CN106431528A - Methods for producing fulvic acid salt, fulvic acid water-soluble fertilizers and aquatic nutrient solution from alcohol waste liquid from waste molasses - Google Patents
Methods for producing fulvic acid salt, fulvic acid water-soluble fertilizers and aquatic nutrient solution from alcohol waste liquid from waste molasses Download PDFInfo
- Publication number
- CN106431528A CN106431528A CN201610859517.5A CN201610859517A CN106431528A CN 106431528 A CN106431528 A CN 106431528A CN 201610859517 A CN201610859517 A CN 201610859517A CN 106431528 A CN106431528 A CN 106431528A
- Authority
- CN
- China
- Prior art keywords
- reaction
- fulvic acid
- salt
- blackstrap
- weight portion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F11/00—Other organic fertilisers
- C05F11/02—Other organic fertilisers from peat, brown coal, and similar vegetable deposits
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/60—Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/20—Liquid fertilisers
- C05G5/23—Solutions
Abstract
The invention discloses methods for producing fulvic acid salt, fulvic acid salt water-soluble fertilizers and aquatic nutrient solution from alcohol waste liquid from waste molasses. The method for producing the fulvic acid salt from the alcohol waste liquid from the waste molasses includes steps of 1), carrying out acidification reaction, to be more specific, adding the alcohol waste liquid from the waste molasses into sulfuric acid solution with the concentration of 30-55%, carrying out stirring acidification reaction, then adding potassium salt into first reaction products, dissolving the potassium salt and continuously stirring the potassium salt and the first reaction products until reaction is completely carried out to obtain products with fulvic acid; 2), carrying out salt forming reaction, to be more specific, adding prepared alkaline solution into the products, obtained at the step 1), with the fulvic acid, carrying out stirring reaction until the products are alkalized and salt is formed, and then cooling the salt until the temperature of the salt reaches the room temperature so as to obtain the fulvic acid salt. The fulvic acid salt water-soluble fertilizers and the aquatic nutrient solution further can be obtained from the fulvic acid salt. The methods have the advantages that the problems of pollution on natural environments and disruption of ecological balance due to discharge of waste liquid obtained after alcohol is produced from existing waste molasses can be solved by the aid of the methods, and excellent economic benefits further can be created.
Description
Technical field
The invention belongs to the cycling and reutilization technical field of sugar industry waste material is and in particular to a kind of given up using blackstrap alcohol
The method that liquid produces fulvic acid salt, fulvic acid salt Water soluble fertilizer and aquatic products nutrient solution.
Background technology
With scientific and technical development, agriculturally also advocate and apply fertilizers scientifically to save dose, improve the utilization rate of fertilizer；
Because China's distribution of water resources is uneven, many local water-saving agriculture advocating water-fertilizer integral.But the production of China at present
Most of Water soluble fertilizer are all inorganic Water soluble fertilizer, and organic water-soluble fertilizer lacks relatively；Inorganic Water soluble fertilizer contains a large amount of inorganic elements, for a long time
Use, soil compaction can be caused, bring extreme influence to agricultural production；Therefore, producing effective organic water-soluble fertilizer becomes agricultural
Inundant trend in field.
Molasses sugar is one of sugar industry byproduct.At present, blackstrap is generally used for producing caramel colorant, monosodium glutamate, sends out
Ferment alcohol (fermenting and producing alcohol is most commonly seen).Above product except caramel colorant produce environmental pollution less in addition to, remaining
The waste water environmental pollution ratio of several prods is more serious, and particularly blackstrap produces waste liquid after alcohol, and pollution is very serious, it
Handling process be world-famous puzzle, once someone with biochemistry, materialization, biogas fermentation, be let down irrigation with water, caused soil compaction,
Seepage impact groundwater quality etc..But because in waste liquid, sucrose is not converted to fulvic acid, it or sucrose, do fertilizer and calcium from
Son generates Calciofon, makes the hardening soil.Do foster shrimp feed dissolve in water fermentation so that water quality is degenerated, treat anoxic in water, go out
Existing BOD and chemical oxygen consumption (COC) are higher, make foster shrimp how sick, dead shrimp phenomenon.
South China Yunnan, Guangxi, Guangdong and Hainan Province are the big provinces of sucrose, about produce more than 6,000 ten thousand tons of sucrose every year, give up
Molasses press 2.5%～3% calculating of sugarcane amount, have 1,500,000 tons/1 year.Be completely used for production alcohol has 7.5 ten thousand tons/year, alcohol
Waste liquid concentrate has 7.5 ten thousand tons/year for 65BX brix.All for doing organic water-soluble fertilizer, 4 can be processed by concentrate per ton
Ton Water soluble fertilizer meter, often produces 3000000 tons of fulvic acid organic water-soluble fertilizer per year.And 60,000 tons/year of potash fertilizer can be reclaimed, nitrogenous fertilizer is 1.8 ten thousand
Ton/year, phosphate fertilizer is 0.75 ten thousand tons/year.And China is as large agricultural country, very big to the demand of chemical fertilizer every year, but due to potash fertilizer
Resource shortage, every year will import in a large number, expend substantial amounts of financial resource and material resource.
But there is presently no what the blackstrap producing in sugar industry alcohol effluent can be processed into by a kind of effective method
Fulvic acid salt or derivatives thereof and fertilizer.
Content of the invention
In order to overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of produced using blackstrap alcohol effluent
The method of fulvic acid salt, produces fulvic acid and derivative using producing the blackstrap that sucrose produces and being used for producing after alcohol waste liquid
Thing, solves the problems, such as that blackstrap produces discharging of waste liquid pollution natural environment, the destruction ecological balance after alcohol, can also produce good simultaneously
Good economic benefit.
For solving the above problems, the technical solution adopted in the present invention is as follows：
The method producing fulvic acid salt using blackstrap alcohol effluent, the method comprises the following steps：
1) acidification reaction：Blackstrap alcohol effluent is added in the sulfuric acid solution that concentration is 30-55%, stirs acidification reaction
Afterwards, add sylvite dissolving, continue stirring to reacting completely, obtain the product containing fulvic acid；
2) salt-forming reaction：In step 1) add aqueous slkali configure in the product containing fulvic acid that obtains, stir instead
Room temperature should be down to alkalizing into salt after the completion of reaction, obtain fulvic acid salt mixture.
As further scheme, utilization blackstrap alcohol effluent of the present invention produces the method for fulvic acid salt also
Including in step 1) evaporation-concentration step before acidification reaction, specifically：Blackstrap alcohol effluent is concentrated by evaporation to not low
In the concentrate of 65Bx brix, in concentrate, sugar content is 30-40%, K2O content is that the liquid of 5-8% is stand-by.
The method producing fulvic acid salt as further scheme, utilization blackstrap alcohol effluent of the present invention
In, step 2) less than 50 DEG C, feed time is controlled to 6-10 hour to controlling reaction temperature.
The method producing fulvic acid salt as further scheme, utilization blackstrap alcohol effluent of the present invention
In, described aqueous slkali is potassium hydroxide saturated solution or phosphorus ammonium salt saturated solution.
Second object of the present invention is to provide one kind to produce fulvic acid salt Water soluble fertilizer using blackstrap alcohol effluent
Method；Concrete scheme is as follows：
The method producing fulvic acid Water soluble fertilizer using blackstrap alcohol effluent, the method comprises the following steps：
1) it is concentrated by evaporation：Blackstrap alcohol effluent is concentrated by evaporation to the concentrate being not less than 65Bx brix, in concentrate
Sugar content is 30-40%, K2O content is that the liquid of 5-8% is stand-by；
2) acidification reaction：The concentration that the blackstrap alcohol effluent of 200-250 weight portion is added 45-55 weight portion is 30-
In 55% sulfuric acid solution, after stirring acidification reaction, add the dissolving of 80-120 parts by weight of phosphoric acid potassium dihydrogen, continue stirring to complete
Reaction, obtains the product containing fulvic acid；
3) salt-forming reaction：In step 1) add the 80-90 weight portion having configured in the product containing fulvic acid that obtains
In potassium hydroxide saturated solution, stirring reaction to alkalizing into salt, reaction temperature can not >=50 DEG C, reaction time 6-10 hour, instead
It is down to room temperature after the completion of answering, obtain fulvic acid potassium；
4) complex reaction：Amino acid 45-66 part in terms of according to weight, citric acid 12-18 part, magnesium sulfate 8-12 part are mixed
Be added to step 3 after closing dissolving) obtained by fulvic acid salt in, stirring reaction, then plus 220-280 parts by weight of urea is through powder
It is added to after broken in reaction system, continue stirring complete to complex reaction；
5) chelatropic reaction：In step 4) in product after complex reaction according to urea quality than for 3:10 ratio adds
Trace element mixing, is subsequently adding the chelating agent of 1-3 weight portion and the deionized water of 20-30 weight portion, mixes；
6) grind and curing：By step 5) product after chelatropic reaction is transferred in grinder and is ground, before grinding plus
Enter 3-8 parts per weight dispersing agent and 3-8 weight portion defoamer；It is ground after stirring, the material stirring curing 2-4 after grinding
My god, obtain fulvic acid Water soluble fertilizer crude product；
7) filter and detection：By step 6) fulvic acid Water soluble fertilizer crude product filtered with no belt vacuum filter, and
Filtrate is carried out with technical indicator detection, detects that qualified filtrate is fulvic acid Water soluble fertilizer..
As further scheme, utilization blackstrap alcohol effluent of the present invention produces the side of fulvic acid Water soluble fertilizer
In method, step 4) reaction time is controlled to 50-70 minute.
As further scheme, utilization blackstrap alcohol effluent of the present invention produces the side of fulvic acid Water soluble fertilizer
In method, maturing process, stirs once every 3-5 hour, the time of stirring is 30-60 minute.
As further scheme, utilization blackstrap alcohol effluent of the present invention produces the side of fulvic acid Water soluble fertilizer
In method, described chelating agent is EDTA；Described dispersant is polyethylene glycol；Described trace element is with copper sulphate, magnesium sulfate, sulfuric acid
Manganese, ferrous sulfate, boric acid, the form of ammonium molybdate are added.
Third object of the present invention is to provide one kind to produce fulvic acid aquatic products nutrition using blackstrap alcohol effluent
The method of liquid；Concrete scheme is as follows：
The method producing fulvic acid aquatic products nutrient solution using blackstrap alcohol effluent, the method comprises the following steps：
1) acidification reaction：It is 30-55% that 500-600 weight portion blackstrap alcohol effluent is added 25-35 weight portion concentration
Sulfuric acid solution in, stirring acidification reaction after, add 30-40 weight portion potassium chloride dissolving, continue stirring to reacting completely, obtain
Product containing fulvic acid；
2) salt-forming reaction：In step 1) add (NH of 70-90 weight portion in the product containing fulvic acid that obtains4)2HPO4, stirring reaction to alkalizing into salt, is down to room temperature after the completion of reaction, obtains fulvic acid ammonium；
3) complex reaction：The urea of 70-90 weight portion is added to step 2) fulvic acid ammonium in, stir molten to urea
Solution, reacts and rises to room temperature to temperature, then by the amino acid 45-66 part in terms of according to weight, citric acid 12-18 part, sulfuric acid
Magnesium 8-12 part mixed dissolution is added in reaction system after the blackstrap alcohol effluent of 45-55 weight portion, continues stirring reaction；
4) chelatropic reaction：The trace element of 1-1.5 weight portion and 0.8-1.2 weight portion are obtained chelating agent and is dissolved in 25-
In the blackstrap alcohol effluent of 35 weight portions grind make its chelatropic reaction 55-65 minute after be added to step 3) reaction system
In, add the dispersant of 3-8 weight portion；
5) grind and curing：By step 4) product after chelatropic reaction is transferred in grinder and is ground, before grinding plus
Enter 3-8 weight portion defoamer；It is ground after stirring, the material stirring after grinding cures 2-4 days, add in maturing process
The digestive pharmaceutical of 3-8 weight portion, is further continued for stirring curing more than 24 hours；Obtain fulvic acid aquatic products nutrient solution crude product；
6) filter and detection：By step 5) fulvic acid aquatic products nutrient solution crude product no belt vacuum filter mistake
Filter, filtrate is fulvic acid aquatic products nutrient solution.
The method producing fulvic acid aquatic products nutrient solution as further scheme, above-mentioned utilization blackstrap alcohol effluent
In, described chelating agent is EDTA；Described dispersant is polyethylene glycol；Described trace element with copper sulphate, magnesium sulfate, manganese sulfate,
Ferrous sulfate, boric acid, the form of ammonium molybdate are added.
Compared to existing technology, the beneficial effects of the present invention is：
1. utilization blackstrap alcohol effluent of the present invention produces the method for fulvic acid salt to useless after sugar industry
The efficient utilization of molasses alcohol waste liquid produces fulvic acid salt, increases economic efficiency, the problems such as overcome environmental pollution；
2. the present invention further utilizes blackstrap alcohol effluent to produce fulvic acid Water soluble fertilizer and aquatic products nutrient solution, solves
Discharge of wastewater destroys balance of nature, the huge behave of protection ocean and rivers, lake current, is produced water-soluble using waste liquid
Fertilizer, improve inorganic fertilizer utilization rate；Greatly reduce inorganic fertilizer to the destruction of soil it is ensured that the good tillage condition in soil, gram
Take a large amount of chemical fertilizer import demands etc.；
3. the fulvic acid Water soluble fertilizer that method of the present invention obtains is applied to planting vegetable and can effectively lower vegetables
Pest and disease damage and spacing content；Dehiscent fruit and shedding can effectively be prevented for growing fruit, improve the yield of fruit；In soil
In fertilising, can effectively change the acid-base value in soil, prevent the hardening soil, have function of improving the soil.
With reference to specific embodiment, the present invention is described in further detail.
Specific embodiment
The method producing fulvic acid salt using blackstrap alcohol effluent, the method comprises the following steps：
1) acidification reaction：Blackstrap alcohol effluent is added in the sulfuric acid solution that concentration is 30-55%, stirs acidification reaction
Afterwards, add sylvite dissolving, continue stirring to reacting completely, obtain the product containing fulvic acid；
2) salt-forming reaction：In step 1) add aqueous slkali configure in the product containing fulvic acid that obtains, stir instead
Room temperature should be down to after the completion of reaction, obtains fulvic acid salt to alkalizing into salt.
In salt-forming steps, feed time is as far as possible slow, because this reaction is exothermic reaction, material reaction temperature not can exceed that
50 DEG C, this step feed time is 3 hours about, and fed continuation reaction 3 hours, treats that material reaction temperature is down to room temperature and is
Good.
As further scheme, utilization blackstrap alcohol effluent of the present invention produces the method for fulvic acid salt also
Including in step 1) evaporation-concentration step before acidification reaction, specifically：Blackstrap alcohol effluent is concentrated by evaporation to not low
In the concentrate of 65Bx brix, in concentrate, sugar content is 30-40%, K2O content is that the liquid of 5-8% is stand-by.
The method producing fulvic acid salt as further scheme, utilization blackstrap alcohol effluent of the present invention
In, step 2) less than 50 DEG C, feed time is controlled to 6-10 hour to controlling reaction temperature.Preferably 8 hours.
The method producing fulvic acid salt as further scheme, utilization blackstrap alcohol effluent of the present invention
In, described aqueous slkali is potassium hydroxide saturated solution or phosphorus ammonium salt.
Second object of the present invention is to provide one kind to produce fulvic acid salt Water soluble fertilizer using blackstrap alcohol effluent
Method；Concrete scheme is as follows：
The method producing fulvic acid Water soluble fertilizer using blackstrap alcohol effluent, the method comprises the following steps：
1) it is concentrated by evaporation：Blackstrap alcohol effluent is concentrated by evaporation to the concentrate being not less than 65Bx brix, in concentrate
Sugar content is 30-40%, K2O content is that the liquid of 5-8% is stand-by；
2) acidification reaction：The concentration that the blackstrap alcohol effluent of 200-250 weight portion is added 45-55 weight portion is 30-
In 55% sulfuric acid solution, after stirring acidification reaction, add the dissolving of 80-120 parts by weight of phosphoric acid potassium dihydrogen, continue stirring to complete
Reaction, obtains the product containing fulvic acid；
3) salt-forming reaction：In step 1) add the 80-90 weight portion having configured in the product containing fulvic acid that obtains
In potassium hydroxide saturated solution, stirring reaction to alkalizing into salt, reaction temperature can not≤50 DEG C, the reaction time is 6-10 hour,
It is down to room temperature after the completion of reaction, obtain fulvic acid potassium；
4) complex reaction：Amino acid 45-66 part in terms of according to weight, citric acid 12-18 part, magnesium sulfate 8-12 part are mixed
Be added to step 3 after closing dissolving) obtained by fulvic acid salt in, stirring reaction, then plus 220-280 parts by weight of urea is through powder
It is added to after broken in reaction system, continue stirring complete to complex reaction；
5) chelatropic reaction：In step 4) in product after complex reaction according to urea quality than for 3:10 ratio adds
Trace element mixing, is subsequently adding the chelating agent of 1-3 weight portion and the deionized water of 20-30 weight portion, mixes；
6) grind and curing：By step 5) product after chelatropic reaction is transferred in grinder and is ground, before the milling
Add 3-8 parts per weight dispersing agent and 3-8 weight portion defoamer；The auximone of 0.2-0.5 weight portion is dissolved in 15-25 weight
In the deionized water of amount part, it is configured to auximone solution, then auximone solution is added after stirring, carry out
Material stirring after once grinding cures 2-4 days, obtains fulvic acid Water soluble fertilizer crude product；
7) filter and detection：By step 6) fulvic acid Water soluble fertilizer crude product filtered with no belt vacuum filter, and
Filtrate is carried out with technical indicator detection, detects that qualified filtrate is fulvic acid Water soluble fertilizer..
4) first in system, add amino acid citric acid and magnesium sulfate in step, add urea and pass through to control instead
Can effectively prevent urea from decomposing ammonia volatilization when pH value is too high between seasonable；As further scheme, profit of the present invention
Producing in the method for fulvic acid Water soluble fertilizer with blackstrap alcohol effluent, step 4) reaction time is controlled to 50-70 minute.
As further scheme, utilization blackstrap alcohol effluent of the present invention produces the side of fulvic acid Water soluble fertilizer
In method, maturing process, stirs once every 3-5 hour, the time of stirring is 30-60 minute.
As further scheme, utilization blackstrap alcohol effluent of the present invention produces the side of fulvic acid Water soluble fertilizer
In method, described chelating agent is EDTA；Described dispersant is polyethylene glycol；Described trace element is with copper sulphate, magnesium sulfate, sulfuric acid
Manganese, ferrous sulfate, boric acid, the form of ammonium molybdate are added.
Third object of the present invention is to provide one kind to produce fulvic acid aquatic products nutrition using blackstrap alcohol effluent
The method of liquid；Concrete scheme is as follows：
The method producing fulvic acid aquatic products nutrient solution using blackstrap alcohol effluent, the method comprises the following steps：
1) acidification reaction：It is 30-55% that 500-600 weight portion blackstrap alcohol effluent is added 25-35 weight portion concentration
Sulfuric acid solution in, stirring acidification reaction after, add 30-40 weight portion potassium chloride dissolving, continue stirring to reacting completely, obtain
Product containing fulvic acid；
2) salt-forming reaction：In step 1) add (NH of 70-90 weight portion in the product containing fulvic acid that obtains4)2HPO4, stirring reaction to alkalizing into salt, is down to room temperature after the completion of reaction, obtains fulvic acid ammonium；
3) complex reaction：The urea of 70-90 weight portion is added to step 2) fulvic acid ammonium in, stir molten to urea
Solution, reacts and rises to room temperature to temperature, then by the amino acid 45-66 part in terms of according to weight, citric acid 12-18 part, sulfuric acid
Magnesium 8-12 part mixed dissolution is added in reaction system after the blackstrap alcohol effluent of 45-55 weight portion, continues stirring reaction；
4) chelatropic reaction：The trace element of 1-1.5 weight portion and 0.8-1.2 weight portion are obtained chelating agent and is dissolved in 25-
In the blackstrap alcohol effluent of 35 weight portions grind make its chelatropic reaction 55-65 minute after be added to step 3) reaction system
In, add the dispersant of 3-8 weight portion；
5) grind and curing：By step 4) product after chelatropic reaction is transferred in grinder and is ground, before grinding plus
Enter 3-8 weight portion defoamer；It is ground after stirring, the material stirring after grinding cures 2-4 days, add in maturing process
The digestive pharmaceutical of 3-8 weight portion, is further continued for stirring curing more than 24 hours；Obtain fulvic acid aquatic products nutrient solution；
6) filter and detection：By step 5) fulvic acid aquatic products nutrient solution crude product no belt vacuum filter mistake
Filter, filtrate is fulvic acid aquatic products nutrient solution.
The method producing fulvic acid aquatic products nutrient solution as further scheme, above-mentioned utilization blackstrap alcohol effluent
In, described chelating agent is EDTA；Described dispersant is polyethylene glycol；Described trace element with copper sulphate, magnesium sulfate, manganese sulfate,
Ferrous sulfate, boric acid, the form of ammonium molybdate are added.
The following is the specific embodiment of part of the present invention, raw material, reagent and the equipment being adopted in the following embodiments
All can be obtained by commercial channel.
Embodiment 1
The method producing fulvic acid Water soluble fertilizer using blackstrap alcohol effluent, the method comprises the following steps：
1) it is concentrated by evaporation：Blackstrap alcohol effluent is concentrated by evaporation to the concentrate being not less than 65Bx brix, in concentrate
Sugar content is 36%, K2O content be 6.5% liquid stand-by；
2) acidification reaction：The concentration that the blackstrap alcohol effluent of 230 weight portions is added 50 weight portions is 50% sulfuric acid
In solution, after stirring acidification reaction, add 100 parts by weight of phosphoric acid potassium dihydrogen dissolvings, continue stirring to reacting completely, obtain containing Huang
The product of humic acid；
3) salt-forming reaction：In step 1) add the hydrogen-oxygen of 88 weight portions having configured in the product containing fulvic acid that obtains
Change in potassium saturated solution, this reaction is exothermic reaction, reaction temperature can not≤50 DEG C, to alkalizing into salt, reaction 3 is little for stirring reaction
When after be down to room temperature, obtain fulvic acid potassium；
4) complex reaction：After 50 parts of the amino acid in terms of according to weight, 15 parts of citric acid, 10 parts of mixed dissolutions of magnesium sulfate
Be added to step 3) obtained by fulvic acid salt in, stirring reaction, then plus 250 parts by weight of urea are added to instead after crushed
Answer in system, continue stirring to complex reaction 60 minutes；
5) chelatropic reaction：In step 4) in product after complex reaction according to urea quality than for 3:10 ratio adds
Trace element mixing, is subsequently adding the chelating agent of 2 weight portions and the deionized water of 25 weight portions, mixes, and reacts 60 minutes；
6) grind and curing：By step 5) product after chelatropic reaction is transferred in grinder and is ground, before grinding plus
Enter 5 parts per weight dispersing agent and 5 weight portion defoamers；It is ground after stirring, the material stirring after grinding cures 3 days again,
Every stirring in 4 hours once, stirring 30-60 minute, obtains fulvic acid Water soluble fertilizer crude product every time；
7) filter and detection：By step 6) fulvic acid Water soluble fertilizer crude product filtered with no belt vacuum filter, filter
Liquid is fulvic acid salt Water soluble fertilizer, and the fulvic acid salt Water soluble fertilizer technical indicator obtaining is detected；
8) pack：To step 7) detect that qualified product is packed.
1. technical indicator detection
The technical target of the product testing result of the fulvic acid salt Water soluble fertilizer obtained by the present embodiment is referring to table 1.
Table 1
| Project | Result |
| Humic acid content | ≥30g/L |
| A great number of elements (N, P, K) | ≥200g/L |
| Water-insoluble | ≤50g/L |
| Proportion | 1.2～1.3 |
| PH value (after water dilutes 200 times) | 4～9 |
2. compliance test result
Fulvic acid Water soluble fertilizer obtained by embodiment 1 is respectively used to apply kind of vegetables (inclusion tomato, green pepper, green cucumber, south
Melon, watermelon), spray fruit (lichee and banana) and for soil fertilizing etc.；By using rear display：Greengrocery, pest and disease damage
Few, product cellulose is few, for no low harmful product；Lichee pericarp is beautiful, and dehiscent fruit is few, and shedding is especially few, and ratio does not spray patent of invention
The shedding of product few 13, banana turns to be yellow core disease less；Using the acid-base value that can change soil in soil, prevent the hardening soil, have
Improve the soil function.
Embodiment 2
The method producing fulvic acid aquatic products nutrient solution using blackstrap alcohol effluent, the method comprises the following steps：
1) acidification reaction：550 weight portion blackstrap alcohol effluents are added the sulphur that 25-35 weight portion concentration is 30-55%
In acid solution, after stirring acidification reaction, add 35 weight portion potassium chloride dissolvings, continue stirring to reaction 90 minutes, obtain containing Huang
The product of humic acid；
2) salt-forming reaction：In step 1) add 80 weight portions having configured in the product containing fulvic acid that obtains
(NH4)2HPO4Solution, stirring reaction more than 3 hours, alkalizes into salt, is down to room temperature after the completion of reaction, obtain fulvic acid ammonium；
3) complex reaction：The urea of 80 weight portions is added to step 2) fulvic acid ammonium in, stir to urea dissolving,
React and rise to room temperature to temperature, then by 5 parts of the amino acid/11 in terms of according to weight, 10 parts of citric acid, 10 parts of mixing of magnesium sulfate
It is added in reaction system after the blackstrap alcohol effluent being dissolved in 50 weight portions, continue stirring reaction 30 minutes；
4) chelatropic reaction：By copper sulphate 0.2 weight portion, magnesium sulfate 0.2 weight portion, manganese sulfate 0.2 weight portion, ferrous sulfate
0.2 weight portion, boric acid 0.2 weight portion, ammonium molybdate 0.2 weight portion 1.0 weight portion obtain chelating agent and are dissolved in the useless of 30 weight portions
Grinding in molasses alcohol waste liquid makes its chelatropic reaction be added to step 3 after 60 minutes) reaction system in, add 5 weight portions
Polyethylene glycol, continues to grind 60 minutes；
5) grind and curing：By step 4) product after chelatropic reaction is transferred in grinder and is ground, before grinding plus
Enter 5 weight portion defoamers；It is ground after stirring, the material stirring after grinding cures 3 days, adds 5 weights in maturing process
The digestive pharmaceutical of amount part, is further continued for stirring curing more than 24 hours；Obtain fulvic acid aquatic products nutrient solution；
6) filter and detection：By step 5) fulvic acid aquatic products nutrient solution crude product no belt vacuum filter mistake
Filter, filtrate is fulvic acid aquatic products nutrient solution, and detects the technical indicator of fulvic acid aquatic products nutrient solution；
7) pack：By fulvic acid aquatic products nutrient solution qualified for above-mentioned detection tri- kinds of specification bags of 5kg, 10kg and 20kg respectively
Dress.
1. technical indicator detection：
The technical target of the product testing result of the fulvic acid aquatic products nutrient solution obtained by the present embodiment is referring to table 2.
Table 2
| Project | Result |
| Humic acid content | ≥36g/L |
| A great number of elements (N, P, K) | >=10% |
| Color | Pitchy thick liquid |
| Proportion | 1.25～1.3 |
| Water-insoluble | ≤ 3% |
| PH value (after water dilutes 200 times) | 4～10 |
Above-mentioned embodiment is only the preferred embodiment of the present invention it is impossible to limit the scope of protection of the invention with this,
The change of any unsubstantiality that those skilled in the art is done on the basis of the present invention and replacement belong to institute of the present invention
Claimed scope.
Claims (10)
1. produce the method for fulvic acid salt it is characterised in that the method comprises the following steps using blackstrap alcohol effluent：
1) acidification reaction：Blackstrap alcohol effluent is added in the sulfuric acid solution that concentration is 30-55%, after stirring acidification reaction,
Add sylvite dissolving, continue stirring to reacting completely, obtain the product containing fulvic acid；
2) salt-forming reaction：In step 1) add the aqueous slkali having configured in the product containing fulvic acid that obtains, stirring reaction is extremely
Alkalize into salt, after the completion of reaction, be down to room temperature, obtain fulvic acid salt.
2. utilization blackstrap alcohol effluent according to claim 1 produces the method for fulvic acid salt it is characterised in that being somebody's turn to do
Method is additionally included in step 1) evaporation-concentration step before acidification reaction, specifically：Blackstrap alcohol effluent is concentrated by evaporation
To the concentrate being not less than 65Bx brix, in concentrate, sugar content is 30-40%, K2O content is that the liquid of 5-8% is stand-by.
3. utilization blackstrap alcohol effluent according to claim 1 produces the method for fulvic acid salt it is characterised in that walking
Rapid 2) controlling reaction temperature is less than 50 DEG C, and feed time is controlled to 6-10 hour.
4. utilization blackstrap alcohol effluent according to claim 1 produces the method for fulvic acid salt it is characterised in that institute
Stating aqueous slkali is potassium hydroxide saturated solution or phosphorus ammonium salt saturated solution.
5. produce the method for fulvic acid Water soluble fertilizer it is characterised in that the method includes following step using blackstrap alcohol effluent
Suddenly：
1) it is concentrated by evaporation：Blackstrap alcohol effluent is concentrated by evaporation to the concentrate being not less than 65Bx brix, sugary in concentrate
Measure as 30-40%, K2O content is that the liquid of 5-8% is stand-by；
2) acidification reaction：The concentration that the blackstrap alcohol effluent of 200-250 weight portion is added 45-55 weight portion is 30-55%
Sulfuric acid solution in, after stirring acidification reaction, add the dissolving of 80-120 parts by weight of phosphoric acid potassium dihydrogen, continue stirring to completely anti-
Should, obtain the product containing fulvic acid；
3) salt-forming reaction：In step 1) add the hydrogen-oxygen of the 80-90 weight portion having configured in the product containing fulvic acid that obtains
Change in potassium saturated solution, stirring reaction, to alkalizing into salt, is down to room temperature after the completion of reaction, obtains fulvic acid potassium mixture；
4) complex reaction：Will be molten to the amino acid 45-66 part in terms of according to weight, citric acid 12-18 part, the mixing of magnesium sulfate 8-12 part
Be added to step 3 after solution) obtained by fulvic acid salt in, stirring reaction, then plus 220-280 parts by weight of urea after crushed
It is added in reaction system, continue stirring complete to complex reaction；
5) chelatropic reaction：In step 4) in product after complex reaction according to urea quality than for 3:10 ratio adds micro
Element mixes, and is subsequently adding the chelating agent of 1-3 weight portion and the deionized water of 20-30 weight portion, mixes；
6) grind and curing：By step 5) product after chelatropic reaction is transferred in grinder and is ground, in process of lapping plus
Enter 3-8 parts per weight dispersing agent and 3-8 weight portion defoamer；The auximone of 0.2-0.5 weight portion is dissolved in 15-25 weight
In the deionized water of part, it is configured to auximone solution, then auximone solution is added in the material of above-mentioned grinding
Stirring curing 2-4 days, obtains fulvic acid salt Water soluble fertilizer crude product；
7) filter and detection：By step 6) fulvic acid Water soluble fertilizer crude product filtered with no belt vacuum filter, and to filter
Liquid carries out technical indicator detection, detects that qualified filtrate is fulvic acid Water soluble fertilizer..
6. the method that utilization blackstrap alcohol effluent according to claim 5 produces fulvic acid Water soluble fertilizer, its feature exists
In step 4) in the reaction time be controlled to 50-70 minute.
7. the method that utilization blackstrap alcohol effluent according to claim 5 produces fulvic acid Water soluble fertilizer, its feature exists
In in maturing process, every the stirring of 3-5 hour once, the time of stirring is 30-60 minute.
8. the method that utilization blackstrap alcohol effluent according to claim 5 produces fulvic acid Water soluble fertilizer, its feature exists
In described chelating agent is EDTA；Described dispersant is polyethylene glycol；Described trace element with copper sulphate, magnesium sulfate, manganese sulfate,
Ferrous sulfate, boric acid, the form of ammonium molybdate are added.
9. using blackstrap alcohol effluent produce fulvic acid aquatic products nutrient solution method it is characterised in that the method include with
Lower step：
1) acidification reaction：500-600 weight portion blackstrap alcohol effluent is added the sulphur that 25-35 weight portion concentration is 30-55%
In acid solution, after stirring acidification reaction, add the dissolving of 30-40 weight portion potassium chloride, continue stirring to reacting completely, obtain containing Huang
The product of humic acid；
2) salt-forming reaction：In step 1) add (NH of 70-90 weight portion in the product containing fulvic acid that obtains4)2HPO4, stir
Mix reaction to alkalizing into salt, be down to room temperature after the completion of reaction, obtain fulvic acid ammonium mixture；
3) complex reaction：The urea of 70-90 weight portion is added to step 2) fulvic acid ammonium in, stir to urea dissolving,
React and rise to room temperature to temperature, then by the amino acid 45-66 part in terms of according to weight, citric acid 12-18 part, magnesium sulfate 8-
12 parts of mixed dissolutions are added in reaction system after the blackstrap alcohol effluent of 45-55 weight portion, continue stirring reaction；
4) chelatropic reaction：The trace element of 1-1.5 weight portion and 0.8-1.2 weight portion are obtained chelating agent and is dissolved in 25-35 weight
Amount part blackstrap alcohol effluent in grind make its chelatropic reaction 55-65 minute after be added to step 3) reaction system in, plus
Enter the dispersant of 3-8 weight portion；
5) grind and curing：By step 4) product after chelatropic reaction is transferred in grinder and is ground, before process of lapping plus
Enter 3-8 weight portion defoamer；It is ground after stirring, the material stirring after grinding cures 2-4 days, add in maturing process
The digestive pharmaceutical of 3-8 weight portion, is further continued for stirring curing more than 24 hours；Obtain fulvic acid aquatic products nutrient solution crude product；
6) filter and detection：By step 5) fulvic acid aquatic products nutrient solution crude product filtered with no belt vacuum filter, filter
Liquid is fulvic acid aquatic products nutrient solution.
10. the method that utilization blackstrap alcohol effluent according to claim 9 produces fulvic acid aquatic products nutrient solution, it is special
Levy and be, described chelating agent is EDTA；Described dispersant is polyethylene glycol；Described trace element is with copper sulphate, magnesium sulfate, sulfuric acid
Manganese, ferrous sulfate, boric acid, the form of ammonium molybdate are added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610859517.5A CN106431528A (en) | 2016-09-28 | 2016-09-28 | Methods for producing fulvic acid salt, fulvic acid water-soluble fertilizers and aquatic nutrient solution from alcohol waste liquid from waste molasses |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610859517.5A CN106431528A (en) | 2016-09-28 | 2016-09-28 | Methods for producing fulvic acid salt, fulvic acid water-soluble fertilizers and aquatic nutrient solution from alcohol waste liquid from waste molasses |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106431528A true CN106431528A (en) | 2017-02-22 |
Family
ID=58170835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610859517.5A Pending CN106431528A (en) | 2016-09-28 | 2016-09-28 | Methods for producing fulvic acid salt, fulvic acid water-soluble fertilizers and aquatic nutrient solution from alcohol waste liquid from waste molasses |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106431528A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485507A (en) * | 2018-12-28 | 2019-03-19 | 云南云叶化肥股份有限公司 | It is a kind of to give up mash as the preparation method and application of raw material humic acid water-soluble fertilizer using cane molasses |
| CN109553475A (en) * | 2018-12-28 | 2019-04-02 | 云南云叶化肥股份有限公司 | It is a kind of to give up mash as the preparation method and application of the fertilizer of raw material using cane molasses |
| CN110734325A (en) * | 2018-12-12 | 2020-01-31 | 湛江市农海科技有限公司 | Production method of fulvic acid salt water-soluble fertilizers |
| CN111285738A (en) * | 2020-03-06 | 2020-06-16 | 湛江市农海科技有限公司 | Biological fulvic acid water-soluble fertilizer and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1607198A (en) * | 2003-10-15 | 2005-04-20 | 石河子市高新农业科学技术服务中心 | Special-purpose liquid fertilizer for spray and drop irrigation and production method thereof |
| CN101798246A (en) * | 2010-03-16 | 2010-08-11 | 陕西鼎华慧农生物科技有限公司 | Water-soluble fertilizer by complexing humic acid with plurality of nutrient elements and preparation method thereof |
| CN102627775A (en) * | 2012-04-12 | 2012-08-08 | 叶长东 | Method for extracting fulvic acid from sugar cane deep processing alcohol slops |
| CN102701871A (en) * | 2012-06-28 | 2012-10-03 | 孟庆华 | Method for producing liquid complexing fertilizer containing nickel |
| CN104016758A (en) * | 2014-05-07 | 2014-09-03 | 广西地源之本肥业有限公司 | Method for preparing special-purpose eucalyptus organic compound fertilizer by utilizing fermenting waste |
-
2016
- 2016-09-28 CN CN201610859517.5A patent/CN106431528A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1607198A (en) * | 2003-10-15 | 2005-04-20 | 石河子市高新农业科学技术服务中心 | Special-purpose liquid fertilizer for spray and drop irrigation and production method thereof |
| CN101798246A (en) * | 2010-03-16 | 2010-08-11 | 陕西鼎华慧农生物科技有限公司 | Water-soluble fertilizer by complexing humic acid with plurality of nutrient elements and preparation method thereof |
| CN102627775A (en) * | 2012-04-12 | 2012-08-08 | 叶长东 | Method for extracting fulvic acid from sugar cane deep processing alcohol slops |
| CN102701871A (en) * | 2012-06-28 | 2012-10-03 | 孟庆华 | Method for producing liquid complexing fertilizer containing nickel |
| CN104016758A (en) * | 2014-05-07 | 2014-09-03 | 广西地源之本肥业有限公司 | Method for preparing special-purpose eucalyptus organic compound fertilizer by utilizing fermenting waste |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110734325A (en) * | 2018-12-12 | 2020-01-31 | 湛江市农海科技有限公司 | Production method of fulvic acid salt water-soluble fertilizers |
| CN109485507A (en) * | 2018-12-28 | 2019-03-19 | 云南云叶化肥股份有限公司 | It is a kind of to give up mash as the preparation method and application of raw material humic acid water-soluble fertilizer using cane molasses |
| CN109553475A (en) * | 2018-12-28 | 2019-04-02 | 云南云叶化肥股份有限公司 | It is a kind of to give up mash as the preparation method and application of the fertilizer of raw material using cane molasses |
| CN111285738A (en) * | 2020-03-06 | 2020-06-16 | 湛江市农海科技有限公司 | Biological fulvic acid water-soluble fertilizer and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104261988B (en) | A kind of salt-soda soil special-purpose suspension liquid composite fertilizer and preparation method thereof | |
| CN101781134B (en) | Tower-smelt organic-inorganic compound fertilizer and preparation method thereof | |
| CN101696129B (en) | Method for producing amino acid organic-inorganic compound fertilizer by using Chinese medicament dregs | |
| CN104355931A (en) | Saline-alkali soil fertilizer and preparation method thereof | |
| CN102936165B (en) | Special compound fertilizer for eucalyptus | |
| CN102120711B (en) | Dual enzymes and double-enzyme serial fertilizer as well as application thereof in agriculture | |
| CN101633587B (en) | Saline-alkali land improving and fertilizing agent and preparation method thereof | |
| CN108191574A (en) | A kind of complex microorganism multielement coating enhanced fertilizer and its manufacturing method | |
| CN102653494B (en) | Efficient functional fertilizer and preparation method thereof | |
| CN106431528A (en) | Methods for producing fulvic acid salt, fulvic acid water-soluble fertilizers and aquatic nutrient solution from alcohol waste liquid from waste molasses | |
| CN105367296A (en) | Water-soluble carbon enzyme granule fertilizer and preparation method thereof | |
| CN104496706A (en) | Ammonium-aldehyde dually-controlled compound fertilizer and preparation method thereof | |
| CN105330437A (en) | Special nutrient package fertilizer for solanaceous vegetables used for red earth wastelands and application method of special nutrient package fertilizer | |
| CN101857480A (en) | Organic compound fertilizer special for areca-nuts | |
| CN105198667A (en) | Preparation method of saline-alkali soil conditioner containing biochemical humic acid | |
| CN106365823A (en) | Slow-release fertilizer special for ecological wheat and preparation method thereof | |
| CN106966777A (en) | A kind of environment-friendly type slow-release bio compoiste fertilizer and preparation method thereof | |
| CN105272750A (en) | Organic bio-fertilizer and preparation method thereof | |
| CN104557310A (en) | Synergistic environment-friendly energy-saving fertilizer for sugarcanes and manufacturing method for fertilizer | |
| CN102249804B (en) | Controlled-release fertilizer special for honeysuckle as well as preparation and application thereof | |
| CN104326792A (en) | Special liquid organic-inorganic mixed fertilizer for rice under the mulched drip irrigation, and preparation method thereof | |
| CN102942402A (en) | Double-activator double-effect corn special-purpose humic acid slow-release fertilizer and preparation method thereof | |
| CN109485507A (en) | It is a kind of to give up mash as the preparation method and application of raw material humic acid water-soluble fertilizer using cane molasses | |
| CN107814600A (en) | A kind of preparation method of acid composite fertilizer | |
| CN107188728A (en) | A kind of enzyme liquid body phosphorus decomposing agent of bioactivation containing potassium and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170222 |
|
| WD01 | Invention patent application deemed withdrawn after publication |