CN104829029B - A kind of processing method of the industrial wastewater of synthetic allantoin - Google Patents
A kind of processing method of the industrial wastewater of synthetic allantoin Download PDFInfo
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Abstract
The invention discloses the processing method of the industrial wastewater of a kind of synthetic allantoin, belong to technical field of waste water processing.The method comprises the following steps: (1), by the industrial wastewater reduced pressure concentration of synthetic allantoin, decrease temperature crystalline, filtration, separates and recovers allantoin；(2) step (1) gained filtrate being neutralized with ammoniacal liquor, neutralizing reaction end is pH7.0 8.2；(3) in step (2) gained neutralizer, add urase catalyst and carry out hydrolysis of urea reaction；(4) being neutralized by step (3) gained hydrolysis liquid sulfuric acid, neutralizing reaction end is pH5 6；(5) by step (4) gained neutralizer reduced pressure concentration, decrease temperature crystalline, filter；(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 post processing.The method had both been effected a radical cure allantoin project environment and had been polluted, and reduced again the comprehensive production cost of allantoin.
Description
Technical field
The present invention relates to the processing method of industrial wastewater, be specifically related to the processing method of the industrial wastewater of a kind of synthetic allantoin, the method can be improved environmental quality and realize comprehensive utilization of energy, belongs to environmental protection and energy conservation field.
Background technology
Allantoin is widely used in the fields such as medicine, daily-use chemical industry and agricultural, mainly uses glyoxalic acid and the urea production technology through condensation reaction synthetic allantoin under sulfuric acid (or other inorganic acid) is catalyzed.Deutsche Bundespatent (DE1939924) discloses the technique of the lower synthetic allantoin of inorganic 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%.The method that it is raw material one-step synthesis allantoin with glyoxal, hydrogen peroxide, urea, the concentrated sulfuric acid and granular activated carbon that Chinese patent (CN1067993C) discloses, product yield is up to more than 60%.The method that it is Material synthesis allantoin with glyoxylic acid solution, urea, catalyst that Chinese patent (CN1765888A) discloses.Yin Dehong et al. reports with glyoxal and urea as raw material at " Liaoning chemical industry " in August, 2002, uses H 2O 2Oxidation, catalyzing and condensing two step synthetic method allantoin, inquired into oxidation mechanism, it is proposed that make the synthetic method of catalyst with mixture of sulfuric phosphoric acid, and allantoin productivity is 60.7 %.Although similar patent or periodical literature report are more, but along with the continuous of ethanol acid production technology is improved in the recent decade, the most frequently used allantoin synthetic method being really applied to industrialized production remains with glyoxalic acid, the urea synthetic method for primary raw material with sulfuric acid as catalyst, the method yield higher (up to 69%～71%), cost is relatively low, thus commonly used by overwhelming majority allantoin manufacturing enterprise both at home and abroad.The glyoxalic acid that is generally used, urea, sulfuric acid catalysis synthetic method maximum has a problem in that in production process and can produce substantial amounts of industrial wastewater, and is difficult to administer.
According to investigation, domestic allantoin yield rises year by year, domestic the most on the rise with outlet.Through technological improvement for many years, the best technical-economic index that the enterprise of domestic actual production allantoin can reach is: allantoin molar yield 71% in terms of glyoxalic acid, the most often produce 1 ton of allantoin product, about need to consume 50% glyoxalic acid solution 1.25 tons, 2 tons of urea, 98% concentrated sulfuric acid 0.33 ton, produce containing urea, ammonium sulfate, allantoin, sulfuric acid and the strongly acid wastewater about 11.5 tons of a certain amount of accessory substance simultaneously, waste water COD is about 6.5-7 ten thousand, ammonia nitrogen ＞ 1500, seriously exceedes applicable legal emissions index.
The feature of allantoin industrial wastewater is: COD is high, ammonia nitrogen is high, component is many, and its difficulty in treatment is: each component is difficult to separate, it is impossible to directly recycle.This waste water has a strong impact on the impurity of product quality because containing, therefore can not apply mechanically by direct circulation, and wastewater processing technology difficulty is relatively big, and processing cost is the highest.Again because its ammonium sulfate and sulfuric acid content too high, with in inorganic base and after, inorganic salt content is the highest, therefore it is up to standard to use biodegradable method also cannot directly process.
About the administering method of the industrial wastewater of synthetic allantoin, Chinese patent (CN102060392A) discloses the method producing waste liquid synthesis of organo-phosphines anti-incrustation corrosion inhibitor with allantoin, for Treatment of Industrial Water；Chinese patent (CN201210593306) discloses the method for a kind of allantoin 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 allantoin manufacturing enterprise because waste water process can not be up to standard and ordered stopping production by local environmental administration.Therefore, this environmental issue the most seriously constrains allantoin industry development, and problem of environmental pollution becomes outstanding problem the most in the urgent need to address.
Producing each constituent content of waste liquid by detection allantoin, a large amount of statistics show, about contain urea 8.70-9.57wt%, pure 1.0-1.2 ton in above-mentioned 11.5 tons of allantoin waste liquids；Liquid containing ammonium sulfate 1.74-2.61wt%, pure 0.2-0.3 ton；Containing allantoin 0.26-0.35wt%, pure 0.03-0.04 ton；Sulfur acid 0.87-1.74wt%, pure 0.1-0.2 ton；Containing accessory substance allantoic acid 1.74-2.17wt%, pure 0.2-0.25 ton；Residual components is water and other trace impurity.I.e. containing a small amount of product allantoin, the urea reacted the most completely and sulfuric acid and other materials (such as ammonium sulfate, allantoic acid) in waste water, this waste water COD and ammonia nitrogen numerical value are the highest, are not suitable for directly discharging.
Summary of the invention
The industrial wastewater of synthetic allantoin is carried out harmless treatment and recycling by the purpose of the present invention, has both effected a radical cure the pollution to environment of the allantoin waste water, reduces again the comprehensive production cost of allantoin.Its principle is as follows: wherein, allantoin product in waste water can reclaim further, ammonium sulfate is the conventional nitrogenous fertilizer of agricultural, there is recycling be worth, urea, sulfuric acid can also be completely converted into ammonium sulfate by chemical reaction and be separated and recovered, organic acid allantoic acid can also carry out innocuously transformation (allantoic acid is converted into its ammonium salt) by chemical reaction, and the mode that sludge incinerator can be used after moisture content is evaporated off to burn carries out harmless treatment and reclaims heat energy.So, then allantoin industrial wastewater can reclaim allantoin, ammonium sulfate and organic raffinat heat energy simultaneously, it is possible to achieve comprehensive utilization of resources, and significantly reduces every environmental protection index of residue waste water (i.e. concentrating fraction), such that it is able to pass through biochemical treatment easily, it is achieved qualified discharge.Described scheme is as follows:
The processing method of the industrial wastewater providing a kind of synthetic allantoin of the present invention, the method comprises the following steps:
Step 1: once concentration, crystallization filter process, by the industrial wastewater reduced pressure concentration of synthetic allantoin, then decrease temperature crystalline, filters, separates and recovers allantoin.
Step 2: once neutralize course of reaction, neutralizes step 1 gained filtrate with ammoniacal liquor, and once neutralizing reaction end is pH7.0-8.2, and making sulfuric acid conversion is ammonium sulfate, and allantoic acid is converted into allantoic acid ammonium.Wherein, this neutralization reaction end can realize the conversion of material, can provide again the reaction condition (optimum reaction condition of urase catalytic reaction is about pH8) of excellence for the reaction of follow-up hydrolysis of urea.
Step 3: hydrolysis of urea course of reaction, adds urase catalyst in step 2 gained neutralizer, and hydrolysis of urea reaction occurs, and making hydrolysis of urea is (NH4)2CO3, urase catalyst has hydrolysis of urea reaction selectivity catalytic action.
Step 4: in secondary and course of reaction, neutralizes step 3 gained hydrolysis liquid sulfuric acid, in secondary and reaction end is pH5-6, makes (NH4)2CO3It is converted into ammonium sulfate.
Step 5: secondary concentration, crystallization filter process, by step 4 gained neutralizer reduced pressure concentration, decrease temperature crystalline, filters, separates and recovers 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: concentrate fraction processing procedure, gained reduced pressure concentration fraction in step 1, step 5 and step 6 is merged, carries out biochemical treatment, qualified discharge or recycling.
In above steps: the industrial wastewater of synthetic allantoin refers to that with glyoxalic acid, urea be the industrial wastewater that the raw material process route synthetic allantoin with sulfuric acid as catalyst produces, and its composition includes: allantoin, urea, ammonium sulfate, sulfuric acid, allantoic acid, water and other impurity.
Wherein, in step 1, once concentration terminal be concentrate weight be 0.25-0.4 times of waste water stoste (industrial wastewater of former synthetic allantoin) weight, primary crystallization temperature is 0-5 DEG C, and the primary crystallization time is 2-3 hour.
Wherein, in step 2, the mass percent concentration once neutralizing use ammoniacal liquor is 20-25%.
Wherein, in step 3, urase is 0.005-0.02:1 with urea-containing mass ratio in waste water stoste, and hydrolysising reacting temperature is 25-45 DEG C, and hydrolysis time is 8-10 hour.
Wherein, in step 4, in secondary and the mass percent concentration of sulfuric acid that uses is 50-70%.
Wherein, in steps of 5, secondary crystallization temperature is 5-10 DEG C, and the secondary crystallization time is 5-6 hour.
Wherein, in step 6, without distillate under the terminal of reduced pressure concentration is temperature 70-80 DEG C and vacuum >=0.095Mpa.
Wherein, in steps of 5, its reduced pressure concentration degree is so that ammonium sulfate crystallization is advisable.In step 1 and 5, use conventional reduced pressure concentration condition.
Specifically, the method includes following steps:
Step 1: once concentration, crystallization filter process, by the industrial wastewater reduced pressure concentration of synthetic allantoin, decrease temperature crystalline, filtration, separation and recovery allantoin, striking point be concentrate weight be 0.25-0.4 times of waste water stoste weight, primary crystallization temperature is 0-5 DEG C, and the primary crystallization time is 2-3 hour.
Step 2: once neutralize course of reaction, once neutralizes step 1 gained filtrate with mass concentration 20-25% ammoniacal liquor, and once neutralizing reaction end 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 course of reaction, adds urase catalyst in step 2 gained neutralizer, carries out hydrolysis of urea reaction, wherein, urase is 0.005-0.02:1 with urea-containing mass ratio in waste water stoste, and hydrolysising reacting temperature is 25-45 DEG C, and hydrolysis time is 8-10 hour.
Step 4: in secondary and course of reaction, carries out secondary neutralization by the sulfuric acid of step 3 gained hydrolysis liquid mass concentration 50-70%, and in secondary and reaction end is pH5-6, the consumption of sulfuric acid is as the criterion so that pH value is up to standard.
Step 5: secondary concentration, crystallization filter process, by step 4 gained neutralizer reduced pressure concentration, decrease temperature crystalline, filters, separates and recovers ammonium sulfate, and secondary crystallization temperature is 5-10 DEG C, and the secondary crystallization 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: concentrate fraction processing procedure, gained fraction in step 1, step 5 and step 6 is merged, discharges after biochemical treatment or recycle.
The beneficial effect comprise that
(1) present invention uses chemical conversion and separation method, by twice N-process, twice condensing crystallizing process and a urea seeding hydrolysis reaction, make multicomponent, high COD, the key component that the allantoin of high ammonia nitrogen produces in waste liquid is efficiently separated, it is separately recovered allantoin, ammonium sulfate and raffinate burn the heat energy produced, and make the concentration fraction COD of output and ammonia nitrogen index be reduced to process scope up to standard easily, it is possible not only to solve the existing intractable technical barrier of allantoin industrial wastewater, comprehensive utilization of resources can also be realized, reduce waste water to process and the comprehensive production cost of allantoin.
(2) present invention process mild condition, produces equipment simple, and cost for wastewater treatment is low, is suitable for industrialized production, can create good economic benefit and social benefit for enterprise.
(3) using the rate of recovery of this method allantoin more than 90%, the rate of recovery of ammonium sulfate is more than 85%, and the purity of ammonium sulfate is more than 97%, and recovering effect is notable.
Accompanying drawing explanation
Fig. 1 is current existing allantoin synthesis technique schematic flow sheet；
Fig. 2 is the process flow diagram of the processing method of the industrial wastewater of the synthetic allantoin that the present invention provides.
Detailed description of the invention
With specific embodiment, the present invention is described in further detail below in conjunction with the accompanying drawings.
The raw material set-up procedure (within being not included in present invention, the only present invention provides representative raw material allantoin industrial wastewater) of the present invention:
Specifically, see Fig. 1, carry out the preparation of allantoin industrial wastewater according to the most the most frequently used glyoxalic acid-urea-sulfuric acid catalysis synthetic route.Preparation method is as follows:
The glyoxalic acid solution 2000kg of 40wt% is put in 5000L enamel condensation reaction still, start stirring, add urea 2500-2600kg, add concentrated sulfuric acid 400-450kg, be heated to 80-85 DEG C, and in 80-85 DEG C of insulation reaction, timing is started in time separating out solid, after being incubated 1-1.5 hour, it is cooled to 65-75 DEG C, continues at 65-75 DEG C of insulation reaction 16-18 hour.Then 25-35 DEG C it is down to, centrifugation, wash filter cake, until washing lotion pH7.0, dry, take filtration cakes torrefaction, obtain allantoin finished product about 1.25-1.28 ton.Filtrate merges with washing lotion, mixing, the referred to as industrial wastewater of synthetic allantoin, about 14-15 ton, and the waste water yield the most often producing 1 ton of allantoin product is about 11-12 ton, as waste water raw material needed for the following present invention.Allantoin finished product is about 69-71% to glyoxalic acid molar yield.
See Fig. 2, the invention provides the processing method of the industrial wastewater of a kind of synthetic allantoin, first pass through once concentration, crystallization filtration, reclaim the allantoin product of residual in allantoin industrial wastewater；Mother liquor is once neutralized to ammoniacal liquor again
PH7.0-8.2, is ammonium sulfate by sulfuric acid conversion, allantoic acid is converted into allantoic acid ammonium；Being subsequently added into urase and carry out the catalyzing hydrolysis of urea, making hydrolysis of urea is (NH4)2CO3；It is neutralized to pH5-6 with sulfuric acid secondary again, makes (NH4)2CO3It is converted into ammonium sulfate；Filtering through secondary concentration, crystallization, separation and recovery can be as agricultural fertilizer or industrial ammonium sulfate again；Finally by mother liquor concentrations, residue sludge incinerator burns, and concentrates gained fraction biochemical method three times and processes.
Embodiment 1, the preparation of the industrial wastewater of synthetic allantoin:
The glyoxalic acid solution 2000kg of 40wt% is put in 5000L condensation reaction still, start stirring, add urea 2560kg, add 98wt% concentrated sulfuric acid 423kg, be heated to 80 DEG C, and in 80-82 DEG C of insulation reaction, timing is started in time separating out solid, after being incubated 1 hour, it is cooled to 70-72 DEG C, continues at 70-72 DEG C of insulation reaction 17 hours.Then 30 DEG C it are cooled to, centrifugation, wash filter cake, until washing lotion pH7.0, dry, take filtration cakes torrefaction, obtain allantoin finished product 1280kg.Filtrate merges with washing lotion, and mixing, the referred to as industrial wastewater of synthetic allantoin, Weighing 14.72 tons (is equivalent to 1 ton of allantoin finished product of every output about output waste water 11.5 tons), as following present example needed raw material.Allantoin finished product is 70.9% to the molar yield of glyoxalic acid.
Seeing table 1, learn by analyzing detection, the composition of 14.72 tons of allantoin industrial wastewaters of this batch is:
Table 1
| Detection project | Urea | Ammonium sulfate | Allantoin | 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 allantoin industrial wastewater as raw material, carries out the trial-production explanation of waste water treatment process of the present invention.Key component and the environmental protection leading indicator of these 1.15 tons of waste water (waste water of i.e. corresponding 0.1 ton of allantoin product) are as shown in table 2:
Table 2
Embodiment 2:
First, the industrial wastewater of synthetic allantoin described in Example 1 1.15 tons, put into reduced pressure concentration in once concentration still, until concentrate weight is stoste weight 0.25 times (i.e. steaming fraction about 862.5kg).Concentrate is cooled to 0-2 DEG C, stirred crystallization 2 hours, centrifugation, be recycled allantoin 4.2kg(and give money as a gift as 3.59kg by actual measurement loss on drying 14.53%).Gained filtrate is once neutralized to ammoniacal liquor pH7.0 again, consumes the ammoniacal liquor 39.5kg of concentration 20.01wt%.Then, adding urase catalyst 2.2kg(with urea-containing weight ratio in waste water stoste is 0.02:1), 25-30 DEG C of hydrolysis of temperature control 8 hours, making hydrolysis of urea is (NH4)2CO3.It is neutralized to pH5.0 with the dilute sulfuric acid secondary of concentration 50wt% again, makes (the NH in feed liquid4)2CO3It is converted into ammonium sulfate, consumes the dilute sulfuric acid 341kg of 50wt%.Then gained neutralizer secondary pressure concentrated, lower the temperature, crystallize 5 hours in 5-6 DEG C, centrifugation, be recycled ammonium sulfate 254.7 kg.Subsequently, by filtrated stock reduced pressure concentration, until concentrating without distillate, end, while hot by thick residue barreled, send sludge incinerator to burn under temperature 70 C and vacuum 0.098Mpa.Finally, three reduced pressure concentration gained fractions are merged, mixing, it is weighed as 1105kg, detection COD be 165mg/L, BOD be 60mg/L, ammonia nitrogen is 80mg/L, biochemical treatment system is sent to process, after process detect COD be 43mg/L, BOD be 8mg/L, ammonia nitrogen is 4.0mg/L, other index is the most qualified, reaches existing national grade one discharge standard (GB8978-2002).
Brief summary: this instance data is the data putting into 1.15 tons of waste water, based on 11.5t waste water/1t product, 1 ton of allantoin of every normal production, gained waste water is through above-mentioned process, 35.9kg allantoin, 2547kg ammonium sulfate and a certain amount of residue can be reclaimed and burn heat energy, concentrate the leading indicators such as the COD of fraction (11.05 tons), ammonia nitrogen to decline to a great extent, through conventional biochemical treatment, i.e. can reach existing national grade one discharge standard.The rate of recovery remaining allantoin in waste water is 91.82%；The rate of recovery of ammonium sulfate is that 87.62%(hydrolysis of urea and sulfuric acid neutralize the overall conversion being converted into ammonium sulfate two-step reaction by 100% estimation, theoretical calculates, original and to generate the total amount of ammonium sulfate be 2906.8kg).After testing, the purity of ammonium sulfate is 98.37%, sells mainly as the raw material of industry or as nitrogen fertilizer in agriculture.
Embodiment 3:
First, the industrial wastewater of synthetic allantoin described in Example 1 1.15 tons, put into reduced pressure concentration in once concentration still, until concentrate weight is stoste weight 0.3 times (i.e. steaming fraction about 805kg).Concentrate is cooled to 2-3 DEG C, stirred crystallization 2.5 hours, centrifugation, be recycled allantoin 4.1kg(and give money as a gift as 3.46kg by actual measurement loss on drying 15.6%).Gained filtrate is once neutralized to ammoniacal liquor pH7.3 again, consumes the ammoniacal liquor 37.4kg of concentration 21.52wt%.Then, adding urase catalyst 1.1kg(with urea-containing weight ratio in waste water stoste is 0.01:1), 28-32 DEG C of hydrolysis of temperature control 8.5 hours, making hydrolysis of urea is (NH4)2CO3.It is neutralized to pH5.5 with the dilute sulfuric acid secondary of concentration 55.4% again, makes (the NH in feed liquid4)2CO3It is converted into ammonium sulfate, consumes the dilute sulfuric acid 305.7kg of 55.4wt%.Then gained neutralizer secondary pressure concentrated, lower the temperature, crystallize 5.5 hours in 7-8 DEG C, centrifugation, be recycled ammonium sulfate 258.5kg.Subsequently, by filtrated stock reduced pressure concentration, until concentrating without distillate, end, while hot by thick residue barreled, send sludge incinerator to burn under temperature 73 DEG C and vacuum 0.096Mpa.Finally, three reduced pressure concentration gained fractions are merged, mixing, it is weighed as 1029kg, detection COD be 161mg/L, BOD be 65mg/L, ammonia nitrogen is 74mg/L, biochemical treatment system is sent to process, after process detect COD be 46mg/L, BOD be 7mg/L, ammonia nitrogen is 4.5mg/L, other index is the most qualified, reaches existing national grade one discharge standard (GB8978-2002).
Brief summary: this instance data is the data putting into 1.15 tons of waste water, based on 11.5t waste water/1t product, 1 ton of allantoin of every normal production, gained waste water, through above-mentioned process, can reclaim 34.6kg allantoin, 2585 kg ammonium sulfate and a certain amount of residue and burn heat energy.Concentrate the leading indicators such as the COD of fraction (10.29 tons), ammonia nitrogen to decline to a great extent, through conventional biochemical treatment, i.e. can reach existing national grade one discharge standard.The rate of recovery remaining allantoin in waste water is 88.49%；The rate of recovery of ammonium sulfate is that 88.93%(hydrolysis of urea and sulfuric acid neutralize the overall conversion being converted into ammonium sulfate two-step reaction by 100% estimation, theoretical calculates, original and to generate the total amount of ammonium sulfate be 2906.8kg).After testing, the purity of ammonium sulfate is 97.98%, sells mainly as the raw material of industry or as nitrogen fertilizer in agriculture.
Embodiment 4:
First, the industrial wastewater of synthetic allantoin described in Example 1 1.15 tons, put into reduced pressure concentration in once concentration still, until concentrate weight is stoste weight 0.4 times (i.e. steaming fraction about 690kg).Concentrate is cooled to 3-5 DEG C, stirred crystallization 3 hours, centrifugation, be recycled allantoin 4.2kg(and give money as a gift as 3.56kg by actual measurement loss on drying 15.3%).Gained filtrate is once neutralized to ammoniacal liquor pH7.8 again, consumes the ammoniacal liquor 36.9kg of concentration 23.95wt%.Then, adding urase catalyst 1.65kg(with urea-containing weight ratio in waste water stoste is 0.015:1), 40-45 DEG C of hydrolysis of temperature control 9 hours, making hydrolysis of urea is (NH4)2CO3.It is neutralized to pH6.0 with the dilute sulfuric acid secondary of concentration 65.1wt% again, makes (the NH in feed liquid4)2CO3It is converted into ammonium sulfate, consumes the dilute sulfuric acid 261kg of 65.1wt%.Then gained neutralizer secondary pressure concentrated, lower the temperature, crystallize 6 hours in 6-8 DEG C, centrifugation, be recycled ammonium sulfate 261.7 kg.Subsequently, by filtrated stock reduced pressure concentration, until concentrating without distillate, end, while hot by thick residue barreled, send sludge incinerator to burn under temperature 80 DEG C and vacuum 0.097Mpa.Finally, three reduced pressure concentration gained fractions are merged, mixing, it is weighed as 1023kg, detection COD be 168mg/L, BOD be 67mg/L, ammonia nitrogen is 79mg/L, biochemical treatment system is sent to process, after process detect COD be 43mg/L, BOD be 6mg/L, ammonia nitrogen is 4.0mg/L, other index is the most qualified, reaches existing national grade one discharge standard (GB8978-2002).
Brief summary: this instance data is the data putting into 1.15 tons of waste water, based on 11.5t waste water/1t product, 1 ton of allantoin of every normal production, gained waste water, through above-mentioned process, can reclaim 35.6kg allantoin, 2617 kg ammonium sulfate and a certain amount of residue and burn heat energy.Concentrate the leading indicators such as the COD of fraction (10.23 tons), ammonia nitrogen to decline to a great extent, through conventional biochemical treatment, i.e. can reach existing national grade one discharge standard.The rate of recovery remaining allantoin in waste water is 91.05%；The rate of recovery of ammonium sulfate is that 90.03%(hydrolysis of urea and sulfuric acid neutralize the overall conversion being converted into ammonium sulfate two-step reaction by 100% estimation, theoretical calculates, original and to generate the total amount of ammonium sulfate be 2906.8kg).After testing, the purity of ammonium sulfate is 97.87%, sells mainly as the raw material of industry or as nitrogen fertilizer in agriculture.
Embodiment 5:
First, the industrial wastewater of synthetic allantoin described in Example 1 1.15 tons, put into reduced pressure concentration in once concentration still, until concentrate weight is stoste weight 0.35 times (i.e. steaming fraction about 747.5kg).Concentrate is cooled to 2-3 DEG C, stirred crystallization 2.5 hours, centrifugation, be recycled allantoin 4.3kg(and give money as a gift as 3.5kg by actual measurement loss on drying 18.6%).Gained filtrate is once neutralized to ammoniacal liquor pH8.2 again, consumes the ammoniacal liquor 33.6kg of concentration 25.0wt%.Then, adding urase catalyst 0.55kg(with urea-containing weight ratio in waste water stoste is 0.005:1), 35-40 DEG C of hydrolysis of temperature control 10 hours, making hydrolysis of urea is (NH4)2CO3.It is neutralized to pH5.5 with the dilute sulfuric acid secondary of concentration 70wt% again, makes (the NH in feed liquid4)2CO3It is converted into ammonium sulfate, consumes the dilute sulfuric acid 243.6kg of 70wt%.Then gained neutralizer secondary pressure concentrated, lower the temperature, crystallize 6 hours in 9-10 DEG C, centrifugation, be recycled ammonium sulfate 262.2kg.Subsequently, by filtrated stock reduced pressure concentration, until concentrating without distillate, end, while hot by thick residue barreled, send sludge incinerator to burn under temperature 76 DEG C and vacuum 0.096Mpa.Finally, three reduced pressure concentration gained fractions are merged, mixing, it is weighed as 1004kg, detection COD be 160mg/L, BOD be 62mg/L, ammonia nitrogen is 79mg/L, biochemical treatment system is sent to process, after process detect COD be 41mg/L, BOD be 6mg/L, ammonia nitrogen is 4.5mg/L, other index is the most qualified, reaches existing national grade one discharge standard (GB8978-2002).
Brief summary: this instance data is the data putting into 1.15 tons of waste water, based on 11.5t waste water/1t product, 1 ton of allantoin of every normal production, gained waste water, through above-mentioned process, can reclaim 35kg allantoin, 2622 kg ammonium sulfate and a certain amount of residue and burn heat energy.Concentrate the leading indicators such as the COD of fraction (10.04 tons), ammonia nitrogen to decline to a great extent, through conventional biochemical treatment, i.e. can reach existing national grade one discharge standard.The rate of recovery remaining allantoin in waste water is 89.51%；The rate of recovery of ammonium sulfate is that 90.20%(hydrolysis of urea and sulfuric acid neutralize the overall conversion being converted into ammonium sulfate two-step reaction by 100% estimation, theoretical calculates, original and to generate the total amount of ammonium sulfate be 2906.8kg).After testing, the purity of ammonium sulfate is 98.47%, sells mainly as the raw material of industry or as nitrogen fertilizer in agriculture.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (9)
1. the processing method of the industrial wastewater of a synthetic allantoin, it is characterised in that the method comprises the following steps:
(1) by the industrial wastewater reduced pressure concentration of synthetic allantoin, decrease temperature crystalline, filtration, separate and recover allantoin；
(2) step (1) gained filtrate being neutralized with ammoniacal liquor, neutralization reaction end is pH7.0-8.2；
(3) in step (2) gained neutralizer, add urase catalyst, carry out hydrolysis of urea reaction；
(4) being neutralized by step (3) gained hydrolysis liquid sulfuric acid, neutralization reaction end is pH5-6；
(5) by step (4) gained neutralizer reduced pressure concentration, decrease temperature crystalline, filter, separate and recover 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 post processing.
The processing method of the industrial wastewater of synthetic allantoin the most according to claim 1, it is characterized in that, in step (1), striking point be concentrate weight be 0.25-0.4 times of waste water stoste weight, crystallization temperature is 0-5 DEG C, and crystallization time is 2-3 hour.
The processing method of the industrial wastewater of synthetic allantoin the most according to claim 1, it is characterised in that in step (2), the mass percent concentration of described ammoniacal liquor is 20-25%.
The processing method of the industrial wastewater of synthetic allantoin the most according to claim 1, it is characterized in that, in step (3), described urase catalyst is 0.005-0.02:1 with urea-containing mass ratio in waste water stoste, hydrolysising reacting temperature is 25-45 DEG C, and hydrolysis time is 8-10 hour.
The processing method of the industrial wastewater of synthetic allantoin the most according to claim 1, it is characterised in that in step (4), the mass percent concentration of described sulfuric acid is 50-70%.
The processing method of the industrial wastewater of synthetic allantoin the most according to claim 1, it is characterised in that in step (5), crystallization temperature is 5-10 DEG C, crystallization time is 5-6 hour.
The processing method of the industrial wastewater of synthetic allantoin the most according to claim 1, it is characterised in that in step (6), the terminal of reduced pressure concentration is without distillate under temperature 70-80 DEG C and vacuum >=0.095Mpa.
The processing method of the industrial wastewater of synthetic allantoin the most according to claim 1, it is characterised 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.
The processing method of the industrial wastewater of synthetic allantoin the most according to claim 1, it is characterised in that the method includes following steps:
(1) by the industrial wastewater reduced pressure concentration of synthetic allantoin, decrease temperature crystalline, filtration, separate and recover allantoin, striking point be concentrate weight be 0.25-0.4 times of waste water stoste weight, crystallization temperature is 0-5 DEG C, and crystallization time is 2-3 hour；
(2) step (1) gained filtrate being neutralized with mass concentration 20-25% ammoniacal liquor, neutralization reaction end is pH7.0-8.2；
(3) in step (2) gained neutralizer, urase catalyst is added, carry out hydrolysis of urea reaction, described urase catalyst is 0.005-0.02:1 with urea-containing mass ratio in waste water stoste, and hydrolysising reacting temperature is 25-45 DEG C, and hydrolysis time is 8-10 hour；
(4) being neutralized by step (3) the gained hydrolysis liquid sulfuric acid of mass concentration 50-70%, neutralization reaction end is pH5-6；
(5) by step (4) gained neutralizer reduced pressure concentration, decrease temperature crystalline, filtering, separate and recover ammonium sulfate, crystallization temperature 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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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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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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