CN105110351A - Method used for simultaneous extraction of ammonium sulfate and ammonium thiocyanate from coking waste liquid - Google Patents
Method used for simultaneous extraction of ammonium sulfate and ammonium thiocyanate from coking waste liquid Download PDFInfo
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- CN105110351A CN105110351A CN201510434396.5A CN201510434396A CN105110351A CN 105110351 A CN105110351 A CN 105110351A CN 201510434396 A CN201510434396 A CN 201510434396A CN 105110351 A CN105110351 A CN 105110351A
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- waste liquid
- coking waste
- ammonium thiocyanate
- ammonium
- ammonium sulfate
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Abstract
The invention discloses a method used for simultaneous extraction of ammonium sulfate and ammonium thiocyanate from coking waste liquid. The method comprises following steps: coking waste liquid is filtered so as to remove impurities, and is delivered into a stirrer; air is pumped into the stirrer, a catalyst is added, and reaction is carried out for 3 to 10h at 50 to 90 DEG C with a pH value ranging from 5 to 6; active carbon is adopted for heating decoloring of filtered coking waste liquid at 55 to 85 DEG C for 0.3 to 1.5h; H2O2 is added for 1 to 3h of oxidation, an obtained product is subjected to evaporative crystallization and filtration, and an obtained crystal is collected; the crystal is delivered into a reactor, an alcohol organic solvent is added, an obtained mixture is mixed fully, and is filtered so as to obtain ammonium sulfate crystal; an obtained ammonium thiocyanate alcoholic solution is subjected to evaporative crystallization so as to obtain ammonium thiocyanate crystal, and an evaporated alcoholic solution is collected and recycled. The method can be used for simultaneous preparation of ammonium sulfate and ammonium thiocyanate; purifying process can be recycled; industrial energy consumption is low; recovery rate of ammonium sulfate and ammonium thiocyanate is high; no waste is discharged; the method is green, and is high in recovery rate, low in cost, and high in purity; and no pollution is caused.
Description
Technical field
The invention belongs to coking liquid waste disposal technique field, be specifically related to a kind of method simultaneously extracting ammonium sulfate and ammonium thiocyanate from coking waste liquid.
Background technology
The waste water that coking waste liquid is coal coke, produce in gas purification and coke chemicals removal process, wastewater discharge is large, water-quality constituents is complicated, main containing organism such as heterocycle and polycyclc aromatic compound tar such as coloured catalyzer, many kinds of metal ions, suspension sulphur, plurality of inorganic salt, phenol, oils, naphthalene, pyridine, quinoline, anthracenes, belong to the high concentrated organic wastewater of poisonous and harmful, difficult degradation.
Current domestic coal chemical enterprise generally adopts HPF method sulfur removal technology, main containing three kinds of salt in the desulfurization waste liquor that this technique produces: (NH
4)
2sO
4, (NH
4)
2s
2o
3, (NH
4) SCN, these three kinds of secondary salts are constantly accumulated in desulphurization system, and desulfuration efficiency is declined, and in circulating water treatment, removing these three kinds of salt becomes key in whole treatment process.
The processing mode of current coking waste liquid mainly adopts biological treatment, activated sludge process, the multiple processing mode such as Biology-iron technology, the objectionable impurities that corresponding processing mode process is different, but these methods are all not good to the treatment effect of ammonia nitrogen, most coal chemical enterprise meeting exclusive segment waste liquid is directly sprayed onto above dump or is sprayed directly on the mixed coal of coal tower and returns coke oven production, and three kinds of salt are constantly accumulated in system, cause the problems such as equipment corrosion is serious, coke quality decline, environmental pollution.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the object of this invention is to provide a kind of method simultaneously extracting ammonium sulfate and ammonium thiocyanate from coking waste liquid, by the mode of oxidation cycle process, improve the purity extracting ammonium sulfate and ammonium thiocyanate in coking waste liquid, effectively can remove (the NH in coking waste liquid
4)
2sO
4, (NH
4)
2s
2o
3, (NH
4) these three kinds of secondary salts of SCN, the salt extracted can be applicable to agricultural chemicals, chemical fertilizer, the aspects such as medication chemistry, can reduce Treatment of Coking Effluent cost, increases service life of equipment, reaches the object of protection of the environment and comprehensive utilization of resources.
To achieve these goals, the technical solution used in the present invention is:
From coking waste liquid, extract a method for ammonium sulfate and ammonium thiocyanate simultaneously, comprise the following steps:
1) first add agitator by after coking waste liquid filtering and impurity removing, blast air, and add catalyzer simultaneously, react 3 ~ 10 hours, pH5 ~ 6, temperature of reaction 50 ~ 90 DEG C;
2) the coking waste liquid after adopting gac to make filtration under the condition of 55 ~ 85 DEG C adds heat decoloring, reaction 0.3 ~ 1.5h;
3) step 2 reaction adds H after terminating
2o
2oxidizing reaction 1 ~ 3h, evaporative crystallization, filtration, collect crystal;
4) crystal in step 3 is added in reactor, and add any amount alcohol organic solvent, fully mix, filter to obtain ammonia sulfate crystal;
5) in step 4 containing ammonium thiocyanate alcoholic solution, to carry out after evaporative crystallization obtaining ammonium thiocyanate crystal, collect the alcoholic solution evaporated and continue to add in step 4 and recycle.
Described catalyzer is the mixture of binuclear phthalocyanine cobalt sulfonic acid ammonia, molybdenum pentachloride, EDTA, and the mass ratio of this mixture and coking waste liquid is 0.3 ~ 10:10000.
Described H
2o
2be 5 ~ 10:100 with the mass ratio of coking waste liquid.
Described peak optimization reaction temperature is 65 DEG C.
Described optimum catalysis time 8h.
Described optimum oxidization time 2h.
Described alcohol organic solvent can select methyl alcohol or ethanol or propyl alcohol or arbitrary proportion mixture.
The invention has the beneficial effects as follows:
The present invention takes simple preparation technology to prepare ammonium sulfate and ammonium thiocyanate simultaneously, and purification process is capable of circulation to carry out, industrial energy consumption is low, the rate of recovery of ammonium sulfate and ammonium thiocyanate is more than 98%, this technique no waste is discharged simultaneously, belong to green purifying technique, there is high-recovery, low cost, high purity, free of contamination advantage.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
From coking waste liquid, extract a method for ammonium sulfate and monoammonium sulfate simultaneously, comprise the following steps:
1) first add agitator by after the coking waste liquid filtering and impurity removing of 1000mL, blast air, and add 0.5g catalyzer simultaneously, react 8 hours, pH5 ~ 6, temperature of reaction 65 DEG C;
2) under the condition of 80 DEG C, heating activated carbon is made to decolour, reaction 1h;
3) step 2 reaction adds 80mLH after terminating
2o
2oxidizing reaction 2h, collecting by filtration crystal after evaporative crystallization;
4) crystal in step 3 is added in reactor, and add ethanol, stir 30min, filter to obtain ammonia sulfate crystal;
5) in step 4 solution, ammonium thiocyanate is dissolved in liquid ethanol, after evaporative crystallization ammonium thiocyanate crystal, simultaneously remaining ethanol continues to add in step 4 and recycles.
Obtain ammonium thiocyanate 123.07g, purity is 99.35%; Ammonium sulfate 89.01g, purity is 99.01%;
Embodiment 2
From coking waste liquid, extract a method for ammonium sulfate and monoammonium sulfate simultaneously, comprise the following steps:
1) first add agitator by after the coking waste liquid filtering and impurity removing of 1000mL, blast air, and add 0.3g catalyzer simultaneously, react 6 hours, pH5 ~ 6, temperature of reaction 55 DEG C;
2) under the condition of 80 DEG C, heating activated carbon is made to decolour, reaction 0.5h;
3) step 2 reaction adds 60mLH after terminating
2o
2oxidizing reaction 2h, collecting by filtration crystal after evaporative crystallization;
4) crystal in step 3 is added in reactor, and add methyl alcohol, stir 20min, filter to obtain ammonia sulfate crystal;
5) in step 4 solution, ammonium thiocyanate is dissolved in liquid methanol, after evaporative crystallization ammonium thiocyanate crystal, simultaneously remaining methyl alcohol continues to add in step 4 and recycles.
Obtain ammonium thiocyanate 111.75g, purity is 98.65%; Ammonium sulfate 85g, purity is 98.16%;
Embodiment 3
From coking waste liquid, extract a method for ammonium sulfate and monoammonium sulfate simultaneously, comprise the following steps:
1) first add agitator by after the coking waste liquid filtering and impurity removing of 1000mL, blast air, and add 0.7g catalyzer simultaneously, react 9 hours, pH5 ~ 6, temperature of reaction 75 DEG C;
2) under the condition of 80 DEG C, heating activated carbon is made to decolour, reaction 1.5h;
3) step 2 reaction adds 100mLH after terminating
2o
2oxidizing reaction 2h, collecting by filtration crystal after evaporative crystallization;
4) crystal in step 3 is added in reactor, and add propyl alcohol, stir 40min, filter to obtain ammonia sulfate crystal;
5) in step 4 solution, ammonium thiocyanate is dissolved in liquid propyl alcohol, after evaporative crystallization ammonium thiocyanate crystal, simultaneously remaining propyl alcohol continues to add in step 4 and recycles.
Obtain ammonium thiocyanate 122.67g, purity is 99.07%; Ammonium sulfate 87.13g, purity is 98.65%.
The data that integrated embodiment 1,2,3 obtains, adopt this technique to extract ammonium thiocyanate in coking waste liquid and ammonium sulfate for existing extraction process, purity is high.
Claims (7)
1. from coking waste liquid, extract a method for ammonium sulfate and monoammonium sulfate simultaneously, it is characterized in that, comprise the following steps:
1) first add agitator by after coking waste liquid filtering and impurity removing, blast air, and add catalyzer simultaneously, react 3 ~ 10 hours, pH5 ~ 6, temperature of reaction 50 ~ 90 DEG C;
2) the coking waste liquid after adopting gac to make filtration under the condition of 55 ~ 85 DEG C adds heat decoloring, reaction 0.3 ~ 1.5h;
3) step 2 reaction adds H after terminating
2o
2oxidizing reaction 1 ~ 3h, evaporative crystallization, filtration, collect crystal;
4) crystal in step 3 is added in reactor, and add any amount alcohol organic solvent, fully mix, filter to obtain ammonia sulfate crystal;
5) in step 4 containing ammonium thiocyanate alcoholic solution, to carry out after evaporative crystallization obtaining ammonium thiocyanate crystal, collect the alcoholic solution evaporated and continue to add in step 4 and recycle.
2. a kind of method simultaneously extracting ammonium sulfate and ammonium thiocyanate from coking waste liquid according to claim 1, it is characterized in that, described catalyzer is the mixture of binuclear phthalocyanine cobalt sulfonic acid ammonia, molybdenum pentachloride, EDTA, and the mass ratio of this mixture and coking waste liquid is 0.3 ~ 10:10000.
3. a kind of method simultaneously extracting ammonium sulfate and ammonium thiocyanate from coking waste liquid according to claim 1, is characterized in that, described H
2o
2be 5 ~ 10:100 with the mass ratio of coking waste liquid.
4. a kind of method simultaneously extracting ammonium sulfate and ammonium thiocyanate from coking waste liquid according to claim 1, is characterized in that, described peak optimization reaction temperature is 65 DEG C.
5. a kind of method simultaneously extracting ammonium sulfate and ammonium thiocyanate from coking waste liquid according to claim 1, is characterized in that, described optimum catalysis time 8h.
6. a kind of method simultaneously extracting ammonium sulfate and ammonium thiocyanate from coking waste liquid according to claim 1, is characterized in that, described optimum oxidization time 2h.
7. a kind of method simultaneously extracting ammonium sulfate and ammonium thiocyanate from coking waste liquid according to claim 1, is characterized in that, described alcohol organic solvent can select methyl alcohol or ethanol or propyl alcohol or arbitrary proportion mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510434396.5A CN105110351A (en) | 2015-07-23 | 2015-07-23 | Method used for simultaneous extraction of ammonium sulfate and ammonium thiocyanate from coking waste liquid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510434396.5A CN105110351A (en) | 2015-07-23 | 2015-07-23 | Method used for simultaneous extraction of ammonium sulfate and ammonium thiocyanate from coking waste liquid |
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|---|---|
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| CN201510434396.5A Pending CN105110351A (en) | 2015-07-23 | 2015-07-23 | Method used for simultaneous extraction of ammonium sulfate and ammonium thiocyanate from coking waste liquid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108423906A (en) * | 2018-03-16 | 2018-08-21 | 山西瑞赛科环保科技有限公司 | A kind of wastewater treatment method of substituting thioureido production |
| CN108439430A (en) * | 2018-05-10 | 2018-08-24 | 扬州康龙环保工程有限公司 | The method that ammonium thiocyanate and ammonium sulfate are extracted in oven gas ammonia process of desulfurization waste liquid |
| CN113072473A (en) * | 2021-04-14 | 2021-07-06 | 山西瑞赛科环保科技有限公司 | Clean production method for substituted thiourea |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1277245A (en) * | 2000-04-20 | 2000-12-20 | 江苏苏钢集团有限公司 | Coke-oven gas desulfurizing and decyanating process |
| CN102976361A (en) * | 2012-12-10 | 2013-03-20 | 北京旭阳化工技术研究院有限公司 | Method for extracting high-purity ammonium thiocyanate and ammonium sulphate from coking desulfurization/decyanation waste liquor |
| CN103030207A (en) * | 2012-12-28 | 2013-04-10 | 安徽工业大学 | Method for treating ammonia desulfurization waste liquid by oxidation method |
-
2015
- 2015-07-23 CN CN201510434396.5A patent/CN105110351A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1277245A (en) * | 2000-04-20 | 2000-12-20 | 江苏苏钢集团有限公司 | Coke-oven gas desulfurizing and decyanating process |
| CN102976361A (en) * | 2012-12-10 | 2013-03-20 | 北京旭阳化工技术研究院有限公司 | Method for extracting high-purity ammonium thiocyanate and ammonium sulphate from coking desulfurization/decyanation waste liquor |
| CN103030207A (en) * | 2012-12-28 | 2013-04-10 | 安徽工业大学 | Method for treating ammonia desulfurization waste liquid by oxidation method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108423906A (en) * | 2018-03-16 | 2018-08-21 | 山西瑞赛科环保科技有限公司 | A kind of wastewater treatment method of substituting thioureido production |
| CN108439430A (en) * | 2018-05-10 | 2018-08-24 | 扬州康龙环保工程有限公司 | The method that ammonium thiocyanate and ammonium sulfate are extracted in oven gas ammonia process of desulfurization waste liquid |
| CN108439430B (en) * | 2018-05-10 | 2020-08-25 | 扬州康龙环保工程有限公司 | Method for extracting ammonium thiocyanate and ammonium sulfate from coke oven gas ammonia-process desulfurization waste liquid |
| CN113072473A (en) * | 2021-04-14 | 2021-07-06 | 山西瑞赛科环保科技有限公司 | Clean production method for substituted thiourea |
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Application publication date: 20151202 |