CN103478170A - Preparation method for bromine biocide suitable for high ammonia nitrogen and high COD water quality - Google Patents
Preparation method for bromine biocide suitable for high ammonia nitrogen and high COD water quality Download PDFInfo
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- CN103478170A CN103478170A CN201310426621.1A CN201310426621A CN103478170A CN 103478170 A CN103478170 A CN 103478170A CN 201310426621 A CN201310426621 A CN 201310426621A CN 103478170 A CN103478170 A CN 103478170A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a preparation method for a bromine biocide suitable for high ammonia nitrogen and high COD water quality. The bromine biocide is characterized by comprising, by weight, 2-15% of 2, 2-dibromo-2-nitro ethyl alcohol, 2-10% of metronidazole, 5-15% of glutaric dialdehyde, 10-30% of isothiazolinone, 0.2-2% of citric acid, 0.2-1% of edetic acid, 0.1-1% of cupric nitrate and 10-45% of solvent, and the balance is water; the solvent is one or more of glycerin, 1, 2-propylene glycol, 1, 3-propylene glycol, isopropyl alcohol, diethylene glycol and ethylene glycol. The preparation method includes the steps that the solvent is placed in to a closed or pressure vessel for mixing and dissolving, under the mixing condition, temperature is controlled to be 40-80 DEG C, pressure is controlled to be 0.1Mpa, the 2, 2-dibromo-2-nitro ethyl alcohol is added, and then even mixing is performed; the isothiazolinone, the metronidazole and the glutaric dialdehyde are added, even mixing is performed, then the water, the citric acid, the cupric nitrate and the edetic acid are added, the temperature is kept at 40-80 DEG C, and even mixing is performed until complete dissolution is achieved to obtain the colorless or azury bromine biocide.
Description
Technical field
The invention belongs to the technology on circulating cooling water treatment field, be specifically related to a kind of method for making that is applicable to the bromine class biocide of the high COD water quality of high ammonia nitrogen.
Background technology
China's chemical fertilizer, chemical engineering industry stable development during " 11th Five-Year ", output increases year by year.Within 2011, methanol output surpasses 2,000 ten thousand tons, and average growth rate per annum is about 20%, according to 10 tons of quantity of circulating water that methyl alcohol consumes of annual production, is that 10000m3/h calculates, and the methyl alcohol industry global cycle water yield is 2,000,000 m approximately
3/ h.Within 2011, national synthetic ammonia output is about 5,100 ten thousand tons, according to 100,000 tons of quantity of circulating water that synthetic ammonia consumes of every annual output, is 15000m
3/ h calculates, and the synthetic ammonia industry global cycle water yield is 7,600,000 m approximately
3/ h.Chemical fertilizer, chemical industry circulating water treatment chemicals consumption figure are larger, and the accounting of biocide is many than other industry, and the performance of biocide is undesirable.
In chemical fertilizer, chemical industry circulation, material from leakage is unavoidably arranged, especially ammonia and alcohols are revealed the performance that has a strong impact on biocide, so control of microorganisms is long-standing problem always.Chemical fertilizer, chemical process material from leakage are mainly reflected in following several respects to the harm of circulation:
1. a large amount of material reveals that to cause chlorine be that the consumption of oxidative bactericide increases, and chlorion increases, and simultaneously because chlorine is the strong oxidizing property of bactericide, has increased the corrosivity of water, increases the weight of corrosion of metal.
2. the normal control of the indexs such as ammonia leakage contribution cycle water pH, basicity.In cycle water, the harm of ammonia is mainly because the digestion flora can make ammoxidation become nitrous acid and nitric acid, cause reducing cycle water pH, and nitrite anions is reducing substances, affects the performance of oxidisability biocide.Ammonia react in chlorine and water generates a chlorine ammonia, dichloro ammonia and trichlorine ammonia, and ammonia will increase the consumption of chlorine.In cycle water, ammonia concentration is higher, when chlorine is the biocide deficiency, microbes is out of control, tends to occur that bactericide consumption is high, residual chlorine concentration is put forward phenomenon not high, that chemical oxygen consumption (COC) (COD) increases, turbidity rises, water quality is sent out dirty even blackening, system sticks the increase of mud amount, causes water quality deterioration.When situation is serious, make the chlorination sterilization become difficult, the harm aggravation of microorganism, system water quality extremely worsens, the aggravation of bacterium algae propagation, glutinous cement content increases, and cycle water pH and basicity are low, and corrosivity is strong.Ammonia in oxygenated water can with the copper surface protection film in copper ion and cuprous ion form stably complex compound, cause the stress corrosion cracking of copper alloy.
3. at present in high ammonia nitrogen, high COD cycle water, the difficulty of controlling microorganism is very large, and non-oxidative bactericide also is subject to the limitation of performance.Use separately the isothiazolinone effect undesirable; The quaternary ammonium salt foam is many, often together with defoamer, uses, and has not only affected its performance but also inconvenience; Glutaraldehyde is affected by ammonia, ammonium salt and loses the part bactericidal activity.
Bromine class biocide newly developed is that the biocide ratio has following advantage with chlorine:
1. the speed of killing livestock of bromine is faster than chlorine;
2. it is little that bromine is subject to the impact of ammonia nitrogen, and a bromo-amine and two bromo-amines all have very strong biocidal active, approaches the effect of killing livestock of free bromine;
3. bromine is lower 2～4 times than chlorine to corrosion of metal speed;
4. bromo-amine is faster than the chloramines rate of decay, little to environmental influence, the current no requirement (NR) of brominated amount to discharge water.
Summary of the invention
Technical problem to be solved by this invention is the problem existed for prior art, develop a kind of bromine class biocide that is applicable to high ammonia nitrogen, high COD condition of water quality, effectively solve because the high ammonia nitrogen that chemical fertilizer, chemical process material from leakage cause, the bacterium algae in high COD cycle water grow problem.
The present invention is a kind of method for making that is applicable to the bromine class biocide of the high COD water quality of high ammonia nitrogen; It is characterized in that:
Contain 2 of percentage by weight, the bromo-2-nitroethyl alcohol 2～15% of 2-bis-; Metronidazole 2～10%; Glutaraldehyde 5～15%; Isothiazolinone 10～30%; Citric acid 0.2～2%; Disodium EDTA 0.2～1%; Copper nitrate 0.1～1%; Solvent 10～45%; Surplus is water; Described solvent is one or more in glycerine, 1,2-PD, 1,3-PD, isopropyl alcohol, diethylene glycol (DEG) and ethylene glycol;
Concrete preparation process is as follows: by described glycerine, 1,2-propane diols, 1, one or more in ammediol, isopropyl alcohol, diethylene glycol (DEG), ethylene glycol are placed in airtight or pressure vessel is miscible, under stirring condition, the condition and range of controlling reaction temperature is 40～80 ℃, and controlled pressure is 0.1Mpa, adds 2, the bromo-2-nitroethyl alcohol of 2-bis-, stir; Add isothiazolinone, metronidazole, glutaraldehyde, stir, then add water, citric acid, copper nitrate, disodium EDTA, keep 40～80 ℃, stir to dissolving fully, obtain bromine class biocide colourless or azury.
According to method for making of the present invention, it is characterized in that:
Contain 2 of percentage by weight, the bromo-2-nitroethyl alcohol 3～12% of 2-bis-; Metronidazole 2～8%; Glutaraldehyde 5～12%; Isothiazolinone 10～25%; Citric acid 0.2～1.6%; Disodium EDTA 0.2～0.8%; Copper nitrate 0.1～0.8%; Solvent 15～40%, surplus is water; Wherein said solvent is one or more in glycerine, 1,2-PD, 1,3-PD, isopropyl alcohol, diethylene glycol (DEG), ethylene glycol;
Concrete preparation process is as follows: by glycerine, 1,2-propane diols, 1, one or more in ammediol, isopropyl alcohol, diethylene glycol (DEG), ethylene glycol are placed in airtight or pressure vessel is miscible, under stirring condition, the condition and range of controlling reaction temperature is 40～60 ℃, and controlled pressure is 0.1Mpa, adds 2, the bromo-2-nitroethyl alcohol of 2-bis-, stir; Add isothiazolinone, metronidazole, glutaraldehyde, stir, then add water, citric acid, copper nitrate, disodium EDTA, keep 40～60 ℃, stir to dissolving fully, obtain bromine class biocide colourless or azury.
According to method for making of the present invention, it is characterized in that: the application purpose of bromine class biocide:
The bromine class biocide of preparation is applied to the recirculating cooling water system of industrial cooling circulating water system; Described bromine class biocide is applied to produce the high ammonia nitrogen of chemical fertilizer, chemical products, high COD(ammonia nitrogen concentration > 50mg/L, COD > 100mg/L) water system of water quality characteristics; By add the bromine class biocide of preparation in water, in the unit water yield, adding consistency is 50～100mg/L; Can be used alternatingly with oxidizing bactericide sterilizing rate > 99%; Described bromine class biocide decay decomposition rate is fast, to water quality treatment and environment without negative influence is arranged.
Embodiment
Embodiment 1,
Material by following percentage by weight prepares bromine class biocide:
By ethylene glycol 10%, diethylene glycol (DEG) 20% is placed in airtight or pressure vessel is miscible, under stirring condition, controls 40 ℃ of reaction temperatures, controlled pressure is 0.1Mpa, adds the bromo-2-nitroethyl alcohol 10% of 2,2-bis-, stirs; Add isothiazolinone 15%, metronidazole 8%, glutaraldehyde 5%, stir and within 30 minutes, add again citric acid 1.6%, copper nitrate 0.4%, disodium EDTA 0.8%, deionized water 29.2%, keep 60 ℃, stir to dissolving fully, obtain colourless bromine class biocide.
Embodiment 2,
The bromine class biocide prepared by embodiment 1 is 8 * 10 to initial bacterium number
5hainan fertilizer enterprises circulation water sample of individual/ml carries out sterilization experiment, and in water, ammonia nitrogen concentration is 70mg/L, COD concentration 140mg/L, and killing effect is as shown in the table:
The killing effect of bromine class biocide to heterotrophic bacteria under table 1 variable concentrations
As can be seen from Table 1, bromine class biocide concentration is when 100mg/L, and sterilizing rate reaches 100%.
Embodiment 3,
The bromine class biocide prepared by embodiment 1 carries out sterilization experiment to Hainan fertilizer enterprises circulation water sample, and in water, ammonia nitrogen concentration is 70mg/L, COD concentration 140mg/L, and killing effect is as shown in the table:
The killing effect of table 2 bromine class biocide to different strain
| The bacterial classification class | Heterotroph | Sulfate reducing bacteria | Iron bacteria |
| Initial bacterium number (individual/ml) | 10 6～10 7 | 10 5～10 6 | 10 2～10 3 |
| Drug concentration (mg/L) | 80 | 80 | 80 |
| Sterilizing rate (%) | 99.60 | 99.80 | 99.40 |
As can be seen from Table 2, bromine class biocide concentration is when 80mg/L, and good to the killing effect of different strain, sterilizing rate is equal > 99%.
Embodiment 4,
Bromine class biocide and other biocide prepared by embodiment 1 compare, and respectively Hainan fertilizer enterprises circulation water sample are carried out to sterilization experiment, and in water, ammonia nitrogen concentration is 70mg/L, COD concentration 140mg/L, and killing effect is as shown in the table:
Bromine class biocide and other biocide killing effect to heterotrophic bacteria under table 3 variable concentrations
As can be seen from Table 3, under same concentration, bromine class biocide is better than 1227 and isothiazolinone to the killing effect of heterotrophic bacteria.
Embodiment 5,
Material by following percentage by weight prepares bromine class biocide:
By ethylene glycol 15%, diethylene glycol (DEG) 15% is placed in airtight or pressure vessel is miscible, under stirring condition, controlling reaction temperature is 60 ℃, controlled pressure is 0.1Mpa, adds the bromo-2-nitroethyl alcohol 6% of 2,2-bis-, stirs; Add isothiazolinone 20%, metronidazole 4%, glutaraldehyde 8%, stir and within 30 minutes, add again citric acid 1.2%, copper nitrate 0.6%, disodium EDTA 0.6%, deionized water 29.6%, keep 40 ℃, stir to dissolving fully, obtain bromine class biocide azury.
Embodiment 6,
Press the prepared bromine class biocide of embodiment 5 and repeat embodiment 2,3,4 processes, the prepared bromine class biocide of effect and embodiment 1 is suitable, when the bromo-2-nitroethyl alcohol 6% of 2,2-bis-is described, just can play good bactericidal effect, can further reduce product cost, be convenient to industrialization and go into operation.
Embodiment 7,
Bromine class biocide of the present invention is applied in the Enterprises water of Hainan production synthetic ammonia chemical fertilizer, methanol product, at high ammonia nitrogen, high COD(ammonia nitrogen concentration > 50mg/L, COD > 100mg/L) under the condition of water quality characteristics, by add the bromine class biocide prepared by embodiment 5 in water, the adding consistency of (take and possess watermeter) in water is 50～100mg/L, can control preferably the bacterium algae and grow, and can be used alternatingly with oxidizing bactericide sterilizing rate 99%.
Claims (3)
1. a method for making that is applicable to the bromine class biocide of the high COD water quality of high ammonia nitrogen; It is characterized in that:
Contain 2 of percentage by weight, the bromo-2-nitroethyl alcohol 2～15% of 2-bis-; Metronidazole 2～10%; Glutaraldehyde 5～15%; Isothiazolinone 10～30%; Citric acid 0.2～2%; Disodium EDTA 0.2～1%; Copper nitrate 0.1～1%; Solvent 10～45%; Surplus is water; Described solvent is one or more in glycerine, 1,2-PD, 1,3-PD, isopropyl alcohol, diethylene glycol (DEG) and ethylene glycol;
Concrete preparation process is as follows: by described glycerine, 1,2-propane diols, 1, one or more in ammediol, isopropyl alcohol, diethylene glycol (DEG), ethylene glycol are placed in airtight or pressure vessel is miscible, under stirring condition, the condition and range of controlling reaction temperature is 40～80 ℃, and controlled pressure is 0.1Mpa, adds 2, the bromo-2-nitroethyl alcohol of 2-bis-, stir; Add isothiazolinone, metronidazole, glutaraldehyde, stir, then add water, citric acid, copper nitrate, disodium EDTA, keep 40～80 ℃, stir to dissolving fully, obtain bromine class biocide colourless or azury.
2. according to method for making claimed in claim 1, it is characterized in that:
Contain 2 of percentage by weight, the bromo-2-nitroethyl alcohol 3～12% of 2-bis-; Metronidazole 2～8%; Glutaraldehyde 5～12%; Isothiazolinone 10～25%; Citric acid 0.2～1.6%; Disodium EDTA 0.2～0.8%; Copper nitrate 0.1～0.8%; Solvent 15～40%, surplus is water; Wherein said solvent is one or more in glycerine, 1,2-PD, 1,3-PD, isopropyl alcohol, diethylene glycol (DEG), ethylene glycol;
Concrete preparation process is as follows: by glycerine, 1,2-propane diols, 1, one or more in ammediol, isopropyl alcohol, diethylene glycol (DEG), ethylene glycol are placed in airtight or pressure vessel is miscible, under stirring condition, the condition and range of controlling reaction temperature is 40～60 ℃, and controlled pressure is 0.1Mpa, adds 2, the bromo-2-nitroethyl alcohol of 2-bis-, stir; Add isothiazolinone, metronidazole, glutaraldehyde, stir, then add water, citric acid, copper nitrate, disodium EDTA, keep 40～60 ℃, stir to dissolving fully, obtain bromine class biocide colourless or azury.
3. according to method for making claimed in claim 1, it is characterized in that: the application purpose of bromine class biocide:
The bromine class biocide of preparation is applied to the recirculating cooling water system of industrial cooling circulating water system; Described bromine class biocide is applied to produce the ammonia nitrogen of chemical fertilizer, chemical products > 50mg/L, COD > water system of water quality characteristics of 100mg/L; By add the described bromine class biocide of preparation in water, in the unit water yield, adding consistency is 50～100mg/L; Can be used alternatingly with oxidizing bactericide sterilizing rate > 99%; Described bromine class biocide decay decomposition rate is fast, to water quality treatment and environment without negative influence is arranged.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103896379A (en) * | 2014-04-01 | 2014-07-02 | 安庆丰源化工有限公司 | Fine chemical wastewater treating agent for efficiently removing COD |
| CN106673164A (en) * | 2017-02-08 | 2017-05-17 | 合肥智慧龙图腾知识产权股份有限公司 | Sewage treatment agent and preparation method thereof |
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Patent Citations (6)
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| EP0364789A1 (en) * | 1988-09-30 | 1990-04-25 | UNION CARBIDE CHEMICALS AND PLASTICS COMPANY INC. (a New York corporation) | Antimicrobial composition and method of use |
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| WO2001006877A1 (en) * | 1999-07-27 | 2001-02-01 | Rhodia Inc. | Hops acid antibacterial compositions |
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| CN103896379A (en) * | 2014-04-01 | 2014-07-02 | 安庆丰源化工有限公司 | Fine chemical wastewater treating agent for efficiently removing COD |
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Application publication date: 20140101 |