CN1415582A - Method for producing borium and magnesium fertilizer by using boric sludge - Google Patents

Abstract

A process for preparing BMg fertilizer from B-contained mud includes such steps as pulverizing, reacting with sulfuric (or nitric) acid at 80-100 deg.c for 5-10 min to make its pH-2.5-5.0, cooling, pulverizing, mixing with ammonium carbonate to make its pH=5.5-9.0, adding borax and water, granulating, drying and screening. Its advantages are high content of water-soluble B2O3, and utilizing waste for lower environmental pollution.

Description

Utilize boron mud to produce the method for boric magnesium fertilizer

Technical field

What the present invention relates to is mineral manure, and the waste residue production that particularly utilizes boron magnesium ore deposit to produce boride contains the mixed fertilizer of magnesium and boron.

Background technology

There is more rich fibrous boron magnesium ore deposit (2MgOB east, Liaoning Province ₂O ₃3H ₂O) and ludwigite (3MgOFeOFe ₂O ₃B ₂O ₃), the two kinds of method processing of applying greatly after the exploitation: one is alkaline process, and with various inorganic base decomposing ores, the finished product are borax; Other method is an acid system, is decomposition agent with various mineral acids, and general the finished product are boric acid.One ton of borax of every production needs the boron magnesium slag (to contain 12%B ₂O ₃) about 4 tons; Produce one ton of boric acid and need boron magnesium slag (the same) 6～7 tons.For many years, borax and boric acid factory are all with the mass production waste residue, and---boron mud---is deposited on the deslagging field, and the many decades of stacking that has really is " pile up like a mountain ".Boron is not poisonous element, but excess is present in soil and the water, all is deleterious to people, animal and crop then.It is reported, have the scholar point out after deliberation the life drink with agricultural irrigation water in the highest 1ppm of being limited to of effective boron content, the control criterion of the effective boron of soil is 8ppm, and enumerates the detrimentally affect of people and animals' excess ingestion boron to health; Crop is in boron is excessive when using toxicity symptom and influence (Wang Yunhua etc. " boron fertilizer " Chemical Industry Press version p82～85 in 1998).Therefore, the stacking of a large amount of boron mud has not only taken the soil, also can serious environment pollution.

For many years, many technician set foot in this problem of utilizing of boron mud, described as CN 1245219A (application number 98114245.1) is to utilize boron mud and fluorite, wedding agent, additive etc. to make boron magnesium compound ball, is used for the steel-making converter slag making, and its slagging speed is fast, sweetening effectiveness good; And for example CN 1309082A (application number 01111140.2) provides in a kind of boron mud from boric acid is produced and reclaims its mesoboric acid, and the actual recovered rate is not high.More than use boron mud amount little, can reduce a little pollution, but DeGrain.And the most promisingly on the boron mud be to make the technical of the fertilizer that contains boron, magnesium utilizing.Be boron and the magnesium that production borax or the boron mud of producing boric acid all contain a great deal of.And one of boron seven kinds of micronutrient elements that to be growth and development of plants essential.Soil lacking boron is the most general, and the soil of states such as West Europe and the former Soviet Union area, the U.S., Japan is boron deficiency all, and many national boron fertilizers have become conventional fertilizer and used.China's soil fertilizer deficiency is quite extensive, rape " colored and unreal " often occurs, and cotton " flower bud and do not spend " is caused the comparatively serious underproduction.Magnesium is the necessary nutritive element of plant-growth, is chlorophyllous moiety, is the activator of plurality of enzymes in the plant materials, can promote photosynthesis, promotes the silicidize of cell walls, improves its diseases and insect pests resistance.CN 1169409A (application number 96117606.7) full nutritious particle fertilizer, ferment with the natural organic fertilizer material, regulate PH6.5～8.0 with boron mud, be equipped with multiple inorganic fertilizer again and make, it has obvious volume increase to paddy rice, corn, cotton and solanberry vegetables, yet boron mud consumption (only accounts for about 6 ‰) very little.CN 1281838A (application number 00122938.9) a kind of high-effective multi-element complex mixed fertilizer that provides, be to add water with boron mud to size mixing, with dilute sulphuric acid neutralization reaction 4h, be 50～70% sulfuric acid reaction 8h with concentration again, make acidifying boron mud PH reach neutral, being mixed with the inorganic fertilizer that contains nitrogen, phosphorus, potassium, zinc, compound and rotten sulfuric acid forms, and with conventional fertile contrast, paddy rice, corn is had production-increasing function significantly.Yet this technology can produce the waste water of a great deal of, and the reaction times oversize (only the reaction of boron mud acid reaches 12h twice), and the problem of most critical is the boron in the boron mud needs just can be converted into solubility under acid (PH≤5) B ₂O ₃, this technology reaction only is neutral, its conversion is not enough certainly.Although boron, Mg content are respectively 1.5%, 8% in the product, in fact effectively boron, effective magnesium are lower, so amount of application is considerable.Also mention in above-mentioned " boron fertilizer " book of quoting, boron mud adds the boric magnesium fertilizer that sulfuric acid makes, and it contains water-soluble B ₂O ₃0.2～0.5%, contain MgO35%, amount of application is every mu of 40～70kg, its water-soluble boron, Mg content are low, can not be absorbed by crop or be unfavorable for that crop absorbs, so consumption is so big.

Summary of the invention

At the deficiency that above-mentioned prior art exists, the invention provides one the boron in the boron mud all changed into water miscible boron, and be mixed with and contain the high effectively operational path of the boric magnesium fertilizer of boron, magnesium.

From carbon alkaline process boron mud composition, contained component is: water-soluble B ₂O ₃0.3～0.5%, solubility in acid B ₂O ₅1.5～3.0%, Mg30～37%, Fe ₂O ₃10～15%, SiO ₂20～28%, CaO3%, Al ₂O ₃2～3%, PH is 8～9.All boron is changed into water-soluble boron must be at acidic conditions (PH≤5), prior art only with its neutralization or react to PH for neutral, obviously be not enough.Fundamental point of the present invention is to react under acidic conditions, and then carries out neutralization reaction with the carbon ammonium, reaches the purpose that this height changes into water-soluble boron.

Its technical scheme is: boron mud joins in the reactor after pulverizing; stir sulfuric acid or nitric acid reaction with 40～75%; (facts have proved the sulfur waste acid of same concentrations; waste nitric acid also can be used) control PH2.5～5.0; because exothermic heat of reaction; its temperature can reach 80～100 ℃, and the reaction times only is 5～10min, and material is stacked; still have a little reaction in the material; and reaction heat makes wherein moisture evaporation totally, and when reducing to room temperature naturally, material is the lump state; with its pulverizing; use the carbon ammonium to mix then, regulating PH to 5.5～9.0, it is delivered to tablets press add water and (also can add a little tackiness agent with it; neutral inert dust) granulation; deliver to hot blast rotating cylinder inner drying, big production import hot blast is 300 ± 50 ℃, and outlet is 80 ± 5 ℃; control moisture below 5%, the screening back.The present invention is in operation, after adding acid-respons, is the siccative operation fully, no waste liquid, spent acid discharging.For favourable reaction, boron mud is pulverized its granularity and is 〉=80 orders, and is same, stacks caked material after the acidifying and also need be crushed to this granularity.This product can directly be used as boric magnesium fertilizer; Also can be used as the raw material of mixed fertilizer, and contain N, P, K or trace element fertilizer and be mixed.In order to reach the user product is wherein contained the requirement of effective boron, magnesium, as water-soluble B ₂O ₃0.5～2.1%, arrest molten MgO5.0～21.0%, can when the boron mud acid, add a certain amount of light-burning magnesium powder or brucite powder (dosage the most for a long time, every 100kg boron mud is no more than 5kg); Also can before granulation, add borax and mixing of materials (dosage be no more than total inventory 5%), and then carry out granulation.These boracics, magnesium material dosage proportioning need according to boron mud ingredient and user the requirement calculating that product contains boron, magnesium to be got.Can be sulfuric acid, nitric acid at acidification reaction with mineral acid, also can use sulfuric acid, the nitric acid of this that reclaim, useless concentration range.With this processing method of the present invention, answer foreign vendor's requirement, produce the higher water-soluble B that contains ₂O ₃, the product of arresting molten MgO, it is very satisfied that result of use is made us, and further enlarges on 50,000 tons/year basis.

Compared with prior art, its outstanding characteristics are to find under guide of theory non-water-soluble B ₂O ₃Be transformed into water-soluble B ₂O ₃Rational operational path, transform under the low pH value condition that reckons without in prior art, react completely, the time is short; Be adjusted to PH5.5～9.0 with the carbon ammonium in addition, acidified soil not only, and increase nitrogenous fertilizer; Contain water-soluble B ₂O ₃, arrest molten MgO height; Owing to become the siccative operation behind the acidification reaction, do not produce, do not have discharging spent acid and waste liquid, avoid secondary pollution; Cost is lower, and economic benefit is considerable.Owing to above reason, result of use is good in addition, for disposing the boron mud that pile up like a mountain, goes back nature and has found practical way with the pure land.

Embodiment example 1

100kg carbon alkaline process boron mud is inserted in the reactor that has stirring, with concentration is that 66% sulfuric acid 70kg adds and wherein carries out acidification reaction, and the reaction times is 5～10min, and this moment, reaction produced heat, make the reaction mass temperature be up to 100 ℃, the water of storeroom evaporates steam and escapes.It is 3.3 that PH is finished in reaction, material is drawn off be deposited in cooling naturally in the groove, and the dried solid and sclerosis of material during room temperature, with its pulverizing, granularity should be able to be passed through 80 mesh sieve holes.Powder and 4kg carbon ammonium, 1.2kg borax are inserted blender and are carried out thorough mixing, and the material that is mixed adds the water granulation, and through warm air drying, the import hot blast is 300 ± 50 ℃, 80 ± 5 ℃ of temperature outs, cooling sieve the heavy 144kg of product of particle diameter 2～4mm＞90%.Product P H＜8, moisture＜5% contains water-soluble B ₂O ₃2.05%, arrest molten MgO20.99%.Example 2

100kg boron mud and 3kg brucite powder are 71% sulfuric acid 80kg acidification reaction with concentration, react 9 minutes, and top temperature is 100 ℃, and PH=2.6 stacks and is cooled to room temperature, pulverizes, add 4kg carbon ammonium and mix, powder-like product 170kg.Get the 100kg powder-like product and add the 80kg neutral clay, add the water granulation, drying, screening, getting granularity is 2～4mm＞90% granulated product, its PH＜8, moisture＜5% contains water-soluble B ₂O ₃Be 1.0%, arrest molten MgO10.0%.Example 3

100kg boron mud is that 46% sulfur waste acid 55kg carries out acidification reaction 9min, 80～100 ℃ of temperature of reaction with concentration, PH=5, stacking is cooled to normal temperature, adds 2kg carbon ammonium and 1.9kg borax, mixes, add the water granulation, drying, cool off, sieve product 128kg, its PH＜8, moisture＜5% contains water-soluble B ₂O ₃1.90%, arrest molten MgO19.15%.

Claims (5)

1, a kind of method of utilizing boron mud to produce boric magnesium fertilizer comprises boron mud and sulfuric acid reaction, it is characterized in that production technique is:

(1) boron mud through pulverizing and concentration are 40～75% sulfuric acid or nitric acid reaction 5～10min, control its PH and reach 2.5～5.0, and temperature of reaction is 80～100 ℃;

(2) reactant is stacked and is cooled to normal temperature, pulverizes, and mixes with it with the carbon ammonium, and regulating PH is 5.5～9.0;

(3) add the water granulation, drying, screening again, making its particle is 2～4mm＞90%.

2, according to the described method of utilizing boron mud to produce boric magnesium fertilizer of claim 1, it is characterized in that in order to realize the water-soluble B of product ₂O ₃Reach 0.5～2.1%, arrest the index of molten MgO5.0～21.0%, adding light-burning magnesium powder or brucite powder when boron mud and sulfuric acid or nitric acid reaction, dosage the most for a long time, every 100kg boron mud is no more than 10kg; Add borax and mix granulation again before granulation, dosage is no more than 5% of total inventory.

3, according to the described method of utilizing boron mud to produce boric magnesium fertilizer of claim 1, it is characterized in that boron dust blowing after the boron mud of described pulverizing and the acidifying, its granularity is 〉=80 orders.

4,, it is characterized in that described sulfuric acid or nitric acid with the reaction of boron mud is sulfuric acid, the nitric acid that gives up or reclaim according to the described method of utilizing boron mud to produce boric magnesium fertilizer of claim 1.

5, according to claim 1 or the 2 described methods of utilizing boron mud to produce boric magnesium fertilizer, add neutral inert dust or neutral caking agent when it is characterized in that adding the water granulation.