added in the lump in 1000～1100 ℃ the fluidizing furnace, just can obtain sulfurous gas and carbonic acid gas furnace gas and calcium oxide solid dust.
In publication number is the Chinese patent application of CN1212241A, also disclose a kind of with the phosphogypsum calcining with prepare the method for hard low alkalinity cement.Replace the plaster of paris and Wingdale, alumina to prepare burden with residue phosphogypsum in the invention, in rotary kiln, fire fast hard low alkalinity cement grog.During preparation cement, add a considerable amount of ardealite instead plasters of paris again, one day ultimate compression strength of the rapid hardening cement that makes surpasses 40MPa, and three days above 50MPa.
Utilizing in the method for these phosphogypsums, nearly all there is the energy consumption height, the cost of handling the solid waste phosphogypsum increases, and product cost also increases thereupon.Seek a kind of method that can reduce ardealite decomposition temperature, just become phosphogypsum to utilize in the process and cut down the consumption of energy, increase a critical aspects of benefit.If the decomposition temperature of phosphogypsum can reduce, then product cost also significantly reduces thereupon.If find after deliberation to make reductive agent with coal, cooperate composite catalyst can reduce the decomposition temperature of phosphogypsum greatly, energy efficient is better disposed and large-scale utilization phosphogypsum.
Three, summary of the invention
The present invention is in the process of phosphogypsum system producing sulfuric acid and jointly cement clinker, provide under a kind of prerequisite of making reductive agent of coal, add composite catalyst and can reduce the decomposition temperature to 700 ℃ of phosphogypsum～750 ℃, reach and cut down the consumption of energy, reduce the purpose of the cost of handling solid waste, main simultaneously compound and the sulfurous gas that generates calcium.Sulfurous gas can directly be used as the relieving haperacidity unstripped gas, and the compound of calcium can directly be used as high quality cement clinker.
The principal reaction that takes place in the entire reaction course is as follows:
2CaSO
4+C＝2CaO+2SO
2+CO
2 ①
CaSO
4+Si+0.5O
2＝CaSiO
3+SO
2 ②
CaSO
4+SiO
2＝CaSiO
3+SO
2+0.5O
2 ③
CaSO
4+Al
2O
3＝Ca(AlO
2)
2+SO
2+0.5O
2 ④
CaSO
4+Fe
2O
3＝Ca(FeO
2)
2+S?O
2+0.5O
2 ⑤
6CaSO
4+4AlPO
4＝2Ca(PO
4)
2+2Al
2O
3+6SO
2+3O
2 ⑥
The present invention finishes according to the following steps:
1, the main chemical compositions mass percent of raw material phosphogypsum is a calcium oxide 27～37%, sulfurous gas 41～51%, ferric oxide 0.08～3.31%, aluminium sesquioxide 0.08～2.65%, Vanadium Pentoxide in FLAKES 0.47～1.28%, fluorine 0.05～0.26%, silicon-dioxide 8.20～15.38%, total amount 100%; Reductive agent coal main chemical compositions mass percent is a moisture 1～2%, ash content 13～21%, and volatile matter 5～13%, fixed carbon 65～80%, total amount is 100%, raw material phosphogypsum and coal are crushed to granularity less than 0.074mm;
2, according to chemical composition mass percent is a magnesium oxide 9.4～29.7%, sodium-chlor 6.7～21.2%, silicon-dioxide 3.5～11.1%, aluminium sesquioxide 1.6～50.8%, ferric oxide 2.8～45.5%, total amount is 100% preparation composite catalyst, and it is crushed to granularity less than 0.074mm;
3, raw material phosphogypsum and coal and the composite catalyst that makes are dried under 95 ℃～100 ℃ respectively to moisture quality percentage composition less than 8%, the time is 1.5～2 hours;
4, heating reduction decomposition stove to 700 ℃～750 ℃, granularity, moisture are met the requirements of phosphogypsum, coal and composite catalyst with 20: (1～2): the mass ratio of (0.5～1) batching and mix after put into reactor, carry out the reaction of phosphogypsum system vitriolic and reacted in 40-60 minute and finish.After apparatus cools, take out residue and analyze, and calculate the rate of decomposition and the desulfurization degree of phosphogypsum, under the prerequisite that reaches identical rate of decomposition and desulfurization degree, relatively react required temperature.
Compare advantage and positively effect that the present invention has with known technology:
(1) composite catalyst composition cheapness cheap and easy to get;
(2) adding of coal and the catalyzer effect having played reduction, catalysis simultaneously and fluxed reduces the decomposition temperature of phosphogypsum effectively;
(3) compare with known technology, phosphogypsum is under the prerequisite that reaches identical rate of decomposition and desulfurization degree, and the decomposition temperature of phosphogypsum has reduced by 250 ℃～320 ℃, has reduced energy consumption;
(4) some elements in coal and the composite catalyst can be directly fixed in the solid product, have diluted the detrimental impurity in the phosphogypsum, can make the solid product of generation directly as the high grade cement raw material simultaneously;
Four, embodiment
Embodiment 1: phosphogypsum main chemical compositions mass percent is: calcium oxide 35.36%, sulfurous gas 47.12%, ferric oxide 3.01%, aluminium sesquioxide 2.05%, Vanadium Pentoxide in FLAKES 1.20%, fluorine 0.06%, silica 1 1.20%; The main chemical compositions mass percent is a moisture 1.71% in the coal, ash content 15.03%, volatile matter 9.02%, fixed carbon 74.24%.And the chemical ingredients mass percent of composite catalyst is a magnesium oxide 20.2%, sodium-chlor 10.9%, silica 1 1.1%, aluminium sesquioxide 27.6%, ferric oxide 30.2%.Join in the tubular reactor that is heated to 700 ℃ after granularity, the satisfactory phosphogypsum of moisture, coal, composite catalyst mixed by mass ratio at 20: 1: 0.5, behind the question response 50min, stop reactor heating, close gas, after treating apparatus cools, take out residue and analyze, with measuring SO in the cement
3Method measure SO in polity's product
3Amount is surveyed S in the solid product with iodimetry,iodometry
2-Content, can calculate CaSO in the solid product according to stoichiometric relation
4, the amount of CaS, according to formula (1) and (2):
Through measuring, analyze, calculate the phosphogypsum rate of decomposition is 98%, and desulfurization degree is 97%.Compare for 1000 ℃ with minimum response temperature in the known technology, temperature of reaction has reduced by 300 ℃, and only this item energy consumption has reduced by 25%, receives the unimaginable technique effect of knowing clearly.
Embodiment 2: phosphogypsum main chemical compositions mass percent is: calcium oxide 36.5%, sulfurous gas 47.9%, ferric oxide 2.24%, aluminium sesquioxide 2.36%, Vanadium Pentoxide in FLAKES 0.85%, fluorine 0.03%, silica 1 0.12%; Main component in the coal: moisture 1.71%, ash content 16.03%, volatile matter 9.02%, fixed carbon 73.24%.And the chemical composition mass percent of composite catalyst is: magnesium oxide 19.6%, sodium-chlor 14.1% silica 1 0.3%, aluminium sesquioxide 23.7%, ferric oxide 32.3%.Join in the tubular reactor that is heated to 720 ℃ after granularity, the satisfactory phosphogypsum of moisture, coal, composite catalyst mixed by mass ratio at 20: 1.5: 0.5.Behind the question response 45min, stop reactor heating, close gas, treat apparatus cools after, take out residue and analyze, use with example 1 in same measurement and method of calculation can to calculate the phosphogypsum rate of decomposition be 99%, desulfurization degree is 97.5%.Compare for 1000 ℃ with minimum response temperature in the known technology, temperature of reaction has reduced by 280 ℃, and only this item energy consumption has reduced by 20%, receives the unimaginable technique effect of knowing clearly.
Claims (2)
1. reduce the method for ardealite decomposition temperature in the phosphogypsum process of preparing sulfuric acid, it is characterized in that: it is finished according to the following steps:
1), raw material phosphogypsum, the fragmentation of reductive agent coal;
2), according to chemical composition mass percent is a magnesium oxide 9.4～29.7%, sodium-chlor 6.7～21.2%, silicon-dioxide 3.5～11.1%, aluminium sesquioxide 1.6～50.8%, ferric oxide 2.8～45.5%, total amount are 100% preparation composite catalyst, and with its fragmentation;
3), raw material phosphogypsum, coal and the composite catalyst that makes are dried under 95 ℃～100 ℃ respectively to moisture quality percentage composition less than 8%;
4), heating reduction decomposition stove to 700 ℃～750 ℃, granularity, moisture are met the requirements of phosphogypsum, coal and composite catalyst with 20: (1～2): the mass ratio of (0.5～1) batching and mix after put into reactor, carry out the reaction of phosphogypsum system vitriolic and reacted in 40-60 minute and finish.
2. reduce the method for ardealite decomposition temperature in the phosphogypsum process of preparing sulfuric acid according to claim 1, it is characterized in that: described raw material phosphogypsum and reductive agent coal and composite catalyst are through being crushed to granularity less than 0.074mm.
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|---|---|---|---|
| CN200710066431A CN101186281B (en) | 2007-12-10 | 2007-12-10 | Method for reducing phosphogypsum decomposition temperature in process of preparing sulfuric acid from phosphogypsum |
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| CN200710066431A CN101186281B (en) | 2007-12-10 | 2007-12-10 | Method for reducing phosphogypsum decomposition temperature in process of preparing sulfuric acid from phosphogypsum |
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| CN101186281B true CN101186281B (en) | 2010-05-26 |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020250A (en) * | 2009-09-18 | 2011-04-20 | 昆明理工大学 | New method for producing sulphuric acid and generation joint product cement by decomposing phosphogypsum through microwave reduction |
| US8623319B2 (en) * | 2010-07-05 | 2014-01-07 | Xiaolin Yin | Process for directly producing sulfur trioxide and sulfuric acid using gypsum as raw material |
| CN102583260A (en) * | 2012-02-13 | 2012-07-18 | 刘立文 | Method for decomposing anhydrite |
| CN103100383B (en) * | 2013-01-30 | 2015-10-21 | 刘立文 | A kind of calcium sulfate decomposes the Catalysts and its preparation method producing sulfuric acid |
| CN103071517B (en) * | 2013-01-30 | 2015-04-15 | 刘立文 | Catalyst for producing calcium oxide by decomposing calcium sulfate and preparation method of catalyst |
| CN103130259A (en) * | 2013-03-18 | 2013-06-05 | 昆明理工大学 | Low-temperature phosphogypsum decomposition method |
| CN104445113A (en) * | 2014-12-08 | 2015-03-25 | 四川有峰环保科技有限公司 | Method and raw material for producing yellow phosphorus or phosphoric acid based on electric furnace |
| CN105129744B (en) * | 2015-07-21 | 2017-10-20 | 湖北湖大天沭新能源材料工业研究设计院有限公司 | A kind of method that ardealite Sulphuric acid co-producing cement is thermally decomposed in advance |
| CN108787993B (en) * | 2018-07-03 | 2023-05-02 | 贵州大学 | Process for preparing acid and co-producing thermosetting casting binder |
| CN108795323B (en) * | 2018-07-03 | 2020-08-25 | 贵州大学 | Method for producing acid by using phosphogypsum and high-sulfur bauxite to produce flame-retardant starch adhesive |
| CN112191240B (en) * | 2020-09-16 | 2023-02-10 | 福泉环保城发展有限公司 | Industrial phosphogypsum waste treatment method |
| CN112960652B (en) * | 2021-05-06 | 2022-01-28 | 西南科技大学 | Method for preparing high-concentration sulfur dioxide gas from industrial byproduct gypsum slag |
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