Background technology
On soil science, humic acids is a complicacy and the mixture of the inhomogenous hydroxybenzene carboxylic acid of molecular weight according to the difference of color and dissolving properties, can be divided into three types, wherein dissolves in acid, alkali and water, and is the yellow humic acid that is called as of yellow solution; Water insoluble and sour, but alkaline soluble and ethanol, and be the hymatomalenic acid that is called as of brown solution; Both be insoluble to acid, also be insoluble to ethanol or acetone, but be dissolved in the alkaline solution and black in color solution be called as pyrotomalenic acid.
At first; Humic acids extracts through peat, brown coal or weathered coal; Promptly be dissolved in earlier in the 0.2M NaOH solution; Get solution part (being Vandyke brown usually) and add hcl acidifying, the dissolved yellow solution is a yellow humic acid, can be used for quantitatively (also characterizing the content of humic acids usually with the content of yellow humic acid); The deposition part contains hymatomalenic acid and pyrotomalenic acid, can further separate with organic solvent.Current useful bacillus, streptomycete and Aspergillus fumigatus come to produce humic acids (referring to one Chinese patent application 200910241362.9) from the cane sugar manufacture residue.
But, to refine sugar and/or uniting in the process of sugaring preparing alcohol (utilizing the molasses containing waste water preparing alcohol of sugaring back generation), the greatest contamination thing of generation is not the solid substance of this easy compression of sugarcane residue, degraded and landfill, but the molasses alcohol fermentation waste liquid.The molasses alcohol fermentation waste liquid is the strong high-COD waste water of a kind of corrodibility (acidity), directly enters environment and can cause serious pollution.
For this reason, people have studied the method that the molasses alcohol fermentation liquid waste disposal is become fertilizer, change harmful to treasure with this.For example, Chinese patent 90110379.9 discloses a kind of method of making organic composite fertilizer, and it concentrates molasses fermented waste liquid evaporation earlier, adds acid digestion then, adds aggregates such as calcium phosphate again, does not wherein utilize microbial fermentation.But because molasses fermented waste liquid itself is acid, it is lower to add acid back pH, therefore causes aggregate such as calcium phosphate to be caused the loss of phosphorus by acidifying easily, influences fertility.
Chinese patent 97112080.3 discloses the method for utilizing molasses alcohol waste liquid to produce active organic compound fertilizer; Its with alcohol slops, bagasse, filter mud and mud mix the back with in the air and the entrained natural aerobic bacteria of material itself ferment, add then near the saprophytic property mikrobe of gathering the production site and ferment.The greatest problem of this method is the difficult quality control of filter mud, mud, aerobic bacteria and saprophytic property mikrobe, and unsettled fermentation will cause the quality of fertilizer product unstable, on industry, be difficult to promote.
Chinese patent 01138281.3 discloses the method for utilizing molasses-spirit lees (alcohol slops) to produce mixed organic manure, and it comprises elder generation with the sodium hydroxide neutralization, and evaporation concentration adds lime slaking more then, mixes with fertilizer at last, does not wherein utilize microbial fermentation.The do not degrade step of other harmful wastes in the molasses alcohol fermentation waste liquid (like alcohol and other volatilizable products etc.) of this method reality, direct evaporation enters atmosphere, causes the environmental pollution of processing plant's periphery.
Chinese patent 200310111476.4 discloses the working method with organic fertilizer, utilizes black mold, viride, Endomycopsis Fibnligera, eel grass genus bacillus and cereuisiae fermentum to come being that main compsn ferments by molasses alcohol waste liquid and bagasse, filter mud mainly.Wherein, the add-on of animal fertilizer and inorganic fertilizer seldom.
Chinese patent 200610123838.5 discloses the method for making the liquid fertilizer raw material; Its core be to earlier to the acidifying of molasses alcohol fermentation waste liquid, destroy yeast and also make metal salt precipitate, add the ammoniacal liquor neutralization then; Add phosphoric acid adjusting pH to 1-2.5, getting the raw material of its filtrating as fertilizer sources.Even the efficient of the bronsted lowry acids and bases bronsted lowry that this method consumption is a large amount of is not said; The filtrating of concentrating the talk of the pH1-2.5 of last formation is acid extremely strong liquid; Itself just be difficult to handle (its corrodibility has just been brought very big intractability); And during the acid and the ammoniacal liquor that add increased volume, diluted own nutritive ingredient (concentration) greatly with regard to not really high waste liquid, more difficulty has been used.
Chinese patent 200810107403.0 discloses the method for using molasses alcohol fermentation liquid as sugarcane liquid fertilizer, and it is exactly in fact that molasses alcohol fermentation liquid dilution back is directly sprayed.But because the inconvenience of transport of liquid, so many liquid only uses and can use at sugar refinery periphery, and difficulty is transported to distant place use.
In sum, the current treatment process that does not also have sophisticated molasses alcohol fermentation waste liquid, and greatly differ from each other between each method, be difficult to substitute and use.Yet the inventor has studied the treatment process of a whole set of molasses alcohol fermentation waste liquid unexpectedly through long-term and arduous research, when handling the molasses alcohol fermentation waste liquid, produces fertilizer, has more advantage than prior art.
Summary of the invention
The technical problem that the present invention will solve is to provide the preparation method of yellow humic acid fertilizer.In addition, the present invention also provides the fertilizer of said working method acquisition and wherein used reagent etc.
Particularly, in first aspect, the invention provides the method for preparing yellow humic acid fertilizer, it comprises:
(1) the molasses alcohol fermentation waste liquid is fed settling tank, add alkali and regulate pH;
(2) leave standstill back precipitation separation and supernatant; Get the same animal excrement of supernatant, sugarcane residue and fermenting agent and mix, wherein said fermenting agent comprises product yellowish fiber Zymomonas mobilis (Cellulomonas flavigena), lactobacterium casei (Lactobacillus casei), Wei Nielande vinelandii (Azotobacter vinelandii), rhizobium leguminosarum (Rhizobium leguminosarum), black mold (Aspergillus niger), aspergillus oryzae (Aspergillus oryzae), special humicola lanuginosa (Humicola insolens) and the block few spore head mold (Rhizopus oligosporus var.tuberosus) of survival;
(3) place the mixture that fermentation step (2) obtains, add deposition then and continue to place, stirring to keep this mixture internal temperature between resting period is 50~60 ℃; With
(4) tunning and the granulation that obtain of drying step (3).
Wherein, alkali is NaOH preferably, in order not increase liquid volume, and preferably NaOH solid or its strong solution.Preferably wherein, the molasses alcohol fermentation waste liquid after regulating the pH value is evaporation concentration further, improves the wherein content of solid substance, and finally uses to be the tart form.But, for save energy, in embodiment of the present invention, the evaporative process that does not consume energy.In this article, the molasses alcohol fermentation waste liquid refers to the waste that system sucrose residual molasses stay behind preparing alcohol, comprises liquid and is suspended in deposition wherein, and this is the waste that needs harmless treatment of existing common (like, the document of this paper background parts).
The molasses alcohol fermentation waste liquid finally should be acid to be used.Although according to prior art, be neutralized to neutrality with alkali earlier, be adjusted to acidity with acid again after the evaporation then, also contain within the scope of the invention.But, be neutralized to neutrality and have a large amount of solid substances and be precipitated out, be unfavorable for fermenting agent fermentation of the present invention; And this process will be wasted more bronsted lowry acids and bases bronsted lowry, and efficient is not high.Therefore, preferably in first aspect of the present invention, directly regulate pH to 5.5~5.9 in the step (1), most preferably directly regulate pH to 5.8.
Preferably in first aspect of the present invention, said fermenting agent be with produce that yellowish fiber Zymomonas mobilis (Cellulomonas flavigena), lactobacterium casei (Lactobacillus casei), Wei Nielande vinelandii (Azotobacter vinelandii), rhizobium leguminosarum (Rhizobium leguminosarum), black mold (Aspergillus niger), aspergillus oryzae (Aspergillus oryzae), special humicola lanuginosa (Humicola insolens) and block few spore head mold (Rhizopus oligosporus var.tuberosus) are inoculated in activation in the substratum of being made up of sugarcane residue, animal excrement, soya-bean cake and fish meal and must.
Mentioned microorganism can be bought from public preservation mechanism through commercial sources; Also can entrust commercial company to cultivate according to common microbial culture method; Combined inoculation activation in the substratum of forming by sugarcane residue, animal excrement, soya-bean cake and fish meal then; Wherein the weight ratio of sugarcane residue, animal excrement, soya-bean cake and fish meal is 1~3: 0.5~1.5: 1~3: 0.5~1.5, be preferably 2: 1: 2: 1.It is 30 ± 3 ℃ that activation temperature remains on.Soak time is looked inoculum size and is decided, and is generally 3~7 days, is preferably 5 days.The content of each bacterium all should be not less than 10 in the final fermenting agent that produces
6Individual/gram.
In this article, the sugarcane residue refers to the residue after the sugarcane system sucrose, is a kind of waste that needs processing.In this article, animal excrement are one or more mixture of cow dung, pig manure or chicken manure, preferably cow dung.This also is the waste that the animal rearing field needs harmless treatment.Because the composition difference in the various wastes is bigger, therefore corresponding part by weight also is very important.Discover according to the inventor; In first aspect of the present invention; The weight ratio of supernatant, animal excrement, sugarcane residue and fermenting agent is 100~1000: 500~2000: 100~500: 1; Be preferably 300~700: 600~1000: 200~400: 1, most preferably be 500: 700: 300: 1.More preferably; The weight ratio of supernatant, deposition, animal excrement, sugarcane residue and fermenting agent is 100~1000: 100~500: 500~2000: 100~500: 1; Be preferably 300~700: 200~400: 600~1000: 200~400: 1, most preferably be 500: 300: 700: 300: 1.
Preferably in first aspect of the present invention, the time of the mixture that wherein placement fermentation step (2) obtains in the step (3) is 1~5 day, is preferably 2~4 days, most preferably is 3 days; And the time of continuing in the step (3) to place is 10~15 days, is preferably 11~14 days, most preferably is 12 days.During this time, too high for fear of internal temperature, can stir this mixture through whipping appts, under the natural ventilation state, take away too much heat.
In second aspect, the invention provides yellow humic acid fertilizer by the described method preparation of first aspect present invention.Although do not add fermenting agent of the present invention, also can generate organic fertilizer through the mikrobe that animal excrement and sugarcane residue etc. carry, wherein yellow humic acid content significantly is lower than yellow humic acid fertilizer of the present invention.In addition; Because sources such as animal excrement and sugarcane residue are complicated, microorganism species wherein is unstable, causes the result of repeatedly fermentation inconsistent; Cause final fertilizer composition (as; Yellow humic acid) differ greatly (like yellow humic acid content is 8~11%, and different batches can differ 25% more than), unsettled like this fertilizer is difficult to apply.
And the extra fermenting agent that added of the present invention makes that the composition (being yellow humic acid at least) of final fertilizer is stable, therefore can be at an easy rate be mixed with composite fertilizer with other fertilizer (like, chemical fertilizer), and is easy to utilize.Preferably in second aspect of the present invention, yellow humic acid fertilizer contains the yellow humic acid of 12~13% (weight), preferably contains the yellow humic acid of 12.4~12.6% (weight).
In the third aspect; The invention provides the method for activation fermenting agent, it comprise producing that yellowish fiber Zymomonas mobilis (Cellulomonas flavigena), lactobacterium casei (Lactobacillus casei), Wei Nielande vinelandii (Azotobacter vinelandii), rhizobium leguminosarum (Rhizobium leguminosarum), black mold (Aspergillus niger), aspergillus oryzae (Aspergillus oryzae), special humicola lanuginosa (Humicola insolens) and block few spore head mold (Rhizopus oligosporus var.tuberosus) are inoculated in activation in the substratum of being made up of sugarcane residue, animal excrement, soya-bean cake and fish meal and must.This method is preferred in the described method of first aspect present invention.
Preferably in the third aspect of the invention, the weight ratio of sugarcane residue, animal excrement, soya-bean cake and fish meal is 1~3: 0.5~1.5: 1~3: 0.5~1.5, be preferably 2: 1: 2: 1.Preferably in the third aspect of the invention, it is 30 ± 3 ℃ that activation temperature remains in addition, and soak time is 3~7 days, is preferably 5 days.The content of each bacterium all should be not less than 10 in the final fermenting agent that produces
6Individual/gram.
The present invention also provides by the described method activatory of third aspect of the invention fermenting agent, and the content that wherein produces the yellowish fiber Zymomonas mobilis is 0.8x10
8~2.0x10
8Individual/gram, the content of lactobacterium casei is 6.0x10
7~1.2x10
8Individual/gram, the content of Wei Nielande vinelandii is 2.0x10
7~8.0x10
7Individual/gram, the content of rhizobium leguminosarum is 1.0x10
8~3.0x10
8Individual/gram, the content of black mold is 7.3x10
6~8.0x10
6Individual/gram, the content of aspergillus oryzae is 6.0x10
6~10.0x10
6Individual/gram, the content of special humicola lanuginosa is 2.0x10
6~8.0x10
6Individual/gram, and the content of block few spore head mold is 5.0x10
6~7.0x10
6Individual/gram, the content that preferably produces the yellowish fiber Zymomonas mobilis is 1.0x10
8~1.7x10
8Individual/gram, the content of lactobacterium casei is 8.2x10
7~1.0x10
8Individual/gram, the content of Wei Nielande vinelandii is 3.7x10
7~5.5x10
7Individual/gram, the content of rhizobium leguminosarum is 1.9x10
8~2.2x10
8Individual/gram, the content of black mold is 7.7x10
6~7.8x10
6Individual/gram, the content of aspergillus oryzae is 8.1x10
6~9.0x10
6Individual/gram, the content of special humicola lanuginosa is 3.9x10
6~5.3x10
6Individual/gram, and the content of block few spore head mold is 5.5x10
6~6.5x10
6Individual/gram.According to the inventor's research, fermenting agent ingredient stability of the present invention.
The present invention has following beneficial effect: the fermentation raw material that method for preparing fertilizer of the present invention can ferment effectively and be made up of molasses alcohol waste liquid, animal excrement and sugarcane residue, and the yellow humic acid fertilizer component that fermentation obtains is stable, is convenient to promote; Method for preparing fertilizer of the present invention is innoxious molasses alcohol waste liquid, animal excrement and these three kinds of wastes of sugarcane residue simultaneously, turn waste into wealth; Method for preparing fertilizer of the present invention can consume mass energy, also needn't consume too much acid, alkali raw material, and treatment scheme is easy, and cost is lower; Fertilizer life-time service of the present invention can effectively be increase soil fertility, and makes crop yield; Fermenting agent bacterial classification of the present invention is stable, adapts to strong.
For the ease of understanding, below will the present invention be described in detail through concrete embodiment.What need particularly point out is that these descriptions only are exemplary descriptions, do not constitute limitation of the scope of the invention.According to the argumentation of this specification sheets, many variations of the present invention, change all are conspicuous concerning one of ordinary skill in the art.
In addition, the present invention has quoted open source literature, and these documents are in order more clearly to describe the present invention, and their full text content is all included this paper in and carried out reference, just looks like that repeated description is the same excessively in this article for their full text.
Embodiment
Below further specify content of the present invention through embodiment.As do not specialize; The conventional means that used technique means is well known to those skilled in the art among the embodiment and commercially available common equipment and reagent can be referring to references such as " comprehensive utilization of humic acids " (Science Press), " microbiology experiment (the 4th edition) " (Higher Education Publishing House), " the outstanding Bacteria Identification handbook of uncle (the 8th edition " (Science Press) and corresponding manufacturers instructions.
The preparation of embodiment 1 fermenting agent
The bacterial classification that present embodiment uses is all listed in the open bacterial classification catalogue of Chinese common micro-organisms culture presevation administrative center (Beijing), can buy.The bacterial classification catalog number of each mikrobe and Chinese common micro-organisms culture presevation administrative center thereof is respectively: produce yellowish fiber Zymomonas mobilis (Cellulomonas flavigena) (numbering 1.1002); Lactobacterium casei (Lactobacillus casei) (numbering 1.62); Wei Nielande vinelandii (Azotobacter vinelandii) (numbering 1.1649); Rhizobium leguminosarum (Rhizobium leguminosarum) (numbering 1.888); Black mold (Aspergillus niger) (numbering 3.6193); Aspergillus oryzae (Aspergillus oryzae) (numbering 3.481), special humicola lanuginosa (Humicola insolens) (numbering 3.4393), and block few spore head mold (Rhizopus oligosporus var.tuberosus) (numbering 3.1145).Entrust Guangxi to be prone to overcharge bio tech ltd through commercial sources above 8 kinds of bacterial classifications and carry out liquid culture respectively according to conventional spawn culture method, centrifugal back is preserved thalline in 4 ℃ and is also paid, and corresponding number of viable is all greater than 10 in the thalline of each bacterial classification
8Individual/gram (weight in wet base).
The above-mentioned thalline of every kind of bacterial classification is got 10g and is mixed; Be dissolved in the 1L saline water, add sugarcane residue (less than 5mm) that 2kg pulverizes, 1kg cow dung, 2kg soya-bean cake (that is, milling process is carried the soybean residuum behind the oil) and 1kg fish meal then; Thorough mixing is even; Under the natural ventilation state, placed 5 days in 30 ± 3 ℃, during every day stir 2 ventilations, promptly get fermenting agent.In order to detect the survival stability of bacterial classification, get the fermenting agent of 3 batches of productions, spawn culture evaluation and counting are carried out in sampling.The survival volume count results is as shown in the table, and it is stable that the bacterial classification quantity of each batch cultivation keeps, and a large amount of survivals is all arranged.
The fermentation of embodiment 2 yellow humic acid fertilizer
The molasses alcohol fermentation waste liquid of sugar refinery discharging is fed settling tank, add the NaOH solid and regulate pH to 5.8, left standstill 2 hours, it is for use with deposition to get supernatant respectively.Get 700kg cow dung and 300kg after crushed particle mix (not adding fermenting agent in the contrast fertiliser prodn) less than the fermenting agent of the sugarcane residue of 5mm and 1kg embodiment 1 preparation; Feed above-mentioned supernatant 500L for use (about 500kg) then; Stir; Heap goes in the fermenter to leave standstill 3 days, adds deposition 300kg then, continues to leave standstill 12 days.During leaving standstill, fertile heap can heat up by nature, measures fertile heap temperature inside, when surpassing 60 ℃, stirs fertile heap so that fertile heap ventilation cooling stops to stir when fertilizer heap inside is lower than 50 ℃.The compost product that finally obtains with directly sending into the tablets press granulation after the drying machine drying, obtains organic fermentation fertilizer and contrast fertilizer.
The yellow humic acid content of organic fermentation fertilizer that sampling and measuring is 3 batches and contrast fertilizer; The result is as shown in the table; With respect to not adding the fertilizer that fermenting agent is produced, yellow humic acid content has promoted about 20%, and therefore organic fermentation fertilizer of the present invention also is called as yellow humic acid fertilizer.
Fertilizer |
Yellow humic acid content (%) |
Yellow humic acid content |
10.2% |
Batch 1 |
12.4% |
Batches 2 |
12.6% |
Batches 3 |
12.6% |
Adopt yellow humic acid fertilizer of the present invention and contrast fertilizer to be used separately as sugarcane field base manure (every mu of 25kg); Used 2 years continuously; 1 year sugarcane yield be significantly difference not, but it is about 3% to use the rate ratio of yellow humic acid fertilizer to use the output of contrast fertilizer to promote in 1 year, shows that yellow humic acid fertilizer of the present invention is with respect to common organic fertilizer; Under the situation of life-time service, can bigger help be arranged, and handle the molasses alcohol fermentation waste liquid is harmless simultaneously improving soil fertility.