CN101717107B - Method for producing precipitated barium sulfate by using gypsum as raw material - Google Patents
Method for producing precipitated barium sulfate by using gypsum as raw material Download PDFInfo
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- CN101717107B CN101717107B CN2009101029631A CN200910102963A CN101717107B CN 101717107 B CN101717107 B CN 101717107B CN 2009101029631 A CN2009101029631 A CN 2009101029631A CN 200910102963 A CN200910102963 A CN 200910102963A CN 101717107 B CN101717107 B CN 101717107B
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Abstract
The invention relates to a method for producing precipitated barium sulfate by using gypsum as a raw material, which comprises the following steps of: firstly adding water into the gypsum, pulping and then introducing ammonia and carbon dioxide (or directly adding ammonium bicarbonate) to produce ammonium sulfate and calcium carbonate as a byproduct through chemical reaction; and then carrying out the chemical reaction on the ammonium sulfate and barium sulfide to produce the precipitated barium sulfate and ammonium sulfide. The invention develops and utilizes a great deal of phosphogypsum as harmful waste residues and gypsum as other industry byproducts and a great deal of carbon dioxide as waste gas, which are discharged in industry, to produce chemical industry products, i.e. the precipitated barium sulfate and the barium sulfide with high added value and wide purposes; and the method is an important breakthrough of environmental improvement and environmental protection industry and can bring great social benefit and economic benefit.
Description
Technical field: the present invention is a kind of to be the method for raw material production process white with the gypsum, belonging to chemical industry, environmental technology field, specifically, is a kind of gypsum of using, comprise phosphogypsum, other industry by-product gypsum and the plaster of paris are the method for raw material production process white.
Background technology: phosphate fertilizer and phosphorous chemical industry industrial production will be discharged a large amount of acid waste residues---phosphogypsum, and one ton of phosphate fertilizer of every production will discharge 4～5 tons of phosphogypsum slags, and China's annual discharging phosphogypsum slag reaches more than ten million ton.The discharging of a large amount of phosphogypsum slags has not only taken a large amount of soils, goes back serious environment pollution.Processing and development and use for phosphogypsum are world-class key subjects and a difficult problem.Each country has all dropped into great amount of manpower and material resources are tackled key problems to this problem in the world, up to the present, only obtaining some achievements on a small scale and on the little purposes, and economic benefit is bad, is difficult to apply.The large-scale development and use of phosphogypsum are not obtained so far as yet the progress of true spirit.
Ammonia synthesizing industry and some other industry are annual to a large amount of greenhouse gases CO of airborne release
2, to CO
2How gas reduces discharging and be used also is a world-famous puzzle.
Emphasis of the present invention is the CO with phosphogypsum and industrial discharge
2Be the raw material production process white, also produce ammonium sulfide and by-product lime carbonate simultaneously, by-product lime carbonate has found the big purposes of phosphogypsum as cement producting material, has fundamentally solved the CO of phosphogypsum and industrial discharge
2The world-famous puzzle how to develop.
The prior art of producing process white is the documents " production method of the process white of chemical technique handbook (Shanghai science tech publishing house, Jiang Tiqian edits, p.90～94) report.Mainly contain:
1, grey black-sulfuric acid process: natural barite is reduced to the barium sulphide (being grey black) of solubility, barium sulphide BaS and sulfuric acid H
2SO
4Reaction can get process white BaSO
4Reaction formula is:
BaS+H
2SO
4＝＝BaSO
4+H
2S
2, grey black-mirabilite method: barium sulphide BaS and saltcake Na
2SO
4Reaction can get process white BaSO
4Reaction formula is:
BaS+Na
2SO
4＝＝BaSO
4+Na
2S
Producing process white both at home and abroad at present all is aforesaid method.
For being that the technology method that raw material is produced process white is not seen bibliographical information with the phosphogypsum.
The object of the invention is: 1, with phosphogypsum, other industry by-product gypsum and the plaster of paris are the raw material production process white, also produce ammonium sulfide and by-product lime carbonate simultaneously, be that raw material is further produced process white and ammonium sulfide more then with ammonium sulfate, the producing and manufacturing technique of while by-product lime carbonate; 2, other gypsum offscum of phosphogypsum slag and other industrial by-product rationally can be utilized; With ammonia synthesizing industry and the annual a large amount of greenhouse gases CO of some other industry to airborne release
2, be used, realize CO
2Gas abatement.The present invention has solved residue phosphogypsum and waste gas CO simultaneously
2The world-famous puzzle of comprehensive utilization is a major contribution to environment protection.
Summary of the invention: for achieving the above object, the present invention is a kind of to be the method for raw material production process white with the gypsum, at first with gypsum according to certain production method, produce ammonium sulfate, then process white and ammonium sulfide are produced in the reaction of ammonium sulfate and barium sulphide, simultaneously by-product lime carbonate.
The gypsum of above-mentioned indication comprises phosphogypsum and the plaster of paris and other industry by-product gypsum.
With gypsum is raw material production process white and ammonium sulfide, and by-product lime carbonate producing and manufacturing technique was divided into for two steps:
The first step is a preparing ammonium sulfate with gypsum, by-product lime carbonate.
The first step is described to be that the production method of preparing ammonium sulfate has two kinds with gypsum:
First method adds water mill with gypsum earlier and becomes slurries, slurries are put into the reactor that has stirrer, at first in reactor, add ammoniacal liquor or feed ammonia, and then feeding carbon dioxide gas, the carbonic acid gas that feeds mainly is to have utilized the waste gas carbonic acid gas of ammonia synthesizing industry to airborne release, also can utilize the CO 2 waste gas of other industrial discharge.Control ammonia (NH well
3) and carbonic acid gas (CO
2) the coupling amount, generally be controlled to be NH
3With CO
2Mole ratio be 2: 1, the NH of feeding
3And CO
2Amount to reach CaSO in the reactor
4All be converted into (NH
4)
2SO
4And CaCO
3Amount till.CaSO when first step reactor
4After all having been reacted, just gas is transported in the next stage reactor by valve control switching.First step reactor just begins discharging, filters, and slag is a lime carbonate, can be used as cement producting material; Filtrate is ammonium sulfate, as the usefulness of producing process white.After the discharging of first step reactor is intact, drop into new gypsum slurries again, and add ammoniacal liquor or feed ammonia, as the reactor of last step absorption gas, its absorbs unabsorbed NH in upper level reactor
3And CO
2Gas.The reactor that the reactor that the original second stage is absorbed absorbs as the gas first step is successively by the previous methods cyclical operation.Generally preferable with 3～4 reactors in series and cyclical operation.
Above-described reactor can be a retort, perhaps reaction tank, perhaps reactive tank, perhaps reactor, perhaps reaction tower.
The main chemical reactions that takes place in reactor is:
2NH
3+CO
2+H
2O＝＝(NH
4)
2CO
3
(NH
4)
2CO
3+CaSO
4＝＝(NH
4)
2SO
4+CaCO
3↓
Second method adds water mill with gypsum and becomes slurries, and gypsum slurries is put into the reactor that has stirrer, adds volatile salt or bicarbonate of ammonia and ammoniacal liquor then in reactor, adds the amount of volatile salt or bicarbonate of ammonia and ammoniacal liquor, with CaSO in the reactor
4Amount, three's mole number equates.The speed of response of this method is fast, and the time is short.
The main chemical reactions that takes place is:
NH
4HCO
3+NH
3＝＝(NH
4)
2CO
3
(NH
4)
2CO
3+CaSO
4＝＝(NH
4)
2SO
4+CaCO
3↓
The product that second method obtains is identical with first method, CaCO
3Slag can be used as cement producting material; (NH
4)
2SO
4Filtrate is as the raw material of producing process white and ammonium sulfide.
The described reactor of second method can be retort equally, perhaps reaction tank, perhaps reactive tank, perhaps reactor, perhaps container such as reaction container, but all do not need airtight because reaction does not have gas to produce.
In second step, second step of whole production method is ammonium sulfate and the barium sulphide reaction that will make, and obtains process white and ammonium sulfide.The barium sulphide raw material is to produce and obtain by the prior art method.Its working method is that the ammoniumsulphate soln that obtains is put in the reactor that has stirrer, adds the barium sulphide solid or adds barium sulfide solution, also ammoniumsulphate soln can be joined in the barium sulfide solution, and reaction is undertaken by following formula:
(NH
4)
2SO
4+BaS＝＝BaSO
4+(NH
4)
2S
After filtration, washing, dry, pulverize, obtain process white product and ammonium sulfide solution.Ammonium sulfide solution just becomes product after packing with bucket.
Beneficial effect: be the raw material production process white 1, with gypsum, also produce ammonium sulfide and by-product lime carbonate simultaneously, this has searched out wide application prospect for phosphogypsum and other industry by-product gypsum refuse, can make the waste residue of chronic pollution environment become valuable raw material, the lime carbonate of by-product can be used as the raw material of producing cement fully, can make phosphorous chemical industry industry become environment-protecting clean industry, good benefits in environment and social benefit are arranged from heavy polluter.2, the technology of the present invention is that raw material production goes out process white and ammonium sulfide all is to be worth higher Chemicals with phosphogypsum and other industry by-product gypsum, it is general to have many uses, the lime carbonate of by-product is fully as cement producting material, therefore, promote this technology, can not bring burden, only can bring huge economic benefit to enterprise to enterprise.3, patented technology of the present invention can be accomplished saving energy, lowering energy consumption and reducing pollutants discharge, and environmental benefit is remarkable especially, is the most significantly must discharge a large amount of greenhouse gases CO to ammonia synthesizing industry or other industry in atmosphere
2Can collect and become useful raw material, this meets the minimizing row carbon of actively advocating countries in the world and controls the universal convention of Greenhouse effect and call.
Embodiment:
Embodiment 1
1, raw material: (1) phosphogypsum contains CaSO
485% source: Guizhou Xiyang Fertilizer Industry Co., Ltd.
(2) barium sulphide, the source: market is bought
(3) CO
2Gas, the source: CO is bought in market
2Steel cylinder gas
(4) ammoniacal liquor, the source: market is bought
2, experimental installation: the self-control retort, the bottom is the cylinder tank of cone, tube diameter: 1200mm, height: 10000mm, volume: 11500mL.
3, implementation and operation and effect: be respectively charged into the dried phosphogypsum of 2kg through the slurries of adding 6000mL water mill one-tenth and the ammoniacal liquor of 428g50% in three retort that are numbered I, II, III.Stirrer with three retort starts earlier, opens the CO of one-level jar then
2Enter valve, close the CO of secondary jar and three grades of jars
2Enter valve.Open CO
2Transferpump, CO
2At first at the bottom of the one-level jar, enter retort, begin to carry out a series of chemical reaction, start the off-gas pump of one-level jar, secondary jar and three grades of jars simultaneously, do not absorb gas in the one-level jar and enter the secondary jar, do not absorb gas in the secondary jar and enter three grades of jars.Feed CO
2Gas by the solution of check one-level jar, is learnt CaSO to 3h
4React completely, turn off CO
2Transferpump.With the discharging of I retort, 6000mL phosphogypsum slurries that the front of packing into again after discharging is intact is identical and the ammoniacal liquor of 428g50%, the CO of unlatching secondary jar
2Enter valve, close the CO of former one-level jar
2Enter valve, open CO
2Transferpump.At this moment the II jar becomes CO
2The one-level jar that absorbs, the III jar becomes CO
2The secondary jar that absorbs, former I jar becomes CO
2Three grades of jars that absorb are through 2.5h, through check, the CaSO in the II jar
4React completely, turn off CO
2Transferpump.With the discharging of II retort.Cyclical operation successively.
Carried out the operation of 6 samples of twice circulation, (the NH that obtains
4)
2SO
4And CaCO
3Relevant data sees Table one.
Table one
Obtain (NH according to table one
4)
2SO
4Add that corresponding BaS obtains corresponding process white and the ammonium sulfide relevant data sees Table two.
Table two
| ?(NH 4) 2SO 4?(g) | Add BaS (g) | Output BaSO 4?(g) | Output is converted into 40% (NH 4) 2S?(g) | |
| 1# | ?1650 | 2114 | ?2914 | ?2108 |
| 2# | ?1644 | 2107 | ?2904 | ?2104 |
| 3# | ?1648 | 2119 | ?2911 | ?2105 |
| 4# | ?1646 | 2109 | ?2907 | ?2103 |
| 5# | ?1643 | 2105 | ?2901 | ?2102 |
| 6# | ?1646 | 2109 | ?2907 | ?2106 |
Phosphogypsum raw material 12000g is used in test, and phosphogypsum contains CaSO
485%, amount to pure CaSO
410200g should produce process white 17486g in theory, actual output process white 17444g, and process white contains BaSO by analysis
499.2%, total recovery is 99.0%.(the NH of output
4)
2S solution is converted into 40% (NH
4)
2S liquid weighs 12628 (g), output 12763g in theory, and output capacity is 98.9%.
Embodiment 2
1, raw material: (1) phosphogypsum contains CaSO
485%, source: Guizhou Xiyang Fertilizer Industry Co., Ltd.
(2) bicarbonate of ammonia, the source: market is bought
(3) ammoniacal liquor, the source: market is bought
(4) barium sulphide, the source: market is bought
2, experiment major equipment a: 12m
3Round tube type has stirrer vertical response jar.
3, implementation method and effect: with 2000kg phosphogypsum dry sample,, add water at 1: 3, wear into 6m with ball mill by solid-to-liquid ratio through fragmentation
3Slurries in the disposable retort of all packing into, add 30% ammoniacal liquor 708kg, open stirrer, slowly evenly add 98% NH
4HCO
31008kg, add material after, continue to stir 30min, discharging is filtered, washing, filtrate, washing lotion merge, and obtain CaCO
3Wet slag 1767kg, water ratio 25% is amounted to dried slag 1325kg.Obtain (NH
4)
2SO
4Solution 7500L, (NH by analysis
4)
2SO
4Concentration is 219g/L, amounts to (NH
4)
2SO
4Clean quality is 1643kg, need use BaS2105kg.
Again with the 7500L (NH that makes
4)
2SO
4Solution joins 12m
3In the retort, start stirrer, progressively the BaS (solid) with 2105kg slowly evenly joins in the retort, add BaS after, continue to stir 6h, discharging is then filtered, washing, output process white 2902kg, (NH
4)
2SO
4Solution 8608L records (NH
4)
2S concentration 98.76g/L, (NH
4)
2The clean quality of S is 8501kg, amounts to 40% (NH
4)
2The S net weight is 2125kg.Process white contains BaSO after testing
499.1%, the output capacity of process white is 99.5%.
Claims (2)
1. one kind is the method for raw material production process white with the gypsum, it is characterized in that at first gypsum being produced ammonium sulfate according to following production method: after gypsum is added the water mill pulping, gypsum slurries is put into the reactor that has stirrer, at first in reactor, add ammoniacal liquor or feed ammonia, and then in reactor, feed carbon dioxide gas, the CaSO in reactor
4Total overall reaction is converted into CaCO
3(NH
4)
2SO
4Then process white and ammonium sulfide are produced in the reaction of ammonium sulfate and barium sulphide;
Wherein gypsum is a phosphogypsum, and carbon dioxide gas is the CO of synthetic ammonia to airborne release
2The CO of gas and other industrial discharge
2Waste gas, described reactor are 2,3 or 4 and are composed in series cyclical operation, the CO that has not been absorbed in the first step reactor
2And NH
3Gas is extracted and is imported the next stage reactor out and continues to absorb CaSO in the first step reactor with pump
4After reaction finishes, will input gas switch the reactor of input next stage by valve control, after the discharging of first step reactor finished, the calcium plaster of packing into absorbed the reactor of tail gas, so series connection and cyclical operation as last step.
2. according to the described method of claim 1, wherein reactor is selected from retort, reaction tank, reactive tank, reactor or reaction tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101029631A CN101717107B (en) | 2009-12-22 | 2009-12-22 | Method for producing precipitated barium sulfate by using gypsum as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101029631A CN101717107B (en) | 2009-12-22 | 2009-12-22 | Method for producing precipitated barium sulfate by using gypsum as raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101717107A CN101717107A (en) | 2010-06-02 |
| CN101717107B true CN101717107B (en) | 2011-12-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101029631A Expired - Fee Related CN101717107B (en) | 2009-12-22 | 2009-12-22 | Method for producing precipitated barium sulfate by using gypsum as raw material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674424B (en) * | 2012-04-28 | 2014-11-05 | 浙江大学 | Method for preparing nanometer calcium carbonate slurry by using waste gypsum as calcium sources, products and application |
| CN103910371A (en) * | 2014-04-17 | 2014-07-09 | 武汉钢铁(集团)公司 | Method for preparing calcium carbonate and coproducing ammonium sulfate by utilizing flue gas desulfurization gypsum or desulfurization ash residues |
| US9682868B2 (en) * | 2015-01-30 | 2017-06-20 | Sparstane Technologies LLC | Partially continuous countercurrent process for converting gypsum to ammonium sulfate and calcium carbonate |
| CN117142507A (en) * | 2023-08-31 | 2023-12-01 | 湖北大础环保科技有限责任公司 | Method for preparing calcium carbonate by phosphogypsum and multistage continuous production system |
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