CN105624095A

CN105624095A - Enrichment culture method for nitrifying bacteria by waste water generated in catalyst production process

Info

Publication number: CN105624095A
Application number: CN201410585589.6A
Authority: CN
Inventors: 高会杰; 孙丹凤; 郭志华; 赵胜楠
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2014-10-28
Filing date: 2014-10-28
Publication date: 2016-06-01
Anticipated expiration: 2034-10-28
Also published as: CN105624095B

Abstract

The invention discloses an enrichment culture method for nitrifying bacteria by waste water generated in a catalyst production process. Active sludge with rich nitrifying bacteria is selected as inoculated sludge firstly; the ammonia-containing waste water generated in the catalyst production process is taken as the culture solution; a way of changing water in batches and gradually increasing the ammonia-nitrogen concentration in a substrate is adopted for culturing; a growth promoter for nitrifying bacteria is supplemented in each time of changing the culture solution; the growth promoter for nitrifying bacteria comprises metal salt and a polyamine substance in parts by weight: including 40-100 parts of metal salt, preferably 50-80 parts, and 5-30 parts of polyamine substance, preferably 10-20 parts; and the metal salt comprises calcium salt, copper salt, magnesium salt and/or ferrous salt. According to the enrichment culture method, industrial waste water is taken as the culture solution and the growth promoter is added for realizing enrichment culture for the nitrifying bacteria, so that the nitrifying bacteria with high tolerance can grow and propagate rapidly within a short time, and the nitrifying bacteria can efficiently degrade ammonia nitrogen in waste water under a high-salinity condition.

Description

Utilize the method that catalyst production process produces waste water enrichment culture nitrifier

Technical field

The invention belongs to biological technical field, be specifically related to a kind of method utilizing and producing waste water enrichment culture nitrifier in catalyst production process.

Background technology

In biological denitrification method, it is no matter traditional nitrification-denitrification, or novel short-cut nitrification-denitrification and short distance nitration-anaerobic ammoxidation all need the Nitrification removal of ammonia and nitrogen through nitrifier. Nitrobacter is in chemotrophy type microorganism. Biological cell is only with the energy preserved with forms such as ATP, it is impossible to directly utilize the free energy that chemical reaction discharges. In good oxygen metabolism, ATP synthesizes mainly through the oxidative phosphorylation of respiratory chain. Ammoxidation phosphorylation efficiency is very low, and the ATP that can be generated by is very limited, and these energy are mainly used in electron transition to higher energy level, and this makes nitrobacteria growth very slow, and the phase is 8 ~ 36h from generation to generation. In the cell wall of nitrifier, peptidoglycan content is low, protein and fat content are high, therefore environmental change is more sensitive, nitrifier adaptability natural in nature and toleration are poor, cannot get the mastery in growth competition with heterotroph microorganism under a lot of conditions. In sewage disposal system, when in activated sludge, nitrifier content is relatively low, rely on regulate the environmental condition such as dissolved oxygen and pH cannot within a short period of time fast-growth breeding, the sewage disposal system removal of ammonia and nitrogen ultimately resulting in existing operation is limited in one's ability, industrially generally can adopt and directly throw in cultured high concentration nitrifier in sewage disposal system to solve this problem. No matter it is in sewage disposal system, directly cultivate nitrifier or outside sewage disposal system, cultivate nitrifier, is required for adding the material promoting growth, the growth rate of nitrifier could be accelerated.

Chinese patent CN200510111874.5, CN200510111876.4, CN200510111877.9 and CN200510111875.X propose the nitrobacteria growth promoter utilizing different metal salt combination respectively, and main component includes molasses, slaine (iron salt, manganese salt, calcium salt and magnesium salt) and adsorbent. After using this accelerator, ammonia nitrogen removal frank can improve more than 20%. But be mainly the materials such as zeolite powder, kieselguhr, Powdered Activated Carbon or flyash due to adsorbent, adding of these adsorbents will certainly increase sludge yield. Chinese patent CN200710010383.0 discloses the enrichment method of high efficiency nitrification bacterium in a kind of activated sludge, is adopt intermittent activated sludge process, is enriched with by gradually stepping up the method for culture fluid ammonia nitrogen concentration; Chinese patent CN201010221166.8 discloses the cultural method of a kind of nitrosation dominant microflora, adopts three optimizing phases to cultivate. More than inventing is all adopt the mode adding ammonium salt to configure culture fluid, and this adds additional the toxigenic capacity of denitrification microorganism.

CN1354786A discloses the cultural method of a kind of activated sludge middle and high concentration nitrifier, it is urinate mud as seed sludge using downflow sludge and dung, with sludge dewatering filtrate or nitrated disengaging liquid for culture fluid, ammonia nitrogen concentration therein is 100��300mg/L, the growth of thalline can be produced inhibitory action higher than 300mg/L by ammonia nitrogen concentration, and the nitrifier being enriched with can not the ammonia nitrogen of enduring high-concentration. When the nitrifier of the method gained processes the ammonia nitrogen concentration sewage higher than more than 300mg/L, it is necessary to be diluted to below 300mg/L reprocessing with sea water or fresh water etc.

Summary of the invention

For the deficiencies in the prior art, the invention provides one and utilize generation waste water enrichment culture nitrifier method in catalyst production process. Nitrifier is carried out enrichment culture in the way of adding growth promoter using industrial wastewater as culture fluid employing by the present invention so that the nitrifier fast-growth at short notice breeding that toleration is strong, the ammonia nitrogen in energy efficient degradation waste water under high Variation of Salinity Condition.

The present invention utilizes generation waste water enrichment culture nitrifier method in catalyst production process, including following content: first select the activated sludge rich in nitrifier as seed sludge, adopt the ammonia-containing water produced in catalyst production process as culture fluid, adopt batch to change water and gradually step up the mode of substrate ammonia nitrogen concentration and cultivate, add nitrobacteria growth promoter while changing culture fluid every time, described nitrobacteria growth promoter includes slaine and polyamines, wherein slaine is 40 ~ 100 weight portions, it is preferably 50 ~ 80 weight portions, polyamines is 5 ~ 30 weight portions, it is preferably 10 ~ 20 weight portions, described slaine is made up of calcium salt, mantoquita, magnesium salt and/or ferrous salt, until nitrifier culture fluid is entirely in catalyst production process produces waste water, and when ammonia nitrogen removal frank is more than 90% in culture fluid in 24h, terminate the incubation in a cycle.

Slaine in nitrobacteria growth promoter of the present invention can be calcium salt, magnesium salt and mantoquita, wherein Ca²⁺��Mg²⁺And Cu²⁺Mol ratio be (5 ~ 15): (5 ~ 25): (0.5 ~ 5), it is preferred to (8 ~ 12): (10 ~ 20): (1 ~ 4); Or calcium salt, ferrous salt and mantoquita, wherein Ca²⁺��Fe²⁺And Cu²⁺Mol ratio be (5 ~ 15): (1 ~ 8): (0.5 ~ 5), it is preferred to (8 ~ 12): (2 ~ 6): (1 ~ 4); Or calcium salt, magnesium salt, ferrous salt and mantoquita, wherein Ca²⁺��Mg²⁺��Fe²⁺And Cu²⁺Mol ratio be (5 ~ 15): (5 ~ 25): (1 ~ 8): (0.5 ~ 5), it is preferred to (8 ~ 12): (10 ~ 20): (2 ~ 6): (1 ~ 4).

Calcium salt in nitrobacteria growth promoter of the present invention is CaSO₄Or CaCl₂, it is preferable that CaSO₄; Magnesium salt is MgSO₄Or MgCl₂, it is preferable that MgSO₄; Ferrous salt is FeSO₄Or FeCl₂, it is preferable that FeSO₄; Mantoquita is CuSO₄Or CuCl₂, it is preferable that CuSO₄. Polyamines in described nitrobacteria growth promoter is spermine, spermidine or both mixture.

Nitrobacteria growth promoter of the present invention can also include mineral acid azanol, and content is 0.5 ~ 15 weight portion, it is preferred to 2 ~ 10 weight portions. Described mineral acid azanol is one or more in oxammonium hydrochloride., oxammonium sulfate. or phosphatic hydroxylamine, it is preferred to oxammonium sulfate.. The appropriate addition of mineral acid azanol can directly participate in the metabolic process of nitrifier as the substrate of azanol oxygen also enzyme, shorten enzymatic reaction process, and the activator simultaneously as cell can accelerated cell growth.

The water quality characteristic producing waste water in catalyst production process of the present invention is: ammonia nitrogen concentration is generally 300 ~ 1000mg/L, COD(Cr method, lower with) concentration is 30 ~ 200mg/L, total salt quantity is 1 ~ 80,000 mg/L, pH7 ~ 11, belongs to alkaline water. Nitrifying bacteria enrichment condition of culture is temperature 18-40 DEG C, it is preferred to 25-35 DEG C; Dissolved oxygen is 1 ~ 5mg/L, it is preferred to 2 ~ 3mg/L; PH is 7.0-9.0, it is preferred to 7.8-8.5.

In nitrifying bacteria enrichment incubation of the present invention, first containing wastewater from catalyst is diluted to ammonia nitrogen concentration less than 100mg/L as initial incubation liquid with low ammonia-containing water, each batch change culture fluid while add growth promoter. Described nitrobacteria growth promoter adds according to promoter concentration 10 ~ 50mg/L in cultivating system, preferably 20 ~ 40mg/L adds, growth promoter all needs to add when changing nitrifier culture fluid every time, in culture fluid, ammonia nitrogen concentration often improves 100mg/L, then promoter concentration increases by 2 ~ 5mg/L.

Compared with prior art, the method have the advantages that

1, the present invention utilizes industrial wastewater to add the mode of growth promoter as culture fluid employing to carry out the cultivation of nitrifier, directly it is added to the nitrifier cultivated in sewage disposal process to have and makes the advantages such as consumption is low, tolerance impact capacity is strong, good sewage processing effect. Compared with prior art, the toxigenic capacity of nitrifier can be reduced on the one hand, the ammonia-containing water produced in catalyst generation process can be processed on the other hand while yeast culture, it is achieved economic benefit and social benefit bumper harvests.

2, the present invention adds the growth promoter of special composition and proportioning in nitrifying bacteria enrichment incubation, make nitrifier under the combined effect of slaine, polyamines and mineral acid azanol, fast-growth breeding at short notice, solving the problem that nitrobacteria growth is slow, after using accelerator, the growth rate of nitrifier can increase by 10 ~ 100 times.

3, the metal ion that in the growth promoter that the present invention uses, the slaine that contains provides is as the element required for nitrobacteria growth, improves the activity of enzyme simultaneously as the component of enzyme, it is possible to fast degradation substrate, accelerates enzymatic reaction process. Polyamines can promote cell proliferation, and with metal ion combined effect, it is possible to accelerate cell proliferation, and settleability and the stability of gather in the crops thalline can be improved, prolongation thalline service life.

Detailed description of the invention

Below in conjunction with specific embodiment, the present invention program is described in detail.

The preparation of embodiment 1 nitrobacteria growth promoter

The preparation method of nitrobacteria growth promoter of the present invention is: (1) prepares metal salt solution according to consisting of and weight portion: slaine is 40 ~ 100 weight portions, being preferably 50 ~ 80 weight portions, described slaine is made up of calcium salt, mantoquita, magnesium salt and/or ferrous salt; (2) by 5 ~ 30 weight portions before using, it is preferred to the polyamines of 10 ~ 20 weight portions joins in metal salt solution. Further, can also add content before using is 0.5 ~ 15 weight portion, it is preferred to the mineral acid azanol of 2 ~ 10 weight portions.

Adopting said method to prepare the nitrobacteria growth promoter of four kinds of models according to the ratio of table 1 accelerator and formula, described promoter concentration is 0.5g/L.

The formula of table 1 accelerator and ratio

The enrichment culture of embodiment 2 nitrifier

First cultivating (reactor is respectively designated as No. 1, No. 2, No. 3, No. 4 and No. 5) in reactor to five parallel nitrifiers and inoculate certain sewage treatment plant activated sludge rich in nitrifier, after inoculation, MLSS is 3000mg/L. Used catalyst production process produces waste water quality feature and nitrifying bacteria enrichment condition of culture in Table 2. First waste water is diluted to ammonia nitrogen concentration be 100mg/L as initial incubation liquid, initial promoter concentration is 20mg/L, and in culture fluid, ammonia nitrogen concentration improves 50mg/L every time, and promoter concentration is every once improving 3mg/L. No. 5 are not added with accelerator as comparison in incubation. After cultivating after a while, in the waste water being entirely in catalyst production process to produce when culture fluid and 24h, ammonia nitrogen removal frank terminates the enrichment culture process in a cycle when reaching 90% in culture fluid. After cultivation terminates, ammonia nitrogen removal frank is in Table 2.

The condition of culture of table 2 nitrifier and result

From the data of table 2, cultivating and terminate rear 1 ~ No. 4 reactor ammonia nitrogen removal frank more than 90%, No. 5 reactor ammonia nitrogen removal franks being not added with accelerator only have 61.3%. As can be seen here, growth promoter is used can to significantly improve nitrifier to catalyst production process produces the clearance of ammonia nitrogen in waste water.

Claims

1. one kind utilizes the method that catalyst production process produces waste water enrichment culture nitrifier, it is characterized in that including following content: first select the activated sludge rich in nitrifier as seed sludge, adopt the ammonia-containing water produced in catalyst production process as culture fluid, adopt batch to change water and gradually step up the mode of substrate ammonia nitrogen concentration and cultivate, add nitrobacteria growth promoter while changing culture fluid every time, described nitrobacteria growth promoter includes slaine and polyamines, wherein slaine is 40 ~ 100 weight portions, polyamines is 5 ~ 30 weight portions, described slaine is by calcium salt, mantoquita, magnesium salt and/or ferrous salt composition, until the waste water that nitrifier culture fluid is entirely in catalyst production process to be produced, and when ammonia nitrogen removal frank is more than 90% in culture fluid in 24h, terminate the incubation in a cycle.

2. method according to claim 1, it is characterised in that: in described nitrobacteria growth promoter, slaine is 50 ~ 80 weight portions, and polyamines is 10 ~ 20 weight portions.

3. method according to claim 1 and 2, it is characterised in that: the slaine in described nitrobacteria growth promoter is calcium salt, magnesium salt and mantoquita, wherein Ca²⁺��Mg²⁺And Cu²⁺Mol ratio be (5 ~ 15): (5 ~ 25): (0.5 ~ 5); Or calcium salt, ferrous salt and mantoquita, wherein Ca²⁺��Fe²⁺And Cu²⁺Mol ratio be (5 ~ 15): (1 ~ 8): (0.5 ~ 5); Or calcium salt, magnesium salt, ferrous salt 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 3, it is characterised in that: when described slaine is calcium salt, magnesium salt and mantoquita, Ca²⁺��Mg²⁺And Cu²⁺Mol ratio be (8 ~ 12): (10 ~ 20): (1 ~ 4); Or when calcium salt, ferrous salt and mantoquita, Ca²⁺��Fe²⁺And Cu²⁺Mol ratio be (8 ~ 12): (2 ~ 6): (1 ~ 4); Or when calcium salt, magnesium salt, ferrous salt and mantoquita, Ca²⁺��Mg²⁺��Fe²⁺And Cu²⁺Mol ratio be (8 ~ 12): (10 ~ 20): (2 ~ 6): (1 ~ 4).

5. method according to claim 3, it is characterised in that: the calcium salt in described nitrobacteria growth promoter is CaSO₄Or CaCl₂; Magnesium salt is MgSO₄Or MgCl₂; Ferrous salt is FeSO₄Or FeCl₂; Mantoquita is CuSO₄Or CuCl₂��

6. method according to claim 1 and 2, it is characterised in that: the polyamines in described nitrobacteria growth promoter is spermine, spermidine or both mixture.

7. method according to claim 1 and 2, it is characterised in that: described nitrobacteria growth promoter also includes mineral acid azanol, and content is 0.5 ~ 15 weight portion.

8. method according to claim 7, it is characterised in that: described mineral acid azanol is one or more in oxammonium hydrochloride., oxammonium sulfate. or phosphatic hydroxylamine, and content is 2 ~ 10 weight portions.

9. method according to claim 1, it is characterised in that: the water quality characteristic producing waste water in described catalyst production process is: ammonia nitrogen concentration is 300 ~ 1000mg/L, COD concentration is 30 ~ 200mg/L, and total salt quantity is 1 ~ 80,000 mg/L, pH7 ~ 11.

10. method according to claim 1, it is characterised in that: described nitrifying bacteria enrichment condition of culture is temperature 18-40 DEG C, it is preferred to 25-35 DEG C; Dissolved oxygen is 1 ~ 5mg/L, it is preferred to 2 ~ 3mg/L; PH is 7.0-9.0, it is preferred to 7.8-8.5.

11. method according to claim 1, it is characterized in that: in described nitrifying bacteria enrichment incubation, first containing wastewater from catalyst is diluted to ammonia nitrogen concentration less than 100mg/L as initial incubation liquid with low ammonia-containing water, add growth promoter while each batch of replacing culture fluid, add according to promoter concentration 10 ~ 50mg/L in cultivating system.

12. the method according to claim 1 or 11, it is characterized in that: described nitrobacteria growth promoter is added according to promoter concentration 20 ~ 40mg/L in cultivating system, in culture fluid, ammonia nitrogen concentration often improves 100mg/L, then promoter concentration increases by 2 ~ 5mg/L.