CN112023647B - Sludge aerobic fermentation deodorant composition, deodorant and preparation and use methods thereof - Google Patents
Sludge aerobic fermentation deodorant composition, deodorant and preparation and use methods thereof Download PDFInfo
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Abstract
The invention relates to the technical field of harmless treatment and recycling of solid wastes, in particular to a sludge aerobic fermentation deodorant composition, a deodorant, and preparation and use methods thereof. The deodorant composition comprises a deodorant I composition and a deodorant II composition, wherein the deodorant I composition comprises 70-80% of an I odor substance absorbing and dissolving agent, 10-15% of sulfate, 5-10% of sulfite, 2-5% of carbonate and 5-10% of permanganate; the deodorant II agent composition comprises 38-45% of II odor substance absorbing and dissolving agent, 25-35% of sulfate, 15-25% of sulfite, 2-4% of carbonate and 5-8% of permanganate; the deodorizing agent III includes a pH adjusting agent. The invention can adopt corresponding deodorization measures aiming at odor components released by sludge of a sewage treatment plant in different stages of aerobic fermentation so as to achieve the effect of high-efficiency deodorization.
Description
Technical Field
The invention relates to the technical field of harmless treatment and recycling of solid wastes, in particular to a sludge aerobic fermentation deodorant composition, a deodorant containing the composition, a preparation method and a use method of the deodorant.
Background
Since the middle and later 20 th century, with the rapid development of industry and agriculture, the height of the water is largeWet solid waste enters the environment and is of concern to technologists and related sectors. During the period of 'Jiu & Wu', the research on the technology for treating and utilizing the excrement in the large-scale livestock and poultry plants is developed by the Kyoho institute of soil and fertilizer of Chinese academy of agricultural sciences, the problem is that innocent treatment process equipment is developed aiming at the excrement in the large-scale chicken and pig farms, meanwhile, the odor component generated in the aerobic fermentation process is quantitatively analyzed, and the deodorization effects of various measures are compared by adopting physical, chemical, biological and biological-physical-chemical comprehensive deodorization measures. The biological measures are to add respectively and simultaneously Streptococcus thermopHilus, saccharomyces cerevisiae, PHotosynthetic bacteria and Actinomyces raydeneyi 5406, also known as 5406 antibiotic bacteria on the basis of aerobic fermentation composite microorganism (14-20 bacteria, 12-15 actinomycetes and 9-12 fungi) inocula. The test result shows that the main effect of the physical method (adding zeolite, weathered coal, sawdust, crop straws and the like in the livestock and poultry manure) is adsorption, and the comprehensive deodorization rate is 50-55%; the comprehensive deodorization rate of a chemical deodorant (chemical drugs are prepared into aqueous solution with certain concentration and sprayed for deodorization) is 60-65%; the deodorization rate is 75-80% by a physical-chemical method; the microbial agent also has a certain deodorization effect, wherein the effect of simultaneously adding the 4 microbial agents and independently adding 5406 microbial agents is best, 50% of odorous substances, yeast and photosynthetic bacteria can be removed, and the deodorization rate is about 40%, wherein the photosynthetic bacteria can remove almost all H 2 S gas, the hot streptococcus bacterium agent has no deodorization effect; the deodorization rate of the 'biological-physical-chemical' comprehensive deodorization measure is 89 percent. That is, the physical-chemical and biological-physical-chemical deodorization measures both reach the limit index of 64% of comprehensive deodorization efficiency specified by the national emission standard of malodorous pollution (GB 14554-93) (Zhang Dou et al, research on high-temperature rapid continuous fermentation deodorization technology of organic materials, proc. Of agricultural environmental sciences, 2004 (4)).
The research on the sludge is more fluctuant, and the treatment process basically refers to large-scale livestock and poultry farm excrement treatment process equipment. The domestic sludge product of the initial sewage treatment plant has low heavy metal content and can be completely put into agriculture. Then, due to the addition of other sewage, particularly industrial sewage, the heavy metal content in the sludge seriously exceeds the standard, so that agricultural departments refuse sludge for agriculture, a large amount of sludge is stockpiled, and the research and the use of the sludge fall into the valley. In order to solve the problem, china sets the 'sludge treatment agricultural argillaceous substance in urban sewage treatment plants' (CJ/T309-2009) standard, but the color is not strong. The standard was then reviewed and revised (by the group of experts in the review by Zhang Daizhiren), entitled "agricultural sludge contamination control Standard" (GB 4284-2018, instead of GB 4284-1984), published 5, month and 14 days in 2018. Since then, sludge agriculture has a real standard, and sludge research is beginning to go on the right way. The governments at all levels pay more and more attention to the protection of the ecological environment, and the urban domestic sewage, the industrial sewage and other sewage are discharged by pipelines, and the domestic sludge is applied to agriculture and gardens, which is the inevitable trend of urban sewage treatment and sludge application.
Deodorization is an important link in sludge innocent treatment, and some studies have been made on a deodorant in the sludge disposal process: CN101941786A discloses an in-situ sludge deodorant, which is a calcium nitrate solution with the mass percentage of 14.32-52.49%; CN106520627A discloses a microbial sludge deodorant, which comprises the following components: streptococcus thermophilus, bacillus subtilis, aspergillus oryzae, photosynthetic bacteria, saccharomyces cerevisiae, lactobacillus casei and pseudomonas putida; CN106007286A discloses a sludge deodorant, which comprises the following components: activated carbon, zeolite, pomace, vinegar-distilled acid, sawdust ash, alum, orange peel and quicklime; CN105819643A discloses a sludge deodorant for treating sewage, which comprises the following components: diatomite, coal powder, bagasse powder, calcium oxide powder, magnesium chloride powder, an active free radical source, an active excitant, permanganate and citric acid; CN101068752A discloses a method of adding an adsorptive carbonaceous mineral pulverized material (brown coal or young brown coal) to sludge to deodorize; CN1438189A discloses a method for deodorizing and detoxifying sludge of an urban sewage treatment plant, which specifically comprises the step of adding additives containing chlorine, iron and calcium, and additives containing sulfur, barium and hydroxyl into the sludge.
However, the research time of the prior art on the deodorant is short, the research content is not sufficient, the above researches do not quantify and compare odor compound indexes (such as sulfide, organic acid, phenol, aliphatic compounds, aromatic compounds and the like), the deodorization effect is not convincing, and the prior deodorant is set for the whole sludge treatment process, does not consider the stage change of odor generation and release in the sludge treatment process, and has weak pertinence, so that the deodorization effect is greatly reduced.
Therefore, the research on the novel deodorant with strong deodorization pertinence and better deodorization effect has important significance on the harmless treatment of the sludge.
Disclosure of Invention
The invention aims to overcome the problems of the existing deodorization method and provide a sludge aerobic fermentation deodorant composition, a deodorant containing the composition, a preparation method of the deodorant and a using method of the deodorant. The preparation and use method of the deodorant can adopt corresponding deodorization measures aiming at odor components released by sludge of a sewage treatment plant in different stages of aerobic fermentation so as to achieve targeted and efficient deodorization effects.
Aiming at the defect that the prior art does not deeply research the odor generation rule, the inventor samples the odor generated in the aerobic fermentation process of the sludge of the urban sewage treatment plant of Shandong province, such as shou guang, flatness, tai' an, jinyang, beijing city Liang, hebei province, family, lingshou, inner Mongolia Huohuote, chifeng and the like, and measures by adopting a gas chromatography-mass spectrometer, wherein the main odor components and the odor have the following properties:
(1)NH 3 : the odor is the component with the largest proportion in odor, and the odor has the property of strong stimulation to nose and eyes; in the aerobic fermentation process of sludge, the nitrogen is NH 3 The form loss of the catalyst is generally 15-20 percent, and can reach 30-35 percent at most;
(2) Sulfide: h 2 S，(NH 4 ) 2 S, thioether, thiol. H 2 S is stinky egg flavor, (NH) 4 ) 2 S shows strong pungent taste, and thioether has rotten cabbage odor; the taste of mercaptans is divided into two categories, low carbon mercaptans (C2-C8) have malodoursAnd irritant, C9 thiols (C) 9 H 19 SH) is instead scented;
(3) Organic acid: C2-C15 straight chain fatty acid, and trace benzoic acid, phenylacetic acid and phenylpropionic acid, wherein the gases have malodor, irritation and corrosivity;
(4) Aldehyde gas: acetaldehyde, propionaldehyde, furfural and phenylpropionaldehyde have irritating and unpleasant odor and have an anesthetic effect on central nerves;
(5) Ketone gas: methyl ketone, ethyl ketone, 3-octanone, butanedione, produce the unpleasant stink, like gaseous aldehyde, the narcotic and function to the central nervous system are stronger;
(6) Phenol gas: phenol, P-cresol, P-ethylphenol and xylenol, which have special phenol odor and can cause chronic poisoning;
(7) Aliphatic hydrocarbons: including alkanes and alkenes; C1-C3 lower alkane is generally tasteless, has low toxicity and weak anesthetic effect; the anesthetic property of the C5-C8 medium hydrocarbon is enhanced along with the increase of the molecular weight; heptane [ CH ] 3 (CH 2 ) 5 CH 3 ]The irritation to skin and mucosa is strong; monoene, diene and polyene all have a certain anesthetic effect;
(8) Aromatic hydrocarbons: benzene, xylene and styrene have strong toxicity and irritation except for having odor;
(9) Heterocyclic compounds: indole, skatole, benzoxazole, benzothiazole, maltol, have a foul odor and toxicity.
These malodorous substances have a common feature that each of the molecular structures thereof has an atomic group (NH) which forms a malodor 3 Except for) such as a thio group (= S), a mercapto group (-SH), a hydroxyl group (-OH), an aldehyde group (-CHO), a carbonyl group (-CO), and a carboxyl group (-COOH), which have different odor properties due to their different structures.
The allowable concentration of the odor generated in the aerobic fermentation process of the sludge is not established in China and abroad, but the allowable concentration of the odor in livestock houses and poultry houses which generate livestock and poultry manure has quantitative standards in Europe and Japan, and only has qualitative description of 'none, weak, obvious, strong and strong' (waste discharge standard establishment instruction in livestock and poultry raising places, 1994) in China, which is compiled by Ministry of agriculture standards and technical specifications. The allowable concentrations of malodorous substances in europe and japan are shown in table 1.
TABLE 1 allowable concentration of odorous substances in poultry houses
Permissible concentrations of odorant compounds in table 1 are cited in the literature:
1)Hortung J.philips V.R.,J.Agric.Engng Res.1994,57:173-189；
2)CерянскийB.M.,Mикроклимаm nmuцеводческиxпомещении,Mocква,колос,1975；
3) The translation of Liu Wenzong, ou Bo, et al, public hazard and toxicant, hazard (organic article), petrochemical Press, 1978.
The high-temperature aerobic fermentation of organic materials is generally divided into three stages at home and abroad: (1) temperature rising stage: after the fermentation material with the water content of about 60 percent enters a fermentation tank, the temperature of the material rises to 55-58 ℃; (2) high temperature stage: the temperature is basically stabilized at 67-72 ℃; (3) cooling: the temperature is reduced to 63-65 ℃, the temperature is maintained for 2d, the temperature is reduced to 52-53 ℃, and when the temperature is reduced to about 45 ℃, the whole fermentation process is completed.
The inventor of the invention finds that the internal rule of the odor generated by aerobic fermentation of sludge cannot be explained by the physical index of temperature rise and fall of the traditional compost, and in order to find a deodorant with better deodorization effect, the deodorization is carried out correspondingly based on the odor generation process, so that the inventor selects two main odor generation and change chemical indexes of organic acid and ammonia as the basis and divides the odor generation process into the following three stages according to the time development sequence by referring to the pH value of a comprehensive index:
(1) And (3) acid glycolysis stage: in the initial stage of aerobic fermentation, the dominant microorganisms are acid-producing bacteria, and the mark of the bacteria is that strong acetic acid smell and small amount of lactic acid and butyric acid smell can be smelled; at this stage, water-soluble organic substances and proteinsSuch nitrogenous organic substances are rapidly decomposed, after which part of the hemicellulose and cellulose is decomposed, producing ammonia (NH) 3 ) Organic acids and sulfur-containing compounds; taking the content of Volatile Organic Acid (VOA) as an index, and when the content of VOA is 65.0mg/kg-70mg/kg (dry basis), indicating that the acid fermentation stage is finished, entering an acid fermentation weakening stage; if the pH value is taken as a second index, the pH value is 8.18-8.33 (North China) when the fermented material is spread, and the pH value at the end of the stage is 7.5-7.6. As the sludge of the sewage treatment plant (the sludge from the belt type vacuum filter) has high water content (more than 80wt percent), the sludge is in an anaerobic fermentation state in the processes of collection, transportation and storage, and heterocyclic compounds such as organic acid, sulfide, indole, skatole, benzoxazole, maltol and the like, and phenolic compounds and ketone compounds are generated.
(2) And (3) acid fermentation weakening stage: when the VOA content of the sludge fermentation material is detected to be 0mg/kg and NH 3 From a maximum of 250 to 300mg/m 3 Reduced to 145.0-160.0mg/m 3 And when the pH value is 7.3-7.4, the fermentation stage is ended, and the alkaline fermentation stage is started. At the beginning of this phase, fat is broken down into monosaccharides and fatty acids; thereafter, the organic acid and soluble nitrogen compounds are decomposed into ammonia (NH) 3 ) Amine (R-NH) 2 ) Carbon dioxide (CO) 2 ) Hydrocarbon, nitrogen (N) 2 ) And so on, at this time, the decomposition of the organic acid is reduced after reaching a peak, and finally the VOA is 0.
(3) Alkaline fermentation stage: when the detected ammonia in the sludge fermentation material is 0mg/m 3 pH 6.8-7.0, organic acid is degraded to CO at the later stage of acid fermentation weakening stage 2 And generating NH 3 The pH value is increased, so the method is called an alkaline fermentation stage; at this stage, the process of humus formation, NH, begins in opposition to the decomposition of organic matter 3 But also into amines and amides, so that no NH can be detected finally 3 (ii) a The low molecular organic compound is converted into the high molecular organic compound in an accelerating way, the temperature begins to drop, a cooling stage is carried out, a large amount of water is evaporated, and finally the whole fermentation process is completed.
According to the odor compound characteristics generated in each fermentation stage, the invention provides, in a first aspect, a deodorant composition comprising a deodorant agent-I composition and/or deodorant agent-II composition which can be stored separately, and optionally a deodorant agent-III; wherein, the deodorant I agent composition comprises an I odor substance absorbing and dissolving agent accounting for 70-80% of the total mass of the deodorant I agent composition, 5-10% of sulfate, 5-10% of sulfite, 2-5% of carbonate and 5-10% of permanganate; the deodorant II agent composition comprises a II odor substance absorption dissolving agent accounting for 38-45% of the total mass of the deodorant II agent composition, 25-35% of sulfate, 15-25% of sulfite, 2-4% of carbonate and 5-8% of permanganate; the deodorant III composition comprises a pH adjuster.
Preferably, said first odorant absorbing dissolver in said deodorant agent composition is a combination of diethylene glycol, 1, 2-propanediol, triethylene glycol and glycerin.
Further, the sulfate in the deodorant I composition is preferably FeSO 4 ·7H 2 O, sulfite is preferably NaHSO 3 The permanganate is preferably KMnO 4 The carbonate is preferably Na 2 CO 3 。
Preferably, the first odorant absorbing dissolver comprises, by mass of the total deodorant composition I, 30% to 40% of diethylene glycol, 25% to 35% of 1, 2-propylene glycol, 2% to 8% of triethylene glycol and 2% to 8% of glycerin.
Preferably, the second odorant absorption dissolving agent in the deodorant II composition is a combination of diethylene glycol, 1, 2-propanediol, triethylene glycol and glycerin.
Preferably, the second odorant absorption dissolver comprises 15% to 25% of diethylene glycol, 10% to 20% of 1, 2-propanediol, 2% to 3% of triethylene glycol and 2% to 3% of glycerol by weight of the total deodorant II composition.
Further, the sulfate in the deodorant II composition is preferably FeSO 4 ·7H 2 O and MgSO 4 ·7H 2 O; the sulfite is preferably NaHSO 3 (ii) a The permanganate is preferably KMnO 4 (ii) a The carbonate is preferably Na 2 CO 3 。
Preferably, the deodorant III agent composition,is substantially NH 3 Absorbent, with only a small amount of NH in the alkaline fermentation stage 3 And (4) releasing. Deodorant III is slightly acidic water solution with pH of 5.0-5.5. Spraying deodorant III to generate NH 4 Cl or (NH) 4 ) 2 SO 4 A stabilizing compound.
According to one embodiment of the invention, the deodorant I composition comprises 30% to 40% of diethylene glycol, 25% to 35% of 1, 2-propylene glycol, 2% to 8% of triethylene glycol, 2% to 8% of glycerol, 5% to 10% of ferrous sulfate (e.g. FeSO) by weight of the total deodorant I composition 4 ·7H 2 O), 5% -10% of NaHSO 3 5% -10% of KMnO 4 And 2% -5% of Na 2 CO 3 。
Preferably, the deodorant I agent composition comprises 32-38% of diethylene glycol, 27-33% of 1, 2-propylene glycol, 3-7% of triethylene glycol, 3-7% of glycerol, 6-9% of ferrous sulfate and 6-9% of NaHSO by mass of the total deodorant I agent composition 3 6% -9% of KMnO 4 And 2% -4% of Na 2 CO 3 。
More preferably, the deodorant agent composition comprises 34-36% of diethylene glycol, 29-31% of 1, 2-propylene glycol, 4.5-5.5% of triethylene glycol, 4.5-5.5% of glycerol, 7-9% of ferrous sulfate and 6-8% of NaHSO based on the total mass of the deodorant agent composition 3 6% -8% of KMnO 4 And 2.5% -3.5% of Na 2 CO 3 。
According to a specific embodiment of the present invention, the deodorant II composition comprises 15% -25% of diethylene glycol, 10% -20% of 1, 2-propylene glycol, 1% -5% of triethylene glycol, 1% -5% of glycerin, 25% -35% of ferrous sulfate (such as FeSO) based on the total mass of the deodorant II composition 4 ·7H 2 O), 1% -3% magnesium sulfate (e.g., mgSO) 4 ·7H 2 O), 15% -25% of NaHSO 3 1% -5% of Na 2 CO 3 And 5% -8% KMnO 4 。
Preferably, the deodorant II composition comprises 15-25% of diethylene glycol and 10-20% of 1,2-Propylene glycol, 1.5% -3.5% of triethylene glycol, 1.5% -3.5% of glycerin, 27% -33% of ferrous sulfate, 1% -2.5% of magnesium sulfate and 17% -23% of NaHSO 3 1.5 to 3.5 percent of Na 2 CO 3 And 5% -7% of KMnO 4 。
More preferably, the deodorant II composition comprises 19-21% of diethylene glycol, 14-16% of 1, 2-propylene glycol, 2-3% of triethylene glycol, 2-3% of glycerol, 29-31% of ferrous sulfate, 1-2% of magnesium sulfate, and 19-21% of NaHSO based on the total mass of the deodorant II composition 3 2% -3% of Na 2 CO 3 And 5.5% -6.5% of KMnO 4 。
In a second aspect, the present invention provides a deodorant comprising deodorant agent I and/or deodorant agent II and optionally deodorant agent III, which can be stored separately, wherein the deodorant agent I, deodorant agent II and deodorant agent III respectively comprise the deodorant agent I composition, deodorant agent II composition and deodorant agent III composition of the aerobic sludge fermentation deodorant composition according to the first aspect of the present invention.
The deodorant may contain any other ingredient conventional in the art as long as it contains the sludge aerobic fermentation deodorant composition according to the first aspect of the present invention, which is within the scope of the deodorant according to the second aspect of the present invention.
According to a specific embodiment, the deodorant of the second aspect of the present invention is a solution, and is an aqueous solution of the deodorant composition I, the deodorant composition II or the deodorant composition III (each of which corresponds to the deodorant composition I, the deodorant composition II and the deodorant composition III), and the concentration is not particularly limited, and a mother liquor having a higher concentration may be prepared as needed and then diluted when used.
In a third aspect, the present invention provides a process for preparing the deodorant of the second aspect, comprising the steps of:
(A1) Preparation of deodorant agent I: subjecting the deodorant composition of the first aspect of the present invention and water to first mixing and first shearing in this order;
(A2) Preparation of deodorant II: subjecting the deodorant composition of the first aspect of the present invention and water to second mixing and second shearing in this order; and optionally also (c) a second set of one or more of,
(A3) Preparation of deodorant III: the deodorant composition of the first aspect of the present invention is subjected to the third conditioning with respect to the deodorant composition of the third aspect of the present invention and water.
Preferably, the first mixing conditions and the second mixing conditions each independently comprise: stirring for 45-60min at 50-60 deg.C, and stirring speed of 60-100r/min.
Preferably, the conditions of the first shearing and the conditions of the second shearing each independently comprise: the shearing time is 4-6min, and the shearing speed is 1.5-2.5 ten thousand r/min.
Preferably, the pH of the deodorant III agent is 5.0 to 5.5. Preferably, HCl is used for adjusting the pH value in a rainy region in the south of the Yangtze river, and H is used in a northern arid and semi-arid region 2 SO 4 The pH value is adjusted.
According to a specific embodiment of the present invention, the method comprises the steps of:
(1) Mixing: adding water and the deodorant I composition (or the deodorant II composition) into a container (a mixing tank or a reaction kettle) according to the mass ratio of 75-80, starting a stirrer, respectively and sequentially adding an absorption dissolving agent and inorganic salt of the deodorant I composition (or the deodorant II composition) according to the mass percentage, stirring for 45-60min at the temperature of 50-60 ℃, wherein the stirring speed is 60-100r/min, fully dissolving and mixing the mixture, and then cooling to the temperature below 40 ℃ for later use;
(2) High shearing: putting the mixture obtained in the step (1) into high-shear equipment, wherein the shearing time is 4-6min, and the shearing speed is 1.5-2.5 ten thousand r/min; respectively obtaining mother liquor of deodorizing agent I and mother liquor of deodorizing agent II (when in use, the mother liquor is diluted by water and then used, for example, the mother liquor is diluted by 8 to 12 times);
(3) Preparation of deodorant III: HCl can be used in the rainy areas in the south of the Yangtze river and H can be used in the arid and semi-arid areas in the north 2 SO 4 And adjusting the pH value of water to 5.0-5.5 to obtain the deodorant III.
The invention provides a use method of the deodorant, which comprises the following steps of carrying out aerobic fermentation on organic fermentation materials (such as sludge of a town sewage treatment plant) in sequence:
(B1) And (3) acid glycolysis stage: from the 2 nd stage after the spreading to the stage when the Volatile Organic Acid (VOA) content of the fermentation material is 65-70mg/kg dry basis, the deodorizing agent I of the second aspect of the invention or the deodorizing agent I prepared by the third aspect is used;
(B2) And (3) acid fermentation weakening stage: the stage from the end of step (B1) to the time when the VOA content of the fermented material is detected to be 0mg/kg, using the deodorizing agent II according to the second aspect of the present invention or the deodorizing agent II prepared according to the third aspect;
(B3) Alkaline fermentation stage: the ammonia content of the fermentation material from the end of step (B2) is 0mg/m 3 At this stage, the deodorizing agent III according to the second aspect of the present invention or the deodorizing agent III prepared according to the third aspect is used.
Preferably, in stage (B1), the termination conditions of the acid glycolysis stage are also such that the pH of the fermented mass is between 7.5 and 7.6.
Preferably, in stage (B1), the deodorant I agent is used in a concentration wherein the mass of deodorant I agent composition is 1.6% to 3.2%, more preferably 2% to 2.5%, of the total mass of deodorant I agent solution; and the dosage of the fermentation material is 3 to 5 percent of the dry basis weight of the fermentation material. The deodorant I can be prepared as a mother liquor having a higher concentration according to circumstances, and can be used by diluting or not diluting according to circumstances so that the concentration thereof is within the above-mentioned range of the use concentration. For example, in the above-mentioned embodiment of the deodorant preparation, the deodorant I is prepared as a mother liquor having a concentration of 20% to 25%, and it is used by diluting it 8 to 12 times at the time of use.
Preferably, in stage (B2), the end conditions of the acid fermentation weakening stage are also simultaneously satisfied with NH of the fermentation material 3 (from a maximum of 250-300mg/m 3 ) The content of (A) is reduced to 145-160mg/m 3 (ii) a Further preferably, the end conditions of the acid fermentation weakening stage also simultaneously satisfy that the pH of the fermentation material is between 7.3 and 7.4.
Preferably, in stage (B2), the deodorant II agent is used at a concentration in which the mass of the deodorant II agent composition accounts for 1.6% to 3.2%, more preferably 2% to 2.5%, of the total mass of the deodorant II agent solution; and the dosage of the fermentation material is 4 to 6 percent of the dry basis weight of the fermentation material. The dilution and use method is the same as the above deodorant I.
Preferably, in the stage (B2), the spraying period of the deodorant II agent may be the whole acid fermentation weakening stage.
Preferably, in stage (B3), the end conditions of the alkaline fermentation stage are also such that the pH of the fermented mass is between 6.8 and 7.0.
Preferably, in stage (B3), the deodorizing III agent is used in an amount of 2% to 3% by weight on a dry basis with respect to the mass of the fermented mass.
Preferably, in stage (B3), the period of spraying of the deodorant III agent may be the entire alkaline fermentation stage.
Preferably, the usage method of the deodorant of the third aspect of the present invention further includes the requirements of the installation and the use of the spray head, the requirements including: high-pressure nozzles are arranged 300-350mm above the walls of the two sides of the fermentation tank, the distance is 800-1200mm (for example 1000 mm), the walls of the two sides are arranged in a staggered manner, the angle is raised by 10-15 degrees, the nozzles on the two sides face to spray, and no dead angle exists; the material turning machine starts to turn the material from the 2 nd after the material spreading, and turns for 1 time at intervals of 1.5-2.5h (for example, 2 h); the material turning machine moves forwards for 800-1200mm (1000 mm for example) every time, the spraying time of the deodorant for one time is 5-10s, and the diameter of the fog drops is 40-50 μm.
The deodorant composition of the present invention and the method of using the same can be regarded as a chemical deodorization method, and the method of the present invention can be carried out in combination with a physical deodorization method and a biological deodorization method, and it is within the ability of those skilled in the art to carry out the method. In any way, as long as the deodorant composition or the deodorizing method of the present invention is used therein, it falls within the scope of the present invention.
Through the technical scheme, compared with the prior art, the invention at least has the following advantages: the invention breaks through the traditional technical thought that only the temperature physical index is adopted at home and abroad, adopts the chemical index, divides the stage of odor generation of aerobic fermentation of sludge in the urban sewage treatment plant again, reveals the odor generation and release rule, and provides the deodorant composition and the deodorization method based on the new technical thought, so that the deodorization process is consistent with the odor generation and release rule, the deodorization effect is excellent, and the compound generated in the deodorization process is stable, odorless and environment-friendly.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or thresholds. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
Drawings
FIG. 1 is an electron micrograph of the deodorant I prepared in example 1.
Detailed Description
The present invention will be described in detail below by way of examples. The described embodiments of the invention are only some, but not all embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
1. Preparation of deodorant
1.1 deodorant I agent composition
(1) Raw materials: see table 2.
TABLE 2 raw material Table for deodorant I agent
(2) Device
1) Mixing tank (or reaction kettle): the sandwich layer is required to be arranged, and the heating and cooling can be carried out; mechanical stirrer, temperature display, feeding tube, etc.
2) The auxiliary equipment comprises: metering pumps, scales, pipelines, etc.
3) High shear device: 3 ten thousand r/min.
(3) Operating procedure
Adding water into a mixing tank (or a reaction kettle), starting a stirrer, sequentially adding the raw materials of the deodorant I composition shown in the table 2, heating to 55 +/-5 ℃, stirring at a speed of 80r/min for 60min, and fully dissolving and mixing; then cooling to below 40 ℃, placing into high shearing equipment, shearing for 5min at 2 ten thousand r/min to obtain deodorant I agent mother liquor, and barreling for use, wherein an electron microscope scanning photo of the deodorant I agent is shown in figure 1. When in use, the mixture is diluted by 10 times with water and then is sprayed for use. The pH value of the mother liquor of the deodorant I is 7.5, and the quality index is shown in Table 3.
TABLE 3 mother liquor quality index for deodorant I composition
| Item | Index (I) |
| Appearance of the product | Pale purple translucent mucus |
| Solid content (%) | 24.09 |
| Water solubility | All water soluble |
| Viscosity (scribble-4 cup, mPa. S) | 125 |
| pH value | 7.5 |
| Particle size (nm) | 25 |
| Combustibility | Does not burn |
| Stability (-5-70 ℃ C.) | No precipitation |
| The shelf life (of a month,>5℃) | 6 |
1.2 deodorant II agent composition
(1) Raw materials: see table 4.
TABLE 4 deodorant II raw material Table
(2) The equipment and operation are the same as those of the deodorizing agent I, and when the deodorizing agent I is used, the deodorizing agent I is diluted by water for 10 times. The pH value of the mother liquor of the deodorization agent II is 7.8.
The deodorant I and II are prepared without adding antiseptic, and therefore, should be stored in cool and dry place with a shelf life of 6 months.
1.3 deodorizing agent III: the pH of the water was adjusted to 5.0 with sulfuric acid for use.
2. Deodorization implementation
2.1 shower nozzle installation and use
(1) Nozzle mounting
A plurality of high-pressure spray heads are arranged 300-350mm above materials on the walls of the two sides of the fermentation tank, the distance between the spray heads is 1000mm, the walls of the two sides of the fermentation tank are arranged in a staggered manner, the spray heads are raised by 10-15 degrees, the spray heads on the two sides face to each other, and no dead angle exists.
(2) Spraying method
When the material is turned by the turning machine once, the material moves forwards for 1000mm, the spraying is automatically controlled once, the spraying time is 8s, and the diameter of the fog drops is 45 mu m.
3. Deodorization operation process
3.1 premix compound
After dehydration to water contentAdding CaO accounting for 8 percent of the dry basis weight of the sludge into 55wt percent of the sludge, adjusting the pH value to 9.5, sequentially adding 10 percent of zeolite with the particle size of-100 meshes, about 10 percent of crushed corncobs (ventilating auxiliary materials, recycled for 5 times, the length of 30-50mm, the width of 20-30 mm) and 1.0 percent of aerobic fermentation composite microbial powder (prepared by Beijing Haidahua environmental science and technology Limited) containing 5406 antibiotic bacteria, uniformly mixing, and feeding into a fermentation tank by using a belt conveyor. Starting Roots blower 1d after spreading (700) 3 H), blowing once every 4h for 20min.
3.2 spraying deodorant
Turning and spraying the deodorant from the 2 nd (namely the 1 st d of aerobic fermentation), and turning for 1 time at an interval of 2 hours, wherein the specific operation is as follows:
(1) And (3) acid glycolysis stage: the fermentation begins and then the stage is carried out, and the amount of the deodorant I agent diluted by water is sprayed in mist in the stage and is 4.0 percent of the dry basis weight of the fermentation material; detecting that the VOA content reaches less than or equal to 70mg/kg (dry basis) and pH is 7.9, indicating that the acid fermentation stage is finished, and entering an acid fermentation weakening stage;
(2) And (3) an acid fermentation weakening stage: the amount of the deodorization II agent diluted by the spray water is 5.0 percent of the dry basis weight of the fermentation material; detecting that the content of VOA is close to 0 and NH 3 The content is 150.0mg/m 3 When the pH value is 7.6, the acid fermentation weakening stage is finished, and the alkaline fermentation stage is started;
(3) Alkaline fermentation stage: spraying a deodorizing III agent in a mist mode, wherein the using amount of the deodorizing III agent is 1.7% of the dry basis weight of the fermentation material; detecting NH 3 When the content is 0 and the pH value is less than or equal to 7.0, the aerobic fermentation of the sludge is finished.
Sampling time of odor:
odor component samples before and after spraying the deodorant were taken at the 2 nd day of each fermentation stage, and the sampling position was 1000mm above the fermented material.
The results of the deodorization tests are shown in Table 5.
TABLE 5 deodorization effect of sludge at different fermentation stages
Note: "-" indicates no detection.
As can be seen from table 5:
(1) In the acid fermentation stage, NH 3 The removal rate of the catalyst is 97.70 percent, the removal rate of sulfides is 95.76 percent, the removal rate of organic acid is 98.50 percent, the removal rate of phenolic compounds is 95.0 percent, the removal rates of ketone compounds and aldehyde compounds are both 98.54 percent, the removal rate of aliphatic hydrocarbon is 95.59 percent, the removal rate of aromatic hydrocarbon is 97.07 percent, and the removal rate of heterocyclic compounds is 95.93 percent;
(2) In the acid fermentation weakening stage, the odorous compound NH 3 The removal rate of organic acid, phenolic compounds, ketone compounds, aldehyde compounds, aliphatic hydrocarbon, aromatic hydrocarbon and heterocyclic compounds is 95.54-99.0 percent;
(3) In the alkaline fermentation stage, NH 3 The deodorization rate was 96.50%, and other odor components were not detected. The comprehensive deodorization rate of the deodorant is 97.03 percent.
It can be seen that by using the deodorant and the deodorizing method of the present embodiment, the contents of each of the malodor components meet the allowable concentrations of the relevant reference standards in europe and japan, and the deodorizing effect is excellent, better than that of the prior known deodorant.
Claims (11)
1. The application method of the deodorant is characterized by comprising the following steps of carrying out aerobic fermentation on an organic fermentation material:
(B1) And (3) acid glycolysis stage: from the 2d after the spreading to the time when the volatile organic acid content of the fermentation material is 65-70mg/kg dry basis, a deodorization I agent is used in the stage, the deodorization I agent contains a deodorization I agent composition, and the deodorization I agent composition comprises an I odor substance absorption dissolving agent accounting for 70-80% of the total mass of the deodorization I agent composition, 5-10% of sulfate, 5-10% of sulfite, 2-5% of carbonate and 5-10% of permanganate; the I odor substance absorbing and dissolving agent comprises 30-40% of diethylene glycol, 25-35% of 1, 2-propylene glycol, 2-8% of triethylene glycol and 2-8% of glycerol in the total mass of the deodorant I agent composition; the sulfate is FeSO 4 ·7H 2 O and/or MgSO 4 ·7H 2 O, the sulfite isNaHSO 3 The carbonate is Na 2 CO 3 The permanganate is KMnO 4 ；
(B2) And (3) acid fermentation weakening stage: a deodorizing agent II used in the stage from the end of the step (B1) to the time when the volatile organic acid content of the fermentation material is detected to be 0mg/kg, wherein the deodorizing agent II contains a deodorizing agent II composition comprising a second odorant absorption-dissolving agent (II) accounting for 38-45% of the total mass of the deodorizing agent II composition, 25-35% of sulfate, 15-25% of sulfite, 2-4% of carbonate and 5-8% of permanganate; the II odor substance absorbing and dissolving agent comprises 15-25% of diethylene glycol, 10-20% of 1, 2-propylene glycol, 2-3% of triethylene glycol and 2-3% of glycerol in percentage by mass of the total mass of the deodorant II agent composition; the sulfate is FeSO 4 ·7H 2 O and/or MgSO 4 ·7H 2 O, the sulfite is NaHSO 3 The carbonate is Na 2 CO 3 The permanganate is KMnO 4 ；
(B3) Alkaline fermentation stage: the ammonia content of the fermentation material from the end of step (B2) is 0mg/m 3 At this stage, a deodorant III agent is used, the deodorant III agent containing a deodorant III agent composition, the deodorant III agent composition including a pH adjuster.
2. The method of claim 1, wherein the deodorant composition comprises about 30% to about 40% diethylene glycol, about 25% to about 35% 1, 2-propanediol, about 2% to about 8% triethylene glycol, about 2% to about 8% glycerin, about 5% to about 10% ferrous sulfate, and about 5% to about 10% NaHSO by weight of the deodorant composition 3 5% -10% of KMnO 4 And 2% -5% of Na 2 CO 3 ；
The deodorant II composition comprises 15-25% of diethylene glycol, 10-20% of 1, 2-propylene glycol, 1-5% of triethylene glycol, 1-5% of glycerol, 25-35% of ferrous sulfate, 1-3% of magnesium sulfate and 15-25% of NaHSO (sodium hydrogen sulfide) 3 1% -5% of Na 2 CO 3 And 5% -8% of KMnO 4 。
3. The method according to claim 1, wherein the deodorant I agent or deodorant II agent is prepared by:
(1) Mixing: adding water and the deodorization agent I composition or the deodorization agent II composition into a container according to the mass ratio of 75-80:20-25, starting a stirrer, respectively and sequentially adding an absorption dissolving agent and an inorganic salt of the deodorization agent I composition or the deodorization agent II composition according to the mass percentage, stirring for 45-60min at the temperature of 50-60 ℃, wherein the stirring speed is 60-100r/min, fully dissolving and mixing the mixture, and then cooling to the temperature below 40 ℃ for later use;
(2) High shearing: and (2) putting the mixture obtained in the step (1) into high-shear equipment, wherein the shearing time is 4-6min, and the shearing speed is 1.5-2.5 ten thousand r/min, so as to respectively obtain a deodorant I agent mother liquor and a deodorant II agent mother liquor.
4. The method of claim 1, wherein the deodorant III agent is prepared by: HCl can be used in the areas with much rain in the south of Yangtze river, and H can be used in the arid and semi-arid areas in the north 2 SO 4 Adjusting the pH value of the water to 5.0-5.5.
5. The process according to claim 1, characterized in that in stage (B1) the termination conditions of the acidolysis stage are also such that the pH of the fermented mass is between 7.5 and 7.6.
6. The method according to claim 5, wherein the deodorant I is used in a concentration of 1.6-3.2% by mass of deodorant I composition based on the total mass of deodorant I solution and in an amount of 3-5% by mass of fermented material on a dry basis.
7. The process according to claim 5, characterized in that in stage (B2), the end conditions of the acid fermentation weakening stage are also simultaneously satisfied with NH of the fermentation mass 3 The content of (A) is reduced to 145-160mg/m 3 And the pH is 7.3-7.4.
8. The method according to claim 7, wherein the deodorant II is used at a concentration wherein the deodorant II composition is present in a range of 1.6% to 3.2% by mass based on the total mass of the deodorant II solution and in an amount of 4% to 6% by mass based on the dry mass of the fermentation material.
9. The process according to claim 5, characterized in that in stage (B3), the end conditions of the alkaline fermentation stage are also simultaneously such that the pH of the fermented mass is between 6.8 and 7.0.
10. The method according to claim 9, wherein the amount of deodorizing agent III is 2% to 3% by mass of the fermented material on a dry basis.
11. The method of any one of claims 1-10, further comprising sprinkler installation and use requirements, the requirements comprising: high-pressure spray heads are arranged 300-350mm above the two side tank walls of the fermentation tank at an interval of 800-1200mm, the two side tank walls are arranged in a staggered way, and the angle is raised by 10 degrees o -15 o The spray heads on the two sides face to spray without dead angles; the material turning machine starts to turn the material from the 2 nd after the material spreading, and turns the material for 1 time at intervals of 1.5-2.5 h; when the material is turned over once by the upender, the material moves forwards by 800-1200mm, the spraying time of the deodorant for spraying once is 5-10s, and the diameter of the fog drops is 40-50 μm.
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| KR100847416B1 (en) * | 2007-12-04 | 2008-07-18 | 김덕렬 | Powder or liquid type composition for removing oder |
| CN101549942A (en) * | 2009-05-08 | 2009-10-07 | 上海城市污染控制工程研究中心有限公司 | Multilayer fermentation chamber sludge high temperature aerobic fermentation process |
| CN103619499B (en) * | 2011-05-19 | 2015-03-25 | 株式会社泰科企划 | Method for processing organic waste and system for processing organic waste |
| CN103960284B (en) * | 2014-05-09 | 2016-02-24 | 尹无忌 | One way of life rubbish deodorizing disinfectant |
| CN106915880A (en) * | 2017-04-10 | 2017-07-04 | 河南永泽环境科技有限公司 | A kind of Sludge deodorant |
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| CH600887A5 (en) * | 1974-05-15 | 1978-06-30 | Ciba Geigy Ag | Deodorisation of waste gases contg. carbon dioxide |
| CN1543002A (en) * | 2003-04-11 | 2004-11-03 | ���µ�����ҵ��ʽ���� | Fuel cell and air purifying apparatus with fuel cell |
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