CN108424207A - Flyash acid system residue of aluminum-extracted prepares the method containing silicon potassium compound fertilizer and the utilization method containing silicon potassium compound fertilizer and flyash - Google Patents
Flyash acid system residue of aluminum-extracted prepares the method containing silicon potassium compound fertilizer and the utilization method containing silicon potassium compound fertilizer and flyash Download PDFInfo
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- CN108424207A CN108424207A CN201810564672.3A CN201810564672A CN108424207A CN 108424207 A CN108424207 A CN 108424207A CN 201810564672 A CN201810564672 A CN 201810564672A CN 108424207 A CN108424207 A CN 108424207A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D1/00—Fertilisers containing potassium
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D3/00—Calcareous fertilisers
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Abstract
The present invention relates to the utilization fields of flyash acid system residue of aluminum-extracted and flyash, disclose flyash acid system residue of aluminum-extracted and prepare the method containing silicon potassium compound fertilizer and the utilization method containing silicon composite fertilizer and flyash.This method includes：(1) in the presence of KOH solution, flyash acid system residue of aluminum-extracted and the source of manure are mixed into slurries, and carry out heating reaction, wherein the source of manure is calcium source and/or magnesium source；(2) reaction product that step (1) obtains is separated by solid-liquid separation, gained filter cake obtains silico-calcium K composite fertilizer, silicon magnesium K composite fertilizer or silico-calcium magnesium-potassium composite fertilizer after being granulated, drying.This method can simplify preparation manipulation, avoid the separation of solid and liquid operation of potassium silicate, reduce the loss of nutrient silicon, calcium, magnesium.
Description
Technical field
The present invention relates to the utilization fields that flyash acid system carries aluminium slag and flyash, and in particular, to flyash acid system carries
Residue of aluminum prepares the method containing silicon potassium compound fertilizer and the utilization method containing silicon potassium compound fertilizer and flyash.
Background technology
Aluminous fly-ash is a kind of novel bauxite resource specific to China, about 10,000,000,000 tons of aluminium oxide of Prospective resources.It is high
The utilization of aluminium powder coal ash can greatly alleviate the problem of China's bauxite resource shortage." a step acid is molten " method is so far one
The ideal aluminous fly-ash of kind extracts aluminium oxide method, but often produces 100 tons of Al2O3By about 130-150 tons of high silicon of discharge
Solid slag -- " residue of aluminum-extracted pulverized fuel ash " is commonly called as white clay in industry.
Currently, the utilization of residue of aluminum-extracted pulverized fuel ash is concentrated mainly on silicon systems product (waterglass, white carbon, silicon powder etc.) system
Standby, basic building materials (cement, ceramic tile, steam-pressing brisk etc.) manufacture, and for producing the fields such as heat preservation, refractory material.More than but
There is different degrees of contradiction in application direction, cause white between product economy added value, market capacity and consumption efficiency
Mud overall utilization rate is relatively low.According to relevant regulations, the solid waste using aluminous fly-ash production alumina system is created,
Comprehensive utilization ratio must reach 96% or more.The current existing various utilization rates utilized of white clay are far from this index is reached, directly
It connects and limits application and popularization that aluminous fly-ash carries aluminum technology.Thus, the high level of white clay, efficient consumption technology are urgently developed.
In international soil circle, siliceous fertilizer is listed in the fourth-largest element fertilizer after nitrogen, phosphorus, potassium.National soil measurement formula
Silica whether will be lacked as technical standard.Siliceous fertilizer has become a kind of new-type fertilizer of 21 century China.Currently, China
Lack the 50-80% or more that tripoli earth accounts for total area under cultivation.By taking rice as an example, the area of the long-term rice cultivation in China is up to more than 3,333 ten thousand
Hectare lacks tripoli earth and accounts for 50% or more.If whole Applying silicon fertilizers, based on volume increase 10%, only this item should can increase production 100 every year
Ten thousand tons of paddy, the production and application for promoting siliceous fertilizer have obviously social and economic benefit.Siliceous fertilizer industry future is considerably long
One period will be in ascent stage, and the market space is huge, competitive pressure very little.In addition, calcium, magnesium are also growth and development of plants institute
Required moderate-element.Si, Ca, Mg are supplemented for soil, can be developed to crop production has collaboration facilitation.
CN1923764A discloses a kind of silicon, calcium and magnesium fertilizer, wherein constitutes the raw material and weight percent of silicon-calcium-magnesium fertilizer
It is water-hardened steel slag and 60-70 %, magnesia unslacked 4-12%, white residue 10-20%, dilute sulfuric acid 15-20%, brine 1-3% than content.Specifically
Preparation method be water quenching slag, light calcined magnesia, white residue etc. mixs in proportion after plus dilute sulfuric acid at 135 DEG C acid burning
20min is to obtain acid product system in acid condition.
CN101591197A discloses a kind of method preparing calcium silicate fertilizer using pre-desiliconizing with high alumina fly ash, including (1) will
Raw material aluminous fly-ash is added sodium hydroxide solution and carries out alkali soluble reaction；(2) sodium silicate solution generated to alkali soluble reaction carries out
It is separated by filtration, dispensing of the filter cake desiliconization flyash as extraction aluminium oxide；(3) add stone into the sodium silicate solution after being separated by filtration
Grey breast precipitation reaction is simultaneously separated by filtration, and filter cake is calcium silicates, and filtrate is sodium hydroxide solution, sodium hydroxide solution return to step
(1) it recycles；(4) filter cake calcium silicates is dried, is levigate, silico-calcium fertilizer product is made.The used process route of this method
The step of (2) be related to the separation of solid and liquid of sodium metasilicate.And sodium silicate solution (being commonly called as " waterglass ") has high viscosity characteristic, when separation
Operating difficulties, filter loss rate are excessively high.Although heat preservation filtering (use 90 DEG C at filter) can be taken, increase filter pressure or
Filter plant is improved, but increases operation difficulty or equipment cost, raises the manufacturing cost containing silicon composite fertilizer.
CN107188766A discloses a kind of coal ash for manufacturing for the method for silicon composite fertilizer, including：(1) fly ash in electric power plant is passed through
Flour mill is handled to 150-200 mesh；(2) flyash after crushing is fully reflected with dilute hydrochloric acid, filters out siliceous filter residue, by this
It is spare after siliceous filter residue drying；(3) by the filtrate in step (2) at 100-150 DEG C evaporative crystallization, obtain chloride containing calcium, chlorine
Change the solid mixture of magnesium crystal；(4) the siliceous filter residue of drying of step (2) is fully reacted with sodium hydroxide solution, is contained
Sodium silicate liquid mixture；(5) liquid mixture containing sodium metasilicate of step (4) is sprayed onto to be granulated on comminutor bed of material and is prepared
Silicon composite fertilizer, the material on bed of material includes humic acid, nitrogenous fertilizer, phosphate fertilizer, potash fertilizer, bentonite and trace-element fertilizer；Wherein, contain
The weight percent difference of sodium silicate liquid mixture, humic acid, nitrogenous fertilizer, phosphate fertilizer, potash fertilizer, bentonite and trace-element fertilizer
For；5-10%, 5-10%, 30-35%, 20-35%, 10-25%, 0.5-1%, 0.5-1%.The preparation side containing silicon composite fertilizer
Method is substantially the mechanical compound of multiple nutritional components.In addition silicon source is sodium silicate solution, Na2O/SiO2Mass ratio >=1, this
The strong basicity Na more than a unit will be introduced while meaning to provide effective silicon of a unit to soil2O, fertilising knot
There is aggravation alkalization of soils or saliferous risk in fruit.
As can be seen that the prior art is being raw material using flyash, siliceous fertilizer and siliceous multiple is prepared using NaOH alkali soluble systems
During Hefei, existing technological deficiency is：(1) sodium element excessively introduces, i.e., in the case of the identical equivalent of offer effective silicon,
A large amount of Na elements are synchronized introducing, and the ratio between soluble sodium and effective silicon cross Na2O/SiO2It is excessively high；(2) it is related to sodium metasilicate to produce with solid phase
When object is separated by solid-liquid separation, easily cause the filter loss of Si, Na excessive, or cause the effective silicon of operating condition, energy consumption cost, product
The deterioration of the indexs such as content.
Invention content
The purpose of the invention is to overcome drawbacks described above, providing flyash acid system residue of aluminum-extracted, to prepare siliceous potassium compound
The method of fertilizer and the utilization method containing silicon potassium compound fertilizer and flyash.
It is found in the present inventor's research, when preparation also contains potassium containing silicon composite fertilizer, such as uses the prior art, still
Potassium silicate solution intermediary is so will produce, and the solution has same defect, i.e. solid product solid-liquid point with sodium silicate solution
From when, easily cause the filter loss of Si, and cause the evil of the indexs such as operating condition, energy consumption cost, product available silicon content
Change.Therefore propose that the present invention is improved.
In order to achieve the above-mentioned object of the invention, a kind of flyash acid system residue of aluminum-extracted of first aspect present invention offer is prepared siliceous
The method of K composite fertilizer, including：
(1) in the presence of KOH solution, flyash acid system residue of aluminum-extracted and the source of manure are mixed into slurries, and heat anti-
It answers, wherein the source of manure is calcium source and/or magnesium source；
(2) reaction product that step (1) obtains is separated by solid-liquid separation, gained filter cake obtains silico-calcium after being granulated, drying
K composite fertilizer, silicon magnesium K composite fertilizer or silico-calcium magnesium-potassium composite fertilizer.
Preferably, when the source of manure is calcium source, the flyash acid system residue of aluminum-extracted is with SiO2Meter, the KOH solution with
In terms of CaO, the weight ratio of flyash acid system residue of aluminum-extracted, KOH solution and calcium source is 1 for KOH meters, the calcium source：1.8-2.3：
0.6-0.8。
Preferably, when the source of manure is calcium source and magnesium source, the flyash acid system residue of aluminum-extracted is with SiO2Meter, the KOH
Solution in terms of KOH, the calcium source in terms of CaO, the magnesium source in terms of MgO, flyash acid system residue of aluminum-extracted, KOH solution, calcium source and
The weight ratio in magnesium source is 1：1.8-2.3：0.1-0.6：0.4-0.04.
Preferably, when the source of manure is magnesium source, the flyash acid system residue of aluminum-extracted is with SiO2Meter, the KOH solution with
In terms of MgO, flyash acid system residue of aluminum-extracted, KOH solution and the weight ratio in magnesium source are 1 for KOH meters, the magnesium source：1.8-2.3：
0.5-0.7。
Preferably, heating reaction temperature is 90-160 DEG C, and heating reaction pressure is normal pressure, and the heating reaction time is 1-5h.
Preferably, this method further includes washing the filter cake, then by obtained by the washing containing soda-wash water and
Filtrate obtained by the separation of solid and liquid merges together the concentrated rear KOH solution for returning to addition step (1) again.
Preferably, after the washing, after the washing, potassium oxide content in terms of butt is 3 weights in the filter cake
% or more is measured, the pH value of the filter cake is not more than 11.5.
Preferably, viscosity of the reaction product at 25 DEG C described in step (2) is 1-4mPas.
It is obtained containing silicon potassium compound fertilizer that second aspect of the present invention provides a kind of method of the present invention, wherein the siliceous potassium
Effective potassium content is 3 weight % or more in composite fertilizer, and the pH value containing silicon potassium compound fertilizer is not more than 11.5；It is described siliceous compound
Fertilizer is silico-calcium K composite fertilizer, silicon magnesium K composite fertilizer or silico-calcium magnesium-potassium composite fertilizer.
Third aspect present invention provides a kind of utilization method of flyash, including：Flyash progress acid system is carried aluminium to obtain
Silicon is prepared in the method for the flyash acid system residue of aluminum-extracted through the invention by aluminium oxide and flyash acid system residue of aluminum-extracted
Calcium K composite fertilizer, silicon magnesium K composite fertilizer or silico-calcium magnesium-potassium composite fertilizer.
Through the above technical solutions, method provided by the invention can significantly simplify technological process, and avoid potassium silicate
Separation of solid and liquid operation, reduce nutrient silicon, calcium, magnesium loss, element silicon filter loss rate be less than 1.0 weight %.It obtains
Composite fertilizer in available silicon content 9-38 weight %, effective content of magnesium 1-50 weight %, the active calcium ion content 1-40 weight %；Agricultural
Harmful solubility Al2O3Less than 8%, effective potassium content is not less than 3 weight %.
It is recycled containing alkali waste water in method provided by the invention, water consumption and the minimum of sewage discharge may be implemented
Change.Without secondary solid waste discharge in method provided by the invention.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the method flow diagram provided by the invention for preparing silico-calcium K composite fertilizer；
Fig. 2 is the method flow diagram provided by the invention for preparing silico-calcium magnesium-potassium composite fertilizer；
Fig. 3 is the method flow diagram provided by the invention for preparing silicon magnesium K composite fertilizer.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The first aspect of the present invention provides a kind of method of the flyash acid system residue of aluminum-extracted preparation containing silicon potassium compound fertilizer, packet
It includes：
(1) in the presence of KOH solution, flyash acid system residue of aluminum-extracted and the source of manure are mixed into slurries, and heat anti-
It answers, wherein the source of manure is calcium source and/or magnesium source；
(2) reaction product that step (1) obtains is separated by solid-liquid separation, gained filter cake obtains silico-calcium after being granulated, drying
K composite fertilizer, silicon magnesium K composite fertilizer or silico-calcium magnesium-potassium composite fertilizer.
In the present invention, flyash acid system residue of aluminum-extracted mainly contains：SiO2、Al2O3And TiO2。SiO2Content be about 70-
80 weight %, Al2O3Content be about 10-15 weight % and TiO2Content be about 3-8 weight %.Such as the Shenhua Inner Mongol is accurate
Ge Er flyash acid system residue of aluminum-extracted, wherein SiO2Content be about 78.7 weight %, Al2O3Content be about 13.4 weight %
And TiO2Content be about 5.2 weight %.Moreover, further show flyash acid system residue of aluminum-extracted progress XRD analysis,
Al2O3Substantially with mullite (3Al2O3·SiO2) form exist, TiO2Carrier is anatase and rutile；There are about 85% Si
Exist as an amorphous form, remaining Si preservations are in mullite and quartz.
According to the present invention, a kind of specific implementation mode, flow as shown in Figure 1.Wherein, it is described when the source of manure is calcium source
Flyash acid system residue of aluminum-extracted is with SiO2Meter, the KOH solution in terms of KOH, the calcium source in terms of CaO, flyash acid system carries aluminium
The weight ratio of residue, KOH solution and calcium source is 1：1.8-2.3：0.6-0.8.
According to the present invention, another specific implementation mode, flow as shown in Figure 2.Wherein, the source of manure is calcium source and magnesium source
When, the flyash acid system residue of aluminum-extracted is with SiO2Meter, the KOH solution in terms of KOH, the calcium source in terms of CaO, the magnesium source
In terms of MgO, flyash acid system residue of aluminum-extracted, KOH solution, calcium source and the weight ratio in magnesium source are 1：1.8-2.3：0.1-0.6：0.4-
0.04。
According to the present invention, another specific implementation mode, flow as shown in Figure 3.Wherein, when the source of manure is magnesium source, institute
Flyash acid system residue of aluminum-extracted is stated with SiO2Meter, the KOH solution in terms of KOH, the magnesium source in terms of MgO, flyash acid system carries
The weight ratio of residue of aluminum, KOH solution and magnesium source is 1：1.8-2.3：0.5-0.7.
By above-mentioned three kinds of specific implementation modes, method provided by the invention may be implemented flyash acid system residue of aluminum-extracted with
The source of manure directly in the presence of KOH it is heated reaction and produce silico-calcium K composite fertilizer, silicon magnesium K composite fertilizer or silico-calcium magnesium-potassium composite fertilizer.
This method can evade production potassium silicate solution intermediate product, and the potassium silicate solution for avoiding viscosity big is separated by filtration operation, drop
The difficulty that low technological process carries out.There is no production potassium silicates for this method, without being separated by filtration for potassium silicate, it is possible to reduce mistake
Filter loss.
In the present invention, the KOH concentration of the KOH solution can be 10-20 weight %.
According to the present invention, the heating reaction can be completed in potassium and the source of manure in flyash acid system residue of aluminum-extracted, KOH
Calcium or calcium, magnesium or magnesium are subjected to chemical change and are combined to obtain accordingly containing silicon potassium compound fertilizer.Preferably, heating reaction
Temperature is 90-160 DEG C, and preferably 90-150 DEG C, heating reaction pressure is normal pressure, and the heating reaction time is 1-5h, preferably 2-
5h.In the present invention, the heating reaction is carried out without pressurizeing, and normal pressure can be normal environment pressure when carrying out the heating reaction
Power under standard state, such as can be 0.1-0.2MPa.Normal pressure is gauge.
According to the present invention, step (1) carries out in the presence of KOH solution, and the reaction product of step (2) is free of potassium silicate, body
It is that viscosity is small, separation of solid and liquid can be completed by conventional filtration；It, can under the premise of the pH of the obtained filter cake meets the requirements
The separative efficiency for not pursuing KOH excessively allows part K element to retain in the product to obtain the comprehensive silicon fertilizer product containing potassium,
Remaining KOH solution can be conveniently separated recycling, recycle, to reduce the cost of KOH materials.Preferably, this method is also
Including washing the filter cake, then by being closed containing the filtrate obtained by soda-wash water and the separation of solid and liquid obtained by the washing
And it is concentrated again together after return to the KOH solution that step (1) is added.Material especially high value can be made full use of
KOH raw materials, and the discharge of lye is avoided to form secondary pollution.The KOH solution of recycling meets above-mentioned for the process of step (1)
Feed intake relationship.
According to the present invention it is possible to recycle the excessive K element in the filter cake by washing separation, siliceous potassium is on the one hand obtained
On the other hand composite fertilizer enables high-cost KOH recycle to reduce cost of material, while avoiding because product pH value is excessively high
And cause the alkalization of soils risk during use.Preferably, after the washing, potassium oxide is contained in terms of butt in the filter cake
Amount is 3 weight % or more, and the pH value of the filter cake is not more than 11.5.Butt refer to the filter cake at 100-120 DEG C air
Solids quality after dry 2-3h is calculating benchmark, and the content of potassium oxide can be measured by XRF methods in solids at this time.
According to the present invention, this method can be to avoid the generation of potassium silicate, and the separation of solid and liquid in step (2) is more simple.It can
With the difficulty or ease detached from the viscosity of reaction product described in step (2).Preferably, reaction product described in step (2) exists
Viscosity at 25 DEG C is 1-4mPas, preferably 1.2-3.8mPas.The viscosity that the reaction product has within this range,
It can be more easily separated by solid-liquid separation compared to potassium silicate solution.
It is obtained containing silicon potassium compound fertilizer that second aspect of the present invention provides a kind of method of the present invention, wherein the siliceous potassium
Effective potassium content is 3 weight % or more in composite fertilizer, and the pH value containing silicon potassium compound fertilizer is not more than 11.5；The siliceous potassium is multiple
Hefei is silico-calcium K composite fertilizer, silicon magnesium K composite fertilizer or silico-calcium magnesium-potassium composite fertilizer.Effective potassium content refers to dissolving in 0.5mol/L
The K of hydrochloric acid solution2O mass accounts for the percentage of sample gross mass, can be measured by ICP-AES methods.
In the present invention, through above-mentioned technical proposal, it is possible to reduce the solid-liquid point of sodium silicate solution must be carried out in the prior art
From and make the loss containing active principle in silicon composite fertilizer.Obtain available silicon content it is high contain silicon potassium compound fertilizer.By calculating, obtain
Containing available silicon content in silicon potassium compound fertilizer up to 40%, far surpass 20% national standard.
Third aspect present invention provides a kind of utilization method of flyash, including：Flyash progress acid system is carried aluminium to obtain
Silicon is prepared in the method for the flyash acid system residue of aluminum-extracted through the invention by aluminium oxide and flyash acid system residue of aluminum-extracted
Calcium K composite fertilizer, silicon magnesium K composite fertilizer or silico-calcium magnesium-potassium composite fertilizer.Flyash can be more effectively utilized, takes into account Commercial cultivation wherein
Bauxite resource.
Wherein, flyash can be the fine ash that catching is got off from the flue gas after the coal combustion that coal-burning power plant is discharged.It can be with
It is to mainly contain SiO2、Al2O3And TiO2。SiO2Content be about 20-40 weight %, Al2O3Content be about 45-60 weight %
And TiO2Content be about 1.5-4.5 weight %.Such as the flyash of power plant of China of Inner Mongol ancient country of Shenhua discharge, wherein SiO2Contain
Amount is about 32.43 weight %, Al2O3Content be about 50.42 weight % and TiO2Content be about 2.14 weight %.
Heretofore described acid system carries aluminium and method well known in the art may be used, and details are not described herein.
The present invention will be described in detail by way of examples below.
The viscosity of reaction product is measured by NDJ-8S type viscosimeters in embodiment and comparative example.Basic principle is rotor
Can be by the acting in opposition torque of liquid in rotary course in testing liquid, the more big then torque of liquid viscosity is bigger；Pass through survey
Determine torque size and obtains testing liquid viscosity number, unit mPas after conversion again.
The measurement of obtained effective silicon containing silicon composite fertilizer, effective calcium, effective magnesium, effective potassium content, soluble alumina
According to Ministry of Agriculture professional standard NY T2272-2012《The measurement of soil conditioner silicon magnesium calcium content》、NY T 3035-2016《Soil
The measurement of earth conditioner aluminium, nickel content》、NY T_2273-2012_《The measurement of soil conditioner _ phosphorus, potassium content》It executes.
Flyash comes from power plant of China of Inner Mongol ancient country of Shenhua, and concrete composition content is as shown in table 1.
Table 1
| Composition | Al2O3 | SiO2 | P2O5 | SO3 | K2O | CaO | TiO2 | Fe2O3 | MgO | Na2O |
| Content, weight % | 50.42 | 32.43 | 0.19 | 4.0 | 0.37 | 3.03 | 2.14 | 1.71 | 0.18 | 0.03 |
Flyash acid system residue of aluminum-extracted (white clay) carrys out autocollimatic Ge Er limited energies responsible company alumina producer, and preparation method can
With as follows：Flyash (power plant of China of Inner Mongol ancient country of Shenhua) 100g is taken, 12mol/L hydrochloric acid solutions are added, are stirred to react at 100 DEG C
30h, filtering obtain rich aluminum solutions and flyash acid system residue of aluminum-extracted after rinsing.Concrete composition content is as shown in table 2.
Table 2
Embodiment 1
Silico-calcium K composite fertilizer preparation is carried out according to flow shown in FIG. 1.
(1) it will take white clay 3g that CaO powder 1.8g is added, the KOH solution 15ml of 18.6 weight % concentration is added, stirring is equal
It is even, obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 100 DEG C of reactor in advance, heat preservation 3h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 3.2mPas.It filtrate and washes
Water amounts to 50ml, is concentrated by evaporation to 15ml, continues to employ to next batch and prepares reactant slurry；It is that silico-calcium potassium is multiple after filter cake drying
Hefei product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 0.3 weight %.
(4) gained silico-calcium K composite fertilizer product is tested through analysis, available silicon content 28.78%, the active calcium ion content
34.25%, effective potassium content 3.91%；Product pH value 11.08.
In preparation process KOH enter product part it is substantially all for soluble effective potassium, all recycling follows remainder
Ring uses, thus KOH overall utilization rates are close to 100%.
Embodiment 2
(1) it will take white clay 3g that CaO powder 1.8g is added, the KOH solution 30ml of 13.3 weight % concentration is added, stirring is equal
It is even, obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 120 DEG C of reactor in advance, heat preservation 5h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 2.5mPas.It filtrate and washes
Water amounts to 50ml, is concentrated by evaporation to 30ml, continues to employ to next batch and prepares reactant slurry；It is that silico-calcium potassium is multiple after filter cake drying
Hefei product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 0.5 weight %.
(4) gained silico-calcium K composite fertilizer product is tested through analysis, available silicon content 26.68%, the active calcium ion content
30.97%, effective potassium content 9.95%；Product pH value 11.3.
With embodiment 1, KOH overall utilization rates are close to 100%.
Embodiment 3
(1) it will take white clay 3g that CaO powder 1.8g is added, the KOH solution 60ml of 6.65 weight % concentration is added, stirring is equal
It is even, obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 140 DEG C of reactor in advance, heat preservation 2h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 1.6mPas.It filtrate and washes
Water amounts to 60ml, is concentrated by evaporation to 15ml, continues to employ to next batch and prepares reactant slurry；It is that silico-calcium potassium is multiple after filter cake drying
Hefei product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 0.5 weight %.
(4) gained silico-calcium K composite fertilizer product is tested through analysis, available silicon content 27.94%, the active calcium ion content
33.45%, effective potassium content 3.43%；Product pH value 11.0.
With embodiment 1, KOH overall utilization rates are close to 100%.
Embodiment 4
(1) it will take white clay 6g that CaO powder 3.2g is added, the KOH solution 30ml of 9.33 weight % concentration is added, stirring is equal
It is even, obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 100 DEG C of reactor in advance, heat preservation 2h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 3.0mPas.It filtrate and washes
Water amounts to 50ml, is concentrated by evaporation to 15ml, continues to employ to next batch and prepares reactant slurry；It is that silico-calcium potassium is multiple after filter cake drying
Hefei product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 0.5 weight %.
(4) gained silico-calcium K composite fertilizer product is tested through analysis, available silicon content 28.12%, the active calcium ion content
37.80%, effective potassium content 3.92%.Product pH value 11.1.
With embodiment 1, KOH overall utilization rates are close to 100%.
Embodiment 5
(1) it will take white clay 6g that CaO powder 2.0g is added, the KOH solution 10ml of 20 weight % concentration is added, stirs evenly,
Obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 100 DEG C of reactor in advance, heat preservation 3.0h is reacted, instead
It should be kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form dissipates to prevent moisture is too fast
It loses；Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 4.6mPas.It filtrate and washes
Water amounts to 50ml, is concentrated by evaporation to 10ml, continues to employ to next batch and prepares reactant slurry；It is that silico-calcium potassium is multiple after filter cake drying
Hefei product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 1.0 weight %.
(4) gained silico-calcium K composite fertilizer product is tested through analysis, available silicon content 13.92%, is less than 20% standard value；
The active calcium ion content 25.92%, effective potassium content 6.89%；Product pH value 11.2.
Embodiment 6
(1) it will take white clay 9g that CaO powder 5.8g is added, the KOH solution 60ml of 20 weight % concentration is added, stirs evenly,
Obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 100 DEG C of reactor in advance, heat preservation 15h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 3.5mPas.It filtrate and washes
Water amounts to 50ml, continues to employ to next batch and prepares reactant slurry；It is silico-calcium K composite fertilizer product after filter cake drying.Si elements
Filter loss (enter filtrate and wash water) rate be less than 1.0 weight %.
(4) gained silico-calcium K composite fertilizer product through analysis test, occur with rock-steady structure zeolite phase (it is not soluble in water or
Acid, aqueous slkali), available silicon content 16.2%, the active calcium ion content 28.9%, effective potassium content is 12.55%, product pH value
11.6。
Comparative example 1
With flour mill by flyash acid system residue of aluminum-extracted grinding to 200 mesh hereinafter, then dilute with a concentration of 20 weight %
Hydrochloric acid, according to 1：The solid-liquid ratio of 3 (g/ml) is fully reacted, and product is filtered to obtain siliceous filter residue, this siliceous filter residue is dried
It is dry spare.The filtrate obtained simultaneously is a small amount of aluminium chloride in 120 DEG C of evaporative crystallization products.By spare siliceous filter residue and concentration
For 25% sodium hydroxide solution, by 1:The ratio of 1.5 (g/ml), is reacted at 80 DEG C, obtains mixing containing sodium silicate liquid
Object.
Take weathered coal 50kg, urea 300kg, monoammonium phosphate 350kg, potassium chloride 250kg, bentonite 5kg, trace element fertilizer
Expect in the 10kg solid mixture 10kg of chlorination magnesium crystal (chloride containing calcium) input comminutors, 50kg is mixed containing sodium silicate liquid
Object is closed to be sprayed onto on above-mentioned bed of material by the fluid jetting head in comminutor, it is 4mm to be granulated to grain size, after drying, packaging
To silicon composite fertilizer.
It is tested through analysis, containing in silicon composite fertilizer, available silicon content is only 1.03 weight %, and the active calcium ion content is about 3 weights
Measure %, soluble Na2O content is 0.83 weight %.Product Na2O：SiO2Ratio=0.81.Effective potassium content 15.8%.
The effective silicon of the technique comes from sodium silicate liquid, and Na elements when providing the effective silicon of unit introduce ratio far above real
Apply example.
Comparative example 2
(1) it takes white clay 3g that the KOH solution 30mL of 20 weight % concentration is added, stirs evenly, obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 110 DEG C of reactor in advance, heat preservation 2.5h is reacted, instead
It should be kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form dissipates to prevent moisture is too fast
It loses；Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 17mPas.Filter cake contains inclined silicon
Sour potassium, it is sticky in paste, filtration difficulty, and be difficult to dry, filter loss (entering filter cake) rate of Si elements is all higher than 10 weights
Measure %.
(4) CaO powder of 1.8g is added in gained filtrate (main component potassium metasilicate), and advance heating is transferred to after stirring evenly
Into 90 DEG C of reactors, heat preservation 20min is reacted, and is kept stirring in reaction process, stir speed (S.S.) 80rpm；Reaction vessel
It is scattered and disappeared for the vessels not under pressure of silent form to prevent moisture is too fast；Reaction pressure is close to normal pressure.
(5) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 2.2mPas.It filtrate and washes
Water amounts to 50mL, is concentrated by evaporation to 20mL, continues to employ to next batch and prepares reactant slurry.
(6) filter cake dries to obtain silico-calcium K composite fertilizer, and analysis test available silicon content only 18.75% is less than 20% standard
Value；The active calcium ion content 39.18%, effective potassium content 5.2%.
A large amount of K, Si elements enter step filter cake described in (3) and lost in preparation process, and KOH recycles efficiency eta
Less than 85%.
Embodiment 7
Silicon magnesium K composite fertilizer is carried out according to flow shown in Fig. 3 to prepare.
(1) it will take white clay 3g that MgO powder 3.6g are added, the KOH solution 15ml of 18.67 weight % concentration is added, stirring is equal
It is even, obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 100 DEG C of reactor in advance, heat preservation 5h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 2.7mPas.It filtrate and washes
Water amounts to 100mL, is concentrated by evaporation to 15mL, continues to employ to next batch and prepares reactant slurry；It is silicon magnesium potassium after filter cake drying
Complex fertilizer product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 1.0 weight %.
(4) gained silicon magnesium K composite fertilizer product is tested through analysis, available silicon content 15.58%, effective content of magnesium
23.82%, effective potassium content 3.39%；Product pH value 11.0.
With embodiment 1, KOH overall utilization rates are close to 100%.
Embodiment 8
(1) it will take white clay 3g that MgO powder 3.6g are added, the KOH solution 15ml of 18.67 weight % concentration is added, stirring is equal
It is even, obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 120 DEG C of reactor in advance, heat preservation 2h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 2.8mPas.It filtrate and washes
Water amounts to 100mL, is concentrated by evaporation to 15mL, continues to employ to next batch and prepares reactant slurry；It is silicon magnesium potassium after filter cake drying
Complex fertilizer product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 1.0 weight %.
(4) gained silicon magnesium K composite fertilizer product is tested through analysis, available silicon content 17.02%, effective content of magnesium
23.51%, effective potassium content 3.43%；Product pH value 10.9.
With embodiment 1, KOH overall utilization rates are close to 100%.
Embodiment 9
(1) it will take white clay 3g that MgO powder 3.6g are added, the KOH solution 30mL of 18.67 weight % concentration is added, stirring is equal
It is even, obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 140 DEG C of reactor in advance, heat preservation 3h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 2.4mPas.It filtrate and washes
Water amounts to 100mL, is concentrated by evaporation to 30mL, continues to employ to next batch and prepares reactant slurry；It is silicon magnesium potassium after filter cake drying
Complex fertilizer product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 1.0 weight %.
(4) gained silicon magnesium K composite fertilizer is tested through analysis, and available silicon content 24.85%, effective content of magnesium 28.42% has
Imitate potassium content 5.37%；Product pH value 11.2.
With embodiment 1, KOH overall utilization rates are close to 100%.
Embodiment 10
(1) it will take white clay 3g that MgO powder 3.6g are added, the KOH solution 30mL of 9.33 weight % concentration is added, stirring is equal
It is even, obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 100 DEG C of reactor in advance, heat preservation 2h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 3.8mPas.It filtrate and washes
Water amounts to 100mL, is concentrated by evaporation to 30mL, continues to employ to next batch and prepares reactant slurry；It is silicon magnesium potassium after filter cake drying
Complex fertilizer product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 1.0 weight %.
(4) gained silicon magnesium K composite fertilizer is tested through analysis, and available silicon content 16.62%, effective content of magnesium 23.17% has
Imitate potassium content 2.44%；Product pH value 10.7.
With embodiment 1, KOH overall utilization rates are close to 100%.
Comparative example 3
(1) it takes white clay 3g that the KOH solution 30mL of 20 weight % concentration is added, stirs evenly, obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 140 DEG C of reactor in advance, heat preservation 1.5h is reacted, instead
It should be kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form dissipates to prevent moisture is too fast
It loses；Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 18mPas.Filter cake contains inclined silicon
Sour potassium, it is sticky in paste, filtration difficulty, and be difficult to dry, filter loss (entering filter cake) rate of Si elements is all higher than 10 weights
Measure %.
(4) CaO powder 0.9g and MgO powder 0.64g is added in gained filtrate (main component potassium metasilicate), after stirring evenly
It is transferred to and is warming up in 60 DEG C of reactor in advance, heat preservation 1h is reacted, and is kept stirring in reaction process, stir speed (S.S.) 80rpm；
Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；Reaction pressure is close to normal pressure.
(5) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 2.3mPas.It filtrate and washes
Water amounts to 50mL, is concentrated by evaporation to 20mL, continues to employ to next batch and prepares reactant slurry.
(6) filter cake dries to obtain silico-calcium magnesium-potassium composite fertilizer, and analysis test available silicon content is 16.30%, is less than 20% mark
Quasi- value；The active calcium ion content 22.50%, effective content of magnesium 17.30%, effective potassium content 4.08%；Product pH value 11.0.
Preparation process energy consumption is that middle KOH recycles efficiency eta less than 85%.
Embodiment 11
The preparation of silico-calcium magnesium-potassium composite fertilizer is carried out according to flow shown in Fig. 2.
(1) it will take white clay 3g that CaO powder 0.9g and MgO powder 0.64g is added, the KOH that 18.67 weight % concentration are added is molten
Liquid 30mL, stirs evenly, and obtains reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 100 DEG C of reactor in advance, heat preservation 2h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 2.6mPas.It filtrate and washes
Water amounts to 30mL, continues to employ to next batch and prepares reactant slurry；It is silico-calcium magnesium-potassium complex fertilizer product after filter cake drying.Si members
Filter loss (entering filtrate and wash water) rate of element is less than 1.0 weight %.
(4) gained silico-calcium magnesium-potassium complex fertilizer product is tested through analysis, available silicon content 22.26%, the active calcium ion content
18.88%, effective content of magnesium 15.84%, effective potassium content 4.64%；Product pH value 11.2.
With embodiment 1, KOH overall utilization rates are close to 100%.
Embodiment 12
(1) it will take white clay 3g that CaO powder 0.9g and MgO powder 0.64g is added, the KOH that 18.67 weight % concentration are added is molten
Liquid 15mL, stirs evenly, and obtains reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 120 DEG C of reactor in advance, heat preservation 3h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 3.8mPas.It filtrate and washes
Water amounts to 60mL, is concentrated by evaporation to 30mL, continues to employ to next batch and prepares reactant slurry；It is silico-calcium magnesium-potassium after filter cake drying
Complex fertilizer product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 1.0 weight %.
(4) gained silico-calcium magnesium-potassium complex fertilizer product is tested through analysis, available silicon content 18.97%, the active calcium ion content
18.99%, effective content of magnesium 13.52%, effective potassium content 2.78%；Product pH value 10.8.
With embodiment 1, KOH overall utilization rates are close to 100%.
Embodiment 13
(1) it will take white clay 3g that CaO powder 0.9g and MgO powder 0.64g is added, the KOH that 18.67 weight % concentration are added is molten
Liquid 15mL, stirs evenly, and obtains reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 140 DEG C of reactor in advance, heat preservation 5h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 3.1mPas.It filtrate and washes
Water amounts to 60mL, is concentrated by evaporation to 15mL, continues to employ to next batch and prepares reactant slurry；It is silico-calcium magnesium-potassium after filter cake drying
Complex fertilizer product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 1.0 weight %.
(4) gained silico-calcium magnesium-potassium complex fertilizer product is tested through analysis, available silicon content 30.47%, the active calcium ion content
18.17%, effective content of magnesium 13.08%, effective potassium content 6.15%；Product pH value 11.1.
With embodiment 1, KOH overall utilization rates are close to 100%.
Embodiment 14
(1) it will take white clay 3g that CaO powder 0.9g and MgO powder 0.64g is added, the KOH that 9.33 weight % concentration are added is molten
Liquid 60mL, stirs evenly, and obtains reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 100 DEG C of reactor in advance, heat preservation 2h is reacted, and is reacted
It is kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form scatters and disappears to prevent moisture is too fast；
Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 3.0mPas.It filtrate and washes
Water amounts to 100mL, is concentrated by evaporation to 60mL, continues to employ to next batch and prepares reactant slurry；It is silicon-calcium-magnesium after filter cake drying
K composite fertilizer product.Filter loss (entering filtrate and wash water) rate of Si elements is less than 1.0 weight %.
(4) gained silico-calcium magnesium-potassium complex fertilizer product is tested through analysis, available silicon content 24.81%, the active calcium ion content
24.46%, effective content of magnesium 17.83%, effective potassium content 1.89%；Product pH value 10.1.
With embodiment 1, KOH overall utilization rates are close to 100%.
Comparative example 4
(1) it takes white clay 3g that the KOH solution 30mL of 13.3 weight % concentration is added, stirs evenly, obtain reactant slurry.
(2) gained reactant slurry is transferred to and is warming up in 140 DEG C of reactor in advance, heat preservation 1.5h is reacted, instead
It should be kept stirring in the process, stir speed (S.S.) 80rpm；Reaction vessel is that the vessels not under pressure of silent form dissipates to prevent moisture is too fast
It loses；Reaction pressure is close to normal pressure.
(3) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 17mPas.Filter cake contains inclined silicon
Sour potassium, it is sticky in paste, filtration difficulty, and be difficult to dry, filter loss (entering filter cake) rate of Si elements is all higher than 10 weights
Measure %.
(4) MgO powder 1.29g are added in gained filtrate (main component potassium metasilicate), and advance heating is transferred to after stirring evenly
Into 60 DEG C of reactors, heat preservation 1h is reacted, and is kept stirring in reaction process, stir speed (S.S.) 80rpm；Reaction vessel is to close
The vessels not under pressure of degree of lip-rounding formula scatters and disappears to prevent moisture is too fast；Reaction pressure is close to normal pressure.
(5) it carries out being separated by solid-liquid separation after reaction and Washing of Filter Cake, reaction product viscosity is 2.1mPas.It filtrate and washes
Water amounts to 100mL, is concentrated by evaporation to 30mL, continues to employ to next batch and prepares reactant slurry.
(6) filter cake dries to obtain silicon magnesium compound fertilizer, and analysis test available silicon content is 11.94%, is less than 20% standard value；
Effective content of magnesium 49.34%, effective potassium content 5.25%；Product pH value 11.0.
Preparation process energy consumption is that middle KOH utilization ratios η is less than 85%.
From the result of above-described embodiment and comparative example can be seen that method provided by the invention can effectively improve it is obtained
The amount retained containing soil nutrient elements in silicon potassium compound fertilizer, available silicon content can be 21-38 weight % in composite fertilizer, effectively
Content of magnesium can be 5-40 weight %, and the active calcium ion content can be 5-40 weight %, and effective potassium content is 1.5-10 weight %；Production
Product pH value is not more than 11.5；Meanwhile the harmful solubility Al of agricultural2O3Content is less than 8%.The composite fertilizer applies to soil alkali-free
Change or salinization risk.
Implement method provided by the invention, the low reaction product of viscosity can be obtained, avoids generating more difficult separation of solid and liquid
Potassium silicate solution.And involved in this method step the heating reaction can lower reaction temperature (90-160 DEG C),
Implement under shorter reaction time (2-5h) and normal pressure.The utilization ratio of white clay is 100%, the KOH solution unreacted portion used
Dividing can recycle, and loss is low and can reduce the discharge containing alkali waste water.
CaO additions are insufficient in embodiment 5, SiO in white clay2Only partial reaction generates hydration CaSiO3Precipitation, also portion
Divide SiO2It is reacted with KOH and generates sticky K2SiO3It causes filtration difficulty and then causes Si element loss (entering alkaline filtrate)；It is surplus
Remaining part divides SiO2Activation is not completed, causes available silicon content low.
In embodiment 6 reaction time it is long to cause zeolite phase (Si-Al-K-O) to generate excessive, Si elements reenter structure
It in stable zeolite crystal, loses activity, is converted into invalid silicon, be the main original for causing available silicon content to be less than embodiment
Cause.K element also largely enter it is zeolite structured in, cause product K too high levels, and it is only 83.7% that KOH, which recycles efficiency, it is former
Expect that cost increases.
Comparative example 1 is the method for the prior art, using sodium silicate liquid mixture, available silicon content in obtained composite fertilizer
It is low, and sodium content is big.Potassium silicate is generated in comparative example 2-4 preparation process, reaction product viscosity is big, silicon, potassium member in filter process
The loss of element is big, and white clay utilization ratio is low, and secondary high alkalinity solid waste discharge amount is big.
In addition, method and process provided by the invention is extremely simple, equipment investment is small, and application range of products is wide, and the market space is big, competing
It is small to strive pressure, good environment and economic benefit can be generated.
Claims (10)
1. a kind of flyash acid system residue of aluminum-extracted prepares the method containing silicon potassium compound fertilizer, including：
(1) in the presence of KOH solution, flyash acid system residue of aluminum-extracted and the source of manure are mixed into slurries, and carry out heating reaction,
Described in the source of manure be calcium source and/or magnesium source；
(2) reaction product that step (1) obtains is separated by solid-liquid separation, it is multiple that gained filter cake obtains silico-calcium potassium after being granulated, drying
Hefei, silicon magnesium K composite fertilizer or silico-calcium magnesium-potassium composite fertilizer.
2. according to the method described in claim 1, wherein, when the source of manure is calcium source, the flyash acid system residue of aluminum-extracted with
SiO2Meter, the KOH solution in terms of KOH, the calcium source in terms of CaO, flyash acid system residue of aluminum-extracted, KOH solution and calcium source
Weight ratio is 1：1.8-2.3：0.6-0.8.
3. according to the method described in claim 1, wherein, when the source of manure is calcium source and magnesium source, the flyash acid system carries aluminium
Residue is with SiO2Meter, the KOH solution in terms of KOH, the calcium source in terms of CaO, in terms of MgO, flyash acid system carries in the magnesium source
Residue of aluminum, KOH solution, calcium source and the weight ratio in magnesium source are 1：1.8-2.3：0.1-0.6：0.4-0.04.
4. according to the method described in claim 1, wherein, when the source of manure is magnesium source, the flyash acid system residue of aluminum-extracted with
SiO2Meter, the KOH solution in terms of KOH, the magnesium source in terms of MgO, flyash acid system residue of aluminum-extracted, KOH solution and magnesium source
Weight ratio is 1：1.8-2.3：0.5-0.7.
5. according to the method described in any one of claim 1-4, wherein heating reaction temperature is 90-160 DEG C, and heating is anti-
It is normal pressure to answer pressure, and the heating reaction time is 1-5h.
6. according to the method described in any one of claim 1-5, wherein this method further includes that the filter cake is carried out water
It washes, then will merge together concentrated rear return again containing the filtrate obtained by soda-wash water and the separation of solid and liquid obtained by the washing
The KOH solution of step (1) is added.
7. according to the method described in claim 6, wherein, after the washing, potassium oxide content in terms of butt in the filter cake
PH value for 3 weight % or more, the filter cake is not more than 11.5.
8. according to the method described in claim 1, wherein, viscosity of the reaction product at 25 DEG C described in step (2) is 1-
4mPa·s。
9. the method described in a kind of any one of claim 1-8 is obtained containing silicon potassium compound fertilizer, wherein the siliceous potassium is multiple
Effective potassium content is 3 weight % or more in Hefei, and the pH value containing silicon potassium compound fertilizer is not more than 11.5；The siliceous potassium is compound
Fertilizer is silico-calcium K composite fertilizer, silicon magnesium K composite fertilizer or silico-calcium magnesium-potassium composite fertilizer.
10. a kind of utilization method of flyash, including：Flyash progress acid system is carried that aluminium obtains aluminium oxide and flyash acid system carries
Silicon is prepared by the method described in any one of claim 1-8 in the flyash acid system residue of aluminum-extracted by residue of aluminum
Calcium K composite fertilizer, silicon magnesium K composite fertilizer or silico-calcium magnesium-potassium composite fertilizer.
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| CN109369286B (en) * | 2018-09-18 | 2021-09-21 | 华南理工大学 | Method for producing medium trace element acid soil conditioner by using fly ash and product |
| CN112430158A (en) * | 2020-12-16 | 2021-03-02 | 锡林郭勒职业学院 | Preparation and application method of compound fertilizer matrix |
| CN115124379A (en) * | 2021-03-24 | 2022-09-30 | 国家能源投资集团有限责任公司 | Granular citrate soluble silicon fertilizer and its preparation method |
| WO2022227182A1 (en) * | 2021-04-28 | 2022-11-03 | 东北大学 | Method for preparing silicon-potassium compound fertilizer by using fly ash |
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