CN1116242A - Adhesive for metal powdered ore prilling (block) - Google Patents
Adhesive for metal powdered ore prilling (block) Download PDFInfo
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- CN1116242A CN1116242A CN 95110218 CN95110218A CN1116242A CN 1116242 A CN1116242 A CN 1116242A CN 95110218 CN95110218 CN 95110218 CN 95110218 A CN95110218 A CN 95110218A CN 1116242 A CN1116242 A CN 1116242A
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- monomer
- mother liquor
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- ester
- vinyl
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Abstract
Said adhesives is composed of mother liquid, monomer, cross-linking agent, initator, neutralizer, and water. The mother is carbohydrate, monomer is soluble, cross-linking agent is methylene diacrylic amide, initator is hydrogen peroxide, neutralizer is sodium hydroxide Said invention can be used in non-ferrous powdered ore prilling to improve prilling rate and quality.
Description
The present invention relates to a kind of ferrous metal sinter mixture granulation that is used for, the tackiness agent of cooled agglomerated pellet agglomeration and non-ferrous metal briquetting particularly relates to a kind of papermaking wastewater of using, through concentrate, oxidizing reaction, graft copolymerization and the polymer adhesive made.
Breeze granulation (piece) is an extremely important link in the metallurgical industry.At present in the granulation of ferrous metal sinter mixture, mainly be to use inorganic adhesive, agglomerate with unslaked lime or white lime.Adopt above-mentioned inorganic adhesive, make that the ball rate is low, intensity difference, return mine many.Cooled agglomerated pellet, the main at present sodium silicate binder that adopts, consumption is big.Because consumption is big, makes a large amount of silicon and sodium enter blast furnace, has influenced reduction index and reduction swellability index, has reduced the quality of iron; Non-ferrous metal briquetting, the producer that has at present adopts the papermaking concentrating spent liquor, because bonding force is poor, usage quantity is big, needs 500～700kg as zinc ore per ton, and technology is complicated, has improved production cost.
Purpose of the present invention, provide a kind of by papermaking wastewater, through concentrating, oxidizing reaction, graft copolymerization is made, and can improve granulation (piece) rate, metal mining powder granulation (piece) tackiness agent that reduces the granulation cost and improve the quality of products.
Metal mining powder granulation (piece) tackiness agent is mixed with by mother liquor, monomer, linking agent, initiator, middle mixture and water; Mother liquor is the carbohydrate that contains polysaccharide structures, and its solids content accounts for total amount 10～50%; Monomer is to be after water-soluble monomer or the hydrolysis to account for mother liquor total amount 10～30% by water-soluble monomer; Linking agent accounts for mother liquor total amount 0.05～0.5%; Initiator accounts for mother liquor total amount 0.05～1.0%; Neutralizing agent, foundation conciliation pH value reaches 3～9 actual needs and decides; Water accounts for total amount 40～70%.
Therefore, metal mining powder granulation of the present invention (piece) tackiness agent is approximately to be made up of 40～70% water and 30～60% water-soluble high molecular polymers.
Adding monomeric purpose in mother liquor, is to make mother liquor modification and grafting.The purpose that adds linking agent is mother liquor after the modification is gained in strength and to prevent the deliquescence that absorbs water.Initiator is a kind of catalyzer, with the accelerated reaction process.
Prescription of the present invention is formed:
One, mother liquor comprises at least a carbohydrate that contains polysaccharide structures.As: starch, Mierocrystalline cellulose, protein, pectin etc. and derivative thereof, the black liquor that paper pulp and alkaline process thereof reclaim, red liquid, sugar refinery and chemical fibre factory's waste liquid enriched material etc. that sulfite pulping reclaims.
Two, monomer: mainly be to become hydrophilic monoene class monomer after wetting ability and the hydrolysis.The basic structure type is:
R is H and alkyl in the formula, and X is mainly
Deng group.Y is generally H in the formula, and there also have to be special, as-OH ,-COOH etc.
1, water-soluble monomer: (1) contains carboxylic acid group's monomer, mainly contain vinylformic acid, methacrylic acid, maleic acid, FUMARIC ACID TECH GRADE etc. and their acid anhydrides and carboxylate salt (an alkali metal salt, ammonium salt, amine salt), as MALEIC ANHYDRIDE, sodium acrylate, vinylformic acid trolamine, sodium methacrylate, sodium maleate etc.
(2) contain the sulfonic group monomer, mainly contain vinyl sulfonic acid, propene sulfonic acid, vinyl toluene sulfonic acid, methacrylic sulfonic acid etc. and their an alkali metal salt thereof, ammonium salt, amine salt etc.
(3) hydroxyl or (ester) ether monomer mainly contain vinylcarbinol, methylallyl alcohol, ethylene glycol, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, vinylformic acid second triethyleneglycol ester, methacrylic acid second triethyleneglycol ester, Propylene glycol monoacrylate, Rocryl 410 etc.
(4) amide-containing monomer, mainly contain acrylamide, Methacrylamide, N-alkyl acrylamide, N.N-dialkyl group acrylamide, N-hydroxyalkyl acrylamide, N.N-dihydroxyalkyl acrylamide, vinyl lactam etc., and contain amino monomers and quaternary ammonium salt monomer etc.
2, after the hydrolysis be water-soluble monomer, this monomer has a hydrolyzable group (ester group, cyano group) at least.
(1) contains the lower alkyl esters of vinyl unsaturated carboxylic acid, mainly contain methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, butyl acrylate, vinylformic acid 2-ethylhexyl ester etc.
(2) contain the vinyl alcohol ester, mainly contain vinyl acetate between to for plastic, acetate propylene, acetic acid methacrylic ester etc.
(3) nitrile group-containing monomer mainly contains vinyl cyanide, methacrylonitrile.
The optimum monomer of the present invention is vinylformic acid or acrylamide.
Three, linking agent:
(1) has non-conjugated many double bond compounds, mainly contain two or trivinyl compound, divinylbenzene, divinyl ether etc.
(2) ester of unsaturated monocarboxylic and polyvalent alcohol or polyepoxide formation.Mainly contain the diacrylate of ethylene glycol, TriMethylolPropane(TMP), glycerine, polyoxyethylene glycol and vinylformic acid formation etc.
(3) unsaturated polyester of unsaturated poly carboxylic acid and polyvalent alcohol formation, bisacrylamide, urine ester, polyoxyethylene glycol diether etc.
(4) polyvalent metal compounds of formation ionomer is as alkali metal compound and Zinc compounds etc.
(5) other can make N-n-methylolacrylamide, glycidyl acrylate, quadrol, oxalic dialdehyde etc. in addition of linking agent.
The optimum linking agent of the present invention is methene base bisacrylamide and N-n-methylolacrylamide.
Four, initiator:
1, peroxide initiator mainly contains benzoyl peroxide, hydrogen peroxide, ammonium persulphate, Potassium Persulphate etc.
2, azo-initiator mainly contains Diisopropyl azodicarboxylate, and other initiator also has cerous nitrate, iron trichloride, pentavalent vanadic salts etc.
Five, neutralizing agent is ammoniacal liquor, potassium hydroxide, sodium hydroxide, thanomin etc.
The production method of metal mining powder granulation (piece) tackiness agent is:
One, according to the actual needs of different metal breeze granulation (piece) tackiness agent, prepares mother liquor, monomer, linking agent, initiator.
Two, mother liquor is joined in the reactor, heating, intensification when reaching the temperature of polymerization requirement, add monomer, linking agent, the initiator for preparing respectively again, make it to take place redox and polyreaction, produce high molecular polymer.Polyreaction is to carry out under 55 ℃～95 ℃ temperature.In 2～8 hours reaction times, polyreaction also can be below or above barometric point outside generally carrying out under barometric point.Reaction is preferably under rare gas element (as the nitrogen) protection to be carried out.Polyreaction produces sizable heat, must in time get rid of.Stirring velocity generally is advisable at 60～80 rev/mins.Lower the temperature when reaction finishes, and transfer pH value, discharging when being cooled to room temperature with neutralizing agent.
Embodiment one,
1, mother liquor preparation.Get the red liquid of sulphite process papermaking reed pulp and concentrate, make its solid content reach 45～55;
2, monomer preparation.Monomer is a vinylformic acid, accounts for mother liquor total amount 8%;
3, initiator preparation.The ammonium persulphate that accounts for mother liquor gross weight 0.1% is dissolved in the deionized water, is made into the aqueous solution;
4, the red concentrated liquor of sulphite process papermaking reed pulp of mother liquor-prepare is put into sugared porcelain reactor; heat to 70～90 ℃; add the monomer vinylformic acid account for mother liquor total amount 8% more respectively and be the initiator ammonium persulfate solution that 1% ammonium persulphate is mixed with by accounting for the mother liquor total amount; reaction is 5 hours under 70～90 ℃ of temperature condition; reaction process is carried out under nitrogen protection.The reactor stirring velocity is 65 rev/mins.Reconcile between the pH value 7～8, be cooled to the room temperature discharging.
Product is a brownish black liquid, solid content 45～55%, and between the pH value 7～8, viscosity 35～55CPaS, surface tension 25～40 dynes per centimeter.
This kind metal mining powder granulation (piece) tackiness agent is mainly used in sinter mixture and granulates.Embodiment two,
1, mother liquor preparation: get the red liquid of sulphite process papermaking reed pulp and concentrate, make its solids content reach 45～55%;
2, monomer preparation: vinylformic acid, quantity are 8% of mother liquor total amount;
3, linking agent preparation: methene base bisacrylamide, it is measured to account for 0.2% of mother liquor total amount, is dissolved in the deionized water, is mixed with the aqueous solution;
4, initiator preparation: the ammonium persulphate that will account for mother liquor gross weight 0.1% is dissolved in the deionized water, is made into the aqueous solution.
5, manufacturing process is identical with embodiment one.
Product is a brownish black liquid, solid content 40～50%, pH value 3～5, viscosity 25～40CPaS.
This tackiness agent is used for cooled agglomerated pellet and adds and be pressed into piece.
Embodiment 3
1, mother liquor preparation: get the red liquid of sulphite process papermaking reed pulp and concentrate, make its solid content reach 45～55%;
2, monomer preparation: vinylformic acid accounts for mother liquor total amount 20%;
3, linking agent preparation: N-n-methylolacrylamide accounts for mother liquor total amount 0.2% and is dissolved in and is made into the aqueous solution in the deionized water;
4, initiator preparation: get 0.5% ammonium persulphate, be dissolved in the deionized water, be made into the aqueous solution.
5, manufacturing process is identical with embodiment one
Product is a brownish black liquid, and solid content is 30～40%, pH value 3～5, viscosity 30～50CPaS.This kind tackiness agent is mainly used in non-ferrous metal breeze briquetting grain and uses.
Metal mining powder granulation of the present invention (piece) tackiness agent is used for the powdered iron ore granulation, granulation rate height, and intensity is big, and good permeability has improved the grade and the quality of iron, has increased output, and capable of reducing energy consumption.Be used for cooled agglomerated pellet, binder dosage is few, and is Well-recovered, can improve the quality of iron.Be used for briquetting of non-ferrous metal breeze such as zinc ore powder, per tonly only use about 20kg, and can simplify the briquetting operation, reduced cost.Because the mother liquor of metal mining powder granulation of the present invention (piece) tackiness agent is to utilize the paper mill waste liquid, therefore reduced pollution, turn waste into wealth, realized comprehensive utilization, have remarkable economic efficiency and social benefit.
Claims (2)
1, metal mining powder granulation (piece) tackiness agent is mixed with by mother liquor, monomer, linking agent, neutralizing agent and water, it is characterized in that:
A, mother liquor are to comprise at least a carbohydrate that contains polysaccharide structures, and its solids content accounts for 10～50% of total amount;
B, monomer are to be water-soluble monomer after water-soluble monomer or the hydrolysis; Water-soluble monomer comprises can be and contains carboxylic acid group's monomer, also can be to contain sulfonic group monomer, hydroxyl or (ester) ether monomer, amide-containing monomer; Containing carboxylic acid group's monomer mainly contains: vinylformic acid, methacrylic acid, maleic acid, FUMARIC ACID TECH GRADE and their acid anhydrides and carboxylate salt, as MALEIC ANHYDRIDE, sodium acrylate, vinylformic acid trolamine, sodium methacrylate, sodium maleate; Contain the sulfonic group monomer and mainly contain vinyl sulfonic acid, propene sulfonic acid, vinyl toluene sulfonic acid, methacrylic sulfonic acid and their an alkali metal salt, ammonium salt, amine salt; Hydroxyl or (ester) ether monomer mainly contain vinylcarbinol, methylallyl alcohol, ethylene glycol, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, vinylformic acid triethyleneglycol ester, Rocryl 410, Propylene glycol monoacrylate, methacrylic acid second triethyleneglycol ester; The amide-containing monomer mainly contains acrylamide, Methacrylamide, N-alkyl acrylamide, NN-dialkyl group acrylamide, N-hydroxyalkyl acrylamide, NN-dihydroxyalkyl acrylamide, vinyl lactam; Water-soluble monomer after the hydrolysis, can be the lower alkyl esters that contains the vinyl unsaturated carboxylic acid, mainly contain methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, butyl acrylate, vinylformic acid 2-ethylhexyl ester, also can be and contain vinyl alcohol ester, nitrile group-containing monomer; Contain the vinyl alcohol ester and mainly contain vinyl acetate between to for plastic, acetate propylene, acetic acid methacrylic ester, the nitrile group-containing monomer mainly contains vinyl cyanide, methacrylonitrile; Monomer accounts for 10～30% of mother liquor total amount;
C, linking agent can be has non-conjugated many double bond compounds, mainly contain two or trivinyl compound, divinylbenzene, divinyl ether, also can be the ester that unsaturated monocarboxylic and polyvalent alcohol or polyepoxide form, mainly contain the diacrylate that ethylene glycol, TriMethylolPropane(TMP), glycerine, polyoxyethylene glycol and vinylformic acid form; Also can be unsaturated polyester, bisacrylamide, urine ester, polyoxyethylene glycol diether, N-n-methylolacrylamide, glycidyl acrylate, quadrol, oxalic dialdehyde that unsaturated poly carboxylic acid and polyvalent alcohol form; Linking agent accounts for 0.05～0.5% of mother liquor total amount;
D, initiator mainly contain: benzoyl peroxide, hydrogen peroxide, ammonium persulphate, Potassium Persulphate, Diisopropyl azodicarboxylate, cerous nitrate, iron trichloride, pentavalent vanadic salts; Initiator accounts for 0.05～1.0% of mother liquor total amount;
E, neutralizing agent are ammoniacal liquor, also can be potassium hydroxide, sodium hydroxide, thanomin; Reconcile pH value to 3～8.
F, solid total content are 30～60%;
2, metal mining powder granulation according to claim 1 (piece) tackiness agent is characterized in that the best group of described mother liquor, monomer, linking agent, initiator, neutralizing agent and water becomes:
A, mother liquor are selected the red concentrated liquor of sulphite process papermaking reed pulp for use, and solids content reaches 45～55%;
B, monomer are vinylformic acid or acrylamide; Monomer accounts for 8% of mother liquor total amount.
C, linking agent are methene base bisacrylamide or N-n-methylolacrylamide, account for 0～0.2% of mother liquor total amount;
D, initiator are ammonium persulphate, account for 0.1～0.5% of mother liquor gross weight;
E, neutralizing agent can be thanomin, reconcile pH value to 3～8;
F, solid total content are 30～60%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95110218A CN1063800C (en) | 1995-05-08 | 1995-05-08 | Adhesive for metal powdered ore prilling (block) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95110218A CN1063800C (en) | 1995-05-08 | 1995-05-08 | Adhesive for metal powdered ore prilling (block) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1116242A true CN1116242A (en) | 1996-02-07 |
| CN1063800C CN1063800C (en) | 2001-03-28 |
Family
ID=5077625
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95110218A Expired - Fee Related CN1063800C (en) | 1995-05-08 | 1995-05-08 | Adhesive for metal powdered ore prilling (block) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1063800C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100339300C (en) * | 2002-06-13 | 2007-09-26 | 钱积才 | Coal quality active carbon forming agent |
| CN105008072A (en) * | 2013-03-04 | 2015-10-28 | 株式会社神户制钢所 | Binder for powder metallurgy, mixed powder for powder metallurgy, and sintered body |
| CN107660230A (en) * | 2015-05-26 | 2018-02-02 | 巴斯夫欧洲公司 | Coal adhesive composition |
| CN107949645A (en) * | 2015-09-02 | 2018-04-20 | 巴斯夫欧洲公司 | Purposes of the hydrophobic associated copolymer as the adhesive of the granulation containing metallic ore |
| CN109311749A (en) * | 2016-06-20 | 2019-02-05 | 高性能聚乙烯有限责任公司 | The enhancing binder with cementing agent material is granulated for iron ore |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1130617A1 (en) * | 1983-04-27 | 1984-12-23 | Ордена Трудового Красного Знамени Научно-Исследовательский И Проектный Институт Обогащения И Механической Обработки Полезных Ископаемых "Уралмеханобр" | Binder for pelletizing iron ore materials |
| CN1055765A (en) * | 1991-06-06 | 1991-10-30 | 海城市轻化工研究所 | Pelletizing additive for sintered compound |
-
1995
- 1995-05-08 CN CN95110218A patent/CN1063800C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100339300C (en) * | 2002-06-13 | 2007-09-26 | 钱积才 | Coal quality active carbon forming agent |
| CN105008072A (en) * | 2013-03-04 | 2015-10-28 | 株式会社神户制钢所 | Binder for powder metallurgy, mixed powder for powder metallurgy, and sintered body |
| CN107660230A (en) * | 2015-05-26 | 2018-02-02 | 巴斯夫欧洲公司 | Coal adhesive composition |
| CN107949645A (en) * | 2015-09-02 | 2018-04-20 | 巴斯夫欧洲公司 | Purposes of the hydrophobic associated copolymer as the adhesive of the granulation containing metallic ore |
| US11072840B2 (en) | 2015-09-02 | 2021-07-27 | Basf Se | Use of hydrophobically associating copolymers as binders for pelletizing metal containing ores |
| CN109311749A (en) * | 2016-06-20 | 2019-02-05 | 高性能聚乙烯有限责任公司 | The enhancing binder with cementing agent material is granulated for iron ore |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1063800C (en) | 2001-03-28 |
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