WO2001049635A1

WO2001049635A1 - Glass fertilizer and the method for producing the same

Info

Publication number: WO2001049635A1
Application number: PCT/CN2001/000003
Authority: WO
Inventors: Shanmao Zhao; Zhao Zhang; Dazhuang Xiao
Original assignee: Shanmao Zhao; Zhao Zhang; Dazhuang Xiao
Priority date: 2000-01-03
Filing date: 2001-01-03
Publication date: 2001-07-12
Also published as: AU2344001A; CN1142122C; CN1302786A

Abstract

The present invention provides a glass fertilizer and the method for producing the same. The process comprises adding coals and vitrified additives into liquid residual slag boiler and burning at high temperatures to obtain a random network body melting glass slurry, quenching the glass slurry with water, drying and grinding, therefore obtaining a powdered glass fertilizer. The process doesn't need too much cost and doesn't make any pollution. According to crop-soil-body multiple needs, adjusting the glass fertilizer's formula to optimize manuring. The glass fertilizer produced by the process is an excellent fertilizer, and on the other hand the process is one of the complex utilization methods of coal slag.

Description

TECHNICAL FIELD The present invention relates to a compound fertilizer, and particularly to a functional glass trace element fertilizer (glass fertilizer for short) that is directly converted from coal ash slag and a method for manufacturing the same. BACKGROUND In normal growth of plants, in addition to absorbing proper amounts of nitrogen, phosphorus, and potassium, medium elements (Ca, Mg, Si, S, etc.) and trace elements (B, Zn, Mo, Cu, Co, Mn, Fe, etc.), these medium and trace elements are also indispensable to the human body. In the 1960s, since the effects of trace elements on plant growth were discovered, many countries have paid more and more attention to the research on the effects and application of trace elements, and produced a variety of trace element compound fertilizers, one of which is glass fertilizer. At present, the main method of producing glass fertilizer is the blast furnace method, and a single glass fertilizer containing zinc, iron, manganese and molybdenum has been produced. This method can produce functional glass fertilizer required for plant growth and human health, but has the following disadvantages: (1) high energy consumption, which consumes about 310Kg of coke per ton _; (2) high consumption, which consumes about 1160 ~ 1300Kg of ore per ton ; (3) severe pollution, due to the high temperature combustion, flue gas into the atmosphere not only NOx, SO ₂ is high, and CO is high; (4) high costs, costs while polluting manure produced per ton of about 1000 If the equipment for denitrification, desulfurization, and CO removal is added, the cost will be as high as about 1,500 yuan, so it is difficult to promote the application of this method. SUMMARY OF THE INVENTION The object of the present invention is to overcome the shortcomings and disadvantages of the prior art, and to provide a glass fertilizer with low cost, no pollution, and containing a variety of elements required by the human body, especially a variety of trace elements. The main technical solutions of the present invention are as follows: A kind of glass fertilizer using coal ash slag as its raw material, its main components include:

CaO 20-40% MgO 3.5-20% CaO + MgO ^ 35%

SiO ₂ 35-50% Α1 ₂ Ο ₃ 3-25% MnO 0.1-3%

ZnO 0.1-2% CuO 0.1-1.5% MoO ₃ 0.01-0.2%

Fe, O, 2-15% P ₂ O, 0.1-2% K _? O 0.1-4.0%, other B, S, F, Na ₂ O are micro: which may further include CoO, Cr ₂ O ₃ SnO ₂ , The content of NiO and V ₂ O ₅ are both 0.001 ~ 2%. A method for preparing glass fertilizer using coal ash slag as a raw material includes:

a. Add coal and vitrification additives to a liquid slagging boiler for combustion at the same time to generate an irregular network of molten glass slurry;

b. Process the glass slurry obtained in step a into powdery glass fertilizer. The vitrification additive described in step a is selected from the group consisting of phosphogypsum, serpentine, forsterite, limestone, quartz sand, silica, dolomite, and magnesite. Wherein step a further comprises the simultaneous addition of manganese, zinc, copper, molybdenum, chromium, tin, nickel-

Detailed description of the invention The composition and content of the glass fertilizer of the present invention (based on glass fertilizer as 100):

CaO 20-40% MgO 3.5-20% CaO + MgO ^ 35%

SiO ₂ 35-50% Α1 ₂ Ο ₃ 3-25% MnO 0.1-3%

ZnO 0.1-2% CuO 0.1-1.5% MoO, 0.01 ~ 0.2% Fe ₂ O ₃ 2-15% P ₂ O ₅ 0.1-2% K ₂ O 0.1-4.0%

The content of CoO, Cr ₂ O ₃ , SnO ₂ , NiO, V ₂ O ₅ is 0.00 2%, and other B, S, F, and Na ₂ O are trace amounts. The specific preparation method of the glass fertilizer of the present invention:

a. Coal, vitrification additives, and functional additives are added to the liquid slagging boiler at the same time, and burned at 1700 ~ 180 ° C to generate an irregular network of molten glass slurry and flue gas. The flue gas is discharged and treated separately;

b. The glass slurry flowing out of the combustion chamber in step a is first quenched and quenched with water, and then dried to a moisture content of less than 0.5%, and finally ground into a powder to obtain the desired finished product; the vitrification additive described in step a It is selected from ores such as phosphogypsum, serpentine, forsterite, limestone, quartz sand, silica, dolomite, magnesite, etc., and the amount is added to ensure that the liquid ash discharged from the boiler is a frit paddle with an irregular network, For specific requirements, please refer to the patent application No. 99121791.2; The functional additive described in step a includes ore containing manganese, zinc, copper, molybdenum, chromium, tin, nickel, and vanadium. The added amount should meet the following technical conditions. :

(1) The amount of phosphate fertilizer required for the fertilizer supply area F (hectares) is basically equal to the amount of phosphate fertilizer produced by burning 1 ton of coal with sulfur slag in a liquid slagging boiler;

(2) The amount of citrate-soluble CaO, MgO, SiO ₂ and CoO required for the fertilizer supply area F is less than or equal to the amount of functional glass fertilizer that should be produced for each ton of coal burned by the boiler and its CaO, MgO, The product of the concentration of SiO ₂ and CoO, that is, the amount of CaO, MgO, Si0 ₂ , CoO (citrate-soluble) contained in the functional glass fertilizer G that should be produced per ton of coal is greater than or equal to the citrate-soluble CaO required by F hectares of farmland each season , MgO, SiO ₂ , CoO. The calculation is as follows:

i) The amount of functional glass fertilizers to be produced per ton of coal determined by technical conditions 1, 2 determines the concentration of trace element oxides in the glass after ash slag vitrification; this concentration is called the glass functional concentration The technical requirement for this concentration is that each trace element oxide is in glass The product of the functional concentration and the amount of functional glass fertilizer that should be produced per ton of coal is greater than or equal to the amount of fertilizer required for this elemental oxide by the crops per ton of coal (F ha). The trace elements of the oxide concentration include manganese, zinc, copper, molybdenum, chromium, tin, nickel, and vanadium. For areas polluted by heavy metals, only manganese, zinc, copper and molybdenum can be identified.

ii) the concentration of functionalized trace element oxides determined by i) to determine the amount of trace element ore to which functional additives should be added per ton of coal to produce functional glass fertilizers,

^J P ₁ O _i * ^A / ¾o ₅ ' ^Λ "(1) In the formula: G — field test to determine the amount of phosphate fertilizer to be applied per hectare (calculated as P ₂ O ₅ , Kg / Ha), which varies by crop and soil But different.

^^ A boiler adopts the invention patent "Comprehensive Utilization Method of Boiler Flue Gas" (Patent Application No. 99127191 · X) The amount of dry-based phosphogypsum (Kg / Kg) emitted by IKg P ₂ O ₅ per ton of coal after conversion of sulfur cycle .

X ¹ —The amount of dry-based phosphogypsum (kg / ton of coal) should be added as an additive for each ton of coal determined by vitrification and functionalization of ash. This number is described in the patent number 99127191.2. From the area of fertilizer supply per ton of coal determined above, the amount of functional glass fertilizer that should be produced per ton of coal can be determined as follows:

G _P ^F _L = FG ^ ₀ / CoO--(2) where: the weight of functional glass fertilizer (kg / ton of coal) should be produced per ton of coal.

G ^. —The amount of citrus soluble cobalt oxide (kg / Ha) should be applied per hectare determined by farmland tests, which varies with soil and crop.

CoO—The concentration (%) of cobalt oxide in the glass frit of the random network body by coal and other additives in the functional glass fertilizer without the addition of cobalt ore, which is equal to:

CoO = (1000 Aar X ^ _o0 + X ¹ X ' _Co0 + X ² X _o0 + ······ χ ¹⁴ Χ ^ _ο + Χ ¹⁵ Χ ^ _ο ) / 0 _Ρί = = (1 OOOAar X ^ .. + ∑ X ^J X |, _o0 ) / G _PL … one (3) where: Aar, X ^. . One is the coal ash content received by the coal, and the cobalt oxide concentration in the ash content (%, pay attention to the absolute value below the decimal point when calculating, such as 35% is 0.35).

X ^j 、 X ^ _O0 (J = 2, -14, 15) —Add the additive phosphogypsum for each ton of coal in turn

(Dry basis) (X ', X ^), serpentine or forsterite (X ² , X _C ² _o0 ) limestone (X ³ ,

X ³ _CoG ), quartz sand or silica (X ⁴ , X ⁴ _C ...), dolomite or magnesite (X ⁵ , X.), manganese ore (X ⁶ , X ⁶ _Co0 ~), zinc ore (X ^{^{_{_{7, X 7 C. 0)}}}} , copper ore ^{(Χ 8, Χ ^.)} , molybdenum ores ^{^{_{(χ 9, x 9 c ..}}} ), chrome ore ^{^{(x 10, x 1 ^)}} , cassiterite (x " , X ¹ ), nickel ore (x ¹² , n _Co0 ), vanadium ore (x ¹³ , xo, selenium-rich coal or ore (X ", X ^l _c ⁴ _a0 , germanium-rich coal or ore (X ¹⁵ , X ^ ...) The amount of addition X ^j (kg / ton of coal) and its percentage concentration of cobalt (%). The percentage calculation should be converted to a decimal. For example, the amount of zinc ore added per ton of coal is 7 kg X ⁷ = 7, zinc oxide contains 0.01% of cobalt and X ⁷ _C is 0.0001.

—The amount of random network glass frit (kg / ton of coal) formed per ton of coal ash slag and additives, which is equal to:

G _PL = 10000 Aar (1 -a _z ) + X ^J (1- X ^J _Z ) ------- (4) where: a _z — coal ash residue at 170 (TC loss (%)), when calculating Converted to decimals.

—The burning loss (%) of the J additives Π00Ό, respectively. Converted to decimals when calculating. For example, if the loss of zinc ore is 50%, the calculation time is 0.5. After determining F, G _P ^F _L > G _P L through the above formula, the trace element ore addition amount XJ (J = 6 ~ 13) is calculated, and the calculation formula is:

f _{) = (F l000Aarm-χ-}

)

X Χ (Π .. (= 1_15) (5) where: X'—in turn, are phosphogypsum, serpentine or forsterite, limestone, quartz sand or silica, dolomite or magnesite, manganese ore, Addition of zinc ore, copper ore, molybdenum ore, chromium ore, tin ore, nickel ore, vanadium ore. X _m0n (j-6-13) is the concentration of the Jth oxide in i ore (j = 6-13), namely manganese oxide, zinc oxide, copper oxide, molybdenum oxide, chromium oxide, tin oxide, nickel oxide Vanadium oxide concentration (%).

- adding the homogeneous forces Π IJ X '(i = l- 16) containing items oxide J _{_{_{(J m O n = i m}}} O n (j = I = 1 16).) Concentration (% :). i = l-5 are CaO, MgO, SiO ₂ , A1 ₂ 0 ₃ , Fe ₂ O ₃ (FeO); i = J = 6-13 are MnO, ZnO, CuO, MoO ₃ , and Cr ₂ 0 respectively. ₃ , SnO, NiO, V ₂ O ₅ ; 1 = 14-16 are SeO ₂ , GeO, and CoO, respectively. H _m ^a . _n —I _m O _n (J = i = 1 1-16) fertilizing amount of soluble citrus fertilizer (Kg / Ha) determined for farmland experiments. Through the above five formulas and their corresponding test data, the amount of trace elements added can be calculated. Obviously, this is a method feature in the manufacture of functional glass fertilizers (Mr. Claus is right, it should be written in the power requirements Go). However, it should be noted that when the agricultural crop is rice, which has a large demand for SiO ₂ (ie, G _m ^a . _N ) and the cobalt content in the sulfur zinc ore and sulfur copper ore is very large, the cobalt ore is not calculated at this time. The number of G _P ^F L may not be large enough to cause insufficient SiO2.

G _P ^F _L · SiO ₂ <F ·, (6) At this time, G _p ^F _t should use the silica concentration percentage SiO ₂ determined after vitrification of ash to determine the amount of functional glass fertilizer that should be produced per ton of coal. Genkou:

G _P ^F _L = F · / SiO ₂ (7)

Where G _P ^F — functional glass fertilizer (kg / ton of coal) should be produced per ton of coal determined by the SiO ₂ concentration in the glass:

₈₁₀₂ amount (Kg / Ha) should be applied per hectare field trials determined Citrate Soluble

Another technical feature of functional glass fertilizer is that the ratio between the concentration of each functional element is similar to the element ratio in plants, that is:

Ca: Mg: Mn: Zn: Cu: Mo «0.6: 0.3: 0.02: 0.05: 0.01: 0.005 (8) The functionalized concentration is the concentration after the addition of the trace element ore, and the concentration before the addition is the glass transition concentration. The concentration is formed by the trace elements carried by the coal and the glass transition additive. The functionalized glass gains as follows: The weight of trace element ore after deducting the loss of burning into the glass. In the past, the trace elements required for plant growth were mainly supplied by soil or water. Therefore, it is easy to cause trace element imbalances. As a result, the variety of trace elements required by humans from food is incomplete, and the quantity or proportion is imbalanced. And human beings have certain requirements for each nutrient element. Excessive amounts will poison crops and the human body, and lack of them will also cause functional diseases, such as corn deficiency, white bud disease, tobacco manganese deficiency, chlorotic necrosis of leaves, and human deficiency. Magnesium causes leukemia, manganese deficiency causes lung cancer, zinc and copper deficiency can cause heart disease, dementia, male infertility, dwarf, and molybdenum deficiency can cause esophageal cancer. Now we can use modern analysis methods to supplement the trace element content in the soil and the amount of trace elements required by various plants in the form of the functional glass fertilizer of the present invention to ensure the balance of trace elements required by the plant and make the human body Can get the required nutrients. The water quenching, drying and grinding described in step b are all known methods, that is, the water is quenched from the granulation box below the slagging outlet of the boiler combustion chamber to a granular glass body of less than 10 mm, and then drained in the drain material 3 In ~ 4 hours, the water content is reduced to less than 4%, and then the water content is reduced to less than 0.5% by air drying. Finally, the conventional silicon fertilizer or glass fertilizer grinding technology is used to directly grind the powdered glass fertilizer. The harmful impurities of glass fertilizer meet the international standards for glass silicon fertilizer, that is, nickel, chromium, and titanium are less than 0.06%, 6%, and 3% (based on effective SiO ₂ ). The functional glass fertilizer of the present invention is suitable for use as a base fertilizer with NPK fertilizer. BEST MODE FOR CARRYING OUT THE INVENTION The present invention is further described below with reference to specific examples. This embodiment uses a horizontal cyclone furnace with a slag catching rate of 85%; the coal burning is China Taiyuan Coal. The calorific value is 25600Kj / Kg, the base ash content of coal is 21.48%, and the loss on ignition rate is 0.4%. After testing, the ash removal rate is 5%, and the fly ash remelting rate is 11.76%. 1. See Table 2 for the amount of additives and chemical composition. The experiment adopts a sulfur cycle invention patent ("Boiler Flue Gas Comprehensive Utilization Method" Application No.

99217191.2) technology, only functional additives need to be added, the amount of addition is shown in Table 2, the obtained glass slurry is water-quenched, dried, and ground to obtain the required functional glass fertilizer, and its chemical composition is shown in Table 3. The glass fertilizer of the present invention is mixed with NPK fertilizer to be used as a base fertilizer for planting rice. The soil element content in the paddy field is shown in Table 4. The fertilizer application rates of NPK + functional glass fertilizer and NPK ternary compound fertilizer are shown in Table 5 respectively. And Table 6. The NPK fertilizer label in Table 5 is N: P ₂ O ₅ : K ₂ O 14: 8: 6; please refer to the “Chinese Fertilizer Handbook” for the percentage content of the crop. The “Proportion” column is based on N = 2, such as fertilizer The content of P in A is 91.7Kg / Ha.

^ = 0.51

357 and so on; the column of "Comparison △" in Fertilizer B is the ratio in Fertilizer B-the percentage content of the crop. For example, the "Comparison △" of P in Fertilizer B is 0.52-0.5 = + 0.02, and the "Comparison △" in K "Is 0.74- 1. 5 =-0.76, and so on. It can be seen from Table 6 that human rice does not suffer from functional diseases such as Ca, Mg, Mn, Zn, Cu, Mo, Co, Sn, Cr, Fe, Ni, V and other elements that are deficient in functional rice. Increased production of functional health rice

6780- 6000 ~ _Γ ,

= l .20Kg

600 main advantages and effects of the present invention: Since the present invention relies on the liquid slagging boiler based on the sulfur cycle technology in the "Method for Comprehensive Utilization of Boiler Flue Gas" with the patent application number of 99127191.2, a glass slurry containing medium and trace elements is obtained and glass fertilizer is produced, so the following effects : (1) China's liquid slagging cyclone manufactures silicon, silicon-calcium-magnesium fertilizers. Because there are no denitration and desulfurization devices, the NOx and sulfide content in the flue gas discharged into the atmosphere is high, and it is a pollution type that does not meet international emission standards. Production and the sulfur cycle technology used in the present invention reduce the dust and laughter emissions from boiler flue gas to zero, reduce NOx by about 97%, and SO ₂ by about 90%, which is clean production; (2) Phosphogypsum The phosphogypsum is partially or completely replaced by the phosphogypsum. The phosphogypsum of the present invention is a by-product of phosphoric acid production in the sulfur cycle process, so the cost can be reduced, and pollution of coal ash slag, phosphogypsum, and pyrite slag can be eliminated, so that tritium emissions can be reduced 95%, which can do more with less; (3) the addition of serpentine, quartz sand, dolomite and other ores increased the silicon and magnesium content and increased the degree of vitrification. This water-quenched granular vitreous body has few crystals and high vitreous content in fly ash, making it more viable as a glass fertilizer. The increase in magnesium content makes the calcium-magnesium ratio more reasonable and the fertilizer efficiency increased. (4) This The method of the invention can determine the content of nutrient elements in glass fertilizer according to the comprehensive needs of crops-soil-human body and adjust its formula to reflect the balanced supply of nutrients in order to achieve the purpose of optimizing fertilization; (5) the boiler combustion of the present invention The glass slurry discharged from the chamber can not only make glass fertilizer, but the excess can also be used as raw material for the production of rock wool, thereby ensuring no ash and slag emissions from the boiler.

Table 1 Properties of Taiyuan coal in China

X-Table 2 Additive amount and chemical composition

Ore Origin Addition Chemical I points,%

kg / T coal CaO MgO si0 ₂ A1 ₂ 0 ₃ Fe ₂ 0 ₃ MnO ZnO CuO? X Mo0 ₃ Lost phosphorous gypsum Liuyang, Hunan 21 1.53 31.28 0.23 9.09 1.87 1.45 53.5 Phosphate ore generation w 0

X "Serpentine Shaanxi 140.34 0.30 39.53 40.1 1 0.66 5.14 6 X 7.5 X 3 X 14.1 1 Heimulin 10— ³ 10— ³ 10— ³ Limestone Funing, Hebei 43.94 53 0.66 3.00 0.63 0.44 6 χ 0.60 7.5 X 3 X 41.5 Camp 10— ³ 10— ³ 10— ³ Quartz sand sea sand 0--99.50------0.5 Dolomite Liaoning Yingkou 63.57 29.50 21.10 1 0.50 1.10 6 χ 0.60 3 X 46.5 Chenjiabao 10- ³ 10 — ³ rhodochrosite, Liaoning Xingcheng 9.66---------60 sphalerite Nanjing 7.76------62.2--37 Qixia Mountain

Sulfur copper mine Jiangxi Dexing 1.94-------62.5-36 Molybdenum concentrate Liaoning 0.18--------60 35 Yang Zunzi Chemical composition of functional glass fertilizer

Table 4 Table of soil element contents (mg / kg)

Table 6 Functional glass fertilizer and NPK ternary compound fertilizer and application

NPK ternary compound fertilizer individual yield and quality comparison table

Item Grain yield Functional element content (mg / kg)

Yield increase Ca Mg Fe Mn Zn Cu Mo Co Amplitude Biological standard value (US standard / Japanese standard)

Kg / Ha% 140/78-/ 1310 8.7 / 13.4 20.1 / 31.5 19.4 / 22.3 2.2 / 3.3 1.6 / 0.42 0.02 / 0.02 Fertilizer A 6000-80 600 8 21 10 1.2 0.20 0.015 Fertilizer B 6780 13 150 1500 15 36 23 3.5 0.80 0.03

Table 5 Comparison of NPK ternary compound fertilizer and (NPK + functional glass fertilizer) fertilizer application rates

Composition of Compound Fertilizers Urea Phosphoric Acid-As Potassium Chloride Functional Glass Fertilizer Regression Rate of Organic Fertilizer (%)

Composition grade N = 46% P ₂ 0 ₅ = 57% ₂ C1 = 60% SeO ₂ = 202PPm; Grain-converted man urinates straw and returns it to the field

N = l l% GeO = 248PPm

Fertilizer A 697 336.5 (N = 37) 263 0 37.5 90

Fertilizer B 697 336.5 (N = 37) 263 600 37.5 90

Fertilization carry element oxides (except N, S, B)

Element and oxygen N PA ₂ 0 CaO MgO FeO MnO ZnO CuO M0O3 CoO BS Si0 ₂ Compound name

Unit Kg / Ha Kg / Ha Kg / Ha Kg / Ha Kg / Ha Kg / Ha Kg / Ha Kg / Ha g / Ha g Ha g Ha Kg / Ha Kg / Ha Kg / Ha Fertilizer A 357 191.8 158 0 0 0 0 0 0 0 0 0 0 0 Fertilizer B 357 194.86 ¾ 160 140 84 7.5 5.3 5.85 1512 150 34.8 0.03 0.18 218.46 Fertilizer quality comparison:

Element name NPK Ca Mg Fe Mn Zn Cu Mo Co BS Si0 ₂ Crop percentage 2 0.5 1. 5 0.6 0.3 0.02 0.05 0.01 0.001 0.0001-0.005 0.5 Rice content 5-10 Fertilizer content 357 91.7 131.12 0 0 0 0 0 0 0 0 0 0 0

A ratio 2 0.51 0.73 0 0 0 0 0 0 0 0 0 0 0 0 fertilizer content 357 93.17 132.78 100 50.17 5.85 4.1 4.70 1.21 0.01 0.0275 0.03 0.18 218.4 material ratio 2 0.52 0.74 0.56 0.28 0.032 0.023 0.026 0.0068 0.0005 0.00015 0.00017 0.001 1.218

B Comparison △ 0 +0.02 -0.76 -0.04 -0.02 +0.012 -0.03 +0.016 +0.0058 +0.0004--0.0046 -0.499 -3.78

Claims

Claim

1. A glass fertilizer using coal ash slag as its raw material. Its main components include:

CaO 20- 40% MgO 3.5 -20% CaO + MgO ^ 35%

SiO ₂ 35- 50% Α1 ₂ Ο _{3 3} ~ '25% MnO 0.1-3%

ZnO 0.1 '-2% CuO 0.1' -1.5% MoO ₃ 0.01-0.2%

Fe ₂ O ₃ 2-15% P ₂ O ₅ 0.1 '-2%

2. The glass fertilizer according to claim 1, further comprising trace amounts of 8 and 8.

3. The glass fertilizer according to claim 1, further comprising CoO, Cr ₂ OO

4. A method for preparing glass fertilizer using coal ash slag as a raw material, comprising:

O

a. Add coal and vitrification additives to a liquid slagging boiler for combustion at the same time to generate an irregular network of molten glass slurry; 0

b. Process the glass slurry obtained in step a into powdery glass fertilizer.

5. The method according to claim 4, wherein the vitrification additive in step a is selected from the group consisting of gypsum, serpentine or forsterite, limestone, quartz sand or silica, dolomite or magnesite.

6. The method according to claim 4, wherein step a further comprises simultaneously adding ore containing manganese, zinc, copper, molybdenum, chromium, tin, nickel, vanadium trace elements.