CN101844749A - Method for producing concentrated sulfuric acid and co-producing industrial salt and gypsum by using phosphogypsum - Google Patents
Method for producing concentrated sulfuric acid and co-producing industrial salt and gypsum by using phosphogypsum Download PDFInfo
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- CN101844749A CN101844749A CN201019050041A CN201019050041A CN101844749A CN 101844749 A CN101844749 A CN 101844749A CN 201019050041 A CN201019050041 A CN 201019050041A CN 201019050041 A CN201019050041 A CN 201019050041A CN 101844749 A CN101844749 A CN 101844749A
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- phosphogypsum
- sulfuric acid
- industrial salt
- vitriol oil
- producing
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Abstract
The invention provides a method for producing concentrated sulfuric acid and co-producing industrial salt and gypsum by using phosphorgypsum. In the method, after purifying industrial phosphogypsum by using dilute hydrochloric acid, the purified phosphogypsum and sodium sulfate react to generate the concentrated sulfuric acid; and the industrial salt and the gypsum are co-produced at the same time. The method has the characteristics of reasonable production process, simple production equipment, less investment, high profit, elimination of industrial chemical waste residue and environment protection.
Description
Technical field
The present invention relates to the technical field of the phosphogypsum comprehensive regulation and utilization, particularly, relate to a kind of method of producing vitriol oil coproduction Industrial Salt and plaster stone with phosphogypsum.
Background technology
Phosphogypsum is the solid trade waste that discharges in the Wet-process Phosphoric Acid Production process, produces 1 ton of phosphoric acid (with P
2O
5Meter) can produce the phosphogypsum of 4.5-5 ton.Along with developing rapidly of phosphate fertilizer and high-concentration phosphoric acid industry, the quantity discharged of phosphogypsum slag increases day by day.2008, world's phosphogypsum annual emissions reached 2.8 hundred million tons, and China also surpasses 5,000 ten thousand tons, accounts for more than 70% of industry by-product gypsum.The content of calcium sulfate surpasses 90% in the phosphogypsum, is a kind of important reclaimed gypsum resource, especially concerning construction industry, phosphogypsum as the raw material of producing cement, because it is cheap, is had huge economic.As number of patent application is 200810056189, denomination of invention is the patent of invention of the sulfuric acid modified method of phosphogypsum, disclose by sulfuric acid and mixed with the phosphogypsum raw material, the phosphogypsum to reaction product carries out obtaining after the neutralizing treatment modification can be used for making cement and gypsum.
Yet,, influenced the application of phosphogypsum as cement and gypsum in the feedstock production construction industry owing to also contain objectionable impuritiess such as Vanadium Pentoxide in FLAKES, fluorine and free acid in the phosphogypsum.At present, China is no more than 20% of phosphogypsum annual production to the utilization ratio of phosphogypsum.Method processing such as stockyard are all taked to discharge, are provided with to most of phosphogypsum, therefore caused the serious environmental pollution, in certain areas, even also causes surface water and phreatic pollution.
Therefore, demanding studying new phosphogypsum urgently uses and treatment process.
Summary of the invention
In order to overcome the deficiency of prior art, the invention provides and a kind ofly prepare the method for vitriol oil coproduction Industrial Salt and plaster stone with phosphogypsum, this method production technique is reasonable, and production unit is simple, invests for a short time, and the profit height has been eliminated chemical sludge, has protected environment.
Technical scheme of the present invention is: a kind of method for preparing vitriol oil coproduction Industrial Salt and plaster stone with phosphogypsum, be after industry is produced phosphogypsum and purified with dilute hydrochloric acid, with the sodium sulfate reaction, to make the vitriol oil again, while coproduction Industrial Salt and plaster stone, its concrete steps are as follows:
(1) purification of phosphogypsum: the amount of converting the pure substance calcium sulfate that is contained in the industrial phosphogypsum earlier, and configuration dilute hydrochloric acid solution, is 1: 0.34～0.74 to put in the purification reactor (1) phosphogypsum and dilute hydrochloric acid solution according to the ratio of the quality of calcium sulfate and hydrogenchloride pure substance, carries out chemical reaction under slowly stirring;
(2) then with reaction product suction filtration in the first suction filtration machine (2), obtain clarifying calcium chloride and vitriolic mixing solutions and filter cake;
(3) be 1: 1.08～1.48 to put in the synthesizer (3) obtaining clarifying calcium chloride and vitriolic mixing solutions and sodium sulfate mass ratio in the step (2), under slowly stirring, carrying out chemical reaction according to the pure substance of calcium chloride and sulfuric acid and sodium sulfate;
(4) reaction product that step (3) is made suction filtration in the second suction filtration machine (4) obtains clarifying sodium-chlor and sulfuric acid mixed solution and white calcium sulfate filter cake;
(5) clarifying sodium-chlor that step (4) is made and sulfuric acid mixed solution are knocked down in the underpressure distillation device (5) and are distilled deeply, when treating that sodium-chlor is all separated out, distillating liquid is entered water cooler (6) cooling, thereby isolate solid sodium chloride and concentrated sulfuric acid solution.
The solid sodium chloride of step (5) gained with distilled water wash after first whizzer (7) is centrifugal, separate washing water and purified solid sodium chloride, purified solid sodium chloride after first pulverizer (8) is pulverized, promptly get Industrial Salt (14).
Described washing water are mixed into that heavily to steam the refining concentration that obtains in the concentrated sulfuric acid solution of step (5) gained be the vitriol oil (13) more than 96%.
After the calcium sulfate filter cake of described white washes with water, successively through second whizzer (9) centrifuge dehydration, moisture eliminator (10) drying, second pulverizer (11) is pulverized, and promptly gets plaster stone (12) product.
Of the present inventionly prepare the method for vitriol oil coproduction Industrial Salt and plaster stone with phosphogypsum, its chemical equation is:
CaSO
4+2HCl＝＝＝CaCl
2+H
2SO
4
CaCl
2+H
2SO
4+Na
2SO
4＝＝＝H
2SO
4+2NaCl+CaSO
4↓
Beneficial effect of the present invention is: the present invention is the actual demand from market; adopt the method for preparing vitriol oil coproduction Industrial Salt and plaster stone with phosphogypsum of developing of chemical method success; this method production technique is reasonable; production unit is simple; invest little; the profit height has been eliminated chemical sludge, has protected environment.
Description of drawings
Fig. 1 prepares the process flow diagram of the method for vitriol oil coproduction Industrial Salt and plaster stone for of the present invention with phosphogypsum, wherein
1---cleaner 2---suction filtration machine 3---synthesizer
4---suction filtration machine 5---underpressure distillation device 6---water coolers
7---first whizzer 8---first pulverizer 9---, second whizzers
10---moisture eliminator 11---second pulverizer 12---plaster stone
13---vitriol oil 14---Industrial Salt.
Embodiment
Essence for a better understanding of the present invention further describes the present invention below with reference to specific embodiment.
Embodiment one:
Convert the amount of the pure substance calcium sulfate that is contained in the industrial phosphogypsum product earlier, get the industrial phosphogypsum product that contains pure calcium sulfate 500kg, put at 1: 0.34 in the cleaner (1) according to the mass ratio of the pure substance of calcium sulfate and hydrogenchloride with dilute hydrochloric acid solution, carry out chemical reaction under slowly stirring; Then, obtain clarifying calcium chloride and vitriolic mixing solutions and filter cake with reaction product suction filtration in the first suction filtration machine (2); Only contain a spot of impurity in the described filter cake, described filter cake is buried or burn; Above-mentioned mixing solutions and the sodium sulfate that obtains clarifying calcium chloride 258.5kg and sulfuric acid 228.22kg is put into synthesizer (3) lining according to the mass ratio of the pure substance of calcium chloride and sodium sulfate at 1: 1.08, under slowly stirring, carry out chemical reaction; Then, obtain the calcium sulfate filter cake of clarifying sodium-chlor and sulfuric acid mixed solution and white with reaction product suction filtration in the second suction filtration machine (4); Clarifying sodium-chlor and sulfuric acid mixture liquid enter underpressure distillation device (5) and distill deeply, when treating that sodium-chlor is all separated out, distillating liquid is entered water cooler (6) cooling, thereby isolate solid sodium chloride and concentrated sulfuric acid solution.
Described solid sodium chloride washes with water after first whizzer (7) is centrifugal, separate washing water and purified solid sodium chloride, purified solid sodium chloride after first pulverizer (8) is pulverized, packing becomes Industrial Salt (14), and the output of Industrial Salt is 230.05kg.
Described washing water are mixed into that heavily to steam the refining fine concentration that obtains in the described concentrated sulfuric acid solution be the vitriol oil (13) more than 96%, and the output of the vitriol oil is 228.22kg.
After described calcium sulfate filter cake washes with water, successively through second whizzer (9) centrifuge dehydration, moisture eliminator (10) drying, second pulverizer (11) is pulverized, and then is packaged into plaster stone (12) product, and the output of plaster stone is 267.40kg.
Embodiment two:
Convert the amount of the pure substance calcium sulfate that is contained in the industrial phosphogypsum product earlier, get the industrial phosphogypsum product that contains pure calcium sulfate 500kg, put at 1: 0.54 in the cleaner (1) according to the mass ratio of the pure substance of calcium sulfate and hydrogenchloride with dilute hydrochloric acid solution, carry out chemical reaction under slowly stirring; Then, obtain clarifying calcium chloride and vitriolic mixing solutions and filter cake with reaction product suction filtration in the first suction filtration machine (2); Only contain a spot of impurity in the described filter cake, described filter cake is buried or burn; Above-mentioned mixing solutions and the sodium sulfate that obtains clarifying calcium chloride 410.55kg and sulfuric acid 362.47kg is put into synthesizer (3) lining according to the mass ratio of the pure substance of calcium chloride and sodium sulfate at 1: 1.28, under slowly stirring, carry out chemical reaction; Then, obtain the calcium sulfate filter cake of clarifying sodium-chlor and sulfuric acid mixed solution and white with reaction product suction filtration in the second suction filtration machine (4); Clarifying sodium-chlor and sulfuric acid mixture liquid enter underpressure distillation device (5) and distill deeply, when treating that sodium-chlor is all separated out, distillating liquid is entered water cooler (6) cooling, thereby isolate solid sodium chloride and concentrated sulfuric acid solution.
Described solid sodium chloride washes with water after first whizzer (7) is centrifugal, separate washing water and purified solid sodium chloride, purified solid sodium chloride after first pulverizer (8) is pulverized, packing becomes Industrial Salt (14), and the output of Industrial Salt is 432.74kg.
Described washing water are mixed into that heavily to steam the refining fine concentration that obtains in the described concentrated sulfuric acid solution be the vitriol oil (13) more than 96%, and the output of the vitriol oil is 362.47kg.
After described calcium sulfate filter cake washes with water, successively through second whizzer (9) centrifuge dehydration, moisture eliminator (10) drying, second pulverizer (11) is pulverized, and then is packaged into plaster stone (12) product, and the output of plaster stone is 503.02kg.
The foregoing description is preferred embodiment of the present invention, is not to be used for limiting the scope of the present invention, so all equivalences of being done with the described structure of claim of the present invention, feature and principle change or modify, all should be included within the claim scope of the present invention.
Claims (4)
1. one kind prepares the method for vitriol oil coproduction Industrial Salt and plaster stone with phosphogypsum, it is characterized in that, be after industry is produced phosphogypsum and purified with dilute hydrochloric acid, with the sodium sulfate reaction, to make the vitriol oil again, and coproduction Industrial Salt and plaster stone simultaneously, its concrete steps are as follows:
(1) purification of phosphogypsum: the amount of converting the pure substance calcium sulfate that is contained in the industrial phosphogypsum earlier, and configuration dilute hydrochloric acid solution, is 1: 0.34～0.74 to put in the purification reactor (1) phosphogypsum and dilute hydrochloric acid solution according to the ratio of the quality of calcium sulfate and hydrogenchloride pure substance, carries out chemical reaction under slowly stirring;
(2) then with reaction product suction filtration in the first suction filtration machine (2), obtain calcium chloride and vitriolic mixing solutions and filter cake;
(3) be 1: 1.08～1.48 to put in the synthesizer (3) obtaining calcium chloride and vitriolic mixing solutions and sodium sulfate mass ratio in the step (2), under slowly stirring, carrying out chemical reaction according to the pure substance of calcium chloride and sulfuric acid and sodium sulfate;
(4) reaction product that step (3) is made suction filtration in the second suction filtration machine (4) obtains sodium-chlor and sulfuric acid mixed solution and calcium sulfate filter cake;
(5) sodium-chlor that step (4) is made and sulfuric acid mixed solution are knocked down in the underpressure distillation device (5) and are distilled deeply, when treating that sodium-chlor is all separated out, distillating liquid is entered water cooler (6) cooling, thereby isolate solid sodium chloride and concentrated sulfuric acid solution.
2. method of producing vitriol oil coproduction Industrial Salt and plaster stone with phosphogypsum as claimed in claim 1, it is characterized in that, the solid sodium chloride of step (5) gained uses distilled water wash after first whizzer (7) is centrifugal, separate washing water and purified solid sodium chloride, purified solid sodium chloride after first pulverizer (8) is pulverized, promptly get Industrial Salt (14).
3. method of producing vitriol oil coproduction Industrial Salt and plaster stone with phosphogypsum as claimed in claim 1, it is characterized in that described washing water are mixed into that heavily to steam the refining concentration that obtains in the concentrated sulfuric acid solution of step (5) gained be the vitriol oil (13) more than 96%.
4. method of producing vitriol oil coproduction Industrial Salt and plaster stone with phosphogypsum as claimed in claim 1, it is characterized in that, after described calcium sulfate filter cake washes with water, successively through second whizzer (9) centrifuge dehydration, moisture eliminator (10) drying, second pulverizer (11) is pulverized, and promptly gets plaster stone (12) product.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201019050041A CN101844749A (en) | 2010-02-11 | 2010-02-11 | Method for producing concentrated sulfuric acid and co-producing industrial salt and gypsum by using phosphogypsum |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201019050041A CN101844749A (en) | 2010-02-11 | 2010-02-11 | Method for producing concentrated sulfuric acid and co-producing industrial salt and gypsum by using phosphogypsum |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006698A (en) * | 2016-05-23 | 2016-10-12 | 中国建筑第八工程局有限公司 | Phosphorus gypsum purification treatment method |
| CN112110470A (en) * | 2020-09-25 | 2020-12-22 | 福泉环保城发展有限公司 | Phosphogypsum waste residue treatment method |
| CN115849404A (en) * | 2022-12-02 | 2023-03-28 | 贵州大学 | Method for removing sodium and fixing sodium by utilizing crystal form conversion process of phosphogypsum in solution under normal pressure |
-
2010
- 2010-02-11 CN CN201019050041A patent/CN101844749A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006698A (en) * | 2016-05-23 | 2016-10-12 | 中国建筑第八工程局有限公司 | Phosphorus gypsum purification treatment method |
| CN112110470A (en) * | 2020-09-25 | 2020-12-22 | 福泉环保城发展有限公司 | Phosphogypsum waste residue treatment method |
| CN115849404A (en) * | 2022-12-02 | 2023-03-28 | 贵州大学 | Method for removing sodium and fixing sodium by utilizing crystal form conversion process of phosphogypsum in solution under normal pressure |
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Open date: 20100929 |