CN103496714A - Method for producing industrial grade superior ammonium sulfate through coked coarse ammonium sulfate - Google Patents
Method for producing industrial grade superior ammonium sulfate through coked coarse ammonium sulfate Download PDFInfo
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- CN103496714A CN103496714A CN201310495567.6A CN201310495567A CN103496714A CN 103496714 A CN103496714 A CN 103496714A CN 201310495567 A CN201310495567 A CN 201310495567A CN 103496714 A CN103496714 A CN 103496714A
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Abstract
The invention particularly relates to a method for producing industrial grade superior ammonium sulfate through coked coarse ammonium sulfate. According to the technical scheme, the method comprises the steps that the pH value of a coked coarse ammonium sulfate aqueous solution is adjusted through NaOH, activated carbon is further added, and the aqueous solution is filtered, so that a coked coarse ammonium sulfate crystallization mother solution is obtained; an acidity adjusting agent, a crystal habit modification agent and seed crystals are added to the mother solution and crystals are cultivated; finally, evaporative crystallization is conducted, so that ammonium sulfate crystals are obtained. The method for producing the industrial grade superior ammonium sulfate through the coked coarse ammonium sulfate has the advantages that the quality of a coked coarse ammonium sulfate product is remarkably improved, the particle size distribution of the ammonium sulfate product which is produced with the coked coarse ammonium sulfate serving as a raw material is concentrated, the average particle size is controllable, the surface is smooth, the purity is high, the liquidity is good, and the standard of an industrial grade superior product can be met.
Description
Technical field
The invention belongs to the industrial crystallization technical field, be specifically related to the method for the thick sulphur ammonium of a kind of coking manufacture level premium grads sulphur ammonium.
Background technology
Coked thiamine is large industry byproduct that coke oven gas purification produces.7 meter 63,2 * 65 hole of a JN60-60 type coke oven of producing 2000000 t coke per year, sulphur ammonium output can reach 30,000 t/a.And China's coke output since nineteen ninety-three is sure to occupy first place, the world always, within 2011, break through 400,000,000 t, therefore the output of domestic coked thiamine is huge.Ammonium sulfate is important nitrogenous fertilizer, industrial agent, food catalyzer, the buffer reagent of also can printing and dyeing, leather deliming agent etc.
At present, the most domestic coke-oven plant adopts the saturex method to produce the sulphur ammonium more.Coked thiamine is due to the impact of impurity often with grey, green, blueness, furvous or redness, and crystallization mostly is needle-like, sheet or Powdered, and the particle of moulding is very little, and median size is no more than 0.5mm; And moisture, acidity exceed standard.The easy moisture absorption of sulphur ammonium crystal caking, large in atmospheric moisture, the little and water content of crystal grain is particularly serious when high.Sulphur ammonium after the moisture absorption all is corrosive to iron and steel, cement and gunnysack etc., easily causes storage, transportation and uses difficulty.
The quality of coked thiamine must meet the quality standard (in Table 1) on industry and agricultural, otherwise must carry out separation and purification to it.Current coked thiamine, because containing impurity, the shade deviations such as tar, coke tar refuse, can only be used as agrochemical, the low and sales difficulty of product price.
Table 1 ammonium sulfate quality standard
Summary of the invention
The present invention aims to provide a kind of coked thiamine quality product that improves to reach the Technical Solving of industrial premium grads.
The concrete steps of technical scheme that the present invention for achieving the above object, adopts are:
Step 1, under the speed conditions of normal pressure, 40 ~ 100 ℃ and 300～500r/min, the thick sulphur aqueous ammonium of the coking that first compound concentration is 40 ~ 50wt%; Regulate the thick sulphur aqueous ammonium of coking pH=7 ~ 9 with NaOH again; Then add the gac that accounts for the thick sulphur ammonium of coking 1 ~ 5wt% in the thick sulphur aqueous ammonium of coking, after insulated and stirred 0.5 ~ 1h, insulation is filtered, and makes the thick sulphur crystalline ammonium of coking mother liquor;
Step 2, under the speed conditions of normal pressure, 40 ~ 100 ℃ and 300～500r/min, add acid regulator in the thick sulphur crystalline ammonium of the coking mother liquor first prepared to step 1, make its mother liquor pH=5 ~ 7; Add crystal habit modifier and crystal seed again in mother liquor, insulated and stirred growing the grain 15 ~ 30min, make and be suspended magma;
Under step 3, the speed conditions that is 0.02 ~ 0.08MPa, 40 ~ 100 ℃ and 300～500r/min in normal pressure or vacuum tightness, to carry out evaporative crystallization to magma suspension density be 250 ~ 1000g/L to the magma that is suspended first prepared by step 2; Natural cooling down or temperature control are cooled to room temperature again; Filter, filtrate is returned to the thick sulphur aqueous ammonium of step 1 preparation coking; Filtration cakes torrefaction obtains sulphur ammonium crystal.
Described acid regulator is one or more the combination in oxalic acid, phosphoric acid, citric acid, hydrochloric acid and sulfuric acid.
Described crystal habit modifier is one or more the combination in sulphamide, urea, magnesium salts, zinc salt, manganese salt and mantoquita, 0.05 ~ 1.0wt% that the add-on of crystal habit modifier is product sulphur ammonium crystal;
Magnesium salts can be a kind of in magnesium chloride, magnesium nitrate and sal epsom;
Zinc salt can be a kind of in zinc chloride, zinc nitrate and zinc sulfate;
Manganese salt can be a kind of in Manganous chloride tetrahydrate, manganous nitrate and manganous sulfate;
Mantoquita can be a kind of in cupric chloride, nitric acid copper and copper sulfate.
Described crystal seed refers to sulphur ammonium crystal, 0.1～5wt% that the crystal seed add-on is sulphur crystalline ammonium product population.
Described while adding seed size to be 200 ~ 230 order, more than in product, 30 ~ 50 purpose sulphur ammonium crystal account for 90wt%;
Described while adding seed size to be 170 ~ 200 order, more than in product, 20 ~ 30 purpose sulphur ammonium crystal account for 90wt%;
Described while adding seed size to be 140 ~ 170 order, more than in product, 18 ~ 25 purpose sulphur ammonium crystal account for 90wt%;
Described while adding seed size to be 100 ~ 120 order, more than in product, 14 ~ 20 purpose sulphur ammonium crystal account for 90wt%.
Owing to adopting technique scheme, the present invention compared with prior art has following positively effect:
(1) method of the thick sulphur ammonium of coking involved in the present invention manufacture level premium grads sulphur ammonium, first utilize NaOH to remove the Al in the thick sulphur ammonium of coking
3+, Fe
3+, the impurity such as arsenic, not only can improve sulphur ammonium purified product look level, also can reduce its foreign matter content.Existing bibliographical information Fe
3+can slow down the growth velocity of sulphur ammonium crystal, Al
3+and Fe
3+can generate Al (OH) under sulphur ammonium alkalescence crystalline environment
3, Fe (OH)
3brown colloid and affect the look level of ammonium sulfate products, the S in sulphur crystalline ammonium mother liquor
2-also can generate dark red or orange As with arsenic
2s
3colloid.
(2) method of the thick sulphur ammonium of coking involved in the present invention manufacture level premium grads sulphur ammonium, add gac both can realize decolouring, also can remove newly-generated Al (OH) in the insoluble impurities such as tar in the thick sulphur ammonium of coking, coke tar refuse and above-mentioned (1)
3, Fe (OH)
3and As
2s
3colloid etc.Tar in the thick sulphur crystalline ammonium of coking mother liquor easily is attached to sulphur ammonium plane of crystal and hinders the crystal growth, and tar, coke tar refuse, Al (OH)
3, Fe (OH)
3and As
2s
3the insoluble impuritiess such as colloid are the important factors that affects sulphur ammonium crystal purity and look level.
(3) method of the thick sulphur ammonium of coking involved in the present invention manufacture level premium grads sulphur ammonium, be conducive to the adding of the weak acid environment of sulphur crystalline ammonium mother liquor and crystal habit modifier the short-thick type sulphur ammonium crystal that growth is larger, the size that the adding of different mass and granularity crystal seed can regulate and control ammonium sulfate products crystal master granularity and the homogeneity of size-grade distribution.
Therefore, the present invention has the characteristics of the thick ammonium sulfate products quality of the coking of significantly improving, and the ammonium sulfate products size-grade distribution that the thick sulphur ammonium of the coking of take is raw material production is concentrated, mean particle size is controlled, any surface finish, purity is high and good fluidity, can reach industrial premium grads specification.
Embodiment
Below in conjunction with embodiment, the invention will be further described, is not the restriction to its protection domain.
embodiment 1
The method of the thick sulphur ammonium of a kind of coking manufacture level premium grads sulphur ammonium, its concrete steps are:
Step 1, under the speed conditions of normal pressure, 40 ~ 60 ℃ and 300～400r/min, the thick sulphur aqueous ammonium of the coking that first compound concentration is 40 ~ 45wt%; Regulate the thick sulphur aqueous ammonium of coking pH=7 ~ 8 with NaOH again; Then add the gac that accounts for the thick sulphur ammonium of coking 1 ~ 3wt% in the thick sulphur aqueous ammonium of coking, after insulated and stirred 0.5 ~ 1h, insulation is filtered, and makes the thick sulphur crystalline ammonium of coking mother liquor;
Step 2, under the speed conditions of normal pressure, 40 ~ 60 ℃ and 300～400r/min, add acid regulator in the thick sulphur crystalline ammonium of the coking mother liquor first prepared to step 1, make its mother liquor pH=5 ~ 6; Add crystal habit modifier and crystal seed again in mother liquor, insulated and stirred growing the grain 15 ~ 30min, make and be suspended magma;
Step 3, under the speed conditions of normal pressure, 40 ~ 60 ℃ and 300～400r/min, to carry out evaporative crystallization to magma suspension density be 250 ~ 500g/L to the magma that is suspended first prepared by step 2; Natural cooling down or temperature control are cooled to room temperature again; Filter, filtrate is returned to the thick sulphur aqueous ammonium of step 1 preparation coking; Filtration cakes torrefaction obtains sulphur ammonium crystal.
Acid regulator described in the present embodiment is oxalic acid; Described crystal habit modifier is a kind of in magnesium chloride, magnesium nitrate and sal epsom, 0.05 ~ 1.0wt% that the add-on of crystal habit modifier is product sulphur ammonium crystal; Described crystal seed refers to sulphur ammonium crystal, 0.1～5wt% that the crystal seed add-on is sulphur crystalline ammonium product population, and seed size is 200 ~ 230 orders.
More than in the present embodiment gained ammonium sulfate products crystal, 30 ~ 50 purpose sulphur ammonium crystal account for 90wt%.
embodiment 2
Step 1, under the speed conditions of normal pressure, 60 ~ 80 ℃ and 350～450r/min, the thick sulphur aqueous ammonium of the coking that first compound concentration is 43 ~ 48wt%; Regulate the thick sulphur aqueous ammonium of coking pH=8 ~ 9 with NaOH again; Then add the gac that accounts for the thick sulphur ammonium of coking 2 ~ 4wt% in the thick sulphur aqueous ammonium of coking, after insulated and stirred 0.5 ~ 1h, insulation is filtered, and makes the thick sulphur crystalline ammonium of coking mother liquor;
Step 2, under the speed conditions of normal pressure, 60 ~ 80 ℃ and 350～450r/min, add acid regulator in the thick sulphur crystalline ammonium of the coking mother liquor first prepared to step 1, make its mother liquor pH=6 ~ 7; Add crystal habit modifier and crystal seed again in mother liquor, insulated and stirred growing the grain 15 ~ 30min, make and be suspended magma;
Under step 3, the speed conditions that is 0.02 ~ 0.08MPa, 60 ~ 80 ℃ and 350～450r/min in vacuum tightness, to carry out evaporative crystallization to magma suspension density be 500 ~ 750g/L to the magma that is suspended first prepared by step 2; Natural cooling down or temperature control are cooled to room temperature again; Filter, filtrate is returned to the thick sulphur aqueous ammonium of step 1 preparation coking; Filtration cakes torrefaction obtains sulphur ammonium crystal.
Acid regulator described in the present embodiment is phosphoric acid; Described crystal habit modifier is a kind of in zinc chloride, zinc nitrate and zinc sulfate, 0.05 ~ 1.0wt% that the add-on of crystal habit modifier is product sulphur ammonium crystal; Described crystal seed refers to sulphur ammonium crystal, 0.1～5wt% that the crystal seed add-on is sulphur crystalline ammonium product population, and seed size is 170 ~ 200 orders.
More than in the present embodiment gained ammonium sulfate products crystal, 20 ~ 30 purpose sulphur ammonium crystal account for 90wt%.
embodiment 3
Step 1, under the speed conditions of normal pressure, 80 ~ 100 ℃ and 350～500r/min, the thick sulphur aqueous ammonium of the coking that first compound concentration is 45 ~ 50wt%; Regulate the thick sulphur aqueous ammonium of coking pH=7 ~ 9 with NaOH again; Then add the gac that accounts for the thick sulphur ammonium of coking 3 ~ 5wt% in the thick sulphur aqueous ammonium of coking, after insulated and stirred 0.5 ~ 1h, insulation is filtered, and makes the thick sulphur crystalline ammonium of coking mother liquor;
Step 2, under the speed conditions of normal pressure, 80 ~ 100 ℃ and 350～500r/min, add acid regulator in the thick sulphur crystalline ammonium of the coking mother liquor first prepared to step 1, make its mother liquor pH=5 ~ 7; Add crystal habit modifier and crystal seed again in mother liquor, insulated and stirred growing the grain 15 ~ 30min, make and be suspended magma;
Step 3, under the speed conditions of normal pressure, 80 ~ 100 ℃ and 350～500r/min, to carry out evaporative crystallization to magma suspension density be 750 ~ 1000g/L to the magma that is suspended first prepared by step 2; Natural cooling down or temperature control are cooled to room temperature again; Filter, filtrate is returned to the thick sulphur aqueous ammonium of step 1 preparation coking; Filtration cakes torrefaction obtains sulphur ammonium crystal.
Acid regulator described in the present embodiment is citric acid; Described crystal habit modifier is a kind of in Manganous chloride tetrahydrate, manganous nitrate and manganous sulfate, 0.05 ~ 1.0wt% that the add-on of crystal habit modifier is product sulphur ammonium crystal; Described crystal seed refers to sulphur ammonium crystal, 0.1～5wt% that the crystal seed add-on is sulphur crystalline ammonium product population, and seed size is 140 ~ 170 orders.
More than in the present embodiment gained ammonium sulfate products crystal, 18 ~ 25 purpose sulphur ammonium crystal account for 90wt%.
embodiment 4
In the present embodiment, except crystal habit modifier, be that hydrochloric acid, crystal habit modifier are that a kind of in cupric chloride, nitric acid copper and copper sulfate, other are with embodiment 1.
embodiment 5
In the present embodiment, except crystal habit modifier is sulfuric acid and citric acid, other are with embodiment 2.
embodiment 6
In the present embodiment, except crystal habit modifier, be that oxalic acid and citric acid, crystal habit modifier are urea and magnesium nitrate, other are with embodiment 3.
embodiment 7
In the present embodiment, except crystal habit modifier, be that phosphoric acid, hydrochloric acid and sulfuric acid, crystal habit modifier are magnesium chloride, zinc chloride and Manganous chloride tetrahydrate, other are with embodiment 1.
embodiment 8
In the present embodiment, except crystal habit modifier, be that oxalic acid, citric acid, hydrochloric acid and sulfuric acid, crystal habit modifier are urea, magnesium nitrate, zinc nitrate and cupric nitrate, other are with embodiment 2.
Claims (5)
1. the method for the thick sulphur ammonium of a coking manufacture level premium grads sulphur ammonium, is characterized in that, specifically completes according to the following steps:
Step 1, under the speed conditions of normal pressure, 40 ~ 100 ℃ and 300～500r/min, the thick sulphur aqueous ammonium of the coking that first compound concentration is 40 ~ 50wt%; Regulate the thick sulphur aqueous ammonium of coking pH=7 ~ 9 with NaOH again; Then add the gac that accounts for the thick sulphur ammonium of coking 1 ~ 5wt% in the thick sulphur aqueous ammonium of coking, after insulated and stirred 0.5 ~ 1h, insulation is filtered, and makes the thick sulphur crystalline ammonium of coking mother liquor;
Step 2, under the speed conditions of normal pressure, 40 ~ 100 ℃ and 300～500r/min, add acid regulator in the thick sulphur crystalline ammonium of the coking mother liquor first prepared to step 1, make its mother liquor pH=5 ~ 7; Add crystal habit modifier and crystal seed again in mother liquor, insulated and stirred growing the grain 15 ~ 30min, make and be suspended magma;
Under step 3, the speed conditions that is 0.02 ~ 0.08MPa, 40 ~ 100 ℃ and 300～500r/min in normal pressure or vacuum tightness, to carry out evaporative crystallization to magma suspension density be 250 ~ 1000g/L to the magma that is suspended first prepared by step 2; Natural cooling down or temperature control are cooled to room temperature again; Filter, filtrate is returned to the thick sulphur aqueous ammonium of step 1 preparation coking; Filtration cakes torrefaction obtains sulphur ammonium crystal.
2. the method for the thick sulphur ammonium of coking as claimed in claim 1 manufacture level premium grads sulphur ammonium, is characterized in that, described acid regulator is one or more the combination in oxalic acid, phosphoric acid, citric acid, hydrochloric acid and sulfuric acid.
3. the method for the thick sulphur ammonium of coking as claimed in claim 1 manufacture level premium grads sulphur ammonium, it is characterized in that, described crystal habit modifier is one or more the combination in sulphamide, urea, magnesium salts, zinc salt, manganese salt and mantoquita, 0.05 ~ 1.0wt% that the add-on of crystal habit modifier is product sulphur ammonium crystal;
Magnesium salts can be a kind of in magnesium chloride, magnesium nitrate and sal epsom;
Zinc salt can be a kind of in zinc chloride, zinc nitrate and zinc sulfate;
Manganese salt can be a kind of in Manganous chloride tetrahydrate, manganous nitrate and manganous sulfate;
Mantoquita can be a kind of in cupric chloride, nitric acid copper and copper sulfate.
4. the method for the thick sulphur ammonium of coking as claimed in claim 1 manufacture level premium grads sulphur ammonium, is characterized in that, described crystal seed refers to sulphur ammonium crystal, 0.1～5wt% that the crystal seed add-on is sulphur crystalline ammonium product population.
5. as the method for claim 1, the thick sulphur ammonium of 4 described coking manufacture level premium grads sulphur ammonium, it is characterized in that:
Described while adding seed size to be 200 ~ 230 order, more than in product, 30 ~ 50 purpose sulphur ammonium crystal account for 90wt%;
Described while adding seed size to be 170 ~ 200 order, more than in product, 20 ~ 30 purpose sulphur ammonium crystal account for 90wt%;
Described while adding seed size to be 140 ~ 170 order, more than in product, 18 ~ 25 purpose sulphur ammonium crystal account for 90wt%;
Described while adding seed size to be 100 ~ 120 order, more than in product, 14 ~ 20 purpose sulphur ammonium crystal account for 90wt%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108483463A (en) * | 2018-03-19 | 2018-09-04 | 江苏燎原环保科技股份有限公司 | A method of preparing high-quality ammonium sulfate using coking desulfurization decyanation waste liquid |
| CN111592012A (en) * | 2020-05-18 | 2020-08-28 | 太仓市新星轻工助剂厂 | Preparation method of high-purity ammonium sulfate for water treatment flocculation initiator |
-
2013
- 2013-10-22 CN CN201310495567.6A patent/CN103496714A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108483463A (en) * | 2018-03-19 | 2018-09-04 | 江苏燎原环保科技股份有限公司 | A method of preparing high-quality ammonium sulfate using coking desulfurization decyanation waste liquid |
| CN108483463B (en) * | 2018-03-19 | 2021-07-30 | 江苏燎原环保科技股份有限公司 | Method for preparing high-quality ammonium sulfate by using coking desulfurization and decyanation waste liquid |
| CN111592012A (en) * | 2020-05-18 | 2020-08-28 | 太仓市新星轻工助剂厂 | Preparation method of high-purity ammonium sulfate for water treatment flocculation initiator |
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Application publication date: 20140108 |