CN106746158A - A kind of coal water slurry gasification process produces the deepness denitrogenation method for treating of waste water - Google Patents
A kind of coal water slurry gasification process produces the deepness denitrogenation method for treating of waste water Download PDFInfo
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Abstract
The present invention relates to the deepness denitrogenation method for treating that a kind of coal water slurry gasification process produces waste water, including（1）Increase air-dissolving air-float system in the front end of SBR techniques；（2）During startup, to microbial growth promoters are added in SBR sewage disposal systems, the growth promoter includes slaine, polyamines, organic acid azanol and Na2SO3, wherein the slaine is made up of calcium salt, mantoquita, magnesium salts and/or ferrous salt；（3）Every the 3-5 SBR cycle of operation, to denitrogenation microbial inoculum is added in SBR system, stop adding when water outlet ammonia nitrogen concentration is less than 50mg/L, and total nitrogen concentration is less than 50mg/L.The inventive method sets air-dissolving air-float before SBR techniques, and adding microbial growth promoters in SBR by way of denitrogenation microbial inoculum is combined, advanced treating is carried out to the nitrogen-containing pollutant in waste water by short-cut nitrification and denitrification technique, water outlet meets the requirement of reusing sewage.
Description
Technical field
The invention belongs to environmental project technical field of waste water processing, it is related to a kind for the treatment of method for denitrogenation of waste water, more particularly, to the deepness denitrogenation method for treating that waste water is produced during a kind of coal water slurry gasification.
Background technology
Coal Gasification belongs to the basic technology of Coal Energy Source conversion, is an important ring in clean coal utilization link.Wherein Texaco's water coal slurry pressurized gasification technology because with flow simple, environmental pollution it is few, it is strong to coal adaptability many advantages, such as be used widely.The waste water that coal water slurry gasification process is produced is because of the major pollutants for being free of tar and heavy metal ion, cyanide and phenols content is relatively low, carboxylic acid compounds are composition waste water COD, the good biodegradability of waste water.The most of sewage treatment plant that all enters of waste water is produced to use SBR PROCESS FOR TREATMENTs during current coal water slurry gasification, ammonia nitrogen and COD this two pollutants concentration can be less than qualified discharge value in waste water after treatment, qualified discharge can be realized, but usually can not meet reuse requirement because total nitrogen and salt content are high.
SBR techniques（Sequencing batch reactor）It is a kind of activated sludge sewage disposal technology run by intermittent aerating mode, will be aerated-stops the supple of gas or steam stirring-sedimentation-draining and be placed on completion in same structures, saves occupation of land and invest；There is constantly alternate aerobic and anaerobic metabolism environment because the special method of operation of SBR methods allows in bioreactor simultaneously so that the technique possesses diversified biological flora structure and stronger anti impulsion load ability and processes the ability of poisonous and high concentrated organic wastewater.But because coal water slurry gasification ammonia nitrogen in waste water content is higher, carbon-nitrogen ratio is low in waste water, so higher by nitrate concentration after biochemical treatment, salt content is higher, cannot function as circulating Water circulation, the SBR system being currently in operation is because ash content is more in activated sludge so that sewage disposal system is unstable to the removal effect of ammonia nitrogen.Other Texaco water co al slurry gasification process specifies to adding calcium carbonate in coal as cosolvent so that coal gasification washings turn into high rigidity, high alkalinity, high concentrtion, pH water quality high, to sewage treatment up to standard and recycles and brings bigger difficulty.
As the limitation to nitrogen-containing pollutant discharge standard in waste water is more and more stricter, there is an emission request in the developed country such as the U.S., France and Japan to the total nitrogen in treatment water outlet, and China《Urban wastewater treatment firm pollutant emission standard》（GB18918-2002）Middle one-level B standard proposes the requirement of total nitrogen.What on January 1st, 2008 carried out《Jiangsu TAI HU AREA urban wastewater treatment firm and priority industry industry discharge of major pollutant limit value》（DB32）The index of control total nitrogen is increased first.《Ammonia synthesizing industry pollution discharge standard》（GB13458-2013）、《Heterocyclic pesticide industrial water pollution thing discharge standard》（GB21523-2008）、《Nitric acid industry pollutant emission standard》（GB26131-2010）With《Petroleum refining industry pollutant emission standard》（Exposure draft）Etc. the index for both increasing control total nitrogen.2 months 2010, Environmental Protection Department issue《Coking industry pollutant emission standard》（Exposure draft）Total nitrogen performance assessment criteria, direct waste discharge requirement total nitrogen≤15mg/L, indirect waste discharge requirement total nitrogen≤30mg/L are increased to coking enterprise discharge of wastewater.As can be seen here, total nitrogen concentration of emission requirement is proposed in more discharge standards, therefore total nitrogen in waste water must be processed.
CN201110126057.2 discloses a kind of method of utilization microbiological treatment coal chemical industrial waste water total nitrogen, present invention mainly solves the technical problem that existing A/O Process for Effluent total nitrogen cannot be effectively controlled, be not suitable for solving the problems, such as that SBR techniques have total nitrogen and cannot be effectively addressed.201210242756 disclose a kind of method of utilization microbiological treatment coal water slurry gasification waste water, and waste water sequentially enters regulating reservoir, multi-function pool, Composite denitrification pond and sedimentation basin, final water outlet up to standard；Stirring and aerator are added with multi-function pool, are furnished with aerator in Composite denitrification pond；And respectively at microbe carrier and the environmental microorganism preparation of 1.5%-4.0% that respective volume 1.0%-2.5% is added in multi-function pool and Composite denitrification pond.After being processed through the invention, coal water slurry gasification ammonia nitrogen in waste water can be controlled in below 15mg/L, and COD can be controlled in below 100mg/L, and the COD of circulating cooling make-up water is from reusing sewage（Concentration is less than 60mg/L）Index also have certain distance, that is to say, that reusing sewage requirement can not be met through COD concentration in the waste water after handled by the patent of invention, in addition it is also necessary to further could consider reuse after treatment.
Existing biological treatment, mainly carries out denitrogenation processing by traditional nitration denitrification process.For coal gasification waste water, because carbon-nitrogen ratio is low, if processed using short-cut nitrification and denitrification technique, on the one hand nitration reaction course, time-consuming, reduction sludge yield can be shortened, on the other hand can also substantially reduce in nitrifying process to the consumption in the consumption of dissolved oxygen and denitrification process to carbon source, substantially reduce operating cost.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides the deepness denitrogenation method for treating that a kind of coal water slurry gasification process produces waste water.The method sets air-dissolving air-float before SBR techniques, and adding microbial growth promoters in SBR by way of denitrogenation microbial inoculum is combined, advanced treating is carried out to the nitrogen-containing pollutant in waste water by short-cut nitrification and denitrification technique, water outlet meets the requirement of reusing sewage.The inventive method simple possible, it is particularly suitable for processing the advanced nitrogen treatment of the coal water slurry gasification waste water that disclosure satisfy that qualified discharge but be not suitable for reuse, while the reaction mechanism mechanism of reaction is shortened, the consumption to dissolved oxygen and carbon source can be reduced, substantially reduce a ton cost of water treatment.
Coal water slurry gasification process of the present invention produces the deepness denitrogenation method for treating of waste water, including following content：
（1）Increase air-dissolving air-float system in the front end of SBR techniques；
（2）During startup, to microbial growth promoters are added in SBR sewage disposal systems, the growth promoter includes slaine, polyamines, organic acid azanol and Na2SO3, wherein the slaine is made up of calcium salt, mantoquita, magnesium salts and/or ferrous salt；
（3）Every the 3-5 SBR cycle of operation, to denitrogenation microbial inoculum is added in SBR system, stop adding when water outlet ammonia nitrogen concentration is less than 50mg/L, and total nitrogen concentration is less than 50mg/L.
In microbial growth promoters of the present invention, slaine is 40-100 weight portions, preferably 50-80 weight portions, and polyamines are 5-30 weight portions, preferably 10-20 weight portions, and organic acid azanol is 0.05-1.5 weight portions, preferably 0.1-1.0 weight portions, Na2SO3It is 10-40 weight portions, preferably 20-30 weight portions.
In microbial growth promoters of the present invention, slaine can be calcium salt, molysite and mantoquita, wherein Ca2+、Fe2+And Cu2+Mol ratio be（5-15）:（1-8）:（0.5-5）, preferably（8-12）:（2-6）:（1-4）；Or calcium salt, magnesium salts and mantoquita, wherein Ca2+、Mg2+And Cu2+Mol ratio be（5-15）:（5-25）:（0.5-5）, preferably（8-12）:（10-20）:（1-4）；Or calcium salt, magnesium salts, molysite and mantoquita, wherein Ca2+、Mg2+、Fe2+And Cu2+Mol ratio be（5-15）:（5-25）:（1-8）:（0.5-5）, preferably（8-12）:（10-20）:（2-6）:（1-4）.
In microbial growth promoters of the present invention, calcium salt is CaSO4Or CaCl2, magnesium salts is MgSO4Or MgCl2, mantoquita is CuSO4Or CuCl2, molysite is FeSO4Or FeCl2。
In microbial growth promoters of the present invention, the polyamines are the mixture of spermine, spermidine or both.The organic acid azanol is the mixture of formic acid azanol, hydroxylamine acetate or both.
In the present invention, the microbial growth promoters are added with water inlet, and dosage is added according to promoter concentration 10-40mg/L in sewage disposal system, and preferably 20-30mg/L is added.
In the present invention, arthrobacterium is contained in the denitrogenation microbial inoculum（Arthrobacter
creatinolyticus）FDN-1, Shui Shi Flavobacterium（Flavobacterium mizutaii）FDN-2, Paracoccus denitrificans (Paracoccus denitrificans)
DN-3, Methylobacterium (Methylobacterium
phyllosphaerae) SDN-3, marsh cock Salmonella（Kocuria palustris）FSDN-A and Staphylococcus cohnis (Staphylococcus cohnii）One or more in FSDN-C, six kinds of bacterial strains are respectively the bacterial strain described in CN102465105, CN102465106, CN102465104, CN102465103, CN103103141, CN103103142, it is preserved in " China Committee for Culture Collection of Microorganisms's common micro-organisms center " respectively on March 11st, 2010 and on July 14th, 2011, deposit number is respectively CGMCC No.3657, CGMCC No.3659, CGMCC No.3658, CGMCC No.3660, CGMCC NO.5061 and CGMCC NO.5062。Preferably use the microbial inoculum described in CN201210130645.8, including marsh cock Salmonella FSDN-A, arthrobacterium FDN-1, Shui Shi Flavobacterium FDN-2, five kinds of bacterial strains of Paracoccus denitrificans DN-3 and Methylobacterium SDN-3, above-mentioned thalline mixes in proportion again after can individually cultivating directly can also be mixed in proportion, be preferably directly mixed in proportion.The denitrogenation microbial inoculum is added once every the 3-5 SBR cycle of operation, and entering water volume ratio 0.05%-0.15% according to microbial inoculum and each cycle is added, and stops adding when water outlet ammonia nitrogen concentration is less than 15mg/L, and total nitrogen concentration is less than 25mg/L.
In the present invention, coal water slurry gasification process produces the waste water that waste water is generation during texaco coal-water slurry gasification, ammonia nitrogen concentration to be generally 100-1000mg/L, COD（Cr methods, similarly hereinafter）It is 200-1000mg/L, phenol ＜ 20mg/L, cyanide is 10-40mg/L, total salt quantity is 2000-5000mg/L, and calcium ion is 600-1500mg/L, and magnesium ion is 30-80mg/L, also contains many kinds of metal ions of a small amount of arsenic, lead, iron, copper etc. 20.
In the present invention, described air-dissolving air-float system is well-known to those skilled in the art.The operating pressure of air-dissolving air-float is 0.5-1.5MPa.The main purpose of air-dissolving air-float is to remove the ash in sewage, improves the validity of sludge, and then improve biochemical effects.The present invention increases air-dissolving air-float system in SBR before processings, can effectively reduce influence of the lime-ash in waste water to subsequent biochemical system, it is ensured that system stable operation.
In the present invention, described SBR sewage disposal systems shorten aeration time in the starting stage of operation, extend mixing time, and aeration time and the ratio of mixing time are 2-5 within a cycle of operation:1.
It is used in the present invention by slaine, polyamines, organic acid azanol and Na2SO3The accelerator of composition, in addition to it can promote the growth of denitrification microorganism, improve enzymatic activity, the polyamines in accelerator can improve the settleability and stability of activated sludge, extend the service life of thalline；Organic acid azanol and Na2SO3Cooperation add, contribute to the dissolved oxygen of control system, suppress the activity of nitrite oxidase, shorten nitration reaction process, be more beneficial for denitrogenation microbial inoculum and play denitrification, it is possible to achieve short-cut nitrification and denitrification denitrogenation, and then improve the treatment effeciency of sewage.High-effective microorganism used in the present invention is except can be in addition to denitrogenation, can also be by the use of nutriment of some minor metallic elements as own growth in sewage, by the use of the calcium ion in sewage as the carrier of growth of microorganism, unnecessary calcium ion is combined generation precipitation with the carbon dioxide in hydroxide ion or air, it is blended in activated sludge and enhances the flocculability of sludge, the reduction of salt content can be realized while denitrogenation, for reusing sewage provides condition as recirculated water.
Mating reaction by adding the close microorganism of condition of culture and growth promoter of the invention, short-cut nitrification and denitrification removing total nitrogen can be realized while ammonia nitrogen removal efficiency is improved, substantially reduce in nitrifying process to the consumption in the consumption of dissolved oxygen and denitrification process to carbon source, substantially reduce operating cost, it is ensured that system stable operation.The method can avoid relatively costly bi-membrane method, optimized by existing sewage treatment process, improve the disposal ability of existing sewage disposal system, reduce the indexs such as salt content and basicity in sewage as far as possible by biochemical process, advanced nitrogen is carried out to the nitrogen-containing pollutant in waste water, condition is provided for reusing sewage does circulating cooling make-up water.The inventive method simple possible, the strong adaptability of microorganism, denitrification effect is good, is particularly suitable for processing the advanced nitrogen treatment of the coal water slurry gasification waste water that disclosure satisfy that qualified discharge but be not suitable for reuse.
Specific embodiment
The inventive method is described in further detail below by embodiment.
The preparation of the microbial growth promoters of embodiment 1
Microbial growth promoters used herein are prepared according to the method described in CN201410585483.6, CN201410585481.7 and CN201410585655.X, it is preferred to use prepared by CN201410585655.X methods describeds.The ratio and formula for being first according to the microbial growth promoters of table 1 prepare metal salt solution, using preceding by polyamines, organic acid azanol and Na2SO3It is added in metal salt solution, prepares microbial growth promoters I-III, the promoter concentration is 0.5g/L.
The formula and ratio of the microbial growth promoters of table 1
The preparation of the denitrogenation microbial inoculum of embodiment 2
The denitrogenation microbial inoculum that the inventive method is used includes marsh cock Salmonella FSDN-A, arthrobacterium FDN-1, Shui Shi Flavobacterium FDN-2, five kinds of bacterial strains of Paracoccus denitrificans DN-3 and Methylobacterium SDN-3, the microbial bacterial agent for being used according to CN201210130645.8 embodiment 1 described in method be prepared, be finally obtained according to different proportion harvest bacterial suspension A（Five kinds of bacterial strain volume ratios are 1:1:1:1:1）With bacteria suspension B（Five kinds of bacterial strain volume ratios are 1:1:2:1.5:3）.
The result of the waste water of embodiment 3
The waste water produced in certain enterprise's Texaco Water-coal-mud Gasification Technology hydrogen production process, is processed using the technique of five groups of SBR alternate runs.Ammonia nitrogen concentration is 300mg/L, COD for 450mg/L, total salt quantity are 2000-2800mg/L in water inlet, after former SBR PROCESS FOR TREATMENTs, ammonia nitrogen concentration is that 50mg/L or so, COD are 200mg/L or so less than 50mg/L, total nitrogen concentration in water outlet, total salt quantity is 3200mg/L or so, on the one hand the waste water be that water outlet ammonia nitrogen can not be up to standard, on the other hand it is salt content high, and ton cost of water treatment is 0.8 yuan.
Processed using the inventive method, detailed process is as follows：（1）Increase air-dissolving air-float system in the front end of SBR techniques, the operating pressure for controlling air-dissolving air-float is 1.0MPa.（2）To in SBR system microbial growth promoters are added according to promoter concentration 25mg/L in sewage disposal system.（3）Every 3 SBR cycles of operation, according to denitrogenation microbial inoculum and the volume ratio 0.1% of each cycle water inlet to the denitrogenation microbial inoculum added in SBR sewage disposal systems described in CN201210130645.8, add after different accelerator and microbial inoculum coordinate treatment 10 days, water outlet ammonia nitrogen and total nitrogen concentration are shown in Table 2.
The system effluent quality index of table 2
From the point of view of table 2, after adding accelerator and denitrogenation microbial inoculum cooperation treatment, system water outlet ammonia nitrogen concentration is less than 25mg/L less than 5mg/L, total nitrogen concentration, and waste water realizes advanced nitrogen treatment, and ton cost of water treatment is down to 0.5 yuan by original 0.8 yuan.Individually although add denitrogenation microbial inoculum and accelerator has reached certain treatment effect, but system water outlet ammonia nitrogen and total nitrogen concentration are still higher, are not carried out advanced treating.
The result of the waste water of comparative example 1
Treatment is with the identical waste water of embodiment 1, except that using the microbial growth promoters described in patent CN201410585590.9, although can also realize advanced treating, want to reach treatment effect same as Example 1, add accelerator and microbial inoculum coordinates process time to be 20 days.As can be seen here, using the inventive method while advanced treating is realized, can substantially shorten process time, improve sewage treating efficiency.
Claims (10)
1. a kind of coal water slurry gasification process produces the deepness denitrogenation method for treating of waste water, it is characterised in that including following content：
（1）Increase air-dissolving air-float system in the front end of SBR techniques；
（2）During startup, to microbial growth promoters are added in SBR sewage disposal systems, the growth promoter includes slaine, polyamines, organic acid azanol and Na2SO3, wherein the slaine is made up of calcium salt, mantoquita, magnesium salts and/or ferrous salt；
（3）Every the 3-5 SBR cycle of operation, to denitrogenation microbial inoculum is added in SBR system, stop adding when water outlet ammonia nitrogen concentration is less than 50mg/L, and total nitrogen concentration is less than 50mg/L.
2. method according to claim 1, it is characterised in that：In the microbial growth promoters, slaine is 40-100 weight portions, and polyamines are 5-30 weight portions, and organic acid azanol is 0.05-1.5 weight portions, Na2SO3It is 10-40 weight portions.
3. method according to claim 1 and 2, it is characterised in that：In the microbial growth promoters, slaine is calcium salt, molysite and mantoquita, wherein Ca2+、Fe2+And Cu2+Mol ratio be（5-15）:（1-8）:（0.5-5）；Or calcium salt, magnesium salts and mantoquita, wherein Ca2+、Mg2+And Cu2+Mol ratio be（5-15）:（5-25）:（0.5-5）；Or calcium salt, magnesium salts, molysite and mantoquita, wherein Ca2+、Mg2+、Fe2+And Cu2+Mol ratio be（5-15）:（5-25）:（1-8）:（0.5-5）.
4. method according to claim 1 and 2, it is characterised in that：In the microbial growth promoters, calcium salt is CaSO4Or CaCl2, magnesium salts is MgSO4Or MgCl2, mantoquita is CuSO4Or CuCl2, molysite is FeSO4Or FeCl2；The polyamines are the mixture of spermine, spermidine or both；The organic acid azanol is the mixture of formic acid azanol, hydroxylamine acetate or both.
5. method according to claim 1, it is characterised in that：The microbial growth promoters are added with water inlet, and dosage is added according to promoter concentration 10-40mg/L in sewage disposal system.
6. method according to claim 1, it is characterised in that：Contain arthrobacterium in the denitrogenation microbial inoculum（Arthrobacter creatinolyticus）FDN-1, Shui Shi Flavobacterium（Flavobacterium mizutaii）FDN-2, Paracoccus denitrificans (Paracoccus denitrificans)
DN-3, Methylobacterium (Methylobacterium phyllosphaerae)
SDN-3, marsh cock Salmonella（Kocuria palustris）FSDN-A and Staphylococcus cohnis (Staphylococcus cohnii）One or more in FSDN-C, six kinds of bacterial strains are respectively the bacterial strain described in CN102465105, CN102465106, CN102465104, CN102465103, CN103103141, CN103103142。
7. method according to claim 1, it is characterised in that：Described denitrogenation microbial inoculum uses the microbial inoculum described in CN201210130645.8.
8. the method according to claim 1,6 or 7, it is characterised in that：The denitrogenation microbial inoculum is added once every the 3-5 SBR cycle of operation, and entering water volume ratio 0.05%-0.15% according to microbial inoculum and each cycle is added, and stops adding when water outlet ammonia nitrogen concentration is less than 15mg/L, and total nitrogen concentration is less than 25mg/L.
9. method according to claim 1, it is characterised in that：The coal water slurry gasification process produces the waste water that waste water is generation during texaco coal-water slurry gasification, ammonia nitrogen concentration is generally 100-1000mg/L, COD is 200-1000mg/L, phenol ＜ 20mg/L, cyanide is 10-40mg/L, and total salt quantity is 2000-5000mg/L, and calcium ion is 600-1500mg/L, magnesium ion is 30-80mg/L, also contains many kinds of metal ions of a small amount of arsenic, lead, iron, copper etc. 20.
10. method according to claim 1, it is characterised in that：The SBR processing systems shorten aeration time in the operation starting stage, extend mixing time, and aeration time and the ratio of mixing time are 2-5 within a cycle of operation:1.
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