CN108149010A - Low burn consumption pelletizing binder and preparation method thereof - Google Patents

Abstract

The present invention discloses a kind of low burn consumption pelletizing binder and preparation method thereof, is mixed by sodium-ionized bentonite, modified anti-knock agent, compound carbonaceous reducing agent, native starch, cellulose family macromolecule, thickener.Compared with prior art, low burn consumption pelletizing binder science selection each component provided by the invention, rational proportion forms, and improves pellet quality, improves cracking temperature of green pel let, it reduces blast furnace ironmaking and smelts burnup, make to return mine and significantly reduce, improve rate of reduction, refining coke-iron-rate is greatly reduced, output increased, pelletizing crushing strength are big；The compression strength of ball and finished pellet is not only increased, the full Iron grade of finished ball nodulizing improves more than 1.5%, the economic benefit with apparent energy-saving and production-increase.

Description

Low burn consumption pelletizing binder and preparation method thereof

Technical field

The present invention relates to the bright more particularly to a kind of low burns in the preconditioning technique field for being related to Iron Ore Powder, iron dust containing and sludge Consume pelletizing binder and preparation method thereof.

Background technology

China Steel yield keeps rapid growth for years, becomes world steel big country.Incident environmental protection is asked Topic also becomes increasingly conspicuous, and the pollution of trade waste produced by Iron and Steel Enterprises in China influences location periphery increasingly severely Environment, and start restrict enterprise itself development.Therefore, it eliminates trade waste pollution, realize clean manufacturing, particularly place The trade wastes such as the various dust that reason production each process generates are the weights that China's steel and iron industry keeps sustainable and healthy development from now on Want index.

Steel-making dust, which is freezed off, to form enters back into after type rotary kiln sintered, realizes resource recycling, both reduces environment Pollution, reduces energy consumption, and it is the various dust that will be generated in steel manufacture process to freeze off knot moulding process, and it is appropriate to add Adhesive after mixing, under a certain pressure, makes mixing material by the bulk for pressing to definite shape, size, density and intensity Material consolidates using corresponding low temperature drying (300 DEG C of ＜), makes the agglomerate with higher-strength.The agglomerate can be with The cooling agent of raw material and converter smelting as blast furnace process, the raw material for being also used as direct-reduction and melting and reducing use.

The defects of prior art：It freezes off at present and forms the adhesive that type mainly uses and be divided into bentonite and organic bond, The application of bentonite adhesive is ripe, and price is relatively low, but it burns residual rate height, seriously reduces pellet ferrous grade, increases height The quantity of slag that stove ironmaking is smelted, declines blast furnace coefficient, and burnup rises；Organic bond adhesive effect is good, and dosage is few, but its price Height, using upper immature, it is anti-that fatal defects are that organic binder bond can be aoxidized during the preheating and baking that heats up, be decomposed etc. Should, the thermal stress of generation can destroy preheating spherical structure, cause preheated ball very low, while also bring environmental issue.

Invention content

For solution more than technical problem, the present invention provides low burn consumption pelletizing binder and preparation method thereof, to solve tradition Bentonite adhesive burns residual rate height, reduces pellet Iron grade, increases blast furnace ironmaking and smelts burnup and be difficult in adapt to iron ore original The problems such as requirement of material moisture and balling-up moisture.

The technical solution adopted by the present invention is as follows：A kind of low burn consumes pelletizing binder, and key is by following mass fraction Raw material composition：55-65 parts of sodium-ionized bentonite, modified 1-5 parts of anti-knock agent, carbonaceous reducing agent 3-7 parts compound, native starch 6-15 Part, 10-20 parts of cellulose family macromolecule, 5-8 parts of thickener.

Preferably, the mass fraction of the raw material is：60 parts of sodium-ionized bentonite, modified 4 parts of anti-knock agent, compound carbonaceous reducing agent 6 parts, 12 parts of native starch, 15 parts of cellulose family macromolecule, 7 parts of thickener.

Preferably, the sodium-ionized bentonite is obtained using following methods：Sodium alginate and sodium carbonate are dissolved in water, stirred After mixing uniformly, compound sodium modified solution is obtained；Then the compound sodium modified solution is added to the natural calcium base after grinding swollen In profit soil, mixed serum is obtained after mixing；Dimethyldioctadecylammonium ammonium chloride is added in the mixed serum of gained, is adjusted PH value is saved after 5-7, to be warming up to 70-100 DEG C, at this temperature, add in vinyl alcohol while stirring, is stirred to react 2-4 hours, instead It by reaction product successively drying, crushing and should grind after the completion to get the sodium-ionized bentonite；Wherein, sodium alginate, sodium carbonate Mass ratio with calcium-base bentonite is 3~25：1~8：100.

Preferably, the calcium-base bentonite grind size is less than 0.5mm.

Preferably, the modified anti-knock agent is obtained using following methods：It is 10-18 by mass ratio：50 polyacrylamide Reaction kettle is put into, and add in conditioning agent with magnesium iron sand, the mass ratio of the conditioning agent and magnesium iron sand is 0.5:100, at normal temperatures Stirring, grinds altogether after mixing, obtains the modified magnesium iron sand, and granularity is -0.065mm grade mass fraction >=80%.

Preferably, MgO and Fe in the magnesium iron sand₂O₃Mass fraction be respectively a and b, a >=85%wt, 8%wt >=b >= 12%wt；The conditioning agent is FeCl₃、MgCl₂Or Fe₂(SO₄)₃In one kind.

Preferably, the compound carbonaceous reducing agent is obtained using following methods：It is 50~60 by mass ratio：40~50 oil Burnt and low culm is uniformly mixed to obtain mixed material；Then it will be sequentially added in mixed material and be equivalent to mixed material quality 2% The waterglass of wt~4%wt and the water for being equivalent to mixed material quality 8%wt~12%wt are uniformly mixed, at 50~60 DEG C Stir 2h, discharging；30~50min is dried under the conditions of being again 100~140 DEG C in wind-warm syndrome, the composite carbonaceous reducing agent is prepared.

Preferably, it is respectively 85~90%wt, 55~65%wt carbon content to be fixed in the petroleum coke, low culm.

Preferably, the cellulose family macromolecule is in methylcellulose, carboxymethyl cellulose, hydroxypropyl methyl cellulose One or two；The native starch is cornstarch, potato starch；The thickener is over cure acid, peroxidating Hydrogen.

A kind of preparation method of low burn consumption pelletizing binder, key are to carry out according to the following steps：

Step 1: sodium-ionized bentonite, modified anti-knock agent and compound carbonaceous reducing agent are prepared respectively；

Step 2: the sodium-ionized bentonite obtained in step 1, cellulose family macromolecule, thickener and modified anti-knock agent are added Enter into reaction kettle, be heated to 60~90 DEG C, reaction is mixed, control 300~600r/min of mixing speed, react 30min The mass ratio of sampling plus water progress viscosimetric analysis afterwards, sample and water is 1:1, after its viscosity reaches 5000cp, discharging is mixed Close object A；

Step 3: compound carbonaceous reducing agent, native starch are uniformly mixed to obtain mixture B；

Step 4: the mixture B obtained in the mixture A and step 3 that are obtained in step 2 is added in blender simultaneously After mixing, it puts into and the powder that average grain diameter is 42-74um is ground into grinder, obtain finished product.

Compared with prior art, low burn provided by the invention consumption pelletizing binder science selection each component, rational proportion and Into the advantageous effect with the following aspects：

1st, improve pellet quality, improve green ball strength and burst temperature, improve pelletizing crushing strength and full Iron grade.Calcium Base bentonite is modified jointly by sodium alginate, sodium carbonate and dimethyldioctadecylammonium ammonium chloride, and three is to calcium Synergistic function is generated in base bentonite modifying process.Na⁺It can enter and replace part Ca in ca-montmorillonite crystal layer²⁺, two The double octadecyl ammonium chlorides of methyl will cover the support of flake interlamellar spacing greatly, may advantageously facilitate further being smoothed out for sodium modification；It is special It is not to be chemically bonded between dimethyldioctadecylammonium ammonium chloride and the functional group of alginic acid, in montmorillonite lamella and outside All form organic organic modification for being connected, being conducive to calcium-base bentonite；Pellet can be improved by introducing modified anti-knock agent High temperature metallurgical properties, green ball strength and burst temperature reduce the reduction swellability rate of pellet；Introducing compound carbonaceous reducing agent can carry Refining coke-iron-rate is greatly reduced in high rate of reduction.

2nd, low burn of the invention consumption pelletizing binder is added directly into as a kind of starchy binder in iron ore raw material, is bonded Agent energy sticking large quantity of moisture, thus the suitable upper limit of the binding agent to iron ore raw material moisture is improved, it is thrown so as to reduce drying equipment Provide cost and drying process energy consumption.

3rd, the low burn consumption pelletizing binder dosage that prepared by the present invention is accounted in the range of iron ore butt quality 0.3~0.8%, green-ball Free-electron model intensity for 8~12 times/1m, burst temperature is more than 650 DEG C, and preheated pellets compression strength is more than 450N/ or more, Agglomerates compression strength reaches 2500N/ or more, and the full Iron grade of finished ball nodulizing can improve more than 1.5%.

Specific embodiment

For those skilled in the art is made to be better understood from technical scheme of the present invention, with reference to subordinate list and specific embodiment party Formula elaborates to the present invention.

Embodiment 1：A kind of low burn consumes pelletizing binder

By low burn consume pelletizing binder in each raw material the mass fraction as described in table 1 mixes respectively, obtain 3 groups of differences and mix Low burn consumption pelletizing binder I~III of composition and division in a proportion example.

The low burn consumption pelletizing binder of 1 different mixing proportion of table (mass fraction)

Embodiment 2：Low burn consumes the preparation of pelletizing binder

Step 1: the preparation of sodium-ionized bentonite：Sodium alginate and sodium carbonate are dissolved in water, after stirring evenly, obtained Compound sodium modified solution；Then the compound sodium modified solution is added in the natural calcium-base bentonite after grinding, the calcium Base bentonite grind size is less than 0.5mm, obtains mixed serum after mixing；Dimethyl is added in the mixed serum of gained Double octadecyl ammonium chlorides adjust pH value after 5-7, to be warming up to 70-100 DEG C, at this temperature, adding in ethylene while stirring Alcohol is stirred to react 2-4 hours, by reaction product successively drying, crushing and grinding to get the sodium swelling after the completion of reaction Soil；Wherein, the mass ratio of sodium alginate, sodium carbonate and calcium-base bentonite is 3：1：100.

The preparation of modified anti-knock agent：It is 10 by mass ratio：50 polyacrylamide and magnesium iron sand input reaction kettle, and add in FeCl₃, FeCl₃Mass ratio with magnesium iron sand is 0.5:100, it stirs, grinds altogether after mixing at normal temperatures, obtain the modification Magnesium iron sand, granularity are -0.065mm grade mass fraction >=80%；MgO and Fe in the magnesium iron sand₂O₃Mass fraction difference For a and b, a >=85%wt, 8%wt >=b >=12%wt.

The preparation of compound carbonaceous reducing agent：It is 50 by mass ratio：40 petroleum coke and low culm are uniformly mixed to obtain mixture Expect, it is respectively 85~90%wt, 55~65%wt to fix carbon content in the petroleum coke and low culm；It then will be in mixed material It sequentially adds the waterglass for being equivalent to mixed material quality 2%wt~4%wt and is equivalent to mixed material quality 8%wt~12% The water of wt is uniformly mixed, and is discharged after stirring 2h at 50~60 DEG C；Again wind-warm syndrome for dry 30 under the conditions of 100~140 DEG C~ The composite carbonaceous reducing agent is prepared in 50min.

Step 2: by 5 parts of 10 parts of 55 parts of sodium-ionized bentonite, cellulose family macromolecule, thickener being obtained in step 1 and Modified 1 part of anti-knock agent is added in reaction kettle, is heated to 60~90 DEG C, is mixed and is reacted, and control mixing speed 300~ The mass ratio of sampling plus water progress viscosimetric analysis after 600r/min, reaction 30min, sample and water is 1:1, when its viscosity reaches After 5000cp, discharging obtains mixture A；

Step 3: compound 3 parts of carbonaceous reducing agent, 6 parts of native starch are uniformly mixed and obtain mixture B；

Step 4: the mixture B obtained in the mixture A and step 3 that are obtained in step 2 is added in blender simultaneously After mixing, it puts into and the powder that average grain diameter is 42-74um is ground into grinder, obtain low burn consumption pelletizing binder I.

The performance test results：Ratio according to iron ore concentrate butt quality 0.2% is accounted for is added in iron ore concentrate and is made after mixing Ball.The shatter strength of green pellet obtained is 8 times/1m, and burst temperature is 650 DEG C, and pre- hot-bulb compression strength is 455N/, roasting Ball compression strength is 2532N/, and the full Iron grade TFe of finished ball is 68.39%.

Embodiment 3：Low burn consumes the preparation of pelletizing binder

Step 1: the preparation of sodium-ionized bentonite：Sodium alginate and sodium carbonate are dissolved in water, after stirring evenly, obtained Compound sodium modified solution；Then the compound sodium modified solution is added in the natural calcium-base bentonite after grinding, the calcium Base bentonite grind size is less than 0.5mm, obtains mixed serum after mixing；Dimethyl is added in the mixed serum of gained Double octadecyl ammonium chlorides adjust pH value after 5-7, to be warming up to 70-100 DEG C, at this temperature, adding in ethylene while stirring Alcohol is stirred to react 2-4 hours, by reaction product successively drying, crushing and grinding to get the sodium swelling after the completion of reaction Soil；Wherein, the mass ratio of sodium alginate, sodium carbonate and calcium-base bentonite is 25：8：100.

The preparation of modified anti-knock agent：It is 18 by mass ratio：50 polyacrylamide and magnesium iron sand input reaction kettle, and add in MgCl₂, MgCl₂Mass ratio with magnesium iron sand is 0.5:100, it stirs, grinds altogether after mixing at normal temperatures, obtain the modification Magnesium iron sand, granularity are -0.065mm grade mass fraction >=80%；MgO and Fe in the magnesium iron sand₂O₃Mass fraction difference For a and b, a >=85%wt, 8%wt >=b >=12%wt.

The preparation of compound carbonaceous reducing agent：It is 60 by mass ratio：50 petroleum coke and low culm are uniformly mixed to obtain mixture Expect, it is respectively 85~90%wt, 55~65%wt to fix carbon content in the petroleum coke and low culm；It then will be in mixed material It sequentially adds the waterglass for being equivalent to mixed material quality 2%wt~4%wt and is equivalent to mixed material quality 8%wt~12% The water of wt is uniformly mixed, and is discharged after stirring 2h at 50~60 DEG C；Again wind-warm syndrome for dry 30 under the conditions of 100~140 DEG C~ The composite carbonaceous reducing agent is prepared in 50min.

Step 2: by 8 parts of 20 parts of 65 parts of sodium-ionized bentonite, cellulose family macromolecule, thickener being obtained in step 1 and Modified 5 parts of anti-knock agent is added in reaction kettle, is heated to 60~90 DEG C, is mixed and is reacted, and control mixing speed 300~ The mass ratio of sampling plus water progress viscosimetric analysis after 600r/min, reaction 30min, sample and water is 1:1, when its viscosity reaches After 5000cp, discharging obtains mixture A；

Step 3: compound 7 parts of carbonaceous reducing agent, 15 parts of native starch are uniformly mixed and obtain mixture B；

Step 4: the mixture B obtained in the mixture A and step 3 that are obtained in step 2 is added in blender simultaneously After mixing, it puts into and the powder that average grain diameter is 42-74um is ground into grinder, obtain low burn consumption pelletizing binder II.

The performance test results：Ratio according to iron ore concentrate butt quality 0.3% is accounted for is added in iron ore concentrate and is made after mixing Ball.The shatter strength of green pellet obtained is 9.8 times/1m, and burst temperature is 720 DEG C, and pre- hot-bulb compression strength is 468N/, roasting It is 2583N/ to burn ball compression strength, and the full Iron grade TFe of finished ball is 67.83%.

Embodiment 4：Low burn consumes the preparation of pelletizing binder

Step 1: the preparation of sodium-ionized bentonite：Sodium alginate and sodium carbonate are dissolved in water, after stirring evenly, obtained Compound sodium modified solution；Then the compound sodium modified solution is added in the natural calcium-base bentonite after grinding, the calcium Base bentonite grind size is less than 0.5mm, obtains mixed serum after mixing；Dimethyl is added in the mixed serum of gained Double octadecyl ammonium chlorides adjust pH value after 5-7, to be warming up to 70-100 DEG C, at this temperature, adding in ethylene while stirring Alcohol is stirred to react 2-4 hours, by reaction product successively drying, crushing and grinding to get the sodium swelling after the completion of reaction Soil；Wherein, the mass ratio of sodium alginate, sodium carbonate and calcium-base bentonite is 20：5：100.

The preparation of modified anti-knock agent：It is 15 by mass ratio：50 polyacrylamide and magnesium iron sand input reaction kettle, and add in Fe₂(SO₄)₃, Fe₂(SO₄)₃Mass ratio with magnesium iron sand is 0.5:100, it stirs, grinds altogether after mixing at normal temperatures, obtain institute Modified magnesium iron sand is stated, granularity is -0.065mm grade mass fraction >=80%；MgO and Fe in the magnesium iron sand₂O₃Quality point Number is respectively a and b, a >=85%wt, 8%wt >=b >=12%wt.

The preparation of compound carbonaceous reducing agent：It is 55 by mass ratio：45 petroleum coke and low culm are uniformly mixed to obtain mixture Expect, it is respectively 85~90%wt, 55~65%wt to fix carbon content in the petroleum coke and low culm；It then will be in mixed material It sequentially adds the waterglass for being equivalent to mixed material quality 2%wt~4%wt and is equivalent to mixed material quality 8%wt~12% The water of wt is uniformly mixed, and is discharged after stirring 2h at 50~60 DEG C；Again wind-warm syndrome for dry 30 under the conditions of 100~140 DEG C~ The composite carbonaceous reducing agent is prepared in 50min.

Step 2: by 7 parts of 15 parts of 60 parts of sodium-ionized bentonite, cellulose family macromolecule, thickener being obtained in step 1 and Modified 4 parts of anti-knock agent is added in reaction kettle, is heated to 60~90 DEG C, is mixed and is reacted, and control mixing speed 300~ The mass ratio of sampling plus water progress viscosimetric analysis after 600r/min, reaction 30min, sample and water is 1:1, when its viscosity reaches After 5000cp, discharging obtains mixture A；

Step 3: compound 6 parts of carbonaceous reducing agent, 12 parts of native starch are uniformly mixed and obtain mixture B；

Step 4: the mixture B obtained in the mixture A and step 3 that are obtained in step 2 is added in blender simultaneously After mixing, it puts into and the powder that average grain diameter is 42-74um is ground into grinder, obtain low burn consumption pelletizing binder III.

The performance test results：Ratio according to iron ore concentrate butt quality 0.3% is accounted for is added in iron ore concentrate and is made after mixing Ball.The shatter strength of green pellet obtained is 11.6 times/1m, and burst temperature is 710 DEG C, and pre- hot-bulb compression strength is 495N/, roasting It is 2578N/ to burn ball compression strength, and the full Iron grade TFe of finished ball is 68.57%.

Embodiment 5：Comparative example

Natural montmorillonite is added to mixing in iron ore concentrate according to the mass ratio for accounting for iron ore concentrate butt quality 2.5%, is passed through Pelletizing after profit mill pretreatment, gained shatter strength of green pellet are 5.3 times/1m, and burst temperature is 618 DEG C, and pre- hot-bulb compression strength is 410N/, roasting ball compression strength is 2535N/, and the full Iron grade TFe of finished ball agglomerate is 66.76%.

Finally it is to be appreciated that foregoing description is merely a preferred embodiment of the present invention, those skilled in the art is in the present invention Enlightenment under, under the premise of without prejudice to present inventive concept and claim, expression, such change as multiple types can be made It changes and each falls within protection scope of the present invention.

Claims (10)

1. a kind of low burn consumes pelletizing binder, it is characterised in that is made of the raw material of following mass fraction：Sodium-ionized bentonite 55-65 Part, carbonaceous reducing agent 3-7 parts compound, 6-15 parts of native starch, 10-20 parts of cellulose family macromolecule, increases modified 1-5 parts of anti-knock agent Thick dose 5-8 parts.

2. low burn according to claim 1 consumes pelletizing binder, it is characterised in that the mass fraction of the raw material is：Sodium 60 parts of bentonite, modified 4 parts of anti-knock agent, 6 parts of compound carbonaceous reducing agent, 12 parts of native starch, 15 parts of cellulose family macromolecule, thickening 7 parts of agent.

3. low burn according to claim 1 or 2 consumes pelletizing binder, it is characterised in that the sodium-ionized bentonite is using following Method obtains：Sodium alginate and sodium carbonate are dissolved in water, after stirring evenly, obtain compound sodium modified solution；Then by institute It states in the natural calcium-base bentonite after compound sodium modified solution is added to grinding, obtains mixed serum after mixing；In gained Mixed serum in add in dimethyldioctadecylammonium ammonium chloride, adjust pH value after 5-7, to be warming up to 70-100 DEG C, it is warm herein Under degree, vinyl alcohol is added in while stirring, is stirred to react 2-4 hours, and reaction product is dried, crushed and ground successively after the completion of reaction Mill is to get the sodium-ionized bentonite；Wherein, the mass ratio of sodium alginate, sodium carbonate and calcium-base bentonite is 3~25：1~8： 100。

4. low burn according to claim 3 consumes pelletizing binder, it is characterised in that：The calcium-base bentonite grind size is small In 0.5mm.

5. low burn according to claim 1 or 2 consumes pelletizing binder, it is characterised in that the modified anti-knock agent is using following Method obtains：It is 10-18 by mass ratio：50 polyacrylamide and magnesium iron sand input reaction kettle, and conditioning agent is added in, the tune The mass ratio for saving agent and magnesium iron sand is 0.5:100, it stirs, grinds altogether after mixing at normal temperatures, obtain the modified magnesium iron sand, Its granularity is -0.065mm grade mass fraction >=80%.

6. low burn according to claim 5 consumes pelletizing binder, it is characterised in that：MgO and Fe in the magnesium iron sand₂O₃'s Mass fraction is respectively a and b, a >=85%wt, 8%wt >=b >=12%wt；The conditioning agent is FeCl₃、MgCl₂Or Fe₂ (SO₄)₃In one kind.

7. low burn according to claim 1 or 2 consumes pelletizing binder, it is characterised in that：The compound carbonaceous reducing agent uses Following methods obtain：It is 50~60 by mass ratio：40~50 petroleum coke and low culm are uniformly mixed to obtain mixed material；Then The waterglass for being equivalent to mixed material quality 2%wt~4%wt will be sequentially added in mixed material and is equivalent to mixed material matter The water of 8%wt~12%wt is measured, is uniformly mixed, 2h, discharging are stirred at 50~60 DEG C；It is again 100~140 DEG C of conditions in wind-warm syndrome 30~50min of lower baking, is prepared the composite carbonaceous reducing agent.

8. low burn according to claim 7 consumes pelletizing binder, it is characterised in that：It is fixed in the petroleum coke, low culm Carbon content is respectively 85~90%wt, 55~65%wt.

9. pelletizing binder is consumed according to claim 1,2,4,6 or 8 any one of them low burns, it is characterised in that：The fiber Plain family macromolecule is one or both of methylcellulose, carboxymethyl cellulose, hydroxypropyl methyl cellulose；The natural shallow lake Powder is cornstarch, potato starch；The thickener is over cure acid, hydrogen peroxide.

10. a kind of preparation method for preparing claim 1-9 any one of them low burn consumption pelletizing binder, it is characterised in that press Following steps carry out：

Step 1: sodium-ionized bentonite, modified anti-knock agent and compound carbonaceous reducing agent are prepared respectively；

Step 2: the sodium-ionized bentonite obtained in step 1, cellulose family macromolecule, thickener and modified anti-knock agent are added to In reaction kettle, 60~90 DEG C are heated to, reaction is mixed, controls 300~600r/min of mixing speed, is taken after reacting 30min Sample adds water to carry out viscosimetric analysis, and the mass ratio of sample and water is 1:1, after its viscosity reaches 5000cp, discharging obtains mixture A；

Step 3: compound carbonaceous reducing agent, native starch are uniformly mixed to obtain mixture B；

Step 4: the mixture B obtained in the mixture A and step 3 that are obtained in step 2 is added into stirrer for mixing simultaneously After uniformly, the powder for being ground into that average grain diameter is 42-74um is put into grinder, obtains finished product.