CN105936602A - Method for producing sponge fertilizer from pickling waste liquid and waste lignin - Google Patents
Method for producing sponge fertilizer from pickling waste liquid and waste lignin Download PDFInfo
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- CN105936602A CN105936602A CN201610274485.2A CN201610274485A CN105936602A CN 105936602 A CN105936602 A CN 105936602A CN 201610274485 A CN201610274485 A CN 201610274485A CN 105936602 A CN105936602 A CN 105936602A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
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Abstract
The invention discloses a method for producing a sponge fertilizer from pickling waste liquid and waste lignin, and relates to the technical field of fertilizer production process. The method comprises the steps: in a waste black liquid produced from alkaline-process pulping of a papermaking factory, adding a steel pickling waste acid liquid, then adding ammonium persulfate as a catalyst, and adding sodium superoxide as an initiator; heating the materials with hot flue gas, carrying out heat preservation for a period of time in a normal pressure vessel with stirring, and making the materials subjected to a chemical reaction, to generate modified lignin; and then cooperating with biological bacteria and nitrogen, phosphorus and potassium auxiliary materials, and thus obtaining the sponge fertilizer. The method has the beneficial effects that the wastes are used for treating the wastes, processing problems of two kinds of industrial waste liquids are solved, and the sponge fertilizer is an organic fertilizer having great gap in production agriculture, has the fertilizer efficiency significantly improved compared with similar products, can obtain remarkable economic benefits and environmental-protection benefits, and has the advantages of simple equipment, simple method, easy implementation and the like.
Description
Technical field
The present invention relates to production technique for fertilizer technical field, be specifically related to a kind of pickle liquor and the method for waste wood quality production sponge fertilizer.
Background technology
Lignin is widely present in large nature, and it constitutes about 1/3rd of land plant Biomass；Lignin is the macromolecular compound of a kind of complexity, it constitutes the main component of plant skeleton with cellulose and hemicellulose, the CO2 that photosynthesis of plant is fixed has a big chunk to transform into lignin, in other words, the solar energy being stored in plant by photosynthesis, lignin about account for 40%；At nature, the reserves of lignin are only second to cellulose, the most all regenerate with the speed of 50,000,000,000 tons；China's Forest Resources is not the abundantest, and crops Fructus Citri tangerinae bar has 5-6 hundred million tons every year；China's pulp and paper industry to isolate about 1.4 hundred million tons of celluloses every year from plant, the lignin of by-product about 50,000,000 tons simultaneously, the Main Ingredients and Appearance of " black liquor " of pulp and paper industry discharge is lignin, but up to now, China burns after being still directly discharged into rivers or concentrate with " black liquor " more than 95% lignin, seldom it is utilized effectively, not only wastes resource, go back serious environment pollution.But, the exhaustion day by day of fossil energy, the developing rapidly of the abundant reserves of lignin, lignin science, determine the sustainable developability of the economic benefit of lignin；Because lignin cost is relatively low, it and derivant thereof have several functions, and the industrial purposes of lignin is wide, as the Source Organic Matter of organic fertilizer, and also should be the most good.It is generally accepted that for lignin be by C-0 key or the natural phenolic macromolecular compound of the bonded crosslinking net of C-C by phenylpropyl unit, lignin molecule has the various active groups such as aromatic radical, phenol carboxyl, alcohol carboxyl, carbonyl, carboxyl, have renewable, degradable and the advantage such as nontoxic concurrently, and it is considered excellent green chemical industry raw material, research to chemical modification of lignin, can be greatly improved the Practical Performance of lignin.
It addition, the pickling iron and steel of China's steel and iron industry, produce substantial amounts of acid waste liquid, if with sulfuric acid washing, spent acid content 6-8% (percentage by weight, as follows) left and right, ferrous sulfate about 7-9%；If with chlorohydric acid pickling, spent acid content about 7-9%, ferrous chloride about 25-33%；These spent acid, are not the most reasonably utilized.
Summary of the invention
It is an object of the invention to provide a kind of pickle liquor and the method for waste wood quality production sponge fertilizer, its treatment of wastes with processes of wastes against one another, solve a process difficult problem for two kinds of industrial wastes simultaneously, it is to produce the organic fertilizer that agriculturally breach is bigger, fertilizer efficiency significantly improves than like product, significant economic benefit and environmental benefit can be received, and there is the advantages such as equipment is simple, method is simple, easy enforcement.
In order to solve the problem existing for background technology, the main production raw material of the present invention comprises pickle liquor and waste wood quality, and its concrete production method step is:
(1) waste black liquor that Alkaline Pulping is produced, in the solid of waste black liquor, Organic substance accounts for more than 2/3rds (weight ratios), first waste black liquor is put in the heating of band passageway the uncovered equipment of normal pressure with agitator, then, adding pickling iron and steel acid pickle under constant agitation in waste black liquor, addition is the 5-10% (percentage by weight, as follows) of waste black liquor；
(2) under agitation, adding Ammonium persulfate. powder in waste black liquor, addition is the 0.5-0.9% of waste black liquor amount；
(3) then, adding sodium superoxide powder under agitation in waste black liquor, addition is the 0.03-0.06% of waste black liquor amount；
(4) under continuing stirring condition, by the flue gas of heat, above-mentioned waste black liquor is gradually heated up, makes temperature of charge 98-102 DEG C, react 20-25 minute, the methoxyl group mass fraction of the modified lignin resin in waste black liquor can be made to be reduced to about 12% by original 18%；Oxidisability electrolyte and the reaction of waste wood quality, generate similar foam product；
(5) then, above-mentioned material is put in the container of another band stirring, at normal temperatures and pressures, add appropriate biological inoculum and carbamide, MAP, potassium chloride adjuvant, after mix homogeneously, pack with Plastic Drum, prepare sponge fertilizer.
The pickling iron and steel acid pickle added described in step (1), sulfur acid 6-8%, ferrous sulfate 7-9%.
The pickling iron and steel acid pickle added described in step (1), hydrochloric 7-9%, chloride containing ferrous iron 25-33%.
The Ammonium persulfate. added described in step (2) is technical grade certified products, chemical formula (NH4) 2S2O8, molecular weight 228.19, colourless or white crystalline powder, quality standard: ZB/TG12021-90, technical grade seconds, containing Ammonium persulfate. >=95.0%, iron content (Fe)≤0.004%, containing heavy metal (in terms of Pb)≤0.005%, aqueous≤0.3%.
The sodium superoxide added described in step (3) is technical grade certified products, and chemical formula NaO2, molecular weight 54.99, yellow crystalline powder, quality index is: containing effective oxygen >=35.5%, containing calcium oxide=3.5 scholar 0.5, carbonated≤1%.
After using said structure, present invention have the beneficial effect that its treatment of wastes with processes of wastes against one another, solve a process difficult problem for two kinds of industrial wastes simultaneously, it is to produce the organic fertilizer that agriculturally breach is bigger, fertilizer efficiency significantly improves than like product, significant economic benefit and environmental benefit can be received, and there is the advantages such as equipment is simple, method is simple, easy enforcement.
Accompanying drawing explanation
Fig. 1 is the technological process of production schematic diagram of the present invention.
Detailed description of the invention
The present invention is further illustrated below in conjunction with the accompanying drawings.
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with the drawings and the specific embodiments, the present invention is further elaborated.Should be appreciated that detailed description of the invention described herein, only in order to explain the present invention, is not intended to limit the present invention.
As it is shown in figure 1, the main production raw material of the present invention comprises pickle liquor and waste wood quality, its concrete production method step is:
(1) waste black liquor that Alkaline Pulping is produced, in the solid of waste black liquor, Organic substance accounts for more than 2/3rds (weight ratios), first waste black liquor is put in the heating of band passageway the uncovered equipment of normal pressure with agitator, then, adding pickling iron and steel acid pickle under constant agitation in waste black liquor, addition is the 5-10% (percentage by weight, as follows) of waste black liquor；
(2) under agitation, adding Ammonium persulfate. powder in waste black liquor, addition is the 0.5-0.9% of waste black liquor amount；
(3) then, adding sodium superoxide powder under agitation in waste black liquor, addition is the 0.03-0.06% of waste black liquor amount；
(4) under continuing stirring condition, by the flue gas of heat, above-mentioned waste black liquor is gradually heated up, makes temperature of charge 98-102 DEG C, react 20-25 minute, the methoxyl group mass fraction of the modified lignin resin in waste black liquor can be made to be reduced to about 12% by original 18%；Due to oxidisability electrolyte and the reaction of waste wood quality of the present invention, similar foam product can be generated, be therefore referred to as sponge fertilizer；
(5) then, above-mentioned material is put in the container of another band stirring, at normal temperatures and pressures, add appropriate biological inoculum and carbamide, MAP, potassium chloride adjuvant, after mix homogeneously, pack with Plastic Drum, prepare sponge fertilizer.
The pickling iron and steel acid pickle added described in step (1), sulfur acid 6-8%, ferrous sulfate 7-9%.
The pickling iron and steel acid pickle added described in step (1), hydrochloric 7-9%, chloride containing ferrous iron 25-33%.
The Ammonium persulfate. added described in step (2) is technical grade certified products, chemical formula (NH4) 2S2O8, molecular weight 228.19, colourless or white crystalline powder, quality standard: ZB/TG12021-90, technical grade seconds, containing Ammonium persulfate. >=95.0%, iron content (Fe)≤0.004%, containing heavy metal (in terms of Pb)≤0.005%, aqueous≤0.3%, the catalyst action of its chemically reactive.
The sodium superoxide added described in step (3) is technical grade certified products, chemical formula NaO2, molecular weight 54.99, yellow crystalline powder, quality index is: containing effective oxygen >=35.5%, containing calcium oxide=3.5 scholar 0.5, carbonated≤1%, the initiator effect of its chemically reactive.
It is characteristic of the invention that and utilize pickling iron and steel acid pickle to process Industry Waste lignin, making catalyst with Ammonium persulfate., initiator made by sodium superoxide, generates sponge fertilizer.In process of production, it is necessary to grasp the degree of depth that reaction is carried out, three are controlled big because usually controlling reaction depth: (1) catalyst and initiator addition；(2) reaction temperature；(3) response time；When catalyst and initiator addition is many, reaction temperature is high, the response time is long, the modification that can make lignin is the most thorough, and the adjuvant simultaneously consumed is many, cost also can increase.Therefore, above three should have been controlled to adjust because usually controlling the quality of production and cost, in the hope of receiving bigger economic benefit.
The operation principle of this detailed description of the invention is: in the waste black liquor that paper mill soda pulping process produces, add the acid pickle of pickling iron and steel, then add Ammonium persulfate. and make catalyst, add sodium superoxide and make initiator, heat above-mentioned material with hot flue gases, in the non-pressure vessel of band stirring, insulation a period of time, make material pass through chemical reaction, generate modified lignin resin, then mix biological inoculum and nitrogen, phosphorus, potassium adjuvant, i.e. can get sponge fertilizer.
The above, only in order to technical scheme to be described and unrestricted, other amendment or equivalent that technical scheme is made by those of ordinary skill in the art, without departing from the spirit and scope of technical solution of the present invention, all should contain in the middle of scope of the presently claimed invention.
Claims (5)
1. the method that a pickle liquor and waste wood quality produce sponge fertilizer, it is characterised in that the main production raw material of the present invention comprises pickle liquor and waste wood quality, and its concrete production method step is:
(1) waste black liquor that Alkaline Pulping is produced, in the solid of waste black liquor, Organic substance accounts for more than 2/3rds (weight ratios), first waste black liquor is put in the heating of band passageway the uncovered equipment of normal pressure with agitator, then, adding pickling iron and steel acid pickle under constant agitation in waste black liquor, addition is the 5-10% (percentage by weight, as follows) of waste black liquor；
(2) under agitation, adding Ammonium persulfate. powder in waste black liquor, addition is the 0.5-0.9% of waste black liquor amount；
(3) then, adding sodium superoxide powder under agitation in waste black liquor, addition is the 0.03-0.06% of waste black liquor amount；
(4) under continuing stirring condition, by the flue gas of heat, above-mentioned waste black liquor is gradually heated up, makes temperature of charge 98-102 DEG C, react 20-25 minute, the methoxyl group mass fraction of the modified lignin resin in waste black liquor can be made to be reduced to about 12% by original 18%；Oxidisability electrolyte and the reaction of waste wood quality, generate similar foam product；
(5) then, above-mentioned material is put in the container of another band stirring, at normal temperatures and pressures, add appropriate biological inoculum and carbamide, MAP, potassium chloride adjuvant, after mix homogeneously, pack with Plastic Drum, prepare sponge fertilizer.
The method that a kind of pickle liquor the most according to claim 1 and waste wood quality produce sponge fertilizer, it is characterised in that the pickling iron and steel acid pickle added described in step (1), sulfur acid 6-8%, ferrous sulfate 7-9%.
The method that a kind of pickle liquor the most according to claim 1 and waste wood quality produce sponge fertilizer, it is characterised in that the pickling iron and steel acid pickle added described in step (1), hydrochloric 7-9%, chloride containing ferrous iron 25-33%.
The method that a kind of pickle liquor the most according to claim 1 and waste wood quality produce sponge fertilizer, it is characterized in that the Ammonium persulfate. added described in step (2) is technical grade certified products, chemical formula (NH4) 2S2O8, molecular weight 228.19, colourless or white crystalline powder, quality standard: ZB/TG12021-90, technical grade seconds, containing Ammonium persulfate. >=95.0%, iron content (Fe)≤0.004%, containing heavy metal (in terms of Pb)≤0.005%, aqueous≤0.3%.
The method that a kind of pickle liquor the most according to claim 1 and waste wood quality produce sponge fertilizer, it is characterized in that the sodium superoxide added described in step (3) is technical grade certified products, chemical formula NaO2, molecular weight 54.99, yellow crystalline powder, quality index is: containing effective oxygen >=35.5%, containing calcium oxide=3.5 scholar 0.5, carbonated≤1%.
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| CN201610274485.2A CN105936602A (en) | 2016-04-28 | 2016-04-28 | Method for producing sponge fertilizer from pickling waste liquid and waste lignin |
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| CN201610274485.2A CN105936602A (en) | 2016-04-28 | 2016-04-28 | Method for producing sponge fertilizer from pickling waste liquid and waste lignin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107287585A (en) * | 2016-03-31 | 2017-10-24 | 深圳市志邦科技有限公司 | A kind of environmentally friendly Bluing in Normal Temperature method of steel |
| CN107652070A (en) * | 2017-11-06 | 2018-02-02 | 张培栋 | Ecological sponge fertilizer is produced with the Chinese medicine slag treatment of wastes with processes of wastes against one another |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475406A (en) * | 2009-01-13 | 2009-07-08 | 温奕区 | Method for producing thick slurry fertilizer from industrial waste organic based on the concept of 'using waste to control waste' |
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2016
- 2016-04-28 CN CN201610274485.2A patent/CN105936602A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475406A (en) * | 2009-01-13 | 2009-07-08 | 温奕区 | Method for producing thick slurry fertilizer from industrial waste organic based on the concept of 'using waste to control waste' |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107287585A (en) * | 2016-03-31 | 2017-10-24 | 深圳市志邦科技有限公司 | A kind of environmentally friendly Bluing in Normal Temperature method of steel |
| CN107652070A (en) * | 2017-11-06 | 2018-02-02 | 张培栋 | Ecological sponge fertilizer is produced with the Chinese medicine slag treatment of wastes with processes of wastes against one another |
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Application publication date: 20160914 |