CN102408257B - Microelement-introducing weathered coal activating agent as well as activation method and application - Google Patents
Microelement-introducing weathered coal activating agent as well as activation method and application Download PDFInfo
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- CN102408257B CN102408257B CN2011102248525A CN201110224852A CN102408257B CN 102408257 B CN102408257 B CN 102408257B CN 2011102248525 A CN2011102248525 A CN 2011102248525A CN 201110224852 A CN201110224852 A CN 201110224852A CN 102408257 B CN102408257 B CN 102408257B
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Abstract
The invention relates to a microelement-introducing weathered coal activating agent as well as an activation method and application. The activating agent is an aqueous solution containing zinc-ammonia complex ion, is prepared by reacting zinc salt aqueous solution and excessive ammonia water, and is used for extracting humic acid in weathered coal. The activation method comprises the steps of uniformly spraying the activating agent to the surface of weathered coal, uniformly stirring, reacting at the temperature of 40-50 DEG C for 2-3 hours, and placing for 10-20 hours to obtain activated weathered coal. By the method, the extraction rate of water-soluble humic acid is improved, nitrogen is introduced and microelements required by crops are also introduced to form chelate with humic acid, and the high-temperature stability of water-soluble humic acid is improved. The prepared activated weathered coal fertilizer can be widely applied to various crops and soil.
Description
Technical field
The present invention relates to a kind of weathered coal activating technology, relate in particular to a kind of can introduce the trace element the weathered coal activator and the application in fertiliser production.
Background technology
China has very abundant weathered coal resource, mainly is distributed in the many areas of open coal mines distribution such as Xinjiang, the Inner Mongol, Shanxi, is not utilized effectively so far.The a large amount of humic acidss that exist in the weathered coal are a kind of natural high moleculer eompounds, not only have a very wide range of applications in fields such as metallurgy, chemical industry and environment protection, and can be used as important fertilizer and growth regulator use in agriculture production.Yet the humic acids that exists in the elegance and talent coal exists mainly with the form of calcium, magnesium insolubles, therefore, takes effective activating technology that the form of humic acids with fulvo acid salt extracted from weathered coal, and very important meaning is arranged.
The weathered coal activation method mainly contains alkali extraction method, acid extraction method, biosolubilization method etc.Wherein acid extraction method is impure more, and biosolubilization method complicated operation should not be promoted in industrial production.Most widely used is alkali extraction method: join caustic soda soln after will weathered coal pulverizing, and the solution drying can be got fulvo acid sodium solid after heating then elimination precipitation; Referring to CN101152987A.It is insufficient that yet this type of activation method extracts, and cost is higher, and to the production unit seriously corroded, the product pH value that obtains is too high, easily crop and soil produced detrimentally affect.
In recent years, in order to have improved the extraction efficiency of Humic Acid from Weathered Coal, and give humate other function, there is pair activating technology to be further improved, for example CN1587303A relates to the alkalimetal silicate method, and the function of humic acid fertilizer is namely arranged with the fertilizer of this method configuration, also has the effect of siliceous fertilizer; CN 102070375 usefulness sodium hydroxide and urea are that humic urea solution that activator is made carries out coating to fertilizer and prepares sustained-controll-release fertiliser; CN 101570551A adopts N-quinone and borax mixture to significantly improve the extraction yield of humic acids, and greatly reduces the consumption of NaOH.Yet above activating technology exists the cost of choosing activator higher, and production unit is special, easily environment is produced the defectives such as pollution, has restricted its widespread use in fertiliser production.
Summary of the invention
For the defective on the deficiencies in the prior art and the production technique, the invention provides a kind of new weathered coal activating technology, specifically, the invention provides a kind of weathered coal activator and activation method and application of introducing trace element.
Weathered coal activating technology cost of the present invention is low, and processing unit is not had particular requirement, has not only improved the extraction yield of Humic Acid from Weathered Coal, also can introduce simultaneously zinc and humic acids and form inner complex.The organic content that the humic acid fertilizer that makes thus can not only improve in the soil can also satisfy crop for the demand of trace element.
Technical scheme of the present invention is as follows:
A kind of weathered coal activator, the aqueous solution that contains the zinc ammonium complex ion, made by zinc salt solution and the reaction of excess of ammonia water, wherein the mass ratio of zinc salt and water, ammoniacal liquor is 22～25: 43～45: 35～30, and under room temperature, mix to the formation settled solution and get final product.
Chemical reaction is as follows:
Zn(OH)
2+4NH
3＝[Zn(NH
3)
4]
2++2OH
-
Preferred according to the present invention, described zinc salt is selected from the water-soluble zinc salts such as zinc sulfate, zinc chloride or zinc nitrate, wherein preferably sulfuric acid zinc.
Preferred according to the present invention, described zinc salt purity is 95～98wt%; Described ammonia concn is 20-25wt%.
Preferred according to the present invention, the mass ratio of described zinc salt and water, ammoniacal liquor is 23～24: 44: 32～33.
A kind of activation method of weathered coal, step is as follows:
The granularity of weathered coal is ground to below 10 orders, adds the above-mentioned activator of the present invention, described activator accounts for weathered coal quality 20～30wt%, mixes, and 40～50 ℃ of reactions 2～3 hours, then room temperature was placed 10～20 hours; Must activate weathered coal.
According to aforesaid method, the present invention is preferred, the activator that accounts for weathered coal quality 25wt% evenly is sprayed onto weathered coal surface and stirs, and reaction is 2.5 hours in the time of 45 ℃, covered with plastic film, and room temperature was placed 12～15 hours; Must activate weathered coal.
According to aforesaid method, continue following steps, make respectively different activation weathered coal application products:
Above gained activation weathered coal is joined in the water of 2～5 times of activation weathered coal quality, filtration discards insolubles, with the filtrate drying crystalline, obtain the inner complex product of fulvo acid ammonia and fulvo acid zinc, perhaps the direct can of gained filtrate is become Liquid Fertilizer.The inner complex product of resulting fulvo acid ammonia and fulvo acid zinc can be directly used in makes the humic acid water-soluble fertilizer that contains trace element.
Weathered coal after the above-mentioned activation and urea, phosphate fertilizer and potash fertilizer are mixed by the prior art granulation, get organic-inorganic compound fertilizer.
Above gained weathered coal added account for the microbiobacterial agent EM composite fungus agent of its quality 1/3 and 1/5 wilkinite mixes, get soil conditioner.Use as soil conditioner.
According to aforesaid method, the preferred weathered coal granularity of the present invention is less than 10 orders, and water content is 10-15wt% approximately, and total humic acid content is 45wt%, and fulvo acid content wherein is 5wt%.
Compare with traditional activation method, activator of the present invention and activation method generate the inner complex of fulvo acid ammonia and fulvo acid zinc in reaction process, can make the activation rate of fulvo acid salt in the weathered coal improve about 10%, the most of fulvo acid salt that extracts still can stable existence under 150 ℃ of high temperature, reduced the loss amount of high temperature granulation, other method greatly reduces cost relatively, and introduced the essential trace element of crop, form inner complex with humic acids, made fertilizer through still can stable existence after the high temperature granulation.Carry out the weathered coal activation experiment with different activators and the results are shown in Table 1.
The test weathered coal: produce in Shanxi, and water content is 10-15wt% approximately, and total humic acid content is 45wt%, and fulvo acid content wherein is 5wt%.Be crushed to below 10 orders.
Fulvo acid extracted amount in table 1. weathered coal
It is high that the present invention has not only overcome the highly basic activating cost, the defective of complex process, also solved the unsettled problem of ammoniation process effect, make activation weathered coal fertilizer with activator of the present invention and activation method and not only can improve soil, satisfy crop to the demand of the macroelement such as nitrogen phosphorus potassium, and replenished simultaneously the required trace element of crop, can be widely used in all kinds of crops and soil.Also to have preparation technology simple in the present invention in addition, and cost is low, is fit to fast, the advantage of scale operation.
Embodiment
The present invention will be further described below in conjunction with embodiment, raw materials used being described as follows among the embodiment:
Weathered coal, from Shanxi, fineness is 100 orders approximately, and water content is 10-15wt% approximately, and total humic acid content is 45wt%, and fulvo acid content is 5wt%;
Zinc sulfate, Tianjin Ke Miou reagent company, technical pure, purity are 97%;
Ammoniacal liquor, Shanghai chemical reagent work, chemical pure, concentration are 23wt%.
Embodiment 1. joins fully dissolving in the 30ml water with the zinc sulfate of 12.6g, then adds 20ml ammoniacal liquor, is stirred in tempering tank and forms the clarification uniform solution, makes the activator of zinc ammonium complex ion.Weathered coal is crushed to below granularity 10 orders, evenly sprays the activator that accounts for weathered coal total mass 15%, stir with mixing machine, 48 ℃ of lower reactions 2 hours, covered with plastic film was placed 13 hours.Must activate weathered coal, the content of measuring fulvo acid is 38%.
Weathered coal after the above-mentioned activation and urea, phosphate fertilizer and potash fertilizer are mixed, add wilkinite by the prior art granulation, get organic-inorganic compound fertilizer.
Embodiment 2. joins fully dissolving in the 30ml water with the zinc sulfate of 12.6g, then adds 20ml ammoniacal liquor and is stirred to formation clarification uniform solution, makes the activator of zinc ammonium complex ion.Weathered coal is crushed to below granularity 10 orders, evenly sprays the activator that accounts for weathered coal total mass 15%, stir with mixing machine, 45 ℃ of lower reactions 2 hours, covered with plastic film was placed 15 hours.Must activate weathered coal, the content of measuring fulvo acid is 36.5%.
Above gained activation weathered coal is joined in the water of 4 times of activation weathered coal quality, filter and discard insolubles, with the filtrate drying crystalline, obtain the complex compound product of fulvo acid ammonia and fulvo acid zinc.For the manufacture of the humic acid water-soluble fertilizer that contains trace element.
Embodiment 3. joins fully dissolving in the 30ml water with the zinc sulfate of 12.6g, then adds 20ml ammoniacal liquor and is stirred to formation clarification uniform solution, makes the activator of zinc ammonium complex ion.Weathered coal is crushed to below granularity 10 orders, evenly sprays the activator that accounts for weathered coal total mass 20%, stir with mixing machine, 42 ℃ of lower reactions 3 hours, covered with plastic film was placed 12 hours.Must activate weathered coal, the content of measuring fulvo acid is 41.5%.
Above gained activation weathered coal is joined in the water of 3 times of activation weathered coal quality, filter and discard insolubles, become Liquid Fertilizer to use the direct can of filtrate.
Embodiment 4. joins fully dissolving in the 30ml water with the zinc sulfate of 12.6g, then adds 20ml ammoniacal liquor and is stirred to formation clarification uniform solution, makes the activator of zinc ammonium complex ion.Weathered coal is crushed to below granularity 10 orders, evenly sprays the activator that accounts for weathered coal total mass 25%, stir with mixing machine, 45 ℃ of lower reactions 2.5 hours, covered with plastic film was placed 12 hours.Must activate weathered coal, the content of measuring fulvo acid is 42.5%.
Above gained weathered coal added account for the microbiobacterial agent EM composite fungus agent of its quality 1/3 and 1/5 wilkinite mixes, can be used as soil conditioner and use.
Described microbial fermentation microbial inoculum is EM composite fungus agent (EM is the abbreviation of Effective Microorganesms), and it is that 5 sections 10 such as photosynthetic bacteria group, yeast flora, lactobacillus, actinomycete group, mycorhiza flora are belonged to 80 multiple-microorganisms compound a kind of typing microbial inoculum of cultivating in same state.Be brown translucent liquid, the pH value is between 3.5～4.5.Jiangxi Tianyi Biologic Technology Development Co., Ltd. is on sale.
Embodiment 5. joins fully dissolving in the 30ml water with the zinc sulfate of 12.6g, then adds 30ml ammoniacal liquor and is stirred to formation clarification uniform solution, makes the activator of zinc ammonium complex ion.Weathered coal is crushed to below granularity 10 orders, evenly sprays the activator that accounts for weathered coal total mass 15%, stir with mixing machine, 48 ℃ of lower reactions 2 hours, covered with plastic film was placed 13 hours.Must activate weathered coal, the content of measuring fulvo acid is 42%.
Weathered coal after the above-mentioned activation and urea, phosphate fertilizer and potash fertilizer are mixed, add wilkinite by the prior art granulation, get organic-inorganic compound fertilizer.
Embodiment 6. joins fully dissolving in the 30ml water with the zinc chloride of 10.5g, then adds 20ml ammoniacal liquor and is stirred to formation clarification uniform solution, makes the activator of zinc ammonium complex ion.Weathered coal is crushed to below granularity 10 orders, evenly sprays the activator that accounts for weathered coal total mass 15%, stir with mixing machine, 48 ℃ of lower reactions 2 hours, covered with plastic film was placed 15 hours.Must activate weathered coal, the content of measuring fulvo acid is 37.5%.
Weathered coal after the above-mentioned activation and urea, phosphate fertilizer and potash fertilizer are mixed, add wilkinite by the prior art granulation, get organic-inorganic compound fertilizer.
Embodiment 7. joins fully dissolving in the 30ml water with the zinc nitrate of 14.8g, then adds 20ml ammoniacal liquor and is stirred to formation clarification uniform solution, makes the activator of zinc ammonium complex ion.Weathered coal is crushed to below granularity 10 orders, evenly sprays the activator that accounts for weathered coal total mass 15%, stir with mixing machine, 48 ℃ of lower reactions 2 hours, covered with plastic film was placed 14 hours.Must activate weathered coal, the content of measuring fulvo acid is 37%.
Weathered coal after the above-mentioned activation and urea, phosphate fertilizer and potash fertilizer are mixed, add wilkinite by the prior art granulation, get organic-inorganic compound fertilizer.
Claims (10)
1. a weathered coal activator is the aqueous solution that contains the zinc ammonium complex ion, is made by zinc salt solution and the reaction of excess of ammonia water, and wherein the mass ratio of zinc salt and water, ammoniacal liquor is 22～25:43～45:30～35; Being stirred to the formation settled solution under room temperature gets final product.
2. activator as described in claim 1 is characterized in that, described zinc salt is selected from zinc sulfate, zinc chloride or zinc nitrate.
3. activator as described in claim 1 is characterized in that, described zinc salt is zinc sulfate.
4. activator as described in claim 1 is characterized in that, described zinc salt purity is 95-98wt%; Described ammonia concn is 20-25wt%.
5. activator as described in claim 1 is characterized in that, the mass ratio of described zinc salt and water, ammoniacal liquor is 23～24:44:32～33.
6. the activation method of a weathered coal utilizes each described activator of claim 1～5, and step is as follows:
The granularity of weathered coal is ground to below 10 orders, adds described activator and account for weathered coal quality 20～30wt%, mix, 40～50 ℃ of reactions 2～3 hours, then room temperature was placed 10～20 hours; Must activate weathered coal.
7. the activation method of weathered coal as claimed in claim 6 is characterized in that, the activator that accounts for weathered coal quality 25wt% evenly is sprayed onto weathered coal surface and stirs, and 45 ℃ of reactions 2.5 hours, covered with plastic film, room temperature was placed 12～15 hours; Must activate weathered coal.
8. such as the activation method of claim 6 or 7 described weathered coals, it is characterized in that, gained is activated weathered coal to be joined in the water that activates 2～5 times of weathered coal quality, filtration discards insolubles, with the filtrate drying crystalline, obtain the complex compound product of fulvo acid ammonia and fulvo acid zinc, perhaps the direct can of filtrate is become Liquid Fertilizer.
9. such as the activation method of claim 6 or 7 described weathered coals, it is characterized in that, gained is activated weathered coal and urea, phosphate fertilizer and potash fertilizer mix by the prior art granulation, get organic-inorganic compound fertilizer.
10. such as the activation method of claim 6 or 7 described weathered coals, it is characterized in that, above gained weathered coal is added the wilkinite that accounts for the microbiobacterial agent EM composite fungus agent of its quality 1/3 and account for its quality 1/5 mix, get soil conditioner.
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| CN102408257B true CN102408257B (en) | 2013-04-10 |
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| CN104211479B (en) * | 2014-09-03 | 2016-09-28 | 山东聊城鲁西化工第五化肥有限公司 | A kind of humic acids activated form Chemical Mixed Fertilizer and production method thereof |
| CN107324944A (en) * | 2017-06-30 | 2017-11-07 | 李端富 | A kind of fertilizer activator containing organic active group and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1169975A (en) * | 1996-07-08 | 1998-01-14 | 中国科学院山西煤炭化学研究所 | Preparation of complex of humic acids and urea |
| CN1434006A (en) * | 2002-01-21 | 2003-08-06 | 中国科学院山西煤炭化学研究所 | Long-acting humic acid phosphate fertilizer and process for preparing same |
| CN101130465A (en) * | 2007-08-01 | 2008-02-27 | 新疆惠森生物技术有限公司 | Grain type humic acid compound biological fertilizer and manufacturing method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0823012B2 (en) * | 1991-01-25 | 1996-03-06 | 義彦 竹下 | Soil conditioner for plant cultivation and method for producing the same |
| ES2335562B2 (en) * | 2007-03-07 | 2011-11-30 | Timac Agro España, S.A. | HETEROMOLECULAR METALIC COMPLEXES (CHELATES) OF HUMAN NATURE. |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1169975A (en) * | 1996-07-08 | 1998-01-14 | 中国科学院山西煤炭化学研究所 | Preparation of complex of humic acids and urea |
| CN1434006A (en) * | 2002-01-21 | 2003-08-06 | 中国科学院山西煤炭化学研究所 | Long-acting humic acid phosphate fertilizer and process for preparing same |
| CN101130465A (en) * | 2007-08-01 | 2008-02-27 | 新疆惠森生物技术有限公司 | Grain type humic acid compound biological fertilizer and manufacturing method therefor |
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| Title |
|---|
| JP特开平4-363387A 1992.12.16 |
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