CN104829029A - Treatment method of industrial wastewater from synthesis of allantoin - Google Patents
Treatment method of industrial wastewater from synthesis of allantoin Download PDFInfo
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Abstract
The invention discloses a treatment method of industrial wastewater from synthesis of allantoin and belongs to the field of a wastewater treatment technology. The method comprises the following steps: (1) carrying out decompression concentration on industrial wastewater from synthesis of allantoin, carrying out cooling crystallization, filtering, separating and recovering allantoin; (2) neutralizing a filtrate obtained from the step (1) with ammonia until the neutralization reaction endpoint is pH 7.0-8.2; (3) carrying out an urea hydrolysis reaction by adding a urease catalyst into a neutralization solution obtained from the step (2); (4) neutralizing a hydrolysis reaction solution obtained from the step (3) with sulfuric acid until the neutralization reaction endpoint is pH 5-6; (5) carrying out decompression concentration on a neutralization solution obtained from the step (4), carrying out cooling crystallization, and filtering; (6) carrying out decompression concentration on a filtrate obtained from the step (5) to obtain viscous residues; and (7) merging distillates obtained from the steps (1) (5)(6), and processing. By the above method, environment pollution of an allantoin project is fundamentally solved, and comprehensive production costs of allantoin are also reduced.
Description
Technical field
The present invention relates to the treatment process of trade effluent, be specifically related to a kind for the treatment of process of trade effluent of synthetic allantoin, the method can environmental protect quality realize comprehensive utilization of energy, belongs to environment protection and energy conservation field.
Background technology
Wallantoin is widely used in the fields such as medicine, daily-use chemical industry and agricultural, mainly adopts oxoethanoic acid and urea both at home and abroad under sulfuric acid (or other mineral acid) catalysis through the production technique of condensation reaction synthetic allantoin.German Patent (DE1939924) discloses the technique of synthetic allantoin under mineral acid catalysis, and product yield is less than 60%; Japanese Patent Publication (JP5059014) reports hydrochloric acid catalysis synthetic allantoin and product purification technique, product yield about 60%.Chinese patent (CN1067993C) disclose with oxalic dialdehyde, hydrogen peroxide, urea, the vitriol oil and the granulated active carbon method that is raw material one-step synthesis wallantoin, product yield can reach more than 60%.The method that it is Material synthesis wallantoin that Chinese patent (CN1765888A) discloses with glyoxylic acid solution, urea, catalyzer.The people such as Yin Dehong report with oxalic dialdehyde and urea for raw material at " Liaoning chemical industry " in August, 2002, adopt H
2o
2oxidation, catalyzing and condensing two step synthetic method wallantoin, inquire into oxidation mechanism, propose the synthetic method making catalyzer with mixture of sulfuric phosphoric acid, wallantoin productive rate is 60.7 %.Although similar patent or periodical literature are reported more, but along with the continuous progress of ethanol acid production technology in the recent decade, the most frequently used wallantoin synthetic method being really applied to suitability for industrialized production remain with oxoethanoic acid, urea for main raw material take sulfuric acid as the synthetic method of catalyzer, the method yield higher (can 69% ~ 71% be reached), cost is lower, is thus generally adopted by domestic and international most wallantoin manufacturing enterprise.The maximum problem of the oxoethanoic acid be generally used, urea, sulfuric acid catalysis synthetic method is produce a large amount of trade effluents in production process, and is difficult to administer.
According to investigation, domestic wallantoin output rises year by year, domestic all on the rise with outlet.Through technological improvement for many years, the best technico-economical comparison that the enterprise of domestic actual production wallantoin can reach is: in oxoethanoic acid wallantoin molar yield 71%, namely often 1 ton of wallantoin product is produced, about need consumption 50% aqueous glyoxylic acid 1.25 tons, 2 tons, urea, 98% vitriol oil 0.33 ton, produce the strongly acid wastewater about 11.5 tons containing urea, ammonium sulfate, wallantoin, sulfuric acid and a certain amount of by product simultaneously, waste water COD is about 6.5-7 ten thousand, ammonia nitrogen > 1500, seriously exceedes applicable legal emissions index.
The feature of wallantoin trade effluent is: COD is high, ammonia nitrogen is high, component is many, and its difficulty in treatment is: each component is difficult to be separated, and can not directly recycle.This waste water because of containing the impurity having a strong impact on quality product, therefore can not be applied mechanically by direct circulation, and wastewater processing technology difficulty is comparatively large, and processing cost is very high.Again because its ammonium sulfate and sulfuric acid content too high, with in mineral alkali and after, inorganic salt content is very high, therefore it is up to standard to adopt biodegradable method also cannot directly process.
About the administering method of the trade effluent of synthetic allantoin, Chinese patent (CN102060392A) discloses the method for producing waste liquid synthesis of organo-phosphines anti-incrustation corrosion inhibitor with wallantoin, for Treatment of Industrial Water; Chinese patent (CN201210593306) discloses the method for a kind of wallantoin synthesis waste liquid synthetic powder nitric acid.Pertinent literature is less, and domestic technique personnel lack the further investigation to this environmental issue.
According to investigations, between 2014-2015, domestic You Duojia wallantoin manufacturing enterprise is because wastewater treatment can not be up to standard and ordered stopping production by local environmental administration.Therefore, this environmental issue seriously constrains wallantoin industry development, and problem of environmental pollution becomes current outstanding problem in the urgent need to address.
The each component concentration of waste liquid is produced, a large amount of statistic data display by detecting wallantoin, about containing urea 8.70-9.57wt% in above-mentioned 11.5 tons of wallantoin waste liquids, pure 1.0-1.2 ton; Liquid containing ammonium sulfate 1.74-2.61wt%, pure 0.2-0.3 ton; Containing wallantoin 0.26-0.35wt%, pure 0.03-0.04 ton; Sulfur acid 0.87-1.74wt%, pure 0.1-0.2 ton; Containing by product allantoic acid 1.74-2.17wt%, pure 0.2-0.25 ton; Remaining component is water and other trace impurity.Namely the urea containing a small amount of product wallantoin, non-complete reaction in waste water and sulfuric acid and other materials (as ammonium sulfate, allantoic acid), this waste water COD and ammonia nitrogen numerical value all very high, be not suitable for direct discharge.
Summary of the invention
The trade effluent of synthetic allantoin is carried out harmless treatment and recycling by object of the present invention, has both effected a radical cure the pollution of wallantoin waste water to environment, again reduces the comprehensive production cost of wallantoin.Its principle is as follows: wherein, wallantoin product in waste water can reclaim further, ammonium sulfate is the conventional nitrogenous fertilizer of agricultural, have to recycle and be worth, urea, sulfuric acid also can all be converted into ammonium sulfate by chemical reaction and be able to Separation and Recovery, organic acid allantoic acid also can carry out innocuously transformation (allantoic acid is converted into its ammonium salt) by chemical reaction, and the mode of steaming except sludge incinerator being adopted to burn after moisture content is carried out harmless treatment and reclaims heat energy.So, then wallantoin trade effluent can reclaim wallantoin, ammonium sulfate and organic raffinat heat energy simultaneously, can realize comprehensive utilization of resources, and significantly reduces every environmental protection index of residue waste water (i.e. concentrated fraction), thus biochemical treatment can be passed through easily, realize qualified discharge.Described scheme is as follows:
The treatment process providing a kind of trade effluent of synthetic allantoin of the present invention, the method comprises the following steps:
Step 1: once concentration, crystallization filtration procedure, by the trade effluent concentrating under reduced pressure of synthetic allantoin, then decrease temperature crystalline, filters, Separation and Recovery wallantoin.
Step 2: a neutralization reaction process, by step 1 gained filtrate ammonia neutralization, one time neutralization reaction terminal is pH7.0-8.2, and make sulfuric acid conversion be ammonium sulfate, allantoic acid is converted into allantoic acid ammonium.Wherein, this neutralization reaction terminal can realize the conversion of material, can provide excellent reaction conditions (optimum reaction condition of urase catalyzed reaction is about pH8) again for follow-up hydrolysis of urea reaction.
Step 3: hydrolysis of urea reaction process, adds urase catalyzer in step 2 gained neutralizer, hydrolysis of urea reaction occurs, makes hydrolysis of urea be (NH
4)
2cO
3, urase catalyzer has the katalysis of hydrolysis of urea reaction specificity.
Step 4: Two-step neutralization reaction process, neutralized by step 3 gained hydrolysis reaction liquid sulfuric acid, Two-step neutralization reaction end is pH5-6, makes (NH
4)
2cO
3be converted into ammonium sulfate.
Step 5: secondary concentration, crystallization filtration procedure, by step 4 gained neutralizer concentrating under reduced pressure, decrease temperature crystalline, filters, Separation and Recovery ammonium sulfate.
Step 6: mother liquid disposal process, by step 5 gained filtrate reduced in volume, thick residue send sludge incinerator to burn.
Step 7: concentrated fraction treating processes, merges gained concentrating under reduced pressure fraction in step 1, step 5 and step 6, carry out biochemical treatment, qualified discharge or recycling.
In above steps: the trade effluent of synthetic allantoin refers to the trade effluent produced with the operational path synthetic allantoin of oxoethanoic acid, urea to be raw material with sulfuric acid be catalyzer, and its composition comprises: wallantoin, urea, ammonium sulfate, sulfuric acid, allantoic acid, water and other impurity.
Wherein, in step 1, doubly, primary crystallization temperature is 0-5 DEG C to the 0.25-0.4 of once concentration terminal to be concentrated solution weight be waste water stoste (trade effluent of former synthetic allantoin) weight, and the primary crystallization time is 2-3 hour.
Wherein, in step 2, once neutralization uses the mass percent concentration of ammoniacal liquor to be 20-25%.
Wherein, in step 3, in urase and waste water stoste, urea-containing mass ratio is 0.005-0.02:1, and hydrolysising reacting temperature is 25-45 DEG C, and hydrolysis time is 8-10 hour.
Wherein, in step 4, the mass percent concentration of the sulfuric acid of Two-step neutralization use is 50-70%.
Wherein, in steps of 5, secondary crystal temperature is 5-10 DEG C, and the secondary crystal time is 5-6 hour.
Wherein, in step 6, the terminal of concentrating under reduced pressure is without distillate under temperature 70-80 DEG C and vacuum tightness >=0.095Mpa.
Wherein, in steps of 5, its concentrating under reduced pressure degree is so that ammonium sulfate crystallization is advisable.In step 1 and 5, adopt conventional concentrating under reduced pressure condition.
Particularly, the method comprises following steps:
Step 1: once concentration, crystallization filtration procedure, by the trade effluent concentrating under reduced pressure of synthetic allantoin, decrease temperature crystalline, filtration, Separation and Recovery wallantoin, the 0.25-0.4 of striking point to be concentrated solution weight be waste water stoste weight doubly, primary crystallization temperature is 0-5 DEG C, and the primary crystallization time is 2-3 hour.
Step 2: a neutralization reaction process, once neutralizes step 1 gained filtrate with mass concentration 20-25% ammoniacal liquor, and a neutralization reaction terminal is pH7.0-8.2, and the consumption of ammoniacal liquor is as the criterion so that pH value is up to standard.
Step 3: hydrolysis of urea reaction process, adds urase catalyzer, carries out hydrolysis of urea reaction in step 2 gained neutralizer, wherein, in urase and waste water stoste, urea-containing mass ratio is 0.005-0.02:1, and hydrolysising reacting temperature is 25-45 DEG C, and hydrolysis time is 8-10 hour.
Step 4: Two-step neutralization reaction process, the sulfuric acid of step 3 gained hydrolysis reaction liquid mass concentration 50-70% is carried out Two-step neutralization, and Two-step neutralization reaction end is pH5-6, and the consumption of sulfuric acid is as the criterion so that pH value is up to standard.
Step 5: secondary concentration, crystallization filtration procedure, by step 4 gained neutralizer concentrating under reduced pressure, decrease temperature crystalline, filter, Separation and Recovery ammonium sulfate, secondary crystal temperature is 5-10 DEG C, and the secondary crystal time is 5-6 hour.
Step 6: mother liquid disposal process, by step 5 gained filtrate reduced in volume, the thick residue obtained send sludge incinerator to burn.
Step 7: concentrated fraction treating processes, merges gained fraction in step 1, step 5 and step 6, discharge or recycling after biochemical treatment.
Beneficial effect of the present invention comprises:
(1) the present invention adopts chemical conversion and separation method, by twice N-process, twice condensing crystal process and a urea seeding hydrolysis reaction, make polycomponent, high COD, the main ingredient that the wallantoin of high ammonia nitrogen is produced in waste liquid is able to effective separation, reclaim wallantoin respectively, ammonium sulfate and raffinate burn the heat energy produced, and make the concentrated fraction COD of output and ammonia nitrogen index be reduced to and can process scope up to standard easily, not only can solve the unmanageable technical barrier of existing wallantoin trade effluent, comprehensive utilization of resources can also be realized, reduce wastewater treatment and the comprehensive production cost of wallantoin.
(2) present invention process mild condition, production unit is simple, and cost for wastewater treatment is low, is suitable for suitability for industrialized production, can create good economic benefit and social benefit for enterprise.
(3) adopt the rate of recovery of present method wallantoin to be greater than 90%, the rate of recovery of ammonium sulfate is greater than 85%, and the purity of ammonium sulfate is greater than 97%, and recovering effect is remarkable.
Accompanying drawing explanation
Fig. 1 is current existing wallantoin synthesis technique schematic flow sheet;
Fig. 2 is the process flow diagram of the treatment process of the trade effluent of synthetic allantoin provided by the invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Starting material set-up procedure of the present invention (be not included within content of the present invention, be only and the invention provides representative starting material---wallantoin trade effluent):
Particularly, see Fig. 1, carry out the preparation of wallantoin trade effluent both at home and abroad according to current the most frequently used oxoethanoic acid-urea-sulfuric acid catalysis synthetic route.Preparation method is as follows:
The aqueous glyoxylic acid 2000kg of 40wt% is dropped in 5000L lass lining condensation reaction still, start and stir, add urea 2500-2600kg, add vitriol oil 400-450kg, be heated to 80-85 DEG C, and in 80-85 DEG C of insulation reaction, timing is started when precipitation solid, be incubated after 1-1.5 hour, be cooled to 65-75 DEG C, continue at 65-75 DEG C of insulation reaction 16-18 hour.Then be down to 25-35 DEG C, centrifugation, washing filter cake, until washing lotion pH7.0, dry, get filtration cakes torrefaction, obtain wallantoin finished product and be about 1.25-1.28 ton.Filtrate and washing lotion merge, and mixing, is called the trade effluent of synthetic allantoin, about 14-15 ton, and the waste water output of namely often producing 1 ton of wallantoin product is about 11-12 ton, as following waste water raw material required for the present invention.Wallantoin finished product is about 69-71% to oxoethanoic acid molar yield.
See Fig. 2, the invention provides a kind for the treatment of process of trade effluent of synthetic allantoin, first filtered by once concentration, crystallization, reclaim wallantoin product residual in wallantoin trade effluent; Mother liquor is once neutralized to pH7.0-8.2 with ammoniacal liquor again, is ammonium sulfate, allantoic acid is converted into allantoic acid ammonium by sulfuric acid conversion; Then add the catalytic hydrolysis that urase carries out urea, make hydrolysis of urea be (NH
4)
2cO
3; Use sulfuric acid Two-step neutralization to pH5-6 again, make (NH
4)
2cO
3be converted into ammonium sulfate; Filter through secondary concentration, crystallization, Separation and Recovery can be used as agricultural fertilizer or industrial ammonium sulfate again; Finally by mother liquor concentrations, residue sludge incinerator burns, the process of three concentrated gained fraction biochemical methods.
Embodiment 1, the preparation of the trade effluent of synthetic allantoin:
The aqueous glyoxylic acid 2000kg of 40wt% is dropped in 5000L condensation reaction still, start and stir, add urea 2560kg, add 98wt% vitriol oil 423kg, be heated to 80 DEG C, and in 80-82 DEG C of insulation reaction, timing is started when precipitation solid, be incubated after 1 hour, be cooled to 70-72 DEG C, continue at 70-72 DEG C of insulation reaction 17 hours.Then be cooled to 30 DEG C, centrifugation, washing filter cake, until washing lotion pH7.0, dry, get filtration cakes torrefaction, obtain wallantoin finished product 1280kg.Filtrate and washing lotion merge, and mixing, be called the trade effluent of synthetic allantoin, Weighing 14.72 tons (be equivalent to every output 1 ton of wallantoin finished product and be about output waste water 11.5 tons), as following example desired raw material of the present invention.Wallantoin finished product is 70.9% to the molar yield of oxoethanoic acid.
See table 1, learnt by analyzing and testing, the composition of this batch 14.72 tons of wallantoin trade effluents is:
Table 1
| Test item | Urea | Ammonium sulfate | Wallantoin | Sulfuric acid | Allantoic acid | Moisture content and other |
| Mass content (%) | 9.56 | 2.42 | 0.34 | 1.35 | 1.75 | 84.58 |
According to another detection, this batch of waste water COD=68750, ammonia nitrogen=1640.
Following example all with 1.15 tons in representative embodiment 1 gained wallantoin trade effluent for raw material, carry out the trial-production explanation of waste water treatment process of the present invention.Main ingredient and the environmental protection leading indicator of these 1.15 tons of waste water (i.e. the waste water of corresponding 0.1 ton of wallantoin product) are as shown in table 2:
Table 2
Embodiment 2:
First, the trade effluent of synthetic allantoin described in Example 1 1.15 tons, drops into concentrating under reduced pressure in once concentration still, until concentrated solution weight is 0.25 times (namely steam fraction and be about 862.5kg) of stoste weight.Concentrated solution is cooled to 0-2 DEG C, stirred crystallization 2 hours, centrifugation, is recycled wallantoin 4.2kg(and gives money as a gift as 3.59kg by actual measurement weight loss on drying 14.53%).Again gained filtrate is once neutralized to pH7.0 with ammoniacal liquor, consumes the ammoniacal liquor 39.5kg of concentration 20.01wt%.Then, adding urea-containing weight ratio in urase catalyzer 2.2kg(and waste water stoste is 0.02:1), temperature control 25-30 DEG C hydrolysis reaction 8 hours, makes hydrolysis of urea be (NH
4)
2cO
3.Use the dilute sulphuric acid Two-step neutralization of concentration 50wt% to pH5.0 again, make (the NH in feed liquid
4)
2cO
3be converted into ammonium sulfate, consume the dilute sulphuric acid 341kg of 50wt%.Then gained neutralizer secondary pressure is concentrated, cooling, in 5-6 DEG C of crystallization 5 hours, centrifugation, was recycled ammonium sulfate 254.7 kg.Subsequently, by filtrated stock concentrating under reduced pressure, until without distillate under temperature 70 C and vacuum tightness 0.098Mpa, terminate concentrated, while hot by thick residue barreled, send sludge incinerator to burn.Finally, three concentrating under reduced pressure gained fractions are merged, mixing, be weighed as 1105kg, detection COD is 165mg/L, BOD is 60mg/L, and ammonia nitrogen is 80mg/L, biochemical treatment system is sent to process, after process, detection COD is 43mg/L, BOD is 8mg/L, and ammonia nitrogen is 4.0mg/L, other index is all qualified, reaches existing national grade one discharge standard (GB8978-2002).
Brief summary: this instance data is the data of input 1.15 tons of waste water, by 11.5t waste water/1t product, every normal production 1 ton of wallantoin, gained waste water is through above-mentioned process, 35.9kg wallantoin, 2547kg ammonium sulfate and a certain amount of residue can be reclaimed and burn heat energy, the leading indicator such as COD, ammonia nitrogen of concentrated fraction (11.05 tons) declines to a great extent, and through conventional biochemical treatment, can reach existing national grade one discharge standard.In waste water, the rate of recovery of residual wallantoin is 91.82%; The rate of recovery of ammonium sulfate is that 87.62%(hydrolysis of urea and sulfuric acid neutralization are converted into the overall conversion of ammonium sulfate two-step reaction by 100% estimation, theoretical calculate, and total amount that is original and generation ammonium sulfate is 2906.8kg).After testing, the purity of ammonium sulfate is 98.37%, sells mainly as industrial raw material or as nitrogen fertilizer in agriculture.
Embodiment 3:
First, the trade effluent of synthetic allantoin described in Example 1 1.15 tons, drops into concentrating under reduced pressure in once concentration still, until concentrated solution weight is 0.3 times (namely steam fraction and be about 805kg) of stoste weight.Concentrated solution is cooled to 2-3 DEG C, stirred crystallization 2.5 hours, centrifugation, is recycled wallantoin 4.1kg(and gives money as a gift as 3.46kg by actual measurement weight loss on drying 15.6%).Again gained filtrate is once neutralized to pH7.3 with ammoniacal liquor, consumes the ammoniacal liquor 37.4kg of concentration 21.52wt%.Then, adding urea-containing weight ratio in urase catalyzer 1.1kg(and waste water stoste is 0.01:1), temperature control 28-32 DEG C hydrolysis reaction 8.5 hours, makes hydrolysis of urea be (NH
4)
2cO
3.Use the dilute sulphuric acid Two-step neutralization of concentration 55.4% to pH5.5 again, make (the NH in feed liquid
4)
2cO
3be converted into ammonium sulfate, consume the dilute sulphuric acid 305.7kg of 55.4wt%.Then gained neutralizer secondary pressure is concentrated, cooling, in 7-8 DEG C of crystallization 5.5 hours, centrifugation, was recycled ammonium sulfate 258.5kg.Subsequently, by filtrated stock concentrating under reduced pressure, until without distillate under temperature 73 DEG C and vacuum tightness 0.096Mpa, terminate concentrated, while hot by thick residue barreled, send sludge incinerator to burn.Finally, three concentrating under reduced pressure gained fractions are merged, mixing, be weighed as 1029kg, detection COD is 161mg/L, BOD is 65mg/L, and ammonia nitrogen is 74mg/L, biochemical treatment system is sent to process, after process, detection COD is 46mg/L, BOD is 7mg/L, and ammonia nitrogen is 4.5mg/L, other index is all qualified, reaches existing national grade one discharge standard (GB8978-2002).
Brief summary: this instance data is the data of input 1.15 tons of waste water, by 11.5t waste water/1t product, every normal production 1 ton of wallantoin, gained waste water, through above-mentioned process, can reclaim 34.6kg wallantoin, 2585 kg ammonium sulfate and a certain amount of residue and burn heat energy.The leading indicator such as COD, ammonia nitrogen of concentrated fraction (10.29 tons) declines to a great extent, and through conventional biochemical treatment, can reach existing national grade one discharge standard.In waste water, the rate of recovery of residual wallantoin is 88.49%; The rate of recovery of ammonium sulfate is that 88.93%(hydrolysis of urea and sulfuric acid neutralization are converted into the overall conversion of ammonium sulfate two-step reaction by 100% estimation, theoretical calculate, and total amount that is original and generation ammonium sulfate is 2906.8kg).After testing, the purity of ammonium sulfate is 97.98%, sells mainly as industrial raw material or as nitrogen fertilizer in agriculture.
Embodiment 4:
First, the trade effluent of synthetic allantoin described in Example 1 1.15 tons, drops into concentrating under reduced pressure in once concentration still, until concentrated solution weight is 0.4 times (namely steam fraction and be about 690kg) of stoste weight.Concentrated solution is cooled to 3-5 DEG C, stirred crystallization 3 hours, centrifugation, is recycled wallantoin 4.2kg(and gives money as a gift as 3.56kg by actual measurement weight loss on drying 15.3%).Again gained filtrate is once neutralized to pH7.8 with ammoniacal liquor, consumes the ammoniacal liquor 36.9kg of concentration 23.95wt%.Then, adding urea-containing weight ratio in urase catalyzer 1.65kg(and waste water stoste is 0.015:1), temperature control 40-45 DEG C hydrolysis reaction 9 hours, makes hydrolysis of urea be (NH
4)
2cO
3.Use the dilute sulphuric acid Two-step neutralization of concentration 65.1wt% to pH6.0 again, make (the NH in feed liquid
4)
2cO
3be converted into ammonium sulfate, consume the dilute sulphuric acid 261kg of 65.1wt%.Then gained neutralizer secondary pressure is concentrated, cooling, in 6-8 DEG C of crystallization 6 hours, centrifugation, was recycled ammonium sulfate 261.7 kg.Subsequently, by filtrated stock concentrating under reduced pressure, until without distillate under temperature 80 DEG C and vacuum tightness 0.097Mpa, terminate concentrated, while hot by thick residue barreled, send sludge incinerator to burn.Finally, three concentrating under reduced pressure gained fractions are merged, mixing, be weighed as 1023kg, detection COD is 168mg/L, BOD is 67mg/L, and ammonia nitrogen is 79mg/L, biochemical treatment system is sent to process, after process, detection COD is 43mg/L, BOD is 6mg/L, and ammonia nitrogen is 4.0mg/L, other index is all qualified, reaches existing national grade one discharge standard (GB8978-2002).
Brief summary: this instance data is the data of input 1.15 tons of waste water, by 11.5t waste water/1t product, every normal production 1 ton of wallantoin, gained waste water, through above-mentioned process, can reclaim 35.6kg wallantoin, 2617 kg ammonium sulfate and a certain amount of residue and burn heat energy.The leading indicator such as COD, ammonia nitrogen of concentrated fraction (10.23 tons) declines to a great extent, and through conventional biochemical treatment, can reach existing national grade one discharge standard.In waste water, the rate of recovery of residual wallantoin is 91.05%; The rate of recovery of ammonium sulfate is that 90.03%(hydrolysis of urea and sulfuric acid neutralization are converted into the overall conversion of ammonium sulfate two-step reaction by 100% estimation, theoretical calculate, and total amount that is original and generation ammonium sulfate is 2906.8kg).After testing, the purity of ammonium sulfate is 97.87%, sells mainly as industrial raw material or as nitrogen fertilizer in agriculture.
Embodiment 5:
First, the trade effluent of synthetic allantoin described in Example 1 1.15 tons, drops into concentrating under reduced pressure in once concentration still, until concentrated solution weight is 0.35 times (namely steam fraction and be about 747.5kg) of stoste weight.Concentrated solution is cooled to 2-3 DEG C, stirred crystallization 2.5 hours, centrifugation, is recycled wallantoin 4.3kg(and gives money as a gift as 3.5kg by actual measurement weight loss on drying 18.6%).Again gained filtrate is once neutralized to pH8.2 with ammoniacal liquor, consumes the ammoniacal liquor 33.6kg of concentration 25.0wt%.Then, adding urea-containing weight ratio in urase catalyzer 0.55kg(and waste water stoste is 0.005:1), temperature control 35-40 DEG C hydrolysis reaction 10 hours, makes hydrolysis of urea be (NH
4)
2cO
3.Use the dilute sulphuric acid Two-step neutralization of concentration 70wt% to pH5.5 again, make (the NH in feed liquid
4)
2cO
3be converted into ammonium sulfate, consume the dilute sulphuric acid 243.6kg of 70wt%.Then gained neutralizer secondary pressure is concentrated, cooling, in 9-10 DEG C of crystallization 6 hours, centrifugation, was recycled ammonium sulfate 262.2kg.Subsequently, by filtrated stock concentrating under reduced pressure, until without distillate under temperature 76 DEG C and vacuum tightness 0.096Mpa, terminate concentrated, while hot by thick residue barreled, send sludge incinerator to burn.Finally, three concentrating under reduced pressure gained fractions are merged, mixing, be weighed as 1004kg, detection COD is 160mg/L, BOD is 62mg/L, and ammonia nitrogen is 79mg/L, biochemical treatment system is sent to process, after process, detection COD is 41mg/L, BOD is 6mg/L, and ammonia nitrogen is 4.5mg/L, other index is all qualified, reaches existing national grade one discharge standard (GB8978-2002).
Brief summary: this instance data is the data of input 1.15 tons of waste water, by 11.5t waste water/1t product, every normal production 1 ton of wallantoin, gained waste water, through above-mentioned process, can reclaim 35kg wallantoin, 2622 kg ammonium sulfate and a certain amount of residue and burn heat energy.The leading indicator such as COD, ammonia nitrogen of concentrated fraction (10.04 tons) declines to a great extent, and through conventional biochemical treatment, can reach existing national grade one discharge standard.In waste water, the rate of recovery of residual wallantoin is 89.51%; The rate of recovery of ammonium sulfate is that 90.20%(hydrolysis of urea and sulfuric acid neutralization are converted into the overall conversion of ammonium sulfate two-step reaction by 100% estimation, theoretical calculate, and total amount that is original and generation ammonium sulfate is 2906.8kg).After testing, the purity of ammonium sulfate is 98.47%, sells mainly as industrial raw material or as nitrogen fertilizer in agriculture.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a treatment process for the trade effluent of synthetic allantoin, is characterized in that, the method comprises the following steps:
(1) by the trade effluent concentrating under reduced pressure of synthetic allantoin, decrease temperature crystalline, filtration, Separation and Recovery wallantoin;
(2) by step (1) gained filtrate ammonia neutralization, neutralization reaction terminal is pH7.0-8.2;
(3) in step (2) gained neutralizer, add urase catalyzer, carry out hydrolysis of urea reaction;
(4) neutralized by step (3) gained hydrolysis reaction liquid sulfuric acid, neutralization reaction terminal is pH5-6;
(5) by step (4) gained neutralizer concentrating under reduced pressure, decrease temperature crystalline, filter, Separation and Recovery ammonium sulfate;
(6) step (5) gained filtrate reduced in volume is obtained thick residue;
(7) gained fraction in step (1), step (5) and step (6) is merged aftertreatment.
2. the treatment process of the trade effluent of synthetic allantoin according to claim 1, it is characterized in that, in step (1), the 0.25-0.4 of striking point to be concentrated solution weight be waste water stoste weight doubly, Tc is 0-5 DEG C, and crystallization time is 2-3 hour.
3. the treatment process of the trade effluent of synthetic allantoin according to claim 1, is characterized in that, in step (2), the mass percent concentration of described ammoniacal liquor is 20-25%.
4. the treatment process of the trade effluent of synthetic allantoin according to claim 1, it is characterized in that, in step (3), in described urase and waste water stoste, urea-containing mass ratio is 0.005-0.02:1, hydrolysising reacting temperature is 25-45 DEG C, and hydrolysis time is 8-10 hour.
5. the treatment process of the trade effluent of synthetic allantoin according to claim 1, is characterized in that, in step (4), the mass percent concentration of described sulfuric acid is 50-70%.
6. the treatment process of the trade effluent of synthetic allantoin according to claim 1, is characterized in that, in step (5), Tc is 5-10 DEG C, and crystallization time is 5-6 hour.
7. the treatment process of the trade effluent of synthetic allantoin according to claim 1, is characterized in that, in step (6), the terminal of concentrating under reduced pressure is without distillate under temperature 70-80 DEG C and vacuum tightness >=0.095Mpa.
8. the treatment process of the trade effluent of synthetic allantoin according to claim 1, is characterized in that, in step (6), described thick residue send sludge incinerator to burn; In step (7), discharge after biochemical treatment after gained fraction in step (1), step (5) and step (6) is merged.
9. the treatment process of the trade effluent of synthetic allantoin according to claim 1, is characterized in that, the method comprises following steps:
(1) by the trade effluent concentrating under reduced pressure of synthetic allantoin, decrease temperature crystalline, filtration, Separation and Recovery wallantoin, doubly, Tc is 0-5 DEG C to the 0.25-0.4 of striking point to be concentrated solution weight be waste water stoste weight, and crystallization time is 2-3 hour;
(2) step (1) gained filtrate neutralized with mass concentration 20-25% ammoniacal liquor, neutralization reaction terminal is pH7.0-8.2;
(3) in step (2) gained neutralizer, urase catalyzer is added, carry out hydrolysis of urea reaction, in described urase and waste water stoste, urea-containing mass ratio is 0.005-0.02:1, and hydrolysising reacting temperature is 25-45 DEG C, and hydrolysis time is 8-10 hour;
(4) neutralized by step (3) the gained hydrolysis reaction liquid sulfuric acid of mass concentration 50-70%, neutralization reaction terminal is pH5-6;
(5) by step (4) gained neutralizer concentrating under reduced pressure, decrease temperature crystalline, filter, Separation and Recovery ammonium sulfate, Tc is 5-10 DEG C, and crystallization time is 5-6 hour;
(6) by step (5) gained filtrate reduced in volume, the thick residue obtained send sludge incinerator to burn;
(7) gained fraction in step (1), step (5) and step (6) is merged, discharge after biochemical treatment.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106348524A (en) * | 2016-08-30 | 2017-01-25 | 芜湖华海生物工程有限公司 | Treatment process for high-concentration allantoin production wastewater |
| CN107698086A (en) * | 2017-11-07 | 2018-02-16 | 山西恩泽生物技术有限公司 | The integrated conduct method of Enzymes Industry waste water |
| CN107746312A (en) * | 2017-11-30 | 2018-03-02 | 芜湖华海生物科技股份有限公司 | Allantoin produces the post-processing approach of waste water |
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| CN1271728A (en) * | 1999-04-27 | 2000-11-01 | 贺楚华 | Process for synthesizing allantoin |
| CN102060392A (en) * | 2010-11-22 | 2011-05-18 | 天津市职业大学 | Method for synthesizing antiincrustation corrosion inhibitor by using waste liquid generated in allantoin production |
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| FR2698347A1 (en) * | 1992-11-24 | 1994-05-27 | Bron Jean Pierre | Compsn. for treating water, contg. chloro deriv. of allantoin or of glycoluril - used in prodn. of drinkable water or for industrial or domestic use. |
| CN1271728A (en) * | 1999-04-27 | 2000-11-01 | 贺楚华 | Process for synthesizing allantoin |
| CN102060392A (en) * | 2010-11-22 | 2011-05-18 | 天津市职业大学 | Method for synthesizing antiincrustation corrosion inhibitor by using waste liquid generated in allantoin production |
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| CN106348524A (en) * | 2016-08-30 | 2017-01-25 | 芜湖华海生物工程有限公司 | Treatment process for high-concentration allantoin production wastewater |
| CN107698086A (en) * | 2017-11-07 | 2018-02-16 | 山西恩泽生物技术有限公司 | The integrated conduct method of Enzymes Industry waste water |
| CN107746312A (en) * | 2017-11-30 | 2018-03-02 | 芜湖华海生物科技股份有限公司 | Allantoin produces the post-processing approach of waste water |
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| CN104829029B (en) | 2016-09-07 |
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