CN106754583B - Biological agent for maintaining stability of circulating cooling water system and preparation method and application thereof - Google Patents
Biological agent for maintaining stability of circulating cooling water system and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of industrial water treatment, and relates to a biological agent for maintaining stability of a circulating cooling water system, and a preparation method and application thereof.
Description
Technical Field
The invention belongs to the technical field of industrial water treatment, and particularly relates to a biological agent for maintaining stability of a circulating cooling water system, and a preparation method and application thereof.
Background
The concentration multiple is the ratio of the salt content in the circulating water to the salt content in the supplementing water, is an important index of the industrial circulating water, and generally increases the concentration multiple, reduces the water supplementing amount and the sewage discharge amount, and realizes energy conservation and emission reduction in order to reduce the production cost and improve the reuse rate of the water. However, with the increase of the concentration multiple of the circulating cooling water, on one hand, the concentration of scaling ions such as calcium, magnesium and the like is higher and higher, scaling tends to be serious, and in addition, with the increase of the water temperature, the solubility of some dissolved salts is reduced on the contrary, so that the dissolved salts are separated out from the water to form scale, the heat transfer efficiency is reduced if the water temperature is low, and the heat exchanger is blocked if the water temperature is high; on the other hand, along with the increase of the cycle number, the concentration of dissolved salts in water is increased, the conductivity of water is increased, the electrochemical corrosion of a system is aggravated, the concentration of corrosive ions such as chloride ions and sulfate ions in the salts is increased, the corrosivity of the water is also increased, the chloride ions not only easily cause stress corrosion to stainless steel, but also can hinder the passivation of metal and damage a passivation film with a protective effect on the surface of the metal; on the other hand, in the open type circulating cooling water system, microorganisms in the air continuously enter a water body, the temperature and pH value range in the circulating cooling water system is just suitable for the growth of various microorganisms in the environment, meanwhile, the concentration of the microorganisms in the circulating cooling water and nutrients such as carbonate, nitrate, phosphate, organic matters and the like required by the growth of the microorganisms are increased due to circulating concentration, and the water collecting tank and the cooling tower are exposed outdoors all the year round and have sufficient sunlight, so that good conditions are provided for the growth and the propagation of the microorganisms, and the two problems of microbial slime and microbial corrosion are caused by the mass propagation of harmful microorganisms including slime producing bacteria, iron depositing bacteria, sulfide producing bacteria, acid producing bacteria and the like.
In order to solve the problems of scaling, corrosion and algae breeding and improve the concentration multiple of circulating water, treating agents including scale inhibitors, corrosion inhibitors and bactericidal algicide (biocide) are required to be added into a circulating cooling water system. The currently used agents such as scale inhibitors, corrosion inhibitors, bactericidal algicide and the like are mainly chemical drugs and have the following defects: firstly, the common phosphorus and zinc salt corrosion and scale inhibitor can cause the phosphorus content and heavy metal to exceed the standard, secondary pollution is caused to the environment, and the sterilization and algae removal agent can cause the corrosion of pipelines; the turbidity of the water body is higher, and the allowable concentration times of the chemical agents are limited, generally about 4 times; the chemical method can not operate under the high COD water quality, and the chemical agent can not reduce the salt corrosion; the purchase cost of chemical agents is high, a large amount of chemical agents are needed during circulating water treatment, the control is complex, the labor intensity is high, the comprehensive operation cost is high, and the economic burden of enterprises is increased.
Therefore, the method for maintaining the stability of the circulating cooling water system, which is green and environment-friendly and has a remarkable effect, is developed, and has important significance and market prospect. Patent document 201510767178.3 discloses a method for reducing assimilable organic carbon in circulating water by a biofilm method, wherein 7 kinds of degrading bacteria are thrown into a water body to compete for assimilable organic carbon and nitrogen-containing substances in circulating cooling water, thereby blocking nutrient sources of harmful bacteria and algae and inhibiting the propagation of harmful bacteria and algae. On one hand, the method needs more strains, and increases the culture use cost; on the other hand, the problems of bacteria and algae breeding and chemical corrosion can only be solved, and the problem of scale formation of circulating cooling water cannot be solved.
Disclosure of Invention
The invention aims to provide a biological agent for maintaining the stability of a circulating cooling water system, which utilizes the biological ecological principles of scale dissolving effect, biodegradation, low nutrient restriction and biological competitive discharge of carbonic anhydrase, not only can occupy the ecological position of harmful bacteria and algae in the circulating water system, effectively inhibit the propagation of corrosive bacteria and algae in the circulating water, reduce the oxygen corrosion, microbial corrosion and salt corrosion of the system, but also can dissolve the hard scale generated in the circulating water system, prevent the formation of new hard scale, reduce the turbidity of a water body, improve the quality of the circulating water, maintain the stability of the circulating cooling water system, improve the concentration rate and realize energy conservation and emission reduction.
Another object of the present invention is to provide a method for preparing the biological agent for maintaining the stability of a circulating cooling water system according to the present invention.
It is still another object of the present invention to provide a method for maintaining a stable biological agent treatment circulating water system of a circulating cooling water system according to the present invention.
In order to achieve the purpose, the invention provides the following technical scheme:
a biological preparation for maintaining stability of circulating cooling water system comprises carbonic anhydrase producing bacteria, lactic acid bacteria, yeast, bacillus and photosynthetic bacteria.
According to the biological preparation for maintaining the stability of the circulating cooling water system, the carbonic anhydrase producing bacteria, the lactic acid bacteria, the saccharomycetes, the bacillus and the photosynthetic bacteria can be carbonic anhydrase producing bacteria powder, lactic acid bacteria powder, saccharomycetes powder, bacillus powder and photosynthetic bacteria powder, and can also be carbonic anhydrase producing bacteria liquid, lactic acid bacteria liquid, saccharomycetes liquid, bacillus liquid and photosynthetic bacteria liquid; preferably, the carbonic anhydrase producing bacteria, lactic acid bacteria, yeast, bacillus and photosynthetic bacteria are carbonic anhydrase producing bacteria liquid, lactic acid bacteria liquid, yeast liquid, bacillus liquid and photosynthetic bacteria liquid.
According to the biological preparation for maintaining the stability of the circulating cooling water system, the carbonic anhydrase producing bacteria powder, the lactic acid bacteria powder, the saccharomycete powder, the bacillus powder and the photosynthetic bacteria powder can be prepared by adopting the conventional technology in the field, such as a vacuum freeze drying technology and the like.
According to the biological preparation for maintaining the stability of the circulating cooling water system, the total bacteria number in the carbonic anhydrase producing bacteria liquid, the lactic acid bacteria liquid, the saccharomycete liquid, the bacillus liquid and the photosynthetic bacteria liquid reaches 1010CFU/g is higher than the standard.
According to the biological preparation for maintaining the stability of the circulating cooling water system, the carbonic anhydrase producing bacteria liquid, the lactic acid bacteria liquid, the saccharomycete liquid, the bacillus liquid and the photosynthetic bacteria liquid are prepared according to the volume ratio of 3:2:2:1: 2.
According to the biological preparation for maintaining the stability of the circulating cooling water system, the carbonic anhydrase producing bacteria are Lysinibacillus boronitolerans, the lactic acid bacteria are bifidobacterium bifidum, the yeast is candida, the bacillus is bacillus subtilis, and the photosynthetic bacteria are rhodopseudomonas palustris.
In a second aspect, the present invention provides a method for preparing a biological agent for maintaining the stability of a recirculating cooling water system according to the present invention, comprising the steps of:
step a) strain preparation: preparing stock strains of Lysinibacillus boronitolorans, bifidobacterium bifidum, candida, bacillus subtilis and rhodopseudomonas palustris, and respectively activating the strains;
step b) expanded culture: respectively carrying out amplification culture on the activated strain stock seeds in the step a) to obtain bacterial solutions, and fermenting each bacterial solution through a separate fermentation tank;
step c), mixing bacterial liquid: mixing the five bacterial liquids fermented separately in the step b) to obtain the biological agent for maintaining the stability of the circulating cooling water system.
According to the preparation method of the biological agent for maintaining the stability of the circulating cooling water system, the specific operation of the expanding culture in the step b) is as follows:
first-stage shaking culture: respectively inoculating 5mL of the five activated strain stock seeds obtained in the step a) into corresponding liquid culture media (100mL), and carrying out shaking culture at 25 ℃ for 24-48 h to obtain 500mL of bacterial liquid;
II, aeration culture: inoculating 500mL of the bacterial liquid into a 10L fermentation tank, carrying out aeration culture for 40h at the temperature of 20-25 ℃ and the pH of the solution to obtain 5L of bacterial liquid;
③ three-stage fermentation culture: inoculating 5L of the bacterial liquid into a 100L fermentation tank, carrying out aeration culture for 40h at the temperature of 20-25 ℃ and the pH of the solution is neutral, so as to obtain 50L of bacterial liquid;
fourthly, four-stage fermentation culture: 50L of bacterial liquid is put into a 1 cubic fermentation tank for fermentation until the total microbial count in the fermentation tank reaches 1010CFU/g is higher than the standard.
According to the preparation method of the biological preparation for maintaining the stability of the circulating cooling water system, five bacterial liquids of the microbial preparation in the step c) are Lysinibacillus boronitolerans, bifidobacterium bifidum, candida, bacillus subtilis and rhodopseudomonas palustris according to the volume ratio of 3:2:2:1:2, so that the obtained effect is good.
In a third aspect, the present invention provides a method for treating recirculating cooling water using the biological agent for stabilizing a recirculating cooling water system of the present invention, comprising the steps of:
step 1) putting microorganism nidation filler, namely adding fiber ball filler for providing nidation for microorganisms into a circulating water collecting tank;
and step 2) adding the biological agent for maintaining the stability of the circulating cooling water system, namely adding the biological agent for maintaining the stability of the circulating cooling water system in a circulating water collecting tank, wherein the adding amount is 0.02-0.05% of the water retention amount of circulating water.
According to the method for treating the circulating cooling water by the biological agent for maintaining the stability of the circulating cooling water system, the fiber ball filler in the step 1) is intensively put into a stainless steel framework fixed in a circulating water collecting tank, the stainless steel framework is a rectangular cabinet with a stainless steel net arranged on the surface, and the smooth water flow is ensured while the fiber ball filler is restrained.
According to the method for treating the circulating cooling water by the biological agent for maintaining the stability of the circulating cooling water system, the fiber ball filler in the step 1) is spherical suspension filler, the diameter is 100mm, the adding amount is 70 percent of the volume of the stainless steel framework, and microorganisms can be more uniformly enriched on the fiber ball filler.
In a specific embodiment, the method for treating recirculated cooling water with a biological agent for maintaining the stability of a recirculated cooling water system according to the present invention comprises the steps of:
step A) strain preparation: preparing stock strains of Lysinibacillus boronitolorans, bifidobacterium bifidum, candida, bacillus subtilis and rhodopseudomonas palustris, and respectively activating the strains;
step B) expanded culture: respectively inoculating various activated strain stock seeds in the step A) of 5mL into corresponding liquid culture media (100mL), and carrying out shaking culture at 25 ℃ for 24-48 h to obtain 500mL of bacterial liquid; inoculating the obtained 500mL of bacterial liquid into a 10L fermentation tank, carrying out aeration culture for 40h at the temperature of 20-25 ℃ and the pH of the solution to obtain 5L of bacterial liquid; inoculating the obtained 5L of bacterial liquid into a 100L fermentation tank, carrying out aeration culture for 40h at the temperature of 20-25 ℃ and the pH of the solution to obtain 50L of bacterial liquid; putting 50L of bacterial liquid into a 1-cubic fermentation tank for fermentation;
step C), mixing bacterial liquid: mixing the five bacterial liquids fermented independently in the step B) according to the volume ratio of 3:2:2:1:2 to obtain the biological agent for maintaining the stability of the circulating cooling water system;
step D), putting microorganism implantation fillers, namely putting fiber ball fillers into a stainless steel framework fixed in a circulating water collecting tank;
and E) adding a biological agent for maintaining the stability of the circulating cooling water system, namely adding the biological agent for maintaining the stability of the circulating cooling water system prepared in the step C) into a circulating water collecting tank, wherein the adding amount is 0.02-0.05% of the volume of circulating water.
Has the advantages that: the biological agent for maintaining the stability of the circulating cooling water system can obviously reduce the chemical corrosion speed, the circulating cooling water system added with the biological agent has obviously reduced conductivity, and the sum of the concentrations of sulfate ions and chloride ions is not more than 1500 mg/L;
the biological agent for maintaining the stability of the circulating cooling water system has obvious scale dissolving and scale inhibiting effects, and the hardness and alkalinity value of calcium is far lower than 1100 mg/L;
the biological agent for maintaining the stability of the circulating cooling water system can obviously improve the quality of circulating water, and can reduce the turbidity to about 1 after running for 19 weeks;
the biological agent for maintaining the stability of the circulating cooling water system can efficiently inhibit the propagation of bacteria and algae in the circulating water, and COD is reduced to about 7 after the biological agent runs for 19 weeks;
the biological agent for maintaining the stability of the circulating cooling water system can maintain the dynamic balance of the circulating water system through self metabolism when operating under the condition of low COD, thereby ensuring the normal operation of the circulating water system.
Drawings
FIG. 1 is a view of the outlet of a heat exchange tube of a circulating water cooling system to which a biological agent for stabilizing the circulating cooling water system of the present invention is added;
FIG. 2 is a view of the outlet of the heat exchange tube of the circulating water cooling system without adding the biological agent for maintaining the stability of the circulating cooling water system according to the present invention.
Detailed Description
The present invention is described in further detail below by way of specific embodiments, all of which are commercially available.
Example 1 preparation of a biological agent for maintaining the stability of a recirculating Cooling Water System
Respectively activating five bacteria of Lysinibacillus boronitolerans, bifidobacterium bifidum, candida, bacillus subtilis and rhodopseudomonas palustris into 5mL of Lysinibacillus boronitolerans stock, 5mL of bifidobacterium stock, 5mL of candida stock, 5mL of bacillus subtilis stock and 5mL of rhodopseudomonas palustris stock;
inoculating 5mL of Lysinibacillus boronitolorans stock strain into 100mL of liquid culture medium, and performing shake culture at 30 ℃ for 48h to obtain 500mLLysinibacillus boronitolorans bacterial liquid; inoculating 500mL of Lysinibacillus boronitolorans bacterial solution into a 10L fermentation tank, keeping the temperature at 25-30 ℃, keeping the pH of the solution neutral, and carrying out aeration culture for 40h to obtain 5L of Lysinibacillus boronitolorans bacterial solution; inoculating 5L of Lysinibacillus boronitolerans bacterial liquid into a 100L fermentation tank, keeping the temperature at 25-30 ℃, keeping the pH of the solution neutral, and carrying out aeration culture for 40h to obtain 50L of Lysinibacillus boronitolerans bacterial liquid; then 50L of Lysinibacillus boronitolorans bacterial liquid is put into a 1 cubic Lysinibacillus boronitolorans fermentation tank for fermentation until the total microbial bacterial count in the fermentation tank reaches 1010CFU/g is above; performing amplification culture on Bifidobacterium bifidum stock, Candida stock, Bacillus subtilis stock and Rhodopseudomonas palustris stock by the same method;
mixing the above respectively expanded Lysinibacillus boronitolorans bacterial liquid, Bifidobacterium bifidum bacterial liquid, Candida bacterial liquid, Bacillus subtilis bacterial liquid and Rhodopseudomonas palustris bacterial liquid according to the volume ratio of 3:2:2:1:2 to prepare the biological preparation for maintaining the stability of the circulating cooling water system.
Example 2 use of biological Agents to stabilize recirculating Cooling Water systems
The biological agent for maintaining the stability of the circulating cooling water system prepared in the example 1 is added into a circulating water pool according to the proportion of 0.02 percent of the volume of circulating water, fiber ball fillers accounting for 70 percent of the volume of a stainless steel framework are added into the stainless steel framework fixed in the circulating water pool, the water quality experimental data of the circulating cooling water running for different time are shown in a table 1,
TABLE 1
As can be seen from table 1: after the biological agent for maintaining the stability of the circulating cooling water system is used in the circulating water system, COD is gradually reduced along with the utilization of a large amount of assimilable organic carbon by microorganisms, and the water quality of circulating water is obviously improved along with the continuous decomposition of dirt and bacteria and algae in further biodegradation; sulfate ions and chloride ions are corrosive ions, the sulfate ions can be combined with calcium ions in circulating water to generate calcium carbonate scale, the chloride ions can cause pitting corrosion, crevice corrosion and stress corrosion of metal and alloy, the content of the sulfate ions and the chloride ions has important influence on the scaling and corrosion of a system, and in a system for adding a preparation, the sum of the concentrations of the two ions is less than an allowable value of 1500 mg/L; the total iron content in the circulating water can be used as a basis for estimating the corrosion condition of steel equipment, and the total iron content of a system for adding biological agents is less than 0.5mg/L of the requirement; the value of calcium hardness and alkalinity reflects the scaling trend of a circulating water system, when the value of calcium hardness and alkalinity is higher than 1500ml/L, the scaling risk of the system is large, the index of the system for adding the preparation is far smaller than a specified value, and the scaling phenomenon is avoided; the concentration ratio of the system is increased, and the water discharge and water supplement are reduced.
Comparing the corrosion degree of the circulating water cooling system using the biological agent for maintaining the stability of the circulating cooling water system and the corrosion degree of the circulating water cooling system not using the biological agent for maintaining the stability of the circulating cooling water system, the corrosion condition of the outlet of the heat exchange tube after operation for 19 weeks is shown in figures 1 and 2, the outlet of the heat exchange tube of the system using the biological agent for maintaining the stability of the circulating cooling water system in figure 1 is smooth and almost has no scale deposit, the outlet of the heat exchange tube of the system not using the biological agent for maintaining the stability of the circulating cooling water system in figure 2 has white deposit, and a large amount of bubbles are generated by adding acid and dissolving, thus showing that the scale dissolving and scale inhibiting effects of the biological agent for maintaining the stability of the circulating.
Comparing the conductivity of the cooling water circulating system using the biological agent for maintaining the stability of the circulating cooling water system and the conductivity of the cooling water circulating system using the common chemical agent under different concentration ratios, the result is shown in table 2, and the conductivity of the cooling water circulating system using the biological agent is obviously lower than the value of the chemical agent under the concentration ratio (lower than 4 times) under the operation of higher concentration ratio (more than 4 times), namely the salt content of the circulating cooling water system using the biological agent is reduced, and the salt corrosion is reduced.
TABLE 2
After the circulating water cooling system which is made of the biological system and used for maintaining the stability of the circulating cooling water system is operated for 19 weeks, the corrosion rates of carbon steel, copper alloy and stainless steel are detected, the results are shown in table 3, and the corrosion rates of the carbon steel, the copper alloy and the stainless steel are all superior to the national standard, which shows that the biological agent provided by the invention effectively plays a corrosion inhibition effect and shows superior performance.
TABLE 3
The above description is only an example of the present invention, and the common general knowledge of the operation steps and features of the schemes is not described herein. It should be noted that, for those skilled in the art, without departing from the process of the present invention, several variations and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the inventive step of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (5)
1. A biological preparation for maintaining stability of circulating cooling water system comprises carbonic anhydrase producing bacteria, lactic acid bacteria, yeast, bacillus and photosynthetic bacteria;
the carbonic anhydrase producing bacteria, the lactic acid bacteria, the microzyme, the bacillus and the photosynthetic bacteria are carbonic anhydrase producing bacteria liquid, lactic acid bacteria liquid, microzyme liquid, bacillus liquid and photosynthetic bacteria liquid, and the total bacteria number reaches 1010CFU/g is above;
the carbonic anhydrase producing bacteria liquid, the lactic acid bacteria liquid, the saccharomycete liquid, the bacillus liquid and the photosynthetic bacteria liquid are prepared according to the volume ratio of 3:2:2:1: 2;
the carbonic anhydrase producing bacteria are Lysinibacillus boronitolerans, the lactic acid bacteria are bifidobacterium bifidum, the yeast is candida, the bacillus is bacillus subtilis, and the photosynthetic bacteria are rhodopseudomonas palustris.
2. The method of preparing a stable biological agent for a recirculating cooling water system as set forth in claim 1, comprising the steps of:
step a) strain preparation: preparing stock strains of carbonic anhydrase producing bacteria, lactic acid bacteria, saccharomycetes, bacillus and photosynthetic bacteria, and respectively activating the strains;
step b) expanded culture: respectively carrying out amplification culture on the activated strain stock seeds in the step a) to obtain bacterial solutions, and fermenting each bacterial solution through a separate fermentation tank;
step c), mixing bacterial liquid: mixing the five bacterial liquids fermented independently in the step b) according to the volume ratio of the carbonic anhydrase producing bacteria to the lactic acid bacteria to the yeast to the bacillus to the photosynthetic bacteria to be 3:2:2:1:2, and obtaining the biological agent for maintaining the stability of the circulating cooling water system.
3. The method of maintaining a stable biological agent for recirculating cooling water systems as set forth in claim 1 for treating recirculating cooling water comprising the steps of:
step 1), adding microbial implantation filler: adding fiber ball filler into the circulating water collecting tank;
step 2) adding a biological agent for maintaining the stability of the circulating cooling water system: biological agent for maintaining the stability of the circulating cooling water system is added into the circulating water collecting tank, and the adding amount is 0.02-0.05% of the volume of the circulating water.
4. The method for treating circulating cooling water according to claim 3, wherein: the fiber ball filler in the step 1) is intensively put into a stainless steel framework fixed in a circulating water collecting tank.
5. The method for treating circulated cooling water according to claim 4, wherein: the fiber ball filler in the step 1) is spherical suspension filler, the diameter is 100mm, and the adding amount is 70% of the volume of the stainless steel framework.
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| CN109399797A (en) * | 2017-08-15 | 2019-03-01 | 中国石油化工股份有限公司 | Circulating water cooling treatment system and its method of application and circulating water cooling treatment |
| CN109399795B (en) * | 2017-08-15 | 2020-07-21 | 中国石油化工股份有限公司 | System for treating circulating cooling water, application thereof and method for treating circulating cooling water |
| CN109399804A (en) * | 2017-08-15 | 2019-03-01 | 中国石油化工股份有限公司 | Circulating water cooling treatment composition and its method of application and circulating water cooling treatment |
| CN107540098B (en) * | 2017-10-16 | 2020-05-26 | 上海高森水处理有限公司 | Preparation method of environment-friendly composite scale inhibitor |
| CN109928513B (en) * | 2019-03-29 | 2022-02-18 | 重庆为明清缘环保技术研究院有限公司 | Method for treating sewage by using industrial circulating water system |
| CN109928512B (en) * | 2019-03-29 | 2021-10-19 | 重庆为明清缘环保技术研究院有限公司 | Dosing method of microbial preparation for industrial circulating water treatment |
| CN111100806B (en) * | 2019-10-11 | 2022-12-02 | 海南大学 | Areca-nut root rot bactericide prepared by taking boron-resistant lysine bacillus as underpan cells |
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| Title |
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| Dissolving Scale Experiment of Microorganism with High-Yield of Carbonic Anhydrase;Jiangyu Ye et al.;《Computational and Theoretical Nanoscience》;20161231;第13卷;摘要、第3.1节 * |
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| CN106754583A (en) | 2017-05-31 |
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