WO2012016394A1

WO2012016394A1 - Silicon-calcium-magnesium-sulfur fertilizer and its preparation method

Info

Publication number: WO2012016394A1
Application number: PCT/CN2010/077699
Authority: WO
Inventors: 赵慧生; 彭印章; 王素霞; 赵吉锁; 李荣田; 戴宝东
Original assignee: 遵化市励拓环保科技有限公司
Priority date: 2010-08-05
Filing date: 2010-10-13
Publication date: 2012-02-09
Also published as: CN101891521A

Abstract

Silicon-calcium-magnesium-sulfur fertilizer and its preparation method are provided. The fertilizer is in a form of powder or granule and comprises Si > 9, Ca > 14, Mg > 1.5, S > 0.1, Fe > 1.6, and Mn > 0.1 % by weight, and has a pH value of 5.0-8.0. The preparation method comprises (1) selecting steel slag, blast furnace slag, iron-melting furnace slag, iron alloy slag, nonferrous metal slag and fly ash as raw materials, and determining the proportions of said raw materials, (2) mixing them, (3) treating the mixture with sulfuric acid, nitric acid, phosphoric acid and hydrochloride acid, and (4) processing into a form of powder or granule. Said silicon-calcium-magnesium-sulfur fertilizer has advantages of wide adaptability to soils, significant crop yield-increasing effect, simple preparation process, rich raw materials and low production cost.

Description

Silicon calcium magnesium sulfur fertilizer and preparation process thereof

Technical field

The invention relates to a method for producing slag fertilizer by using metallurgical industrial solid waste and related industrial waste as raw materials, in particular to a silicon calcium magnesium sulphur fertilizer and a preparation process thereof. Background technique

1. Development and production of domestic steel slag fertilizer.

Domestic research on slag fertilizer is mainly based on single slag, which is basically not treated by chemical methods, mainly based on the following steel plants:

In 1958, the Institute of Forestry Soils of the Chinese Academy of Sciences studied steel slag in Anshan Iron and Steel Co., Ltd. It is clarified that slag has increased yield in corn, sorghum, rice and cotton in various soils.

In 1980, Yangquan Steel Plant proposed (blast furnace gas ash composite trace element fertilizer) to increase production of vegetables, fruits, corn and rice, and improved the quality of agricultural products.

In 1987, the converter steel slag of Wuyuan Steel Plant was directly processed by physical processing to produce agricultural fertilizer (only suitable for acidic soil). Increase rice, barley, and sweet potatoes, and improve soil.

In 2005, Baosteel's new results of using liquid steel slag to add other elements to process long-acting fertilizers were successfully tested. After the potato planting test, the crop growth was "high" and the harvest increased by more than 15%.

On November 19, 2008, TISCO signed a letter of intent for cooperation with Harsco Group of the United States. The two parties will jointly establish a steel slag tailings treatment and utilization company, and use the world's most advanced treatment technology and management concept to comprehensively utilize steel slag. The main products are cement additives, agricultural fertilizers and fertilizers for golf course lawns.

2. Development and production of foreign steel slag fertilizer.

Foreign countries use metallurgical slag to produce agricultural fertilizer for a long time, many methods: adding materials and chemical treatment in steel slag. (1) Adding materials to the steel slag to make fertilizer.

Soviet Union SU 15404277 added an additive to the molten steel slag for oxygen blowing. After cooling, the upper surface is enriched in phosphorus, and the lower liquid is enriched in iron oxide, which enriches phosphorus to 21.5 % (P ₂ 0 ₅ ).

Brazil BR 8903714 will? , Si, Mg, K mixture, using oxygen to blow into the 1200 ° C residue to make fertilizer.

Belgian BE895197 mixes steel slag with natural phosphate, 20-80% slag, phosphate, aluminate, calcium phosphate 10-40% by water treatment to form H ₃ P0 ₄ , so that the sediment reaches 10-30% (P ₂ 0 ₅ ).

(2) Coordinating ingredients to make fertilizer through ingredients.

曰本J 61170525 blast furnace dust 50kg, CaS0 ₄ · 2H ₂ 0 7kg, slag 500kg mixed cooling is the fertilizer.

East Germany DL261145 lean phosphorus steel slag sludge, converter furnace tumor and dolomite, mixed proportion of Ca, Mg, P fertilizer.

(3) Adjusting the slag fertilizer through the smelting process

曰本J56127717 low silicon pig iron de-S, P plus CaCl ₂ and CaF ₂ to prevent phosphate from becoming an insoluble salt, without hindering the removal of S, P and reducing the melting point of the slag, so as to separate from the molten iron as soon as possible, soluble phosphoric acid Salt is an excellent fertilizer.

British GB1179246 converter steelmaking, by improving the oxygen top blowing, increasing the P content in the slag to obtain alkaline slag fertilizer.

(4) Fertilizer production by chemical treatment.

The hydrated oxide of vanadium in the DE3006264 slag of West Germany, the vanadium salt is leached by the carbonate, and the V ₂ 0 ₂ solution is obtained, and the phosphate fertilizer is obtained.

曰本J01168791 turf soil change agent is to add fertilizer 1-30%, add acid and acid materials 0.5-5%, add mineral humus 1-30%, put the drum and then add polyvinyl acid, The hydroxy cellulose is mixed for 3 minutes and packaged. Summary of the invention

The invention aims to provide a silicon-calcium-magnesium-sulfur fertilizer which has wide adaptability to soil, can be used as a raw material of compound fertilizer, has simple production process, low cost, no solid-liquid gas, and a preparation process thereof.

The technical solution adopted by the present invention is:

A silicon-calcium-magnesium-sulfur fertilizer, which is mainly prepared by using a mixture of steel slag and blast furnace slag and iron slag slag as raw materials, and is prepared by acid-base chemical reaction. The chemical composition thereof contains: at least 9% by weight. Si, at least 14% Ca, at least 1.5% Fe, at least 1.5% Mg, at least 0.1% S, at least 0.1% Mn; pH 5.0 to 8.0.

Preferably, the raw material further comprises one or a combination of two or more of iron alloy slag, non-ferrous metal slag and fly ash.

Preferably, the above-mentioned silicon calcium magnesium sulfur fertilizer has a powder form or a granular form, and has a particle size of 0.15 mm in the form of a powder and a particle size of 0.5 mm to 1 mm in the form of particles.

The preparation process of the above silicon calcium magnesium sulfur fertilizer is carried out as follows:

a. Ingredients: chemistry containing at least 9% Si, at least 14% Ca, at least 1.5% Fe, at least 1.5% Mg, at least 0.1% 8, and at least 0.1% Mn in the silicon calcium magnesium sulphur fertilizer. Component requirements, selection of steel slag, blast furnace slag, iron slag, iron alloy slag, non-ferrous metal slag and fly ash in the raw materials;

b. Mixing: After the steel slag is removed, it is crushed, iron-removed and ground to the required specifications, and then mixed into the mixing machine. After the other slag is removed, it is crushed and ground to the required specifications and then mixed into the mixing machine. , the fly ash is directly mixed into the mixer and mixed with the slag;

c. Acid treatment: Step b The mixture is added with an acid treatment agent for acid-base chemical reaction treatment. The amount of the acid treatment agent is added according to the final pH value of the silicon-calcium-magnesium sulphur fertilizer semi-finished product of 5.0 to 8.0. Acid-base chemical reaction The temperature is controlled between 25 and 60 ° C, and the acid treatment agent comprises sulfuric acid, nitric acid, phosphoric acid and hydrochloric acid;

d. Ingredient granulation: The silicon calcium magnesium sulphur fertilizer semi-finished product obtained in step c is processed into a powdery finished product, granules Degree 0.15mm; or processed into a granular finished product, the particle size is 0.5mm - lmm.

Preferably, the acid treatment agent is prepared by mixing in the following proportions: 40 to 60% of sulfuric acid, 20 to 30% of nitric acid, 10 to 15% of phosphoric acid, and 10 to 15% of hydrochloric acid.

Compared with the prior art, the outstanding features of the present invention are: mixing fertilizers with various slag materials, and preparing raw materials according to soil characteristics, and the prepared fertilizer contains at least 9% Si and at least 14% Ca. At least 1.5% Fe, at least 1.5% Mg, at least 0.1% S, and at least 0.1% Mn, thereby enabling crops to increase production after application of the silicon calcium magnesium sulfate fertilizer of the present invention; by specific chemical treatment It is converted into soluble salt, which greatly enhances the effective plant nutrients for plant absorption. The acid treatment agent used in the chemical treatment uses a mixture of sulfuric acid, nitric acid, phosphoric acid and hydrochloric acid, so that the prepared fertilizer contains a certain amount of crops needed for growth. The N, P, K and other elements can not only achieve the purpose of increasing crop yield, but also greatly improve the quality of the plant fruit and improve its taste, while also greatly improving the disease resistance and lodging resistance of the plant.

The invention makes 100% metallurgical solid waste treatment feasible, and the produced silicon calcium magnesium sulfur fertilizer has wide adaptability to soil, and can be used as raw material of compound fertilizer; the production process is simple, the source of raw materials is sufficient, and the production cost is low. , will not produce solid waste gas, three waste, will not cause secondary environmental pollution. The following table is a statistical table for the yield increase effect of the silicon calcium magnesium sulphur fertilizer crop of the present invention, and the yield increasing effect is obvious.

detailed description

The invention is described in detail below with reference to the examples.

The preparation process of the silicon calcium magnesium sulfur fertilizer according to the embodiment includes the steps of raw material preparation, mechanical processing, chemical processing and compound granulation, and the details are as follows:

Raw material preparation: Table 1 shows the four different raw material formulations of silicon calcium magnesium sulfur fertilizer. Table 2 shows the chemical composition and pH value of the four silicon calcium magnesium sulfur fertilizers.

The machining process is carried out as follows:

After the steel slag removes the bricks and debris, enters the jaw crusher → removes the iron from the iron remover in the belt conveyor, and then removes the iron after the roller mill is removed → the goal mill is machined → processed to the required specifications → ( < 0.15mm ) → Final iron removal → pneumatic conveyor → silo (weight) → spiral mixing mixer.

After the other slag removes bricks and debris, enters the jaw crusher → belt conveyor → sends the roller mill to the goal mill → processes to the required specifications → ( < 0.15mm ) → pneumatic conveyor → silo Heavy) → spiral mixing mixer.

Fly ash → belt conveyor → silo (weight) → spiral mixing mixer.

Chemical processing: Table 3 shows the proportion of acid treatment agent, the ratio of acid treatment agent is satisfied: 40 ~ 60% sulfuric acid, 20 ~ 30% nitric acid, 10 ~ 15% phosphoric acid, 10 ~ 15% hydrochloric acid. The pH value of the semi-finished products of silicon calcium magnesium sulphur fertilizer is controlled within the range of 5.0 ~ 8.0. The chemical processing is carried out as follows:

Dispose of acid treatment agent → container (weight) → spiral stirring mixer (adding acid-base catalyst) → chemical treatment container, chemical treatment for 24-72 hours, acid-base chemical reaction temperature is controlled between 25 ~ 60 °C, After sufficient reaction (decomposition, hydrolysis, complex phase) → dryer → silicon calcium magnesium sulfur fertilizer (semi-finished product).

The granulation of the ingredients is carried out as follows:

Powdered product: Silicon calcium magnesium sulfur fertilizer (semi-finished product) → Mill, grinding to 0.15mm particle size → After passing the inspection → Metering packaging. Granular finished product: Silicon calcium magnesium sulfur fertilizer (semi-finished product) → Mill, 0.15mm particle size → granulator (0.5 -1.0mm), after passing the inspection → metering packaging.

The 1#, 2#, 3#, 4# silicon-calcium-magnesium-sulfur fertilizers prepared according to the above steps were tested in different regions and different crops in Hebei. The test results are shown in Table 4. The test results are remarkable. Table 1 Component Steel slag ί blast furnace, iron slag slag iron alloy slag 1 non-ferrous metal slag fly ash

1 50 15

20% 10% 5%

# % %

2 60 20

20% 0 0

# % %

3 65 10

20% 0 5%

# % %

4 75

25% 0 0 0

# %

The blast furnace and iron slag slag described in Table 1 refers to the mixing of blast furnace slag and iron slag slag in any weight ratio.

. Since the composition of the blast furnace slag and the iron slag are similar, they have the same function in the raw materials, and they can be used alone or in combination.

2

Note: The harmful elements of As, Cd, Hg, Cr and Pb are not listed in Table 2 and are in compliance with national standards. table 3

Component sulfuric acid nitric acid i hydrochloric acid treatment agent 1# 50% 25% 1 15% 10% acid treatment agent 2# 45% 1 25% 15% 15% Note: (1) acid treatment agent 1# treatment 1#, 3 #原料; Acid treatment agent 2# Process 2#, 4# raw materials.

(2) The acid treatment agent concentration is 35%. Table 4

Claims

Claim

A silicon-calcium-magnesium-sulfur fertilizer characterized in that it is prepared by chemically reacting a mixture of blast furnace slag and iron-iron slag in arbitrary ratio with steel slag as a raw material, and chemical composition thereof by weight percentage Containing: at least 9% Si, at least 14% Ca, at least 1.5% Fe, at least 1.5% Mg, at least 0.1% S and at least 0.1% Mn; pH 5.0 to 8.0.

The silicon-calcium-magnesium-sulfur fertilizer according to claim 1, wherein the raw material further comprises one or a combination of two or more of iron alloy slag, non-ferrous metal slag, and fly ash.

The silicon calcium magnesium sulphur fertilizer according to claim 1, wherein the silicon calcium magnesium sulphur fertilizer is in the form of a powder having a particle size of 0.15 mm.

The silicon calcium magnesium sulphur fertilizer according to claim 1, wherein the silicon calcium magnesium sulphur fertilizer has a granular shape and a particle size of 0.5 mm to 1 mm.

A process for producing a silicon calcium magnesium sulfur fertilizer according to any one of claims 1 to 4, characterized in that the following steps are carried out:

a. Ingredients: a chemical composition containing at least 9% Si, at least 14% Ca, at least 1.5% Fe, at least 1.5% Mg, at least 0.1% S, and at least 0.1% Mn in the silicon calcium magnesium sulfur fertilizer. Requirements, selection of steel slag, blast furnace slag, iron slag, iron alloy slag, non-ferrous metal slag and fly ash in the raw materials;

d. granulation: processing the semi-finished silicon calcium magnesium sulphur fertilizer obtained in step c into a powdery finished product, particle size

0.15mm; or processed into a granular product with a particle size of 0.5mm - lmm.

The process according to claim 1, wherein the acid treatment agent is prepared by mixing: 40 to 60% sulfuric acid, 20 to 30% nitric acid, 10 to 15% phosphoric acid, and 10 to 15 hydrochloric acid. %.