CN105967830A - An ore powder displaced organic element fertilizer and a preparing method thereof - Google Patents

Abstract

An ore powder displaced organic element fertilizer and a preparing method thereof are disclosed. The fertilizer is prepared from papermaking black liquid, a sulfuric solution having a concentration of 10 wt%, a formaldehyde solution having a concentration of 5%, sodium sulfite, selenium ore powder, ground phosphate rock, iron ore powder, potassium feldspar powder, a hydrochloric acid solution having a concentration of 10-15%, crop straw, biogas digester fermentation liquid, sugar residues, urea, rice husk residues, plant ash, potassium nitrate and a proper amount of water. After ore powder is soaked with the hydrochloric acid and washed, dense particular ore powder is turned to be loosen and porous, and a part of the ore powder is directly displaced into ion forms free in liquid and then adsorbed by modified lignin particles so as to become organic mineral elements which are easier to absorb. The biogas digester fermentation liquid comprises various microorganisms passing through natural screening, added organic matters are automatically decomposed and fermented, and generated organic acids, and other components are beneficial to crop growth.

Description

A kind of displacement mineral powder organic element fertilizer and preparation method thereof

Technical field

The invention belongs to the Technology field of fertilizer, be specifically related to a kind of displacement mineral powder organic element fertilizer and preparation method thereof.

Background technology

The soda pulp technique that paper industry is widely used, no matter with woody or nonwood plant as raw material, all substantial amounts of black liquor of by-product, the annual black liquor yield in the whole world is about 500,000,000 tons according to statistics, the solid content that there are about 70% in black liquor is Organic substance, and including lignin, hemicellulose and cellulose degradation product etc., lignin is a kind of complicated macromolecular compound being present in major part land plant xylem, quantity is the hugest, estimates that the domestic lignin produced by papermaking every year there are about more than 1,000 ten thousand tons.At present, major part black liquor concentrated to 45 ~ 60% after-combustions, carry out alkali collection, thus causing the huge waste of this Renewable resource of lignin contained therein, black liquid flows into environment, and pollution level is high, containing substantial amounts of organic fiber, inorganic salt and pigment, contained pollutant have accounted for more than the 90% of industrial pollution caused by paper manufacturing thing, and alkalescence is relatively big, color is deep, and stink weight and foam are many, a large amount of dissolved oxygen consumed in water, cause serious destruction to environment.

The sulfonation of black liquid refers to that contained lignin reaction generates the process of lignosulfonate to sulfite ion with black liquor.The methylolation of first paragraph lignin, determines optimal value according to the introduction volume of methylol in lignin；The sulfonation of second segment lignin, determines optimal value according to paste flowing degree, is aided with sulfonation degree and relative molecular mass analysis.The method that wherein methylolation of lignin is to increase lignin activity；Sulfonating reaction is set as pH value≤7, makees sulfonating agent with sodium sulfite, and the lignin structure unit of phenolic and non-phenolic can occur the sulfonating reaction on beneficially α carbon, the most also carries out on γ carbon, but seldom on β carbon.

Black liquid in commercial paper is carried out emphasis utilization, it is subsequently used for the preparation of fertilizer, not only solve black liquid and flow into the environmental pollution that environment causes, also carry out garbage huge profit use, development for slow release fertilizer, the black liquid of main flow is with after caustic lye of soda high temperature steaming slurrying mostly now, originally lignin dissolution becomes alkali lignin, cellulose separates out, the black liquid obtained after leaching cellulose, so general pH is more than 12, total alkali 20 ~ 25%, lignin is 20 ~ 25g/L, and pollution level is high, containing a large amount of fibers, inorganic salt and pigment.

Summary of the invention

It is an object of the invention to huge profit black liquid, for the production of agrochemical, make a kind of granule adsorbing inorganic elements, make fertilizer play the effect of slow release, realize particular by following methods:

A kind of displacement mineral powder organic element fertilizer, it is characterized in that, be made up of the raw material of following weight portion: black liquid 150 ~ 180,10wt% sulfuric acid solution 30 ~ 40,5% formalin 20 ~ 30, sodium sulfite 10 ~ 15, selenium mineral powder 10 ~ 15, ground phosphate rock 30 ~ 45, iron ore powder 20 ~ 26, feldspar in powder 15 ~ 20,10 ~ 15% hydrochloric acid solution 100 ~ 125, agricultural crop straw 35 ~ 50, fen fermentation liquid 60 ~ 70, sugar slag 10 ~ 14, carbamide 3 ~ 5, rice husk slag 6 ~ 10, plant ash 10 ~ 15, potassium nitrate 4 ~ 6 and appropriate water；

A kind of preparation method replacing mineral powder organic element fertilizer, it is characterised in that include following step:

(1) black liquid is joined in reactor, it is heated to boiling, steaming and decocting is concentrated into original 1/3, then heating in water bath is turned to 50 ~ 60 DEG C, insulation, it is slowly stirred 30 ~ 40min with the rotating speed of 120 ~ 150r/min, it is simultaneously introduced 10wt% sulfuric acid solution, sucking filtration obtains lignin particles, crosses clear water and washs 3 ~ 5 times, finally standby after vacuum drying；

(2) lignin particles of (1) gained is joined in the container filling 5% formalin, regulation pH is 10 ~ 11, it is heated to 70 ~ 80 DEG C of insulation reaction 1.2 ~ 1.5h, pH value determination is addition sodium sulfite after neutrality, improve and at temperature 130 ~ 150 DEG C, react 3 ~ 4h, again wash and be dried, obtaining modified lignin particles；

(3) mixing selenium mineral powder, ground phosphate rock, iron ore powder and feldspar in powder, add to the hydrochloric acid solution of 10 ~ 15% hydrochloric acid solutions, be slowly stirred 30 ~ 40min, be subsequently adding the modified lignin resin granule of (2) gained, be heated to 70 ~ 80 DEG C, is incubated absorption 10 ~ 20min；

(4) mixed farming thing straw, rice husk slag and other residual components, pulverize slagging, it is then added in fen fermentation liquid, sealed fermenting 3 ~ 5 days, fermentation material is filtered to obtain after completing, adding to the mixed solution described in (3), stir into the thickener of thickness, slurry-spraying pelletizing makes the spheroidal particle of 3 ~ 5mm particle diameter.

The thinking of the present invention is by acid adding in the black liquid of alkalescence preparation method, the phenates being originally dissolved in alkali is made to make alkali lignin separate out with acid effect, first take a certain amount of black liquid, heating concentrates, the sulfuric acid solution being subsequently adding 10wt% makes the pH of concentrated solution be 2 ~ 3, allows lignin free adsorbing conglomeration form granule in the case of being slowly stirred, and controls mixing speed and makes granule be between 80 ~ 100 mesh sieves, then it is precipitated by the way of sucking filtration, is washed with deionized the lignin particles obtaining flocculating sedimentation 3 ~ 5 times；

Containing various active group in lignin molecule own, humus it is converted into after slowly being degraded by microorganism in soil, and humus is the main component of earth, extremely critical effect is played in growth to plant, soil urease liveness is had certain inhibitory action, promote plant growing, improvement soil etc..But can not single add in fertilizer as organic, organic offer nutrition is provided like that, can not produce with modern fertilizer and contact, and large usage quantity, effect is general, also it is unworthy expending material resources, the manpower transformation to black liquid, does not also meet the consumption that modern fertilizer advocates few, the obvious feature of effect；nullIn view of this point，Lignin is combined granule and carries out chemical modification by us，Make lignosulfonates，It is a kind of good raw material manufacturing ion exchange resin，Become a kind of macromolecular material，Lignin particles is owing to belonging to free settling，Do not add any binding agent，It is cross-linked to each other loosely organized，After making lignosulfonates，Belong to macromolecular structure，Be cross-linked to each other more horn of plenty，It is not easily broken，There is the strongest cation exch ange adsorption ability simultaneously，And the shortcoming overcoming the poorly water-soluble of lignin own，Invention be not intended to prepare pure cation exchange resin，Mainly controlled by certain condition，The combination making lignin particles is tightr，Strengthen its hydrophilic，The lignin molecule simultaneously making particle surface is converted into lignosulfonates，For adsorbing metal cation，After adding fertilizer，Play certain slow release effect.

Beneficial effects of the present invention: not only rich in the metallic ore prime element of one-component in mineral nitrogen stone powder, mixing possibly together with other elements various, therefore it is not the interpolation of single mineral element, after the washing by soaking of persalt, tight granule stone powder becomes loose porous, the form also having part to be directly replaced as ion is free in liquid, the lignin particles absorption that recycling is modified, become organic mineral element, it is easier to be absorbed, fen fermentation liquid exists the various microorganism through Natural Selection, add organic automatic classifying fermentation, the compositions such as the organic acid produced are also beneficial to the growth of crop.

Detailed description of the invention

Embodiment 1:

A kind of displacement mineral powder organic element fertilizer, it is characterized in that, be made up of the raw material of following weight portion (Kg): black liquid 165,10wt% sulfuric acid solution 37,5% formalin 28, sodium sulfite 14, selenium mineral powder 14, ground phosphate rock 33, iron ore powder 22, feldspar in powder 18,10 ~ 15% hydrochloric acid solution 110, agricultural crop straw 39, fen fermentation liquid 66, sugar slag 12, carbamide 4, rice husk slag 8, plant ash 14, potassium nitrate 4 and appropriate water；

A kind of preparation method replacing mineral powder organic element fertilizer, it is characterised in that include following step:

(1) black liquid is joined in reactor, it is heated to boiling, steaming and decocting is concentrated into original 1/3, then heating in water bath is turned to 50 ~ 60 DEG C, insulation, it is slowly stirred 30 ~ 40min with the rotating speed of 120 ~ 150r/min, it is simultaneously introduced 10wt% sulfuric acid solution, sucking filtration obtains lignin particles, crosses clear water and washs 3 ~ 5 times, finally standby after vacuum drying；

(2) lignin particles of (1) gained is joined in the container filling 5% formalin, regulation pH is 10 ~ 11, it is heated to 70 ~ 80 DEG C of insulation reaction 1.2 ~ 1.5h, pH value determination is addition sodium sulfite after neutrality, improve and at temperature 130 ~ 150 DEG C, react 3 ~ 4h, again wash and be dried, obtaining modified lignin particles；

(3) mixing selenium mineral powder, ground phosphate rock, iron ore powder and feldspar in powder, add to the hydrochloric acid solution of 10 ~ 15% hydrochloric acid solutions, be slowly stirred 30 ~ 40min, be subsequently adding the modified lignin resin granule of (2) gained, be heated to 70 ~ 80 DEG C, is incubated absorption 10 ~ 20min；

(4) mixed farming thing straw, rice husk slag and other residual components, pulverize slagging, it is then added in fen fermentation liquid, sealed fermenting 3 ~ 5 days, fermentation material is filtered to obtain after completing, adding to the mixed solution described in (3), stir into the thickener of thickness, slurry-spraying pelletizing makes the spheroidal particle of 3 ~ 5mm particle diameter.

The a kind of of the present invention is used to replace the mineral powder organic element fertilizer planting experiment for crops Semen Maydis, select 5 mu of corn planting bases, need to use as main fertilizer according to corn planting using the fertilizer of the present invention, 5 mu of Yield-increasing Baallus In Maize common fertilizers of matched group, result shows: Semen Maydis and each side growing way of experimental group are superior to matched group, and in soil, the inorganic elements of organic adsorption enriches, the huge profit realizing spent pulping liquor is used, benefit agricultural development, improve corn yield, economic raising 12.4%.

Claims (2)

1. a displacement mineral powder organic element fertilizer, it is characterized in that, be made up of the raw material of following weight portion: black liquid 150 ~ 180,10wt% sulfuric acid solution 30 ~ 40,5% formalin 20 ~ 30, sodium sulfite 10 ~ 15, selenium mineral powder 10 ~ 15, ground phosphate rock 30 ~ 45, iron ore powder 20 ~ 26, feldspar in powder 15 ~ 20,10 ~ 15% hydrochloric acid solution 100 ~ 125, agricultural crop straw 35 ~ 50, fen fermentation liquid 60 ~ 70, sugar slag 10 ~ 14, carbamide 3 ~ 5, rice husk slag 6 ~ 10, plant ash 10 ~ 15, potassium nitrate 4 ~ 6 and appropriate water.

A kind of preparation method replacing mineral powder organic element fertilizer, it is characterised in that include following step:

(1) black liquid is joined in reactor, it is heated to boiling, steaming and decocting is concentrated into original 1/3, then heating in water bath is turned to 50 ~ 60 DEG C, insulation, it is slowly stirred 30 ~ 40min with the rotating speed of 120 ~ 150r/min, it is simultaneously introduced 10wt% sulfuric acid solution, sucking filtration obtains lignin particles, crosses clear water and washs 3 ~ 5 times, finally standby after vacuum drying；

(2) lignin particles of (1) gained is joined in the container filling 5% formalin, regulation pH is 10 ~ 11, it is heated to 70 ~ 80 DEG C of insulation reaction 1.2 ~ 1.5h, pH value determination is addition sodium sulfite after neutrality, improve and at temperature 130 ~ 150 DEG C, react 3 ~ 4h, again wash and be dried, obtaining modified lignin particles；

(3) mixing selenium mineral powder, ground phosphate rock, iron ore powder and feldspar in powder, add to the hydrochloric acid solution of 10 ~ 15% hydrochloric acid solutions, be slowly stirred 30 ~ 40min, be subsequently adding the modified lignin resin granule of (2) gained, be heated to 70 ~ 80 DEG C, is incubated absorption 10 ~ 20min；

(4) mixed farming thing straw, rice husk slag and other residual components, pulverize slagging, it is then added in fen fermentation liquid, sealed fermenting 3 ~ 5 days, fermentation material is filtered to obtain after completing, adding to the mixed solution described in (3), stir into the thickener of thickness, slurry-spraying pelletizing makes the spheroidal particle of 3 ~ 5mm particle diameter.