CN103274857A - Humic acid synergistic ammonium bicarbonate fertilizer and production method thereof - Google Patents
Humic acid synergistic ammonium bicarbonate fertilizer and production method thereof Download PDFInfo
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Abstract
The invention relates to a humic acid synergistic ammonium bicarbonate fertilizer and a production method thereof. The ammonium bicarbonate fertilizer comprises the components in percentage by weight as follows: 0.15%-0.60% of a humic acid synergist and 99.40%-99.85% of ammonium bicarbonate, wherein the content of the humic acid accounts for 0.09%-0.4% of the total weight of the humic acid synergistic ammonium bicarbonate fertilizer. Compared with ordinary ammonium bicarbonate, the humic acid synergistic ammonium bicarbonate fertilizer has the characteristics that the fertilizer is good in yield-increasing effect, high in nutrient utilization rate, environment-friendly and the like. At the same time, the production technology is simple, the cost is low, raw material sources are wide, the operation is easy, the industrial promotion is facilitated, and the like.
Description
[technical field]
The invention belongs to the agrochemicals technical field.More specifically, the present invention relates to a kind of humic acids Synergistic ammonium bicarbonate fertilizer, also relate to the production method of described humic acids Synergistic ammonium bicarbonate fertilizer.
[background technology]
For a long time, utilization rate of fertilizer is low and be the focus that people pay close attention to by its environmental risk of bringing always, and chemical fertilizer application is serious day by day to the negative impact of environment.Countries in the world recognize gradually that all research and development utilization ratio high new slow release fertilizer is one of effective way that improves plant recovery of nutrient.Since the sixties in last century, be the research focus that the various new-type fertilizers research and development of target become world's fertilizer field to improve utilization rate of fertilizer.Making a general survey of the development of domestic and international new-type fertilizer, mainly is to improve fertilizer utilization ratio by the release that technological methods such as organonitrogen chemosynthesis, coating delay nutrient.Wherein, coated with resin fertilizer is the main type of current domestic and international slow release fertilizer product, but applies in field crop because of higher being difficult to of its price, is used for non-agricultural markets such as flowers, lawn more; And the coated slow release fertilizer product requires highly to application technique, if use improper (as spreading fertilizer over the fields) or use under the lack of water condition and will cause bigger nutrient loss, coated fertilizer decomposes in soil slowly, easy residue problem also is subjected to people's attention gradually.Urea formaldehyde (UF) is the organic nitrogen compound of modal new and effective nitrogenous fertilizer, slow liberating nitrogen under water and microbiological deterioration, and price is high and applying environment required characteristics such as height also limited its applying aborning.
Bicarbonate of ammonia is the main body of China's nitrogenous fertilizer in the past always, is the distinctive fertilizer variety of China, because it can be decomposed into NH
3, CO
2And H
2Three kinds of gases of O and disappearing so claim gas fertilizer again, do not contain harmful intermediate product and final degradation production after the decomposition, long-term application does not influence soil property, is one of safest nitrogen fertilizers.Because bicarbonate of ammonia has labile characteristics, the utilization ratio of its nitrogen nutrient is generally lower.Usually reduce its conversion release, improve utilization rate of fertilizer by adding nitrification inhibitor and urease inhibitor, for example CN201110273035 discloses the method for a kind of ammonium fertilizer and nitrification inhibitor compounding application improvement acid soil, described ammonium fertilizer is urea and bicarbonate of ammonia, and nitrification inhibitor is Dyhard RU 100.Nitrogenous fertilizer mixed imposing on topsoil with Dyhard RU 100, and fully mix with soil and to get final product.CN01133415, CN200610134407, CN200610047592, CN200910014242 etc. relate to the performance of using nitrification inhibitor and urease inhibitor to improve ammonium fertilizer.
Last century the nineties (Feng Yuanqi, " opinion new type nitrogen fertilizer-long-acting ammonium bicarbonate ", " chemical fertilizer design ", 2007,45(3): 59-62; Wang Zuyi, Chen Weiwei, Lao Linyao, " application of synergy carbon ammonium on agricultural ", " phosphate fertilizer and multiple fertilizer ", 1995, (3): 77-80), by in bicarbonate of ammonia, adding the ammonium ion stablizer, develop a kind of long-acting ammonium bicarbonate product, in application, obtained certain effect, but this class stability fertilizer can not use at leguminous crop, and higher because of ammonium ion stablizer price, thereby further promote with not using in the production of bicarbonate of ammonia.
CN201210365138 discloses a kind of method of utilizing humate and ammoniacal liquor absorption and stabilizing carbon dioxide, this method comprises humate and ammonia solvent in water, the mixture of gained is joined in the absorption tower, to wherein feeding the gas that contains carbonic acid gas, generate the absorption liquid that contains bicarbonate of ammonia and ammonium humate; The absorption liquid of gained flows in the mechanical dehydration device, and the dehydration back obtains to contain the mixture of bicarbonate of ammonia and ammonium humate.The purpose of this method is to improve absorption and the fixed efficiency of carbonic acid gas, cuts down the consumption of energy, and the humate ratio of interpolation is higher, but not easy to operate, and alkalescence is strong, easily causes the volatilization loss of nitrogen.The objective of the invention is the small molecules humic acids by extracting, add to the form of liquid in the technological process of production of common bicarbonate of ammonia, and with the part or all of water in the humic acids synergy liquid alternative techniques flow process, produce a kind of humic acids Synergistic ammonium bicarbonate product, compare with common bicarbonate of ammonia, this product can effectively reduce the volatilization loss of nitrogen.
Therefore, the inventor by lot of experiments, has finished the present invention finally on the basis of summing up prior art.
[summary of the invention]
[technical problem that will solve]
The purpose of this invention is to provide a kind of humic acids Synergistic ammonium bicarbonate fertilizer.
Another object of the present invention provides the preparation method of described humic acids Synergistic ammonium bicarbonate fertilizer.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of humic acids Synergistic ammonium bicarbonate fertilizer.
Described ammonium bicarbonate fertilizer is made up of 0.15%～0.60% humic acids synergistic agent and 99.40%～99.85% bicarbonate of ammonia by weight, and wherein humic acids content is 0.09%～0.4%.
According to another kind of preferred implementation of the present invention, described ammonium bicarbonate fertilizer is by 0.24%～0.50% humic acids synergistic agent and 99.50%～99.76% bicarbonate of ammonia are formed by weight.
According to another kind of preferred implementation of the present invention, described ammonium bicarbonate fertilizer is by 0.30%～0.42% humic acids synergistic agent and 99.58%～99.70% bicarbonate of ammonia are formed by weight.
The invention still further relates to the production method of described humic acids Synergistic ammonium bicarbonate fertilizer.The step of this production method is as follows:
The preparation of A, humic acids synergy liquid:
With raw material weathered coal or brown coal pulverize the back add 10～12 times of its weight, concentration 0.1%～0.5% sodium hydroxide or potassium hydroxide aqueous solution by weight, heating and continuous boiling 20～30 minutes, carry out centrifugation or filtration then, the heating of supernatant liquor or filtrate is concentrated into solid content is by weight 5%～15%, humic acids content is by weight 3%～10%, obtains humic acids synergy liquid A; Perhaps
0.1%～1.0% sulfuric acid or aqueous nitric acid and Sodium salts humic acids or potassium humate mixed 10～20 minutes according to its weight ratio 3～6: 1 by weight with concentration, carry out centrifugation or filtration then, the heating of supernatant liquor or filtrate is concentrated into solid content is by weight 5%～15%, humic acids content is by weight 3%～10%, obtains humic acids synergy liquid B;
The production of B, humic acids Synergistic ammonium bicarbonate
The humic acids synergy liquid A of steps A preparation or B and strong aqua are added in the strong aqua storage tank according to weight ratio 0.02～0.10:1, stir, successively by carbonization secondary tower and the carbonization king-tower of conventional bicarbonate of ammonia production technique, the ammonia in the strong aqua and carbon dioxide reaction generate bicarbonate of ammonia therein for described humic acids synergy liquid and strong aqua mixture; The bicarbonate of ammonia that generates enters thickener again to be separated with whizzer, dry, obtain described humic acids Synergistic ammonium bicarbonate product, wherein humic acids synergistic agent content is that humic acids content is 0.09%～0.4% in humic acids Synergistic ammonium bicarbonate by weight of fertilizer 0.15%～0.60%.
A preferred embodiment of the invention, in step B, weight ratio according to humic acids synergy liquid A or B and bicarbonate of ammonia is 0.01～0.10:1, humic acids synergy liquid A or the B of steps A preparation are added in the thickener of conventional bicarbonate of ammonia production technique, humic acids synergy liquid A or B enter whizzer with bicarbonate of ammonia, after the centrifugation, remaining humic acids synergy liquid A or B separate the mother liquor that obtains with whizzer and enter mother liquid tank, pass through high-order Ammonic washing tower again, the strong aqua that obtains is again through carbonization secondary tower and carbonization king-tower, ammonia wherein and carbon dioxide reaction generate bicarbonate of ammonia, it enters thickener again, so the humic acids synergy liquid concentration of circulation in its recycle system tends towards stability, humic acids synergistic agent content in its humic acids Synergistic ammonium bicarbonate product also tends towards stability, so obtain described humic acids Synergistic ammonium bicarbonate product, wherein humic acids synergistic agent content is that humic acids content is 0.09%～0.4% in humic acids Synergistic ammonium bicarbonate by weight of fertilizer 0.15%～0.60%.
According to another kind of preferred implementation of the present invention, in step B, weight ratio according to humic acids synergy liquid A or B and bicarbonate of ammonia is 0.01～0.10:1, humic acids synergy liquid A or B are added in the whizzer, after centrifugation, remaining humic acids synergy liquid A or B separate the mother liquor that obtains with whizzer and enter mother liquid tank, pass through high-order Ammonic washing tower again, the strong aqua that obtains is again through carbonization secondary tower and carbonization king-tower, ammonia wherein and carbon dioxide reaction generate bicarbonate of ammonia, it enters thickener, so the humic acids synergy liquid concentration of circulation in its recycle system tends towards stability, humic acids synergistic agent content in its humic acids Synergistic ammonium bicarbonate product also tends towards stability, so obtain described humic acids Synergistic ammonium bicarbonate product, wherein humic acids synergistic agent content is that humic acids content is 0.09%～0.4% in humic acids Synergistic ammonium bicarbonate by weight of fertilizer 0.15%～0.60%.
According to another kind of preferred implementation of the present invention, the fineness of described weathered coal or brown coal is more than 80 orders.
According to another kind of preferred implementation of the present invention, the weight ratio of humic acids synergy liquid A or B and strong aqua is 0.04～0.08:1.
According to another kind of preferred implementation of the present invention, the weight ratio of humic acids synergy liquid A or B and bicarbonate of ammonia is 0.04～0.06:1.
According to another kind of preferred implementation of the present invention, be 50～55 hours described cycling time.
Below the present invention will be described in more detail.
The present invention relates to a kind of humic acids Synergistic ammonium bicarbonate fertilizer.
The present invention mainly is to be raw material with weathered coal or brown coal, extracts wherein humic acids than small molecular weight with diluted alkaline; Or be raw material with Sodium salts humic acids or potassium humate, separate humic acids than small molecular weight with diluted acid, thereby prepare the humic acids synergy liquid.In the bicarbonate of ammonia production process, described humic acids synergy liquid is added in the strong aqua storage tank, fully stir, mix with ammoniacal liquor, produce humic acids Synergistic ammonium bicarbonate product through carbonization system again.Perhaps the humic acids synergy liquid is added in stiff device or the whizzer, the humic acids synergy liquid that centrifugation obtains enters mother liquid tank, and makes humic acids synergy liquid concentration stabilize in the recycle system gradually, generates stay-in-grade humic acids Synergistic ammonium bicarbonate product.
In the present invention, select for use natural humic acid as fertilizer sources nutrient synergistic agent and ammonium ion stablizer to produce the humic acids Synergistic ammonium bicarbonate, it mainly is the plant recovery of nutrient that is used for improving bicarbonate of ammonia by two aspects, contain a large amount of carboxyls, phenolic hydroxyl group, carbonyl isoreactivity group in the humic acids on the one hand, can promote the crop root growth, improve the root system vigor, strengthen the ability that crop absorbs nutrient; On the other hand, these active groups in the humic acids have fixedly ammonium ion, reduce the effect of ammonia loss by volatilization, thereby have improved utilization rate of fertilizer.In addition, humic acids can also improve the resistance (drought resisting, anti-saline and alkaline infiltration, cold-resistant, disease and insect resistance etc.) of crop, and have improve the soil, the effect of culture fertility, raising product quality, these characteristics and advantage are that nutrient stablizers such as nitrification inhibitor and urease inhibitor do not have.
According to the present invention, described humic acids Synergistic ammonium bicarbonate fertilizer is made up of 0.15%～0.60% humic acids synergistic agent and 99.40%～99.85% bicarbonate of ammonia by weight, and wherein humic acids content is 0.09%～0.4%.
In the present invention, described humic acids synergistic agent should be appreciated that and is, adopt humic acids synergy liquid A or the B of the inventive method preparation to be evaporated to the resulting solids in dried back under the drying temperature at its drying process in producing the bicarbonate of ammonia technological process, this solids contains humic acids.
According to the present invention, in humic acids Synergistic ammonium bicarbonate by weight of fertilizer, if the amount of humic acids synergistic agent is lower than 0.15%, then can synergistic effect not remarkable; If the amount of humic acids synergistic agent is higher than 0.60%, then can increase production cost, reduce the nitrogen content of product; Therefore, the amount of humic acids synergistic agent is 0.15%～0.60%, and is appropriate.
Preferably, described ammonium bicarbonate fertilizer is by 0.24%～0.50% humic acids synergistic agent and 99.50%～99.76% bicarbonate of ammonia are formed by weight.
More preferably, described ammonium bicarbonate fertilizer is by 0.30%～0.42% humic acids synergistic agent and 99.58%～99.70% bicarbonate of ammonia are formed by weight.
The present invention relates to the production method of described humic acids Synergistic ammonium bicarbonate fertilizer, concrete production method is referring to accompanying drawing 1.
The step of this production method is as follows:
The preparation of A, humic acids synergy liquid:
With raw material weathered coal or brown coal pulverize the back add 10～12 times of its weight, concentration 0.1%～0.5% sodium hydroxide or potassium hydroxide aqueous solution by weight, heating and continuous boiling 20～30 minutes, carry out centrifugation or filtration then, the heating of supernatant liquor or filtrate is concentrated into solid content is by weight 5%～15%, humic acids content is by weight 3%～10%, obtains humic acids synergy liquid A.
Described weathered coal or brown coal powder are broken to fineness more than 80 orders.Pulverizing weathered coal or the employed equipment of brown coal is the disintegrating apparatus of selling in the market, and for example Weifang powder technology equipment company limited just far away is with the pulverizer of trade(brand)name LHB self-shunting pulverizing mill sale.
Perhaps
0.1%～1.0% sulfuric acid or aqueous nitric acid and Sodium salts humic acids or potassium humate mixed 10～20 minutes according to its weight ratio 3～6: 1 by weight with concentration, carry out centrifugation or filtration then, the heating of supernatant liquor or filtrate is concentrated into solid content is by weight 5%～15%, humic acids content is by weight 3%～10%, obtains humic acids synergy liquid B.
When preparation humic acids synergy liquid; the employed equipment of centrifugation all is the centrifugation apparatus of selling in the market; for example chemical machinery Co., Ltd., Factory in Shanghai is with the whizzer of trade(brand)name horizontal spiral discharge sedimentation centrifuge sale; the whizzer that Jiangsu Mudan Centrifuge Manufacturing Co., Ltd. sells with trade(brand)name SGZ type unloading under scraper whizzer, Suzhou Ba Tuo whizzer are made the whizzer that company limited sells with the airtight whizzer of SB type 3-foot.
In this step, supernatant liquor or filtrate are normally heated concentrated under the condition of 50 ℃-80 ℃ of temperature and pressure≤150kpa.It all is the equipment of selling in the market that heating concentrates employed equipment, and for example the fixed safe vaporizer in Shanghai company limited wins the vacuum concentrator that the medicine equipment company limited of navigating sells with trade(brand)name ZN series vacuum decompression thickener with the thickening equipment of trade(brand)name vacuum decompressioning and concentrating tank sale, vacuum concentrator, the Changzhou that Wenzhou shellfish promise machinery company limited sells with the energy-conservation thickener of trade(brand)name SN series economic benefits and social benefits.
The humic acids content that heating concentrates in the solid substance that obtains is that employing standard NY/T1971-2010 water-soluble fertilizer (humic acids Determination on content) is measured.
The production of B, humic acids Synergistic ammonium bicarbonate
Usually compression arbon dioxide is fed dense
Ammoniacal liquorIn, and under pressure carbon dioxide, place, cool off simultaneously, separate out crystal, again through centrifugation, dehydration and obtain described bicarbonate of ammonia.Particularly, conventional bicarbonate of ammonia production technique referring to document (Kong Xianglin, " production technology of ammonium bicarbonate fertilizer ", " chemical fertilizer industry ", 2001,28(6): 3-4).This step of the present invention is carried out in this conventional bicarbonate of ammonia production technique, so this specification sheets no longer is elaborated to its conventional bicarbonate of ammonia production technique.
The humic acids synergy liquid A of steps A preparation or B and strong aqua are added in the strong aqua storage tank according to weight ratio 0.02～0.10:1, stir, successively by carbonization secondary tower and the carbonization king-tower of conventional bicarbonate of ammonia production technique, the ammonia in the strong aqua and carbon dioxide reaction generate bicarbonate of ammonia therein for described humic acids synergy liquid and strong aqua mixture; The bicarbonate of ammonia that generates enters thickener again to be separated with whizzer, dry, obtain described humic acids Synergistic ammonium bicarbonate product, wherein humic acids synergistic agent content is that humic acids content is 0.09%～0.4% in humic acids Synergistic ammonium bicarbonate by weight of fertilizer 0.15%～0.60%.
Preferably, the weight ratio of humic acids synergy liquid A or B and strong aqua is 0.04～0.08:1.
In humic acids Synergistic ammonium bicarbonate fertiliser production method of the present invention, step B can also adopt following dual mode to implement.
First kind of mode:
Weight ratio according to humic acids synergy liquid A or B and bicarbonate of ammonia is 0.01～0.10:1, humic acids synergy liquid A or the B of steps A preparation are added in the thickener of conventional bicarbonate of ammonia production technique, humic acids synergy liquid A or B enter whizzer with bicarbonate of ammonia, after the centrifugation, remaining humic acids synergy liquid A or B separate the mother liquor that obtains with whizzer and enter mother liquid tank, pass through high-order Ammonic washing tower again, the strong aqua that obtains is again through carbonization secondary tower and carbonization king-tower, ammonia wherein and carbon dioxide reaction generate bicarbonate of ammonia, it enters thickener again, so the humic acids synergy liquid concentration of circulation in its recycle system tends towards stability, humic acids synergistic agent content in its humic acids Synergistic ammonium bicarbonate product also tends towards stability, so obtain described humic acids Synergistic ammonium bicarbonate product, wherein humic acids synergistic agent content is that humic acids content is 0.09%～0.4% in humic acids Synergistic ammonium bicarbonate by weight of fertilizer 0.15%～0.60%.
The second way:
Weight ratio according to humic acids synergy liquid A or B and bicarbonate of ammonia is 0.01～0.10:1, humic acids synergy liquid A or B are added in the whizzer, after centrifugation, remaining humic acids synergy liquid A or B separate the mother liquor that obtains with whizzer and enter mother liquid tank, pass through high-order Ammonic washing tower again, the strong aqua that obtains is again through carbonization secondary tower and carbonization king-tower, ammonia wherein and carbon dioxide reaction generate bicarbonate of ammonia, it enters thickener, so the humic acids synergy liquid concentration of circulation in its recycle system tends towards stability, humic acids synergistic agent content in its humic acids Synergistic ammonium bicarbonate product also tends towards stability, so obtain described humic acids Synergistic ammonium bicarbonate product, wherein humic acids synergistic agent content is that humic acids content is 0.09%～0.4% in humic acids Synergistic ammonium bicarbonate by weight of fertilizer 0.15%～0.60%.
In the present invention, the height that how much can reflect humic acids synergistic agent addition of humic acids content, humic acids content are that employing standard NY/T1971-2010 water-soluble fertilizer (humic acids Determination on content) method is measured.
The existing bicarbonate of ammonia product of Xiao Shouing contains in bicarbonate of ammonia gross weight 3%～4% water in the market, the present invention substitutes part or all of water in the recycle system with the humic acids synergy liquid, make in the humic acids Synergistic ammonium bicarbonate product of production and contain 3%～4% humic acids synergy liquid, be to contain in bicarbonate of ammonia gross weight 0.15%～0.6% humic acids synergistic agent in the humic acids Synergistic ammonium bicarbonate fertilizer product of the present invention, wherein humic acids content is 0.09%～0.4%.
The nutrient content of the prepared humic acids Synergistic ammonium bicarbonate of the present invention can adopt standard method GB8572-88 to measure.
In the present invention, except the equipment that conventional bicarbonate of ammonia production technique is used, the volume pump that the present invention uses is the known volume pumps of those skilled in the art, and for example: the volume pump that machinery limited public affairs in Changzhou howl source are sold with trade(brand)name JYM-I volume pump, JYM-II volume pump and JJM-II plunger type metering pump, De Pamu (Hangzhou) pump industry Science and Technology Ltd. are with trade(brand)name 2DP[M] volume pump sold of ZA series volume pump, go up marine triumphant pump industry Manufacturing Co., Ltd with the volume pump of trade(brand)name JYD Series Hydraulic diaphragm type metering sale.
Humic acids Synergistic ammonium bicarbonate production method of the present invention has following characteristics: the natural humic acid source is wide, cheap, uses safety; On the basis that is not changing existing bicarbonate of ammonia production technique, just can produce Synergistic ammonium bicarbonate by adding simple device, this production technique is simple, and production capacity height, cost are low, and environmental friendliness; According to humic acids Synergistic ammonium bicarbonate product requirement, the part water in the replaceable bicarbonate of ammonia production cycle of the humic acids synergy liquid of the present invention system or whole water.
The present invention utilizes sig water to extract the less part of molecular weight in the humic acids, add in the production process of bicarbonate of ammonia again, produce humic acids Synergistic ammonium bicarbonate product, its characteristics are: humic acids synergistic agent addition is low, efficiently, the nutrient content to fertilizer does not influence; Synergistic ammonium bicarbonate of the present invention is a kind of fertilizer product with good result, on nutrient discharges and utilizes, has strengthened the slow release effect of fertilizer, has improved utilization rate of fertilizer; On effect, can promote the crop root growth, improve the root system vigor, strengthen the ability that crop absorbs nutrient; On benefit, can improve plant recovery of nutrient (5～10 percentage points), can reduce nutrient loss, avoid secondary pollution, reduce agriculture production cost, and it is wide to have raw material sources, transport, use characteristics such as convenient, therefore, humic acids Synergistic ammonium bicarbonate application prospect of the present invention is boundless.
Therefore, product of the present invention is a kind of polyfunctional new and effective fertilizer, it is identical with conventional fertilizer in operation technique, using method is simple and various, can be used for base manure, topdress, also be applicable to drip irrigation system, but also foliage-spray, and this also is characteristics and advantage that other kind slow release fertilizer does not possess.Fertilizer product of the present invention is not residual, free from environmental pollution, environmentally friendly in soil.
Humic acids Synergistic ammonium bicarbonate of the present invention can be used as base manure, the use of topdressing.The usage quantity of humic acids Synergistic ammonium bicarbonate of the present invention needs to determine according to factors such as soil regime, crop varieties, crop growth phase, crop alimentary situations.
[beneficial effect]
The invention has the beneficial effects as follows: humic acids Synergistic ammonium bicarbonate production method of the present invention is on the basis that does not change existing bicarbonate of ammonia production technique, just can produce Synergistic ammonium bicarbonate by adding simple device, this production technique is simple, and production capacity height, cost are low, and environmental friendliness; Part water in the replaceable bicarbonate of ammonia production cycle of the humic acids synergy liquid of the present invention system or whole water.
Humic acids Synergistic ammonium bicarbonate of the present invention has strengthened the slow release effect of fertilizer on nutrient discharges and utilizes, improved utilization rate of fertilizer; On effect, can promote the crop root growth, improve the root system vigor, strengthen the ability that crop absorbs nutrient; On benefit, can improve plant recovery of nutrient (5～10 percentage points), can reduce nutrient loss, avoid secondary pollution, reduce agriculture production cost.Fertilizer product of the present invention is a kind of free from environmental pollution, environment amenable fertilizer.
[description of drawings]
Fig. 1: humic acids Synergistic ammonium bicarbonate fertiliser production schema of the present invention;
1-weathered coal (Sodium salts humic acids or potassium humate), 2-sodium hydroxide or potassium hydroxide solution (sulfuric acid or salpeter solution), 3-enrichment step, 4-humic acids synergy liquid, 5-humic acids synergy liquid storage tank, 6-volume pump, 7-strong aqua storage tank (stiff device or whizzer), 8-carbonating tower, 9-stiff device and whizzer, 10-humic acids Synergistic ammonium bicarbonate product.
[embodiment]
Can understand the present invention better by following embodiment.
Embodiment 1: the production of humic acids Synergistic ammonium bicarbonate fertilizer of the present invention
The implementation step of this embodiment is as follows:
The preparation of A, humic acids synergy liquid:
The pulverizer that use is sold with trade(brand)name LHB self-shunting pulverizing mill by Weifang powder technology equipment company limited just far away, the raw material weathered coal is crushed to adds 10 times of its weight behind 80 orders, concentration is 0.1% aqueous sodium hydroxide solution by weight, heating and continuous boiling 20 minutes, use the whizzer of being sold with trade(brand)name SGZ type unloading under scraper whizzer by Jiangsu Mudan Centrifuge Manufacturing Co., Ltd. to carry out centrifugation then, the supernatant liquor that obtains uses the thickener sold with the trade(brand)name vacuum decompressioning and concentrating tank by the fixed safe vaporizer in Shanghai company limited to heat under the condition of 50～70 ℃ of temperature and pressure 70～100kpa concentratedly to be by weight 5% until solid content, humic acids content is by weight 3%, obtains humic acids synergy liquid A;
The production of B, humic acids Synergistic ammonium bicarbonate
Humic acids synergy liquid A and the strong aqua of steps A preparation are added in the strong aqua storage tank according to weight ratio 0.02:1, stir, successively by carbonization secondary tower and the carbonization king-tower of conventional bicarbonate of ammonia production technique, the ammonia in the strong aqua and carbon dioxide reaction generate bicarbonate of ammonia therein for described humic acids synergy liquid and strong aqua mixture; The bicarbonate of ammonia that generates enters thickener again to be separated with whizzer, and drying obtains described humic acids Synergistic ammonium bicarbonate product.
Humic acids content in this humic acids Synergistic ammonium bicarbonate product is to adopt the method for describing in this specification sheets to measure, and the nutrient content of this humic acids Synergistic ammonium bicarbonate is to adopt standard method GB8572-88 to measure.Its measurement result is as follows:
Bicarbonate of ammonia nitrogen content %=17.07%; Humic acids content=0.095%.
Embodiment 2: the production of humic acids Synergistic ammonium bicarbonate fertilizer of the present invention
The implementation step of this embodiment is as follows:
The preparation of A, humic acids synergy liquid:
The pulverizer that use is sold with the trade(brand)name turbine grinder by Jimo City, Qingdao supper micron mill factory, the raw material weathered coal is crushed to adds 12 times of its weight behind 100 orders, concentration is 0.5% aqueous sodium hydroxide solution by weight, heating and continuous boiling 30 minutes, use the whizzer of being sold with the trade(brand)name horizontal spiral discharge sedimentation centrifuge by Shanghai chemical machinery Co., Ltd., Factory then, the clear liquid that obtains uses the vacuum concentrator sold with the energy-conservation thickener of trade(brand)name SN series economic benefits and social benefits by Wenzhou shellfish promise machinery company limited to heat under the condition of 50～80 ℃ of temperature and pressure 100～120kpa concentratedly to be by weight 15% until solid content, humic acids content is by weight 10%, obtains humic acids synergy liquid A;
The production of B, humic acids Synergistic ammonium bicarbonate
Humic acids synergy liquid A and the strong aqua of steps A preparation are added in the strong aqua storage tank according to weight ratio 0.10:1, stir, successively by carbonization secondary tower and the carbonization king-tower of conventional bicarbonate of ammonia production technique, the ammonia in the strong aqua and carbon dioxide reaction generate bicarbonate of ammonia therein for described humic acids synergy liquid and strong aqua mixture; The bicarbonate of ammonia that generates enters thickener again to be separated with whizzer, and drying obtains described humic acids Synergistic ammonium bicarbonate product.
Humic acids content in this humic acids Synergistic ammonium bicarbonate product is to adopt the method for describing in this specification sheets to measure, and the nutrient content of this humic acids Synergistic ammonium bicarbonate is to adopt standard method GB8572-88 to measure.Its measurement result is as follows:
Bicarbonate of ammonia nitrogen content %=17.01%; Humic acids content %=0.38%.
Embodiment 3: the production of humic acids Synergistic ammonium bicarbonate fertilizer of the present invention
The implementation step of this embodiment is as follows:
The preparation of A, humic acids synergy liquid:
The pulverizer that use is sold with the trade(brand)name turbine grinder by Jimo City, Qingdao supper micron mill factory, the raw material weathered coal is crushed to adds 12 times of its weight behind 90 orders, concentration is 0.2% aqueous sodium hydroxide solution by weight, heating and continuous boiling 25 minutes, use the whizzer of being sold with the airtight whizzer of SB type 3-foot by Suzhou Ba Tuo whizzer manufacturing company limited to carry out centrifugation then, the supernatant liquor that obtains uses and wins vacuum concentrator that boat medicine equipment company limited sells with trade(brand)name ZN series vacuum decompression thickener by Changzhou and heat under the condition of 50～80 ℃ of temperature and pressure 100～150kpa and concentratedly be by weight 8% until solid content, humic acids content is by weight 5%, obtains humic acids synergy liquid A;
The production of B, humic acids Synergistic ammonium bicarbonate
Humic acids synergy liquid A and the strong aqua of steps A preparation are added in the strong aqua storage tank according to weight ratio 0.04:1, stir, successively by carbonization secondary tower and the carbonization king-tower of conventional bicarbonate of ammonia production technique, the ammonia in the strong aqua and carbon dioxide reaction generate bicarbonate of ammonia therein for described humic acids synergy liquid and strong aqua mixture; The bicarbonate of ammonia that generates enters thickener again to be separated with whizzer, and drying obtains described humic acids Synergistic ammonium bicarbonate product.
Humic acids content in this humic acids Synergistic ammonium bicarbonate product is to adopt the method for describing in this specification sheets to measure, and the nutrient content of this humic acids Synergistic ammonium bicarbonate is to adopt standard method GB8572-88 to measure.Its measurement result is as follows:
Bicarbonate of ammonia nitrogen content %=17.05%; Humic acids content %=0.16%.
Embodiment 4: the production of humic acids Synergistic ammonium bicarbonate fertilizer of the present invention
The implementation step of this embodiment is as follows:
The preparation of A, humic acids synergy liquid:
The pulverizer that use is sold with the trade(brand)name turbine grinder by Jimo City, Qingdao supper micron mill factory, the raw material weathered coal is crushed to adds 10 times of its weight behind 85 orders, concentration is 0.4% potassium hydroxide aqueous solution by weight, heating and continuous boiling 28 minutes, use the whizzer of being sold with the airtight whizzer of SB type 3-foot by Suzhou Ba Tuo whizzer manufacturing company limited to carry out centrifugation then, the supernatant liquor that obtains uses and wins vacuum concentrator that boat medicine equipment company limited sells with trade(brand)name ZN series vacuum decompression thickener by Changzhou and heat under the condition of 50～80 ℃ of temperature and pressure 80～120kpa and concentratedly be by weight 12% until solid content, humic acids content is by weight 8%, obtains humic acids synergy liquid A;
The production of B, humic acids Synergistic ammonium bicarbonate
Humic acids synergy liquid A and the strong aqua of steps A preparation are added in the strong aqua storage tank according to weight ratio 0.08:1, stir, successively by carbonization secondary tower and the carbonization king-tower of conventional bicarbonate of ammonia production technique, the ammonia in the strong aqua and carbon dioxide reaction generate bicarbonate of ammonia therein for described humic acids synergy liquid and strong aqua mixture; The bicarbonate of ammonia that generates enters thickener again to be separated with whizzer, and drying obtains described humic acids Synergistic ammonium bicarbonate product.
Humic acids content in this humic acids Synergistic ammonium bicarbonate product is to adopt the method for describing in this specification sheets to measure, and the nutrient content of this humic acids Synergistic ammonium bicarbonate is to adopt standard method GB8572-88 to measure.Its measurement result is as follows:
Bicarbonate of ammonia nitrogen content %=17.03%; Humic acids content %=0.27%.
Embodiment 5: the production of humic acids Synergistic ammonium bicarbonate fertilizer of the present invention
The implementation step of this embodiment is as follows:
The preparation of A, humic acids synergy liquid:
0.4% aqueous sulfuric acid and Sodium salts humic acids mixed 12 minutes according to its weight ratio at 4: 1 by weight with concentration, use the whizzer of being sold with the trade(brand)name horizontal spiral discharge sedimentation centrifuge by Shanghai chemical machinery Co., Ltd., Factory to carry out centrifugation then, obtain humic acids synergy liquid B, its solid content is by weight 15%, and humic acids content is by weight 9%;
The production of B, humic acids Synergistic ammonium bicarbonate
Weight ratio according to humic acids synergy liquid B and bicarbonate of ammonia is 0.01:1, the humic acids synergy liquid B of steps A preparation is added in the thickener of conventional bicarbonate of ammonia production technique, humic acids synergy liquid B enters whizzer with bicarbonate of ammonia, after the centrifugation, remaining humic acids synergy liquid B separates the mother liquor that obtains with whizzer and enters mother liquid tank, pass through high-order Ammonic washing tower again, the strong aqua that obtains is again through carbonization secondary tower and carbonization king-tower, ammonia wherein and carbon dioxide reaction generate bicarbonate of ammonia, it enters thickener again, humic acids synergy liquid concentration after so circulating 50 hours in its recycle system tends towards stability, humic acids synergistic agent content in its humic acids Synergistic ammonium bicarbonate product also tends towards stability, so obtain described humic acids Synergistic ammonium bicarbonate product.
Humic acids content in this humic acids Synergistic ammonium bicarbonate product is to adopt the method for describing in this specification sheets to measure, and the nutrient content of this humic acids Synergistic ammonium bicarbonate is to adopt standard method GB8572-88 to measure.Its measurement result is as follows:
Bicarbonate of ammonia nitrogen content %=17.01%; Humic acids content %=0.31%.
Embodiment 6: the production of humic acids Synergistic ammonium bicarbonate fertilizer of the present invention
The implementation step of this embodiment is as follows:
The preparation of A, humic acids synergy liquid:
With concentration by weight 0.8% aqueous nitric acid and potassium humate mixed at 5: 1 10 minutes according to its weight ratio, obtain humic acids synergy liquid B then after filtration, its solid content is by weight 10%, humic acids content is by weight 6.5%;
The production of B, humic acids Synergistic ammonium bicarbonate
Weight ratio according to humic acids synergy liquid B and bicarbonate of ammonia is 0.10:1, the humic acids synergy liquid B of steps A preparation is added in the thickener of conventional bicarbonate of ammonia production technique, humic acids synergy liquid B enters whizzer with bicarbonate of ammonia, after the centrifugation, remaining humic acids synergy liquid B separates the mother liquor that obtains with whizzer and enters mother liquid tank, pass through high-order Ammonic washing tower again, the strong aqua that obtains is again through carbonization secondary tower and carbonization king-tower, ammonia wherein and carbon dioxide reaction generate bicarbonate of ammonia, it enters thickener again, humic acids synergy liquid concentration after so circulating 52 hours in its recycle system tends towards stability, humic acids synergistic agent content in its humic acids Synergistic ammonium bicarbonate product also tends towards stability, so obtain described humic acids Synergistic ammonium bicarbonate product.
Humic acids content in this humic acids Synergistic ammonium bicarbonate product is to adopt the method for describing in this specification sheets to measure, and the nutrient content of this humic acids Synergistic ammonium bicarbonate is to adopt standard method GB8572-88 to measure.Its measurement result is as follows:
Bicarbonate of ammonia nitrogen content %=17.04%; Humic acids content %=0.22%.
Embodiment 7: the production of humic acids Synergistic ammonium bicarbonate fertilizer of the present invention
The implementation step of this embodiment is as follows:
The preparation of A, humic acids synergy liquid:
0.1% aqueous nitric acid and Sodium salts humic acids mixed 20 minutes according to its weight ratio at 6: 1 by weight with concentration, use the whizzer of being sold with trade(brand)name SGZ type unloading under scraper whizzer by Jiangsu Mudan Centrifuge Manufacturing Co., Ltd. to carry out centrifugation then, collect supernatant liquor, obtain humic acids synergy liquid B, its solid content is by weight 8%, and humic acids content is by weight 3%;
The production of B, humic acids Synergistic ammonium bicarbonate
Weight ratio according to humic acids synergy liquid B and bicarbonate of ammonia is 0.05:1, B adds in the whizzer with the humic acids synergy liquid, after centrifugation, remaining humic acids synergy liquid B separates the mother liquor that obtains with whizzer and enters mother liquid tank, pass through high-order Ammonic washing tower again, the strong aqua that obtains is again through carbonization secondary tower and carbonization king-tower, ammonia wherein and carbon dioxide reaction generate bicarbonate of ammonia, it enters thickener, so circulation is after 55 hours, humic acids synergy liquid concentration in its recycle system tends towards stability, and the humic acids synergistic agent content in its humic acids Synergistic ammonium bicarbonate product also tends towards stability, so obtain described humic acids Synergistic ammonium bicarbonate product.
Humic acids content in this humic acids Synergistic ammonium bicarbonate product is to adopt the method for describing in this specification sheets to measure, and the nutrient content of this humic acids Synergistic ammonium bicarbonate is to adopt standard method GB8572-88 to measure.Its measurement result is as follows:
Bicarbonate of ammonia nitrogen content %=17.05%; Humic acids content %=0.10%.
Embodiment 8: the production of humic acids Synergistic ammonium bicarbonate fertilizer of the present invention
The implementation step of this embodiment is as follows:
The preparation of A, humic acids synergy liquid:
1.0% aqueous sulfuric acid and potassium humate mixed 16 minutes according to its weight ratio at 3: 1 by weight with concentration, use the whizzer of being sold with trade(brand)name SGZ type unloading under scraper whizzer by Jiangsu Mudan Centrifuge Manufacturing Co., Ltd. to carry out centrifugation then, collect supernatant liquor, obtain humic acids synergy liquid B, its solid content is by weight 12%, and humic acids content is by weight 8.5%;
The production of B, humic acids Synergistic ammonium bicarbonate
Weight ratio according to humic acids synergy liquid B and bicarbonate of ammonia is 0.08:1, B adds in the whizzer with the humic acids synergy liquid, after centrifugation, remaining humic acids synergy liquid B separates the mother liquor that obtains with whizzer and enters mother liquid tank, pass through high-order Ammonic washing tower again, the strong aqua that obtains is again through carbonization secondary tower and carbonization king-tower, ammonia wherein and carbon dioxide reaction generate bicarbonate of ammonia, it enters thickener, so the humic acids synergy liquid concentration of circulation in its recycle system tends towards stability, humic acids synergistic agent content in its humic acids Synergistic ammonium bicarbonate product also tends towards stability, so obtain described humic acids Synergistic ammonium bicarbonate product.
Humic acids content in this humic acids Synergistic ammonium bicarbonate product is to adopt the method for describing in this specification sheets to measure, and the nutrient content of this humic acids Synergistic ammonium bicarbonate is to adopt standard method GB8572-88 to measure.Its measurement result is as follows:
Bicarbonate of ammonia nitrogen content %=17.03%; Humic acids content %=0.26%.
Fertilizer test embodiment 1: the ammonia volatilization test
The test implementation step is as follows:
Employing " static absorption process " (Ling Li, Li Shiqing, Li Shengxiu. Study on Ammonia Volatilization from Calcareous Soil [J]. the soil erosion and soil conservation journal, 1999,5 (6): 119～122; Liu Zengbing, Zhao Bingqiang, woods public security. humic acid urea ammonia volatilization characteristic and Study on influencing factors [J]. plant nutrition and fertilizer journal, 2010,16 (1): 208～213) the ammonia volatilization amount of mensuration humic acids Synergistic ammonium bicarbonate product of the present invention.
Take by weighing soil 500g(by 1mm sieve in dry ground), be added in its soil by the 0.84gN/kg soil applying fertilizer amount, clay fertilizer mixes, put into the plastic tank that specification is 15cm * 8.5cm * 17.5cm, regulating its water content is 40% of maxmun field capacity, seal with the plastic closures film, put into the cuvette that 10mL2% boric acid is housed in the bucket, with methyl red-tetrabromo-mcresolsulfonphthalein mixture indicator as indicator, if 2 processing, be respectively the humic acids Synergistic ammonium bicarbonate (HACN) of common bicarbonate of ammonia (CN) and the embodiment of the invention 2 preparations, repeat 3 times.Place intelligent growth cabinet, cultured continuously under the condition of 25 ℃ of temperature during after cultivation the 1st, 3,5,7,9,14 day, is taken out absorption cell in the bucket, is 0.02mol/L H with concentration
2SO
4The solution titration, the pure nitrogen level that converts and volatilize at every turn.
The test-results of this test is listed in the table 1.
Table 1 ammonia volatilization semi-invariant (mg/pot)
The test-results of table 1 clearly illustrates that, after 14 days cultivation, compares with common bicarbonate of ammonia, and humic acids Synergistic ammonium bicarbonate of the present invention can significantly reduce ammonia loss by volatilization, and the ammonia volatilization semi-invariant can reduce by 26.3%.
Fertilizer test embodiment 2: field test
Utilize field test to carry out the compliance test result of fertilizer of the present invention, test-results shows that under the condition that waits the nitrogen nutrient amount, humic acids Synergistic ammonium bicarbonate product of the present invention can obviously improve crop yield, having improved utilization rate of fertilizer, is a kind of environmental friendly fertilizer.Compliance test result test processing setting and the result of product are as follows:
Testing program:
The field test of fertilizer efficiency checking of the present invention is carried out in Yucheng, Shandong, and test arranges: (1) CK1: for not imposing the bicarbonate of ammonia contrast, (China-Arab Fertilizer Co., Ltd produces, N: P with compound fertilizer
2O
5: K
2O=15: 15: 15) 1000kg/hm
2Make base manure; (2) CK2: for imposing common bicarbonate of ammonia contrast, base manure is identical with CK1, and (the ecological fertile company limited already in middle peasant Shun sky produces N17.1%) 877kg/hm to impose bicarbonate of ammonia again in big mouthful of phase of corn
2(3) HACN: base manure is identical with CK1, and consumption is 500kg/hm
2, topdressing with the humic acids Synergistic ammonium bicarbonate product (N17.1%) of the embodiment of the invention 2 preparations, consumption is 439kg/hm
2The experimental plot area is 333.3m
2, each is handled 4 times and repeats random alignment.Other field management is with local farmland.The ripe results of corn back meter produces.The calculating of the apparent utilization ratio of nitrogenous fertilizer is contrast with CK1.
The results are shown in Table 2 for this fertilizer test.
Table 2: the apparent utilization ratio of output and nitrogenous fertilizer
The data processed result of table 2 shows: humic acids Synergistic ammonium bicarbonate product of the present invention is obvious to the effect of increasing production of corn, handles (CK2) volume increase 8.47% than common bicarbonate of ammonia, and the apparent utilization ratio of nitrogenous fertilizer improves 5.62 percentage points.
Fertilizer product of the present invention can obviously reduce the ammonia loss by volatilization of fertilizer, and significantly improves crop yield and the apparent utilization ratio of nitrogenous fertilizer, is a kind of environmental friendliness, economical fertilizer.
This shows that compare with common bicarbonate of ammonia, humic acids Synergistic ammonium bicarbonate of the present invention has characteristics such as good effect of increasing production, plant recovery of nutrient height, environmental friendliness.Have simultaneously that production technology is simple, cost is low, raw material sources are wide, easy handling, be beneficial to Industry Promotion etc.
Claims (10)
1. humic acids Synergistic ammonium bicarbonate fertilizer, it is characterized in that described ammonium bicarbonate fertilizer is made up of 0.15%～0.60% humic acids synergistic agent and 99.40%～99.85% bicarbonate of ammonia, wherein humic acids content is in described ammonium bicarbonate fertilizer gross weight 0.09%～0.4%.
2. humic acids Synergistic ammonium bicarbonate fertilizer according to claim 1 is characterized in that described ammonium bicarbonate fertilizer is by 0.24%～0.50% humic acids synergistic agent and 99.50%～99.76% bicarbonate of ammonia are formed by weight.
3. humic acids Synergistic ammonium bicarbonate fertilizer according to claim 1 is characterized in that described ammonium bicarbonate fertilizer is by 0.30%～0.42% humic acids synergistic agent and 99.58%～99.70% bicarbonate of ammonia are formed by weight.
4. according to the production method of the described humic acids Synergistic ammonium bicarbonate of each claim fertilizer among the claim 1-3, it is characterized in that the step of this production method is as follows:
The preparation of A, humic acids synergy liquid:
With raw material weathered coal or brown coal pulverize the back add 10～12 times of its weight, concentration 0.1%～0.5% sodium hydroxide or potassium hydroxide aqueous solution by weight, heating and continuous boiling 20～30 minutes, carry out centrifugation or filtration then, the heating of supernatant liquor or filtrate is concentrated into solid content is by weight 5%～15%, humic acids content is by weight 3%～10%, obtains humic acids synergy liquid A; Perhaps
0.1%～1.0% sulfuric acid or aqueous nitric acid and Sodium salts humic acids or potassium humate mixed 10～20 minutes according to its weight ratio 3～6: 1 by weight with concentration, carry out centrifugation or filtration then, the heating of supernatant liquor or filtrate is concentrated into solid content is by weight 5%～15%, humic acids content is by weight 3%～10%, obtains humic acids synergy liquid B;
The production of B, humic acids Synergistic ammonium bicarbonate
The humic acids synergy liquid A of steps A preparation or B and strong aqua are added in the strong aqua storage tank according to weight ratio 0.02～0.10:1, stir, successively by carbonization secondary tower and the carbonization king-tower of conventional bicarbonate of ammonia production technique, the ammonia in the strong aqua and carbon dioxide reaction generate bicarbonate of ammonia therein for described humic acids synergy liquid and strong aqua mixture; The bicarbonate of ammonia that generates enters thickener again to be separated with whizzer, dry, obtain described humic acids Synergistic ammonium bicarbonate product, wherein humic acids synergistic agent content is that humic acids content is 0.09%～0.4% in humic acids Synergistic ammonium bicarbonate by weight of fertilizer 0.15%～0.60%.
5. production method according to claim 4, it is characterized in that in step B, weight ratio according to humic acids synergy liquid A or B and bicarbonate of ammonia is 0.01～0.10:1, humic acids synergy liquid A or the B of steps A preparation are added in the thickener of conventional bicarbonate of ammonia production technique, humic acids synergy liquid A or B enter whizzer with bicarbonate of ammonia, after the centrifugation, remaining humic acids synergy liquid A or B separate the mother liquor that obtains with whizzer and enter mother liquid tank, pass through high-order Ammonic washing tower again, the strong aqua that obtains is again through carbonization secondary tower and carbonization king-tower, ammonia wherein and carbon dioxide reaction generate bicarbonate of ammonia, it enters thickener again, so the humic acids synergy liquid concentration of circulation in its recycle system tends towards stability, humic acids synergistic agent content in its humic acids Synergistic ammonium bicarbonate product also tends towards stability, so obtain described humic acids Synergistic ammonium bicarbonate product.
6. production method according to claim 4, it is characterized in that in step B, weight ratio according to humic acids synergy liquid A or B and bicarbonate of ammonia is 0.01～0.10:1, humic acids synergy liquid A or B are added in the whizzer, after centrifugation, remaining humic acids synergy liquid A or B separate the mother liquor that obtains with whizzer and enter mother liquid tank, pass through high-order Ammonic washing tower again, the strong aqua that obtains is again through carbonization secondary tower and carbonization king-tower, ammonia wherein and carbon dioxide reaction generate bicarbonate of ammonia, it enters thickener, so the humic acids synergy liquid concentration of circulation in its recycle system tends towards stability, humic acids synergistic agent content in its humic acids Synergistic ammonium bicarbonate product also tends towards stability, so obtain described humic acids Synergistic ammonium bicarbonate product.
7. method according to claim 4 is characterized in that the fineness of described weathered coal or brown coal is more than 80 orders.
8. method according to claim 7, the weight ratio that it is characterized in that humic acids synergy liquid A or B and strong aqua is 0.04～0.08:1.
9. according to claim 5 or 6 described methods, the weight ratio that it is characterized in that humic acids synergy liquid A or B and bicarbonate of ammonia is 0.04～0.06:1.
10. according to claim 5 or 6 described methods, it is characterized in that be 50～55 hours described cycling time.
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| CN104030763A (en) * | 2014-06-30 | 2014-09-10 | 新疆农垦科学院 | Special water-soluble carbon-contained fertilizer for drip irrigation soybeans |
| CN104973993A (en) * | 2015-06-30 | 2015-10-14 | 新疆锦华肥业有限公司 | Plant water-saving, draught-resistant, and yield-increasing agent and preparation method thereof |
| CN105061116A (en) * | 2015-08-27 | 2015-11-18 | 山西广宇通科技股份有限公司 | Liquid humic acid water-soluble fertilizer production method |
| CN105130535A (en) * | 2015-08-10 | 2015-12-09 | 山西广宇通科技股份有限公司 | Preparation method of humic acid solid water soluble fertilizer |
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