CN104876243A - Cleaning method of biurea mother liquid - Google Patents
Cleaning method of biurea mother liquid Download PDFInfo
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- CN104876243A CN104876243A CN201510178213.8A CN201510178213A CN104876243A CN 104876243 A CN104876243 A CN 104876243A CN 201510178213 A CN201510178213 A CN 201510178213A CN 104876243 A CN104876243 A CN 104876243A
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- dicarbonamide
- hydrazo
- mother liquor
- hydrochloric acid
- sodium
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Abstract
The invention discloses a cleaning method of a biurea mother liquid. The cleaning method comprises the following specific steps: (A) recovering biurea particles with a biurea mother liquid, and absorbing a hydrogen chloride gas into a hydrochloric acid of which the hydrogen chloride content is 11%-15%; (B) separating the 11%-15% hydrochloric acid from separated sodium chloride to obtain a mother liquid A and sodium chloride; (C) absorbing the hydrogen chloride gas with the mother liquid A until the hydrogen chloride content is 31%, and obtaining a mixture of the hydrochloric acid and ammonia chloride crystal; (D) separating the mixture of the hydrochloric acid and the ammonia chloride crystal to obtain the hydrochloric acid and ammonia chloride; and (E) respectively washing the ammonia chloride and the sodium chloride crystal to be neutral, and drying. The cleaning method disclosed by the invention has the beneficial effects that the ammonia chloride and the sodium chloride in the biurea mother liquid are respectively recovered and changed into treasures, so that the emission of sewage is reduced; the comprehensive utilization rate of the biurea mother liquid is improved; the blank that a lot of inorganic salt in the biurea mother liquid cannot be treated or recovered at present is filled; low-cost management with the biurea mother liquid is realized; resources are recovered; and the economic benefits are significant.
Description
Technical field
The present invention relates to environment and re-sources and utilize technical field, be specifically related to a kind of cleaning method of hydrazo-dicarbonamide mother liquor.
Background technology
Hydrazo-dicarbonamide (Biurea) molecular formula: C
2h
6n
4o
2, be the intermediate producing Cellmic C 121.Cellmic C 121 is low due to nontoxic, noresidue, price, and be current purposes one of whipping agent the most widely, its consumption accounts for more than 90% of whipping agent total amount.
Hydrazo-dicarbonamide is the middle product of downstream fine chemistry industry derived in chlor-alkali industry, and main production raw material is urea and chlorine, caustic soda, and as shown in Figure 1, principle is as follows for its hydrochloric acid condensation method technological process of production:
Clorox synthesizes: NaOH+Cl
2→ NaClO+NaCl+H
2o
Hydrazine hydrate synthesizes: NaOH+NaClO+NH
2cONH
2→ NH
2nH
2h
2o+Na
2cO
3+ NaCl
Neutralization: 2HCl+Na
2cO
3→ 2 NaCl+H
2o+CO
2
Condensation: NH
2nH
2h
2o+2HCl → (NH
3nH
3) Cl
2+ H
2o
(NH
3NH
3)Cl
2+NH
2CONH
2→NH
2CONHNHCONH
2+2NH
4Cl
Impure sodium carbonate in the hydrazine hydrate of synthesis procedure synthesis, after cryogenic freezing impurity removal and purification, still nubbin sodium carbonate, in sodium carbonate hydrochloric acid and after, add urea and at high temperature carry out condensation reaction with hydrochloric acid and generate hydrazo-dicarbonamide.Hydrazo-dicarbonamide filtration washing can generate Cellmic C 121 to afterwards neutral and chlorine reaction.
Produce a large amount of waste liquid containing ammonia nitrogen due to final in the process of condensation operation hydrazo-dicarbonamide, in waste liquid, also comprise Cl
-, Na
+plasma, complicated, wherein Cl
-content between 200-220g/L, NH
4 +content, between 40-50g/L, if not treated direct discharge, can make body eutrophication, harm ecotope.Conventional sewage treatment process is the treatment process of " deamination-biochemical treatment-qualified discharge ", the method except to add in alkali and except, also need thin up, physico-chemical pretreatment, add carbon source and carry out biochemical second-stage treatment, treatment unit is large, complex procedures and processing costs is high.
The domestic treatment research to hydrazo-dicarbonamide mother liquor at present, mainly contain following several respects: (1) evaporation concentration reclaims sodium-chlor, ammonia chloride craft, two kinds of products can be obtained respectively, but the light hydrazine hydrate of concentration 3-5% is adopted owing to producing hydrazo-dicarbonamide, produce 1 ton of hydrazo-dicarbonamide, mother liquor amount is 12-15 ton, and in hydrazo-dicarbonamide mother liquor, water content is up to about 70%, and it is large all to evaporate then steam consumption.(2) add alkali stripping-washing and reclaim weak ammonia technique.Experiment proves, water at normal temperature is washed the weak ammonia concentration obtained and is generally no more than 2 ~ 3%, and the lower concentration weak ammonia amount of generation is very big, and use value is very low, and can not directly discharge, and becomes larger source of pollution.(3) oxidizing process, generally, oxidizing process is only applicable to the process of low-concentration ammonia-nitrogen sewage.And utilize the ammonia nitrogen in high density in the hypochlorite oxidation condensed mother liquor produced in chlor-alkali industry and organism, aequum is very big, the secondary chlorine products output of general chlor-alkali enterprises can not meet the demands far away and also processing costs too high.Oxidizing process running cost is higher, and recover materials is worth little, and does not have too large meaning to chlor-alkali or other industry production.Above-mentionedly add the sewage treatment process such as alkali stripping, oxidation, consider the removal of condensed mother liquor middle and high concentration ammonia-state nitrogen only unilaterally, and the inorganic salt still containing complicated high density in sewage after process, suppress follow-up biochemical wastewater treatment.
In addition, above-mentioned latter two hydrazo-dicarbonamide mother liquor processing method is only process as sewage after recovery intermediate hydrazo-dicarbonamide, and the waste liquid after process directly discharges, and does not recycle for the composition in mother liquor, causes great waste to resource; And aforesaid method is in the process of process, needs to drop into a large amount of manpower and materials, thus indirectly improve the production cost of hydrazo-dicarbonamide, seriously hinder further developing of industry.
Summary of the invention
Object of the present invention is just in order to overcome the deficiency of above-mentioned technology, and a kind of cleaning method of hydrazo-dicarbonamide mother liquor is provided, solve a large amount of inorganic salt in hydrazo-dicarbonamide mother liquor and can not get processing the problem of (or being difficult to low-cost processes), turn waste into wealth, reclaim the method for byproduct of reaction.
The object of the invention is to have come by following technical solution.The cleaning method of this hydrazo-dicarbonamide mother liquor, the method concrete steps are as follows: after hydrazo-dicarbonamide mother liquor filtered and recycled hydrazo-dicarbonamide particulate, reclaim the sodium-chlor crystallization of separating out when absorbing hydrogen chloride gas to hydrogen chloride content is 11-15%, in hydrazo-dicarbonamide mother liquor, sodium-chlor crystallization is complete; Through whizzer solid-liquid separation, obtain mother liquor A and sodium-chlor crystallization; Mother liquor A continues the mixture that absorbing hydrogen chloride gas obtains ammonium chloride crystals and hydrochloric acid when hydrogen chloride content is 31%, by the mixture separation of hydrochloric acid and ammonia chloride crystallization, obtain hydrochloric acid and ammonia chloride crystallization, ammonia chloride and sodium-chlor crystallization are washed respectively to neutrality, dry.
Described hydrazo-dicarbonamide mother liquor main component is sodium chloride content 17-20%, ammonium chloride content 10-12%, PH=5 weakly acid soln.
In described hydrazo-dicarbonamide mother liquor, the recovery method of hydrazo-dicarbonamide is: by hydrazo-dicarbonamide mother liquor send into millipore filter, filtering and removing hydrazo-dicarbonamide, hydrazo-dicarbonamide mother liquor send into absorption cell, pass into hydrogen chloride gas, absorb to content of hydrochloric acid be 11-15%.
Mechanism of the present invention: the present invention with hydrazo-dicarbonamide mother liquor for raw material, wherein content of hydrochloric acid is improved by absorbing hydrogen chloride gas, due to common-ion effcet, the sodium-chlor in solution, ammonium chloride are separated out respectively, and separation, washing, drying obtain hydrochloric acid, sodium-chlor, ammonium chloride three kinds of products.After sodium-chlor denitrogenation processing, can be used for chlor-alkali enterprises as the raw material producing caustic soda, also can produce soda ash, other Chemicals, ore smeltings etc.Ammonium chloride is a kind of high-quality chemical fertilizer, also can be used for the industries such as drying battery, store battery, ammonium salt, tanning, plating, medicine, photograph, electrode, tackiness agent.Washing water can retrieval system, and merge with hydrazo-dicarbonamide mother liquor the process carrying out next round, evaporation condensed water is for washing sodium-chlor, ammonium chloride.
Beneficial effect of the present invention is: hydrazo-dicarbonamide mother liquor, by above-mentioned art breading, not only reclaims byproduct sodium-chlor and ammonium chloride, and manufacture hydrochloric acid, improves the comprehensive utilization ratio of waste liquid.Adopt this technique, produce hydrazo-dicarbonamide per ton, 2.4 tons, the recyclable sodium-chlor of its mother liquor, reclaim ammonium chloride 1 ton, by-product 31% technical hydrochloric acid 15 tons.Resource in Recycling of waste liquid, the present invention is a kind of hydrazo-dicarbonamide new cleanproduction process in fact.
Accompanying drawing explanation
Fig. 1 is the production scheme of hydrazo-dicarbonamide.
Fig. 2 is hydrazo-dicarbonamide mother liquor new cleanproduction process schema.
Embodiment
Below by embodiment, the present invention is further elaborated, and help is understood the present invention by embodiment better, but the present invention is not limited only to following embodiment.
The cleaning method of this hydrazo-dicarbonamide mother liquor of the present invention, the method concrete steps are as follows: after hydrazo-dicarbonamide mother liquor filtered and recycled hydrazo-dicarbonamide particulate, reclaim the sodium-chlor crystallization of separating out when absorbing hydrogen chloride gas to hydrogen chloride content is 11-15%, in hydrazo-dicarbonamide mother liquor, sodium-chlor crystallization is complete; Through whizzer solid-liquid separation, obtain mother liquor A and sodium-chlor crystallization; Mother liquor A continues the mixture that absorbing hydrogen chloride gas obtains ammonium chloride crystals and hydrochloric acid when hydrogen chloride content is 31%, by the mixture separation of hydrochloric acid and ammonia chloride crystallization, obtain hydrochloric acid and ammonia chloride crystallization, ammonia chloride and sodium-chlor crystallization are washed respectively to neutrality, dry.
Described hydrazo-dicarbonamide mother liquor main component is sodium chloride content 17-20%, ammonium chloride content 10-12%, PH=5 weakly acid soln.
In described hydrazo-dicarbonamide mother liquor, the recovery method of hydrazo-dicarbonamide is: by hydrazo-dicarbonamide mother liquor send into millipore filter, filtering and removing hydrazo-dicarbonamide, hydrazo-dicarbonamide mother liquor send into absorption cell, pass into hydrogen chloride gas, absorb to content of hydrochloric acid be 11-15%.
One, treating processes, step and result:
1. synthesize hydrazo-dicarbonamide
Get in 1000ml tetra-mouthfuls of round-bottomed flasks that 500ml hydrazine hydrate (hydrazine content 36g/L) adds with mechanical stirring, thermometer, prolong, dropping funnel on, flask is placed in temp .-regulating electric heating boiler clothing.Urea 70.2g is dropped into the ratio of 1:3.9 in hydrazine content.Dissolve completely until urea, in round-bottomed flask, add 31% hydrochloric acid with dropping funnel.When pH value in flask is 4-5, is heated to 107-108 DEG C, and keeps constant temperature.Control hydrochloric acid dripping quantity, maintenance ph value of reaction is 4-5, until arrive reaction end.Through the hydrazo-dicarbonamide that vacuum pump and Büchner funnel suction filtration reclaim mother liquor, washing, drying obtain purity 94-98%, yield 88-91%.
Synthesis hydrazo-dicarbonamide reaction equation is as follows:
(1) neutralization reaction
2HCl+Na
2CO
3→2NaCl+H
2O+CO
2
(2) condensation reaction
NH
2NH
2·H
2O+2HCl→NH
2NH
2·2HCl+H
2O
NH
2NH
2·2HCl+NH
2CONH
2→NH
2CONHNHCONH
2+2NH
4Cl
Table one produces hydrazo-dicarbonamide experimental result and data
| Number of times | Hydrazine hydrate volume (ml) | Hydrazo-dicarbonamide quality (g) | Hydrazo-dicarbonamide purity (%) | Yield (%) |
| 1 | 500 | 59.9 | 97.5 | 88 |
| 2 | 500 | 63.6 | 95 | 91 |
| 3 | 500 | 62.2 | 96 | 90 |
2. hydrazo-dicarbonamide mother liquid disposal
Hydrazo-dicarbonamide mother liquor, by vacuum pump and Büchner funnel suction filtration, removes the micro-hydrazo-dicarbonamide wherein carried secretly.Get filtrate (PH=5) 1000ml, add in the Florence flask of band inlet pipe, vapor pipe.Inlet pipe absorbs under inserting liquid level, and vapor pipe connects the Florence flask of an in-built caustic soda soln, under caustic soda soln liquid level is inserted in outlet, absorbs tail gas, alkali cleaning flask connects drain with caustic soda.Cooling bath put into by absorption bottle and alkali cleaning bottle, keeps absorption temperature≤40 DEG C.Pass into hydrogen chloride gas in inlet pipe, observe absorption liquid, after passing into hydrogenchloride 1min, start there is NaCL crystallization.When HCl content is elevated to 11-14%, stops passing into hydrogen chloride gas, be incubated with vacuum pump and Büchner funnel suction filtration, collect the sodium-chlor and dilute hydrochloric acid that leach.Dilute hydrochloric acid returns in Florence flask, continues absorbing hydrogen chloride gas, controls absorption temperature, continues to pass into hydrogen chloride gas to saturated, and with vacuum pump and Büchner funnel suction filtration, separating ammonium chloride and hydrochloric acid, analyze content of hydrochloric acid.Sodium-chlor and ammonium chloride crystals, respectively with after saturated solution drip washing to neutrality, send into oven drying.
Table two hydrazo-dicarbonamide mother liquor experimental result and data
Two, the instrument related in process:
SHZ-D (111) circulating water type vacuum pump, J-J-1 type timing electric mixer, temp .-regulating electric heating cover, three mouthfuls of round-bottomed flasks, four mouthfuls of round-bottomed flasks, glass ground joint joint, Erlenmeyer flask, plug, condenser, threeway glass ground joint joint, thermometer 2 (0-300 DEG C), graduated cylinders, beaker, iron stand, Büchner funnel, chemical analysis filter paper, filter flask, loft drier, table balance.
The sodium chloride content that hydrazo-dicarbonamide clean preparation method of the present invention finally obtains reaches the standard of Exposure to Sunlight Industrial Salt standard GB/T/T5462-2003 first grade, and ammonium chloride content reaches ammonium chloride standard GB/T 2946-2008 agricultural ammonium chloride grade standard.
By the summary to above-mentioned experiment, can draw: by by hydrazo-dicarbonamide mother liquor absorbing hydrogen chloride, sodium-chlor contained by can making wherein, ammonium chloride are separated out respectively, be convenient to the ammonia-state nitrogen in hydrazo-dicarbonamide and inorganic salt to be converted into the sodium-chlor and ammonium chloride with real economy value, by-product hydrochloric acid simultaneously, not only reduce sewage discharge, and filled up the blank that at present inorganic salt a large amount of in hydrazo-dicarbonamide mother liquor be can not get to process or recovery, hydrazo-dicarbonamide per ton recyclable sodium-chlor 2.3-2.4 ton, reclaim ammonium chloride 1 ton, remarkable in economical benefits, simultaneously can also by-product hydrochloric acid.
Treatment process of the present invention, is applicable to industrialization and runs.The industrialization schema of hydrazo-dicarbonamide mother liquor clean preparation method of the present invention as shown in Figure 2.
Claims (3)
1. the cleaning method of a hydrazo-dicarbonamide mother liquor, it is characterized in that: the method concrete steps are as follows: after hydrazo-dicarbonamide mother liquor filtered and recycled hydrazo-dicarbonamide particulate, reclaim the sodium-chlor crystallization of separating out when absorbing hydrogen chloride gas to hydrogen chloride content is 11-15%, in hydrazo-dicarbonamide mother liquor, sodium-chlor crystallization is complete; Through whizzer solid-liquid separation, obtain mother liquor A and sodium-chlor crystallization; Mother liquor A continues the mixture that absorbing hydrogen chloride gas obtains ammonium chloride crystals and hydrochloric acid when hydrogen chloride content is 31%, by the mixture separation of hydrochloric acid and ammonia chloride crystallization, obtain hydrochloric acid and ammonia chloride crystallization, ammonia chloride and sodium-chlor crystallization are washed respectively to neutrality, dry.
2. the cleaning method of hydrazo-dicarbonamide mother liquor according to claim 1, is characterized in that: described hydrazo-dicarbonamide mother liquor main component is sodium chloride content 17-20%, ammonium chloride content 10-12%, PH=5 weakly acid soln.
3. the cleaning method of hydrazo-dicarbonamide mother liquor according to claim 1, it is characterized in that: in described hydrazo-dicarbonamide mother liquor, the recovery method of hydrazo-dicarbonamide is: hydrazo-dicarbonamide mother liquor is sent into millipore filter, filtering and removing hydrazo-dicarbonamide, hydrazo-dicarbonamide mother liquor sends into absorption cell, pass into hydrogen chloride gas, absorb to content of hydrochloric acid be 11-15%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114853638A (en) * | 2022-05-13 | 2022-08-05 | 宁夏日盛高新产业股份有限公司 | Production method and system of biurea |
| CN115960019A (en) * | 2022-12-30 | 2023-04-14 | 江苏索普化工股份有限公司 | Method for treating ADC foaming agent condensation mother liquor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN204079524U (en) * | 2014-07-14 | 2015-01-07 | 中国平煤神马集团开封东大化工有限公司 | A kind of high salt high ammonia-nitrogen sewage treatment system |
-
2015
- 2015-04-15 CN CN201510178213.8A patent/CN104876243A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN204079524U (en) * | 2014-07-14 | 2015-01-07 | 中国平煤神马集团开封东大化工有限公司 | A kind of high salt high ammonia-nitrogen sewage treatment system |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114853638A (en) * | 2022-05-13 | 2022-08-05 | 宁夏日盛高新产业股份有限公司 | Production method and system of biurea |
| CN115960019A (en) * | 2022-12-30 | 2023-04-14 | 江苏索普化工股份有限公司 | Method for treating ADC foaming agent condensation mother liquor |
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Application publication date: 20150902 |
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