CN109019528A - A kind of technique preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium - Google Patents

A kind of technique preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium Download PDF

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CN109019528A
CN109019528A CN201810714269.4A CN201810714269A CN109019528A CN 109019528 A CN109019528 A CN 109019528A CN 201810714269 A CN201810714269 A CN 201810714269A CN 109019528 A CN109019528 A CN 109019528A
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apple
aluminium
lime fertilizer
potassium
preparing
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李敬
曾羽
路坊海
罗勋
周登凤
陈肖虎
高贵龙
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Blessing Of Guizhou Ecological Fertilizer Co Ltd
Guizhou Institute of Technology
Guizhou Kexin Chemical and Metallurgical Co Ltd
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Blessing Of Guizhou Ecological Fertilizer Co Ltd
Guizhou Institute of Technology
Guizhou Kexin Chemical and Metallurgical Co Ltd
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Publication of CN109019528A publication Critical patent/CN109019528A/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/74—Preparation
    • C01B17/76—Preparation by contact processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/08—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals with sodium carbonate, e.g. sinter processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
    • C01F7/141—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent
    • C01F7/142—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent with carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/20—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts
    • C01F7/26—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts with sulfuric acids or sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
    • C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination
    • 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
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/80—Soil conditioners
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Soil Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Fertilizers (AREA)

Abstract

The invention discloses a kind of techniques for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, include the following steps: that 1) ardealite, potassium-bearing shale, additive and modifying agent are mixed and ground raw material are made；Raw material are sent into kiln and are roasted, clinker is made；2) it dissolves out, and is separated by solid-liquid separation after grinding clinker；3) CO is added into isolated liquid2, white precipitate is then filtered out into rear cleaning, drying and is roasted, aluminium oxide is obtained；4) by isolated filter residue flotation, sulfide is floatingly selected, sulfide is roasted, the flue gas of generation, which is sent into sulfuric acid preparation system, prepares sulfuric acid；5) the remaining residue of flotation is dried and is crushed, up to the dedicated potash-lime fertilizer of apple after addition humic acid, plant ash soil, EDTA chelated magnesium, EDTA chelated zinc and bentonite.The present invention can greatly improve the added value of ardealite and potassium-bearing shale, and the destruction of the dedicated potash-lime fertilizer of apple prepared to apple cultivation soil ph is small, in addition, aluminium recovery and purity is high.

Description

A kind of technique preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium
Technical field
The present invention relates to a kind of techniques for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, belong to field of metallurgy and chemical engineering.
Background technique
Potassium-bearing shale is a kind of silicate ore containing potassium element, also known as sandstone, molecular formula K4Al9[Si15O40] (OH)11, main mineral constituent are as follows: K2O、Fe2O3、Al2O3And SiO2, meanwhile, also contain a small amount of Ca2O, MgO and Na2O.Contain Potassium shale is not soluble in water under normal potassium-bearing shale temperature, is also insoluble in acetic acid, nitric acid, sulfuric acid, alkali and inorganic salts.
The solid slag that ardealite generates when referring in phosphoric acid production with sulfuric acid treating phosphorite, main component are sulfuric acid Calcium (CaSO4), content generally can reach 70~90% or so.In addition, ardealite also contains plurality of impurities: undecomposed phosphorus Mine, phosphoric acid, calcirm-fluoride, iron, aluminium compound, acid non-soluble substance, organic matter of non-washes clean etc..
Apple (scientific name: Maluspumila) is one kind of fruit, is rosaceae Maloideae Malus, and tree is Deciduous tree.The fruit of apple is rich in minerals and vitamins, is one of fruit that people often eat.Apple is a kind of low-heat Food is measured, every 100 grams only generate 60 kilocalories of heats.Nutritional ingredient is soluble big in apple, is easily absorbed by the body, therefore has " running water " Title.It is conducive to dissolve element sulphur, keeps skin lubrication tender." it is said that a daily apple, doctor is far from me ".According to the United Nations Food and agricultural organization's statistics, global apple production in 2013 is 80,820,000 tons, more than 77,180,000 tons of grape, arranges second place of the world (first is banana: 1.067 hundred million tons).Unquestionably, apple is the king of temperate zone fruit.
Now currently, potash-lime fertilizer is one of main fertilizer, mainly with potash fertilizer and calcareous fertilisers in the fertilizer that apple cultivation uses For main base manure, it is prepared after mixing the ingredients such as humic acid, plant ash soil, EDTA chelated magnesium, EDTA chelated zinc and bentonite, and Conventional potash fertilizer and calcareous fertilisers is pure potassium fertilizer and calcium fertilizer, such as potassium chloride, potassium sulfate, potassium dihydrogen phosphate and calcium nitrate, sulphur The potassium calcium base manure preparation cost of sour calcium and calcium dihydrogen phosphate etc., this kind of pure element is higher, for this purpose, due to ardealite and page containing potassium Contain a large amount of calcium constituent and potassium element in rock respectively, meanwhile, waste residue when ardealite is prepared as phosphoric acid has made environment At serious destruction, and potassium-bearing shale, as a kind of main sylvite ore, content in nature is larger, so that phosphorus stone Cream and potassium-bearing shale become the new selection for preparing potash-lime fertilizer.
It is directly by phosphorus stone but now at present in the technique that ardealite and potassium-bearing shale prepare the dedicated potash-lime fertilizer of apple Cream and potassium-bearing shale are prepared after mixing after crushing with other compositions, due to containing a large amount of element sulphur in ardealite, and are contained Contain a large amount of aluminium ion in potassium shale, aluminium hydroxide easy to form after aluminium ion enters in soil makes to release hydrogen in soil Ion destroys the acid-base property of soil, influences the growth of apple, meanwhile, aluminium element and element sulphur are not recycled further It utilizes, greatly reduces the added value of ardealite and potassium-bearing shale.
For this purpose, this researcher is analyzed by component content to potassium-bearing shale and ardealite and chemical characteristic, grind The comprehensive processing technique for having studied carefully a kind of residue phosphogypsum and potassium-bearing shale can greatly improve the additional of ardealite and potassium-bearing shale Value, makes its valuable constituent be fully used, and by being recycled after this process to aluminium ion, drop significantly The destruction of low potash-lime fertilizer to apple cultivation soil ph, provides the processing of residue phosphogypsum and potassium-bearing shale A kind of new approaches.
Goal of the invention
The object of the present invention is to provide a kind of techniques for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium.The present invention The added value of ardealite and potassium-bearing shale can be greatly improved, and to apple cultivation soil is sour for the dedicated potash-lime fertilizer of apple prepared The destruction of alkalinity is small, in addition, aluminium recovery and purity is high.
Technical solution of the present invention
A kind of technique preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, is that potassium-bearing shale is crushed to 150-200 mesh Raw material are mixed and made into ardealite, additive and modifying agent afterwards, controlling the weight ratio of ardealite and potassium-bearing shale in raw material is 1: 0.5-1.5, additive adding proportion is by contained Na in raw material2O and A12O3+Fe2O3The molecular proportion of summation is 1:1 addition, modifying agent Mixed proportion be raw material total weight 10-25%；Raw material are sent into kiln and are roasted, clinker is made；Clinker obtained is ground After dissolve out, and be separated by solid-liquid separation；CO is added into the liquid that separation of solid and liquid obtains2It no longer generates to white precipitate, then will White precipitate filters out rear cleaning, drying, obtains aluminium hydroxide, by resulting Aluminium hydroxide roasting, obtains aluminium oxide；It will be separated by solid-liquid separation The filter residue flotation arrived, floatingly selects sulfide, sulfide is roasted, and the flue gas of generation, which is sent into sulfuric acid preparation system, prepares sulfuric acid； The remaining residue of flotation is dried and crushed, potassium calcium base manure is obtained, humic acid, plant ash soil, EDTA chelating are added into potassium calcium base manure Up to the dedicated potash-lime fertilizer of apple after magnesium, EDTA chelated zinc and bentonite.
The technique above-mentioned for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, in step 1), in the potassium-bearing shale It by mass percentage, include K2O 6-10%, Al2O317-20%, Fe2O35-7%, SiO240-55%.
The technique above-mentioned for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, in step 1), the additive is carbon Sour sodium, sodium sulphate or caustic soda.
The technique above-mentioned for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, in step 1), the modifying agent is nothing Bituminous coal, carbon or gangue.
The technique above-mentioned for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, in step 1), the kiln is that industry is returned Rotary kiln, Industry Tunnel Kiln or industrial shaft kiln.
The technique above-mentioned for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, in step 1), the raw material are in temperature Calcining time 1-3 hours at 1000-1200 DEG C of degree.
The technique above-mentioned for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, it is described to be ground to water mill in step 2), it is molten When out with it is water-soluble go out；It is 3-6:1 that liquid when the dissolution, which consolidates volume ratio,.
The technique above-mentioned for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, in step 3), the roasting is in temperature Calcining time 1-3 hours at 800-1000 DEG C.
The technique above-mentioned for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, is the vulcanization that will be floatingly selected in step 4) Object is placed under the oxygen-enriched environment of 35-50%, is roasted 1-3 hours at 800-1000 DEG C, roasts the flue gas of generation through five oxidations two It is absorbed after vanadium catalysis reaction with the concentrated sulfuric acid and sulfuric acid is made.
The technique above-mentioned for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, in step 5), the filter residue drying is crushed Fineness afterwards is 90-100 mesh, and screen over-size is less than 6%.
The technique above-mentioned for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, in step 5), the dedicated potassium calcium of apple Fertilizer includes 50-80 parts of potassium calcium base manure, 20-50 parts of humic acid, 30-60 parts of plant ash soil, EDTA chelated magnesium 3-8 by weight Part, 3-8 parts of EDTA chelated zinc and 5-15 parts of bentonite.
The technique above-mentioned for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, in step 5), the plant ash soil it is aqueous Amount is 1-6%.
In the present invention, ardealite and potassium-bearing shale react, shown in the principle following reaction formula of recombination: CaSO4(ardealite)+ K2O·SiO2·Al2O3(potassium-bearing shale)+additive+modifying agent → Na2O·Al2O3+CaO·SiO2↓+【S】
From the reaction equation it is found that with the SiO in the CaO and potassium-bearing shale in ardealite2Generate calcium orthosilicate (2CaO SiO2↓) after, obtain soluble fabulous sodium aluminate (Na2O·Al2O3), [S] therein be sulfide, predominantly iron sulfide and Potassium sulfide etc..
Beneficial effect
1, the present invention by being subject to additive and modifying agent by being roasted using ardealite and potassium-bearing shale as primary raw material Grinding dissolution afterwards, can be obtained solution mainly containing sodium aluminate, for recycling aluminium；Meanwhile in raw material roasting process, pass through addition Additive and modifying agent, phosphate radical reaction generates S in ardealite2-, S2-Sulfide is formed with metal ion, is passing through traditional sulphur Roasting can produce sulfur dioxide flue gas and prepare sulfuric acid for recycling after compound floatation process flotates；And flotation is remaining heavy Contain a large amount of calcium and potassium in the residue of shallow lake, apple can be prepared after adding after crushed conducive to the fertilizer component of apple development Dedicated potash-lime fertilizer.Since this technique has not only carried out effective recycling to the aluminium in potassium-bearing shale, is also recycling acid and be prepared for The dedicated potash-lime fertilizer of apple, substantially increases the added value of ardealite and potassium-bearing shale, opens ardealite and potassium-bearing shale is comprehensive The new direction utilized.
2, potassium-bearing shale of the invention and ardealite be during being fabricated to fertilizer, by having carried out time aluminium therein It receives, avoids the destruction of metallic aluminium ion pair soil, improve the fertilizer efficiency of the dedicated potash-lime fertilizer of apple；In addition, potassium calcium of the invention Fertilizer only needs potassium-bearing shale and baking mixed rear be separated by solid-liquid separation of ardealite and additive and modifying agent recycling aluminium, then by residue Flotation roasts recovery acid, and fertilizer component needed for apple is added after residual residue drying, preparation process is simple, substantially reduces The production cost of the dedicated potash-lime fertilizer of apple.
3, reaction principle, roasting recombinate substance, form main silicate, metal sulfide and aluminic acid through the invention Sodium ingredient, and sodium aluminate can be directly dissolved in water, other compositions are in solid residue, it is easily separated because ingredient is clearly demarcated, significantly The rate of recovery of aluminium is improved, simultaneously as ingredient soluble easily in water is mainly sodium aluminate, other compositions are seldom, almost without greatly The purity of the aluminium of recycling is improved greatly.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated, but is not intended as the foundation limited the present invention.
The embodiment of the present invention
In potassium-bearing shale in the following example, by mass percentage, main component be include K2O 6-10%, Al2O317-20%, Fe2O35-7%, SiO240-55%.
Embodiment 1:
A kind of technique preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, steps are as follows:
1) potassium-bearing shale, which is crushed to after 150-200 mesh to mix and grind with ardealite, sodium carbonate and anthracite, is made raw material, Controlling the weight ratio of ardealite and potassium-bearing shale in raw material is 1:0.5, and sodium carbonate adding proportion is by contained Na in raw material2O and A12O3+Fe2O3The molecular proportion of summation is 1:1 addition, and anthracitic mixed proportion is the 10% of raw material total weight；Raw material are sent into In industrial rotary kiln calcining time 3 hours at 1000 DEG C of temperature, clinker is made；
2) by water mill after the grinding of clinker made from step 1), then with it is water-soluble go out and be separated by solid-liquid separation, liquid when dissolution Gu volume ratio is 3:1；
3) CO is added in the liquid isolated into step 2)2It is no longer generated to white precipitate, then by white precipitate Rear cleaning, drying is filtered out, aluminium hydroxide is obtained, by resulting aluminium hydroxide calcining time 3 hours at 800 DEG C of temperature, must be aoxidized Aluminium；
4) by filter residue flotation isolated in step 2), sulfide is floatingly selected, the sulfide floatingly selected is placed in 35% Oxygen-enriched environment under, roasted 3 hours at 800 DEG C, roast the flue gas of generation and use the concentrated sulfuric acid after vanadic anhydride catalysis reaction It absorbs and sulfuric acid is made.
5) drying the remaining residue of flotation in step 4) and being crushed to fineness is 90 mesh, and screen over-size obtains potassium calcium less than 6% Base manure chelates 50 parts of potassium calcium base manure, 20 parts of humic acid, 30 parts of the plant ash soil that water content is 1%, 3 parts of EDTA chelated magnesium, EDTA 5 parts of 3 parts of zinc and bentonite obtain the dedicated potash-lime fertilizer of apple after mixing.
Embodiment 2:
A kind of technique preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, steps are as follows:
1) it mixes and grinds with ardealite, sodium sulphate and carbon after potassium-bearing shale being crushed to 175 mesh and raw material are made, control life The weight ratio of ardealite and potassium-bearing shale is 1:1 in material, and sodium sulphate adding proportion is by contained Na in raw material2O and A12O3+Fe2O3Always The molecular proportion of sum is 1:1 addition, and the mixed proportion of carbon is the 18% of raw material total weight；Raw material are sent into Industry Tunnel Kiln in temperature Calcining time 2 hours at 1100 DEG C of degree, clinker is made；
2) by water mill after the grinding of clinker made from step 1), then with it is water-soluble go out and be separated by solid-liquid separation, liquid when dissolution Gu volume ratio is 5:1；
3) CO is added in the liquid isolated into step 2)2It is no longer generated to white precipitate, then by white precipitate Rear cleaning, drying is filtered out, aluminium hydroxide is obtained, by resulting aluminium hydroxide calcining time 2 hours at 900 DEG C of temperature, must be aoxidized Aluminium；
4) by filter residue flotation isolated in step 2), sulfide is floatingly selected, the sulfide floatingly selected is placed in 42% Oxygen-enriched environment under, roasted 2 hours at 900 DEG C, roast the flue gas of generation and use the concentrated sulfuric acid after vanadic anhydride catalysis reaction It absorbs and sulfuric acid is made.
5) drying the remaining residue of flotation in step 4) and being crushed to fineness is 95 mesh, and screen over-size obtains potassium calcium less than 6% Base manure chelates 60 parts of potassium calcium base manure, 30 parts of humic acid, 40 parts of the plant ash soil that water content is 2%, 4 parts of EDTA chelated magnesium, EDTA 7 parts of 4 parts of zinc and bentonite obtain the dedicated potash-lime fertilizer of apple after mixing.
Embodiment 3:
A kind of technique preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, steps are as follows:
1) it mixes and grinds with ardealite, caustic soda and gangue after potassium-bearing shale being crushed to 200 mesh and raw material are made, control The weight ratio of ardealite and potassium-bearing shale is 1:1.5 in raw material, and caustic soda adding proportion is by contained Na in raw material2O and A12O3+Fe2O3 The molecular proportion of summation is 1:1 addition, and the mixed proportion of gangue is the 25% of raw material total weight；Raw material are sent into industrial shaft kiln Clinker is made in the calcining time 1 hour at 1200 DEG C of temperature；
2) by water mill after the grinding of clinker made from step 1), then with it is water-soluble go out and be separated by solid-liquid separation, liquid when dissolution Gu volume ratio is 6:1；
3) CO is added in the liquid isolated into step 2)2It is no longer generated to white precipitate, then by white precipitate Rear cleaning, drying is filtered out, aluminium hydroxide is obtained, by resulting aluminium hydroxide calcining time 1 hour at 1000 DEG C of temperature, must be aoxidized Aluminium；
4) by filter residue flotation isolated in step 2), sulfide is floatingly selected, the sulfide floatingly selected is placed in 50% Oxygen-enriched environment under, roasted 1 hour at 1000 DEG C, roast the flue gas of generation and use the concentrated sulfuric acid after vanadic anhydride catalysis reaction It absorbs and sulfuric acid is made.
5) drying the remaining residue of flotation in step 4) and being crushed to fineness is 100 mesh, and screen over-size obtains potassium less than 6% Calcium base manure, by 65 parts of potassium calcium base manure, 35 parts of humic acid, plant ash native 45 parts, 5 parts of the EDTA chelated magnesium, EDTA chela that water content is 4% It closes 10 parts of 5 parts of zinc and bentonite and obtains the dedicated potash-lime fertilizer of apple after mixing.
Embodiment 4:
A kind of technique preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, steps are as follows:
1) it mixes and grinds with ardealite, sodium carbonate and carbon after potassium-bearing shale being crushed to 160 mesh and raw material are made, control life The weight ratio of ardealite and potassium-bearing shale is 1:0.7 in material, and sodium carbonate adding proportion is by contained Na in raw material2O and A12O3+Fe2O3 The molecular proportion of summation is 1:1 addition, and the mixed proportion of carbon is the 15% of raw material total weight；Raw material are sent into industrial rotary kiln Clinker is made in calcining time 2.5 hours at 1050 DEG C of temperature；
2) by water mill after the grinding of clinker made from step 1), then with it is water-soluble go out and be separated by solid-liquid separation, liquid when dissolution Gu volume ratio is 4:1；
3) CO is added in the liquid isolated into step 2)2It is no longer generated to white precipitate, then by white precipitate Rear cleaning, drying is filtered out, aluminium hydroxide is obtained, by resulting aluminium hydroxide calcining time 2.5 hours at 850 DEG C of temperature, must be aoxidized Aluminium；
4) by filter residue flotation isolated in step 2), sulfide is floatingly selected, the sulfide floatingly selected is placed in 38% Oxygen-enriched environment under, roasted 2.5 hours at 850 DEG C, roast the flue gas of generation after vanadic anhydride catalysis reaction with dense sulphur Acid, which absorbs, is made sulfuric acid.
5) drying the remaining residue of flotation in step 4) and being crushed to fineness is 92 mesh, and screen over-size obtains potassium calcium less than 6% Base manure chelates 70 parts of potassium calcium base manure, 40 parts of humic acid, 50 parts of the plant ash soil that water content is 5%, 7 parts of EDTA chelated magnesium, EDTA 12 parts of 7 parts of zinc and bentonite obtain the dedicated potash-lime fertilizer of apple after mixing.
Embodiment 5:
A kind of technique preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, which comprises the steps of:
1) it mixes and grinds with ardealite, caustic soda and anthracite after potassium-bearing shale being crushed to 190 mesh and raw material are made, control The weight ratio of ardealite and potassium-bearing shale is 1:1.3 in raw material, and caustic soda adding proportion is by contained Na in raw material2O and A12O3+Fe2O3 The molecular proportion of summation is 1:1 addition, and anthracitic mixed proportion is the 22% of raw material total weight；Raw material are sent into industrial shaft kiln Clinker is made in the calcining time 1.5 hours at 1150 DEG C of temperature；
2) by water mill after the grinding of clinker made from step 1), then with it is water-soluble go out and be separated by solid-liquid separation, liquid when dissolution Gu volume ratio is 5:1；
3) CO is added in the liquid isolated into step 2)2It is no longer generated to white precipitate, then by white precipitate Rear cleaning, drying is filtered out, aluminium hydroxide is obtained, by resulting aluminium hydroxide calcining time 1.5 hours at 950 DEG C of temperature, must be aoxidized Aluminium；
4) by filter residue flotation isolated in step 2), sulfide is floatingly selected, the sulfide floatingly selected is placed in 47% Oxygen-enriched environment under, roasted 1.5 hours at 950 DEG C, roast the flue gas of generation after vanadic anhydride catalysis reaction with dense sulphur Acid, which absorbs, is made sulfuric acid.
5) drying the remaining residue of flotation in step 4) and being crushed to fineness is 98 mesh, and screen over-size obtains potassium calcium less than 6% Base manure chelates 80 parts of potassium calcium base manure, 50 parts of humic acid, 60 parts of the plant ash soil that water content is 6%, 8 parts of EDTA chelated magnesium, EDTA 15 parts of 8 parts of zinc and bentonite obtain the dedicated potash-lime fertilizer of apple after mixing.
In embodiment 1-5, the purity of the rate of recovery of its aluminium oxide and aluminium oxide is detected respectively, as a result such as following table institute Show:
Embodiment The rate of recovery Purity
Embodiment 1 95.7% 99.7%
Embodiment 2 96.4% 99.5%
Embodiment 3 96.1% 99.2%
Embodiment 4 95.7% 99.3%
Embodiment 5 96.2% 99.6%
The apple specialing fertilizer that embodiment 1-5 is prepared is utilized respectively to red fuji apple to apply fertilizer, meanwhile, it utilizes Potassium-bearing shale, which directly mixes, to be fabricated to after calcium sulfate, humic acid, plant ash soil, EDTA chelated magnesium, EDTA chelated zinc and bentonite pair It to red fuji apple applies fertilizer according to the fertilizer of group；Fertilization mode is identical with selecting respectively in a piece of apple orchard in acid-base property 50 plants of target apple trees similar in getting fruit amount are applied fertilizer after upper fruit picking in 1 year according to conventional fertilizer application mode, until under Fruit picking in 1 year terminates, and during which measures the pH value of soil near corresponding apple tree in three times；Meanwhile it being weighed after next year fruit picking The weight of the apple of picking obtains the weight of the result of corresponding fertilising apple tree, its average value is calculated, then with previous year The average weight of weight compare, result is as shown in the table:
As can be seen from the above table, after using fertilizer of the invention, the average fruiting weight of every apple tree increases, This is because the acid-base property of soil is not destroyed, the soil of the pH value in the section is more favorable for the fertilizer elements such as potassium, calcium Absorption therefore increase yield.And it is directly being applied using manufactured fertilizer after potassium-bearing shale and ardealite mixing other elements After fertilizer, the acid-base balance of soil is destroyed, keeps soil weakly acidic, is unfavorable for the absorption of fertilizer efficiency, reduces the yield of apple.

Claims (10)

1. a kind of technique for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, which is characterized in that be to be crushed to potassium-bearing shale Raw material are mixed and made into after 150-200 mesh with ardealite, additive and modifying agent, control the weight of ardealite and potassium-bearing shale in raw material Amount is than being 1:0.5-1.5, and additive adding proportion is by contained Na in raw material2O and A12O3+Fe2O3The molecular proportion of summation adds for 1:1 Add, the mixed proportion of modifying agent is the 10-25% of raw material total weight；Raw material are sent into kiln and are roasted, clinker is made；It will be obtained It dissolves out, and is separated by solid-liquid separation after clinker grinding；CO is added into the liquid that separation of solid and liquid obtains2It is no longer produced to white precipitate It is raw, white precipitate is then filtered out into rear cleaning, drying, obtains aluminium hydroxide, by resulting Aluminium hydroxide roasting, obtains aluminium oxide；It will consolidate The isolated filter residue flotation of liquid, floatingly selects sulfide, sulfide is roasted, and the flue gas of generation, which is sent into sulfuric acid preparation system, to be made Standby sulfuric acid；The remaining residue of flotation is dried and is crushed, potassium calcium base manure is obtained, into potassium calcium base manure add humic acid, plant ash soil, Up to the dedicated potash-lime fertilizer of apple after EDTA chelated magnesium, EDTA chelated zinc and bentonite.
2. the technique according to claim 1 for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, it is characterised in that: step It 1) include K in the potassium-bearing shale by mass percentage in2O 6-10%、Al2O3 17-20%、Fe2O3 5-7%、 SiO2 40-55%。
3. the technique according to claim 1 for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, it is characterised in that: step 1) in, the additive is sodium carbonate, sodium sulphate or caustic soda；The modifying agent is anthracite, carbon or gangue；Described Kiln is industrial rotary kiln, Industry Tunnel Kiln or industrial shaft kiln.
4. the technique according to claim 1 for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, it is characterised in that: step 1) in, the raw material are calcining time 1-3 hours at 1000-1200 DEG C of temperature.
5. the technique according to claim 1 for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, it is characterised in that: step 2) described to be ground to water mill in, when dissolution with it is water-soluble go out；It is 3-6:1 that liquid when the dissolution, which consolidates volume ratio,.
6. the technique according to claim 1 for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, it is characterised in that: step 3) in, the roasting is calcining time 1-3 hours at 800-1000 DEG C of temperature.
7. the technique according to claim 1 for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, it is characterised in that: step 4) it is that the sulfide that will be floatingly selected is placed under the oxygen-enriched environment of 35-50% in, is roasted 1-3 hours at 800-1000 DEG C, is roasted The flue gas of generation, which is absorbed after vanadic anhydride catalysis reaction with the concentrated sulfuric acid, is made sulfuric acid.
8. the technique according to claim 1 for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, it is characterised in that: step 5) in, the residue drying, smashed fineness are 90-100 mesh, and screen over-size is less than 6%.
9. the technique according to claim 1 for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, it is characterised in that: step 5) in, the dedicated potash-lime fertilizer of apple includes 50-80 parts of potassium calcium base manure, 20-50 parts of humic acid, plant ash soil by weight 30-60 parts, 3-8 parts of EDTA chelated magnesium, 3-8 parts of EDTA chelated zinc and 5-15 parts of bentonite.
10. the technique according to claim 1 for preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium, it is characterised in that: step It is rapid 5) in, the water content of the plant ash soil is 1-6%.
CN201810714269.4A 2018-07-03 2018-07-03 A kind of technique preparing the dedicated potash-lime fertilizer of apple and relieving haperacidity recycling aluminium Withdrawn CN109019528A (en)

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