CN106145175A - A kind of method of comprehensive utilization of ardealite - Google Patents

Abstract

The present invention relates to the method for comprehensive utilization of a kind of ardealite, including the purification method of ardealite；The dewatering of ardealite；Ardealite brickmaking；Ardealite plasterboard；Ardealite makes cement additire；Soil conditioner prepared by ardealite；Ardealite produces secondary and micro-element fertilizers.The present invention can fully solve the process problem of ardealite.

Description

A kind of method of comprehensive utilization of ardealite

Technical field

The present invention relates to the method for comprehensive utilization of a kind of ardealite.

Background technology

The main highly concentrated compound fertilizer kind that Lin Anshi China greatly develops, often produces 1 ton of ammonium phosphate product about Discharge 3 tons of phosphogypsum slags.To the end of this century, Wet-Process Phosphoric Acid in The World annual production more than 30,000,000 tons (with P2O5 counts).Produce ardealite more than 1.5 hundred million T/a.The end of the nineties, China's phosphoric acid production by-product Ardealite has reached annual about 3,000,000 tons, it is contemplated that be likely to be breached 10,000,000 T during by 2010.Phosphorus stone The growing amount of cream is much larger than the calcium sulfate aggregate consumption in the world.This situation that supply exceed demand.Make phosphorus stone What cream became ammonium phosphate enterprises one bears greatly, and quite a few enterprise takes at landfill and the method stacked Manage this waste residue.But this processing method also can only be makeshift.Being continuously increased not of ardealite But take a large amount of soil, and surrounding is had undesirable effect.How digestion process this discard Resource, is ammonium phosphate enterprises problem in the urgent need to address.

Summary of the invention

In order to solve the problem that prior art exists, the invention provides a kind of ardealite comprehensive utilization side Method, it is possible to fully solve the process problem of ardealite.

The technical solution adopted in the present invention is:

The method of comprehensive utilization of a kind of ardealite, including the purification method of ardealite；The dehydration of ardealite Method；Ardealite brickmaking；Ardealite plasterboard；Ardealite makes cement additire.

This method also includes that soil conditioner prepared by ardealite；Ardealite produces secondary and micro-element fertilizers.

Beneficial effects of the present invention:

Effectively ardealite can be processed by processing method in above 6 or recycle, save money Source.

Detailed description of the invention

The invention provides the method for comprehensive utilization of a kind of ardealite, be illustrated from following several respects.

The purification method of ardealite

The dopant species contained by ardealite that different Wet Processes of Phosphoric Acids produce is different with content, and they are also Relevant with the kind of phosphorus ore used when producing phosphoric acid and the concrete composition of phosphorus ore.The existence of impurity can be slowed down Setting time during the Gypsum Fibrosum preparata aquation prepared, reduces the intensity of goods.Therefore, ardealite is utilized Various technology all comprise and ardealite is carried out washing separation impurity and neutralizes the processing procedure of free acid. Thereafter dehydrating operations is then identical with the course of processing of the natural gypsum.

Impurity in ardealite has solubility and insoluble two classes.Soluble impurity mainly has three kinds.The One is free phosphoric acid and sulphuric acid, and they can make Gypsum Fibrosum preparata, when building, structural material be had corrosion Property, or model, the equipment of Gypsum Fibrosum prefabricated component processed is produced corrosion.Free acid also extends the solidification of Gypsum Fibrosum Time.The second is the soluble-salts such as one-lime phosphate, phosphorus dicalcium, fluosilicate, their main shadow Sound is also the setting rate of Gypsum Fibrosum of slowing down.The third is sodium, potassium salt, and sodium, potassium salt class can make after drying Plastering surface " brilliant flower " occurs.

Insoluble impurities also has two kinds: some are to exist in phosphorus ore and the most non-when phosphorus ore acid hydrolysis The most stable silica sand, undecomposed mineral and organic matter；Other are common with calcium sulfate when being phosphoric acid ore deposit solution Dicalcium phosphate, other insoluble phosphates and the fluorine compounds of crystallization.Silica sand and unreacted phosphorus ore are thin The quality of Gypsum Fibrosum preparata is affected less by grain, but it has abrasive action to the equipment of ardealite processing procedure； Organic impact is very big, and it makes product gray, the setting rate that slows down, the intensity of reduction goods, Eutectic phosphate also slows down setting rate.

Phosphogypsum purification and drying and dehydrating all can make different arrangements according to the quality condition of ardealite. Such as, when the raw material used by phosphoric acid production is high-grade selected rock phosphate in powder, ardealite is the purest. Gypsum Fibrosum preparata processed just need not use complexity purification run, as long as and before burning, ardealite water is starched again, Filtering or water-solubility impurity is removed in centrifuge dehydration, the removable 80-90%'s of this processed can Solubility impurity.

When ardealite contains higher soluble impurity and organic impurities, water-washable method, adopt By tertiary effluent power whiz device separation of phosphorus Gypsum slurry, in the case, the clearance of water-solubility impurity is big In 95%, organic clearance, depending on original amount, typically can reach sufficiently high separation degree.

Washing floatation, is the concentration that ardealite filter cake adds water to 450g/L, enables pumping, Slip sends into medial launder, adds chemicals at this.Then sending floatation system, flotation cell adds appropriate Flotation agent, separates organic and insoluble impurities.It is in the case, as the purest in ardealite itself, Flotation can be saved and instead filtration washing operation, remove soluble impurity.From floatation system or mistake The ardealite that filter draws off enters thickener, adds clear water and steam at this, to remove remaining solubility And insoluble impurities.Ardealite suspension after purification filters or centrifugal operation is tried one's best free water Content is reduced to minimum level.To reduce the thermal energy consumption of drying and calcining thereafter.

The dewatering of ardealite

Mainly half-H 2 O calcium sulphate (CaSO4-H2O) or the anhydrous slufuric acid that ardealite uses in building materials Calcium (CaSO4).The same with theing cement solidifies, the solidification of Gypsum Fibrosum preparata also has chemical reaction.After Gypsum Fibrosum preparata adds water, Calcium sulfate generation hydration reaction, is transformed into the Gypsum Fibrosum (calcium sulphate dihydrate) of scleroma

2CaSO4 H2O+3H2O====2CaSO4 2H2O

CaSO4+2H2O====CaSO4 2H2O

More than reaction is the ardealite basic chemical reaction as construction material.So ardealite is in building First application in material is through being dehydrated into half water or anhydrous gypsum by phosphogypsum dihydrate.The side of dehydration Method has wet method dehydration, dry method dehydration and calcined dehydration three kinds.

Wet method is dehydrated

Wet method dehydration is the most dissolving crystallized process that carried out in autoclave pressure by ardealite, adds in still Enter chemical addition agent, control the scope of PH 1-3, temperature 120 DEG C, use Steam pressure control temperature, Replace along with the solution of calcium sulphate dihydrate lattice in a kettle..Eutectic impurity in crystallization, sodium, calcium Phosphate be released, change into purity higher half-H 2 O calcium sulphate crystallization.Crystallization filter or from The method of the heart separates and anhydrates, and mother solution can return to phosphoric acid production device, and this method is conducive to improving obtaining of phosphoric acid Rate.

The semi-hydrated gypsum being converted into contains the free water of 10-20%.Whether need further drying and processing, It is decided by purposes thereafter.If directly manufacturing Gypsum Fibrosum product, it is not necessary to be dried, if gone out as dry product Sell and be accomplished by drying immediately.

Dry method is dehydrated

By ardealite the flue gas occurred with natural gas with and stream mode by pneumatic drier,

Emptying after expellant gas is scrubbed.Dried ardealite be sintered in fluidized bed furnace again β- Half-H 2 O calcium sulphate.Heat needed for calcined dehydration is mainly effective by the heating being embedded in boiling furnace charge Steam heating provides.

High-temperature calcination

The calcining of ardealite is to carry out in the rotary furnace of particular design, is separated into difference in stove

Several regions of temperature, during continuous dry work, ardealite is heated by the flame, continuously by not Synthermal region.Temperature ＜ 1000 DEG C reached in calcining furnace.Calcining furnace discharging is coarse, Crush after cooling, be milled into fine powder and be finished product.

Ardealite brickmaking

Available ardealite and sand, cement without processed is dispensing.Make standard under stress The fragment of brick of size, the comprcssive strength of brick, crack factor, water absorption, density wearability all meets building The requirement of industry, it is characterized by employing high pressure, and pressure is the highest, and intensity is the biggest.Dispensing adds a small amount of cement The water absorption that can make goods reduces.Formula is as follows: ardealite 60% cement 2-8% sand 32- 38% moisture content 3-6%.

Ardealite plasterboard

The making of plasterboard is dry Gypsum Fibrosum preparata to be added water size mixing, and calcium plaster is noted on a conveyor, allows Its solidification, then prescinds into plate.

Ardealite makes cement additire

Adding appropriate Gypsum Fibrosum in manufacture of cement to mill together with clinker, water produced mud can keep relatively Operable state for a long time, delays the time theed cement solidifies, and is conducive to strengthening the final of cement simultaneously Intensity.The retarder of by-product ardealite as cement has been done more due to natural gypsum shortage by Japan Research.Research shows, the impurity in ardealite can postpone the setting time of cement, but to concrete Intensity effect is the least, and a small amount of dalcium biphosphate even can increase intensity.Therefore, ardealite people Cement additire, only need to make suitable purified treatment.Making fluorine and phosphorus content drop to a certain degree can expire The requirement of foot making cement additive.As reached requirement, then without purifying.If phosphoric acid process is two Water law, the ardealite purity obtained is poor, need to purify, if phosphoric acid is two water half wet technologies, Only need to be neutralized when half-H 2 O calcium sulphate be hydrated, row pelletize again, dry.

Soil conditioner prepared by ardealite

Gypsum Fibrosum is the calcium source of improvement soda type (Na2CO3, NaHCO3) saline-alkali soil, and can be owing to executing Increase electrolyte after Gypsum Fibrosum and improve the permeability of soil.Gypsum Fibrosum improve oozing property of soil effect be due to The exchangeable sodium (Na+) that the calcium ion (Ca) that it discharges after dissolving may replace in soil, thus can Make sodium salt gradually eccysis.

Na2CO3+CaSO4==CaCO3+Na2SO4

Practice can determine Gypsum Fibrosum according to Cation Exchange Capacity in Soils and desired sodium ion exchange degree Consumption.

Containing high for MgSO4 soil (peasant is commonly called as " Corii Bovis seu Bubali alkali ground "), the modification method of soil, typically Bias toward irrigation and drainage washing and a large amount of applications of farmyard manure material, due to by water source and farm manure number quantitative limitation, It is inconvenient for promoting this kind of modification method.Using ardealite in a large number is then a kind of practical and warp The method of improving the soil of Ji.Due to the mutual antagonism between calcium, magnesium, calcium ion concentration around root system of plant During increase, magnesium ion is just not easily accessed in root, so that the toxic action of excess magnesium is suppressed.Right NaCI type MgSO4 type saline-alkali soil, and also have same with the alkali soil improvement formed after irrigation with saline water soil The effect of sample.

Ardealite contains a small amount of free acid, is allowed in acidity, its PH=2.5-3.5.The phosphoric acid that it contains There is the immediate interest of phosphate fertilizer.Basic soil and phosphoric acid occur to neutralize reaction, particularly have typical case high The lime soil of PH (7.5 ＜ PH ＜ 9.5), has tended to good good effect.Along with in phosphoric acid With, soil mineral dissolves and discharges calcium, ferrum, aluminum, can promote between the flocculation of soil particle, granule Bonding, reduce further the pH value of soil.Improve the effectiveness of indispensable element.In sodium alkaline soil Due to high pH value, the effectiveness of trace element reduces, except B, Mo element in addition to majority trace element (as Fe, Cu, Zn, Mn), only could keep higher activity under mild acid conditions.

Ardealite produces secondary and micro-element fertilizers

Sulfur and calcium are the middle amount essential nutrient elements of plant, and during plant a lack of sulfur, a part of nitrogen can not be formed Protein, causes the quality of agriculture thing, yield to reduce.Sulfur also helps chlorophyll and legume root nodule Formation.Calcium is the essential element constituting plant cell wall, makes cell wall tough and tensile, is not easily broken.Plant During thing calcium deficiency, root growth is bad, and plant is short and small, leaf rolling, and limb jaundice is withered, and the tip of a root rots Dead.The soil lacking calcium and sulfur obviously can be played alimentation by the calcium and the sulfur that discharge after gypsum dissolution, A lack of sulfur has an effect on the quality of crop, and result of the test is shown and shown, using ardealite can increase wheat crops and produce Amount 7%-9%.The effect executing Gypsum Fibrosum is also had an impact by tillage method, ploughs deeply many volume increase Semen Tritici aestivi than raking the soil level 33.6%-38%.Should determine to use the consumption of ardealite according to different soils.

In ardealite, calcium sulfate is slightly soluble in water, dissolubility such as table 1 under different temperatures

Table 1 calcium sulfate dissolubility at different temperatures

Temperature DEG C	0	10	30	40	50	70	100
								Dissolubility	0.1759	0.1928	0.2090	0.2097	0.2038	0.1966	0.1619

As it can be seen from table 1 ardealite is the material being slightly soluble in water, this just provides one for crops Plant the sulfur of slow-acting type, calcareous fertilisers.

The crops such as fruit tree, Oryza sativa L. are relatively big to the demand of calcium, and ardealite is difficult to because its dissolubility is little Meet the demand of growth busy season calcium, to this end, we utilize organic sequestering agent, in activation ardealite Calcium, makes chelating calcium, improves activity and the feed speed of calcium.Deliming in ardealite, element sulphur Outward.Possibly together with other trace element that crops are required, under the effect of chelating agen, its activity is significantly Improve.

The result of China's overall survey of soil shows, moderate-element lacks and the area of famine always accounts for arable land More than the 70% of area.The loss that brings to crops of trace element imbalance in Yin, much larger than N, P, The loss that the imbalance of K is caused.The sulfur of ardealite, calcium content are high, and chemical stability is good, we Research, with ardealite as carrier, chelates trace unit in other with the organic sequestering agent such as aminoacid, humic acids Element, soil and variety of crops for different regions determine the ratio between each element, produce one many Micro-fertilizer during element is organic, this in micro-fertilizer can be used alone, it is possible to blend with the kind of other fertilizer and make With.Mix in BB fertilizer after also can adding compound fertilizer pelletizing, or independent pelletize, be allowed to produce one containing many The efficient BB planting nutrient is fertile.It is effectively improved the fertile utilization rate of fertilizer of BB.This project applicant country Family's patent, and small lot input industrialized production.

BB fertilizer and Chemical Mixed Fertilizer are the main fertilizer varieties of current China fertilizer secondary operations, and development BB is fertile Being the main behave of China's implementation fertilization compositions based on earth measurement, BB fertilizer technique is simple, and convenient use, nutrient is complete Face, is welcome by peasant, but current BB fertilizer still based on N, P, K tri-element blend, no Can meet the needs of fertilization compositions based on earth measurement, our way is organic by containing multiple essential nutrient element In Chelating state, micro-fertile granule adds BB fertilizer by the requirement of soil measurement formula, is allowed to nutrient more comprehensively, and effect is more Significantly, this is just effectively improved the scientific and technological content that BB is fertile.

Fertile and Chemical Mixed Fertilizer the total output of China BB has reached more than 2,000 ten thousand tons.Calculate by addition 20%, Total consumption more than up to 400 ten thousand tons.For ardealite in application agriculturally, this is a huge city ?.

Claims (2)

1. the method for comprehensive utilization of an ardealite, it is characterised in that: include the purification method of ardealite； The dewatering of ardealite；Ardealite brickmaking；Ardealite plasterboard；Ardealite makes cement to be added Agent.

The method of comprehensive utilization of ardealite the most according to claim 1, it is characterised in that: also wrap Include；Soil conditioner prepared by ardealite；Ardealite produces secondary and micro-element fertilizers.