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CN1201482A - agglomeration of mineral fines - Google Patents

agglomeration of mineral fines Download PDF

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Publication number
CN1201482A
CN1201482A CN 96197976 CN96197976A CN1201482A CN 1201482 A CN1201482 A CN 1201482A CN 96197976 CN96197976 CN 96197976 CN 96197976 A CN96197976 A CN 96197976A CN 1201482 A CN1201482 A CN 1201482A
Authority
CN
China
Prior art keywords
tackiness agent
particulate
ester
anions
oxo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN 96197976
Other languages
Chinese (zh)
Inventor
雷蒙德·耶茨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ashland Inc
Original Assignee
Ashland Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ashland Inc filed Critical Ashland Inc
Publication of CN1201482A publication Critical patent/CN1201482A/en
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L5/00Solid fuels
    • C10L5/02Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
    • C10L5/06Methods of shaping, e.g. pelletizing or briquetting
    • C10L5/10Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders
    • C10L5/14Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders with organic binders

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Glanulating (AREA)

Abstract

Mineral fines such as coal fines are agglomerated structures into briquettes or tablets by a cold roll press operation using a binder comprising an ester-cured basic phenol-formaldehyde resole resin, an ester coreactant and an oxyanion to enhance green strength.

Description

The one-tenth piece of mineral particulate
The present invention relates to the one-tenth piece of mineral particulate such as coal dust.
By the agglomerate structure of coal dust manufacturing such as piece or sheet the time, known have various technology.The technology that great majority generally use is the shape that forms the ovum circle by cold roll squeezer operation.In the case, with the tackiness agent mixture of coal in last to about 2.1 * 10 6Kg/m 2Pressure under between two metal rollers, extrude, described two metal rollers respectively have the recess of half oval shape.So the piece that forms drops on from press on the conveyor belt, stores and packs with transfer.
Use the tackiness agent of several types in the method, obtained success in various degree.For example, water glass can produce the piece of medium tenacity, but poor water resistance, and also because the increase of ash content descends the burning of coal value.Tackiness agent as pitch and sulphite basic solution can produce flue gas when coal cinder burns, this obviously is not desirable.
Phenol-formaldehyde the resol resin of known use ester solidified alkalescence can produce the coal cinder of the medium tenacity with good combustion performance, and United States Patent (USP) 4802890 is an example.But, must use work in-process (green) strength additive, be generally starch, to produce higher intensity in the early stage, make the new ovum circle that forms intactly to drop on the conveyor belt.Starch is subject to the attack of bacterium/mould, therefore must use sterilant or fungicide.And, starch add the strength reduction that affiliation produces resol.From the mechanics angle of operation, this system is very complicated owing to need 4 kinds of components.
Therefore still need a kind of tackiness agent that can avoid these defectives basically for coal dust.In addition, this problem is not limited only to coal dust, and this is because of the needs that remain at the various mineral particulates of agglomerated particle or fibers form.
According to an aspect of the present invention, the curable at ambient temperature tackiness agent that is used for agglomeration mineral particulate comprises alkali soluble resol resinox, ester coreagent and strengthens the oxo-anions (oxyanions) of work in-process intensity.
According to the present invention, the method for agglomeration mineral particulate also is provided, wherein, described particulate is bonded to big agglomerate by tackiness agent, described tackiness agent comprises alkaline phenol-formaldehyde, ester coreagent and strengthens the oxo-anions of work in-process intensity.
Therefore, we find to introduce oxo-anions, particularly borate, as the third component, can increase the viscosity of resin-ester mixture fast, and increase the work in-process intensity of this system thus.This can intactly drop on the conveyor belt piece.The quick increase of viscosity it is believed that it is because between first hydroxyl on the resol and oxo-anions resin has taken place and ionic is crosslinked, makes the pH value reduction of coupling resin.For example, the sodium tetraborate of adding 3wt% can make viscosity increase by four times in resin.
The one-tenth piece bonder system that this tackiness agent can be used as the mineral particulate that is used for boning at ambient temperature provides, and described soluble binding agent system comprises that following treating mix to be formed into the independent component of piece mixture with the mineral particulate: (a) alkali soluble resol resinox; (b) ester coreagent; (c) be used to increase the oxo-anions of the work in-process intensity of gained tackiness agent.
This bonder system can be used for the one-tenth piece of mineral particulate such as coal dust.Each component can be sent in the independent container, the size of described container will make component and the particulate in the container form a mixture, and wherein each component is in desirable relative proportion.
Different with the existing system that comprises organic materials such as starch, the piece that the present invention produced is unsuitable for the growth of mould and bacterium.Therefore, they do not need to introduce sterilant or fungicide, and still can keep no mould to form between the shelf lives.
Alkali soluble resol resinox can be for example makes by reacting under alkaline condition as the mono-hydroxy phenol of phenol and cresylol or as the dihydric phenol of Resorcinol and formaldehyde.The mol ratio of monohydroxy or dihydric phenol and formaldehyde is 1: 1-1: 3, but be preferably 1: 1.6-1: 2.0.The basic metal that in this reaction mixture, adds solid or aqueous solution form.Can use the oxyhydroxide of calcium, sodium and potassium, but preferably use the latter.The addition of solid alkali metal can be the 8-18% of weight resin, 12-18% more preferably, but the 11-15% of weight resin most preferably.
Ester coreagent (solidifying agent) can for example be the acetic ester of ethylene glycol, propylene glycol, butyleneglycol and glycerine, as the lactone of propiolactone (propriolactone) and gamma-butyrolactone, and as the carbonic ether of Texacar PC and ethylene carbonate/inferior propyl ester mixture.Also can use the mixture of these esters.
Suitable oxo-anions is borate, aluminate and stannate, but preferred boric acid salt.Oxo-anions can exist as the salt form of potassium or sodium salt.
Be added on the 1-6% that is generally particulate weight as the alkaline resinox amount in the particulate of coal dust, and the amount of ester solidifying agent is the 15-25% of weight resin.Oxo-anions adds with the form of 5% aqueous solution usually, and its addition is the 1-6% of particulate weight.This tittle is usually above the required amount of the particle bigger than particulate particle diameter.
Interpolation in the mineral particulate is preferably in proper order and at first adds oxo-anions, is ester then, is resin at last, and the time between each the interpolation should be enough to each component is dispersed in the mixture.
Bond at ambient temperature, therefore do not need to heat separately component.Like this, when becoming the lump coal powder, do not need or need hardly to change cold roll squeezer operation used when using conventional tackiness agent such as water glass rather than using tackiness agent of the present invention.And coal dust is generally the form of moist mixture, avoided dust problem.
Except that coal dust, agglomeration method of the present invention also can be used for particulate such as the charcoal and the graphite of other types, and other mineral are as quartz, Calucium Silicate powder and pure aluminium silicate.For the mixture of particulate such as the mixture of various charcoal base particulate and fine particles of silica also is feasible.
The maximum particle diameter of coal dust and other particulates is generally and can be preferably the sieve of 3 millimeters square holes by the sieve of 15 millimeters square holes.Therefore particulate comprises maximum particle to above-mentioned particle size range.More preferably, the maximum particle diameter of particulate is the 150-200 order.
In some cases, also wish to add silane to help tackiness agent and mineral example particularly as the bonding between the quartz.If present, the addition of silane is preferably the 0.1-1.0% of weight resin.
The present invention is described by the following examples.
Under the alkaline condition of gentleness, in 450g phenol and 270g 91% paraformaldehyde were reacted 15 minutes in 351g water, with preparation resol resin resinox.After being cooled to 80 ℃, add 93g potassium hydroxide (the 45%w/w aqueous solution), continue reaction down at 80 ℃, increase to 17A (BubbleTube@25 ℃ of The Paint Research Association) until viscosity.Behind the cooling reactant, add 325g potassium hydroxide (the 45%w/w aqueous solution).Add the 4g γ-An Jibingjisanyiyangjiguiwan at last.Final resin has the viscosity (Broookfield ERV-8@20 ℃/Spindle 4/100rpm) of 350 centipoises and 53% solid content (3h@120 ℃).
Comprise 70% hard coal, 20% petroleum coke and 10% bituminous, total water-content and be 8.5% coal dust and the 5% sodium tetraborate aqueous solution of 3 weight %, sneak into the triacetin that comprises equal portions of 1 weight % and the ester of gamma-butyrolactone then.In particulate, add the resin that as above makes of 4 weight % more then, and disperseed 1 minute.
By the roll squeezer technology mixture is formed bulk, the ovum circle that so forms is intactly by falling in the press.Form and measure work in-process intensity in back 30 seconds, its value is for about 2.46 * 10 4-3.16 * 10 4Kg/m 2(35-45 psi).After 24 hours, coal cinder has good scratch hardness, and compressive strength increases to about 9.84 * 10 4-1.12 * 105kg/m 2(140-160psi), and the submergence test shows they be water-proof.Combustion testing shows that this coal cinder has excellent hot strength, and only emits very small amount of flue gas.
Water with 3 weight % replaces the 5% sodium tetraborate aqueous solution, repeats above-mentioned one-tenth piece process.Ovum circle disintegration ground above 70% falls from roll squeezer, proves almost without any the work in-process intensity that can measure.

Claims (12)

1, a kind of curable at ambient temperature tackiness agent that is used for agglomeration mineral particulate, the oxo-anions that it comprises alkali soluble resol resinox, ester coreagent and strengthens work in-process intensity.
2, a kind of one-tenth piece bonder system of the mineral particulate that is used for boning at ambient temperature, it comprises that following treating mix to be formed into the independent component of piece mixture with the mineral particulate: (a) alkali soluble resol resinox; (b) ester coreagent; (c) be used to increase the oxo-anions of the work in-process intensity of gained tackiness agent.
3, tackiness agent as claimed in claim 1 or system as claimed in claim 2, wherein, described resin is to react under alkaline condition by mono-hydroxy phenol or dihydric phenol and formaldehyde to make, and the mol ratio of described monohydroxy or dihydric phenol and formaldehyde is 1: 1-1: 3.
4, tackiness agent as claimed in claim 3 or system, wherein, the oxyhydroxide of calcium, sodium and potassium provides alkaline condition, and their amount is the 8-18% of weight resin.
5, as the tackiness agent or the system of any aforementioned claim, wherein, the ester coreagent is acetic ester, lactone or carbonic ether, and the amount of this ester coreagent is the 15-25% of weight resin.
6, as the tackiness agent or the system of any aforementioned claim, wherein, described oxo-anions is borate, aluminate and stannate.
7, as the tackiness agent of any aforementioned claim, it comprises silane in addition, and its consumption is the 0.1-1.0% of weight resin.
8, a kind of method of agglomeration mineral particulate wherein, is bonded to big agglomerate by tackiness agent with described particulate, and described tackiness agent comprises alkaline phenol-formaldehyde, ester coreagent and strengthens the oxo-anions of work in-process intensity.
9, a kind of method of agglomeration mineral particulate, wherein, by as the tackiness agent of claim 1-7 or system with as described in particulate be bonded to big agglomerate.
10, as the method for claim 8 or 9, wherein, described mineral are coals, and big agglomerate is ovate that forms by cold roll squeezer operation.
11, as the method for claim 8-10, wherein, the amount that is added on the resin in the particulate is the 1-6% of particulate weight, and the amount of oxo-anions is the 0.05-0.3% of particulate weight.
12, as the method for claim 8-11, wherein, at first adding oxo-anions, is ester then, is resin at last, and the interpolation of component should be dispersed in the mixture before next component adds.
CN 96197976 1995-10-11 1996-10-10 agglomeration of mineral fines Pending CN1201482A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9520818.7 1995-10-11
GBGB9520818.7A GB9520818D0 (en) 1995-10-11 1995-10-11 Briquetting of mineral fines

Publications (1)

Publication Number Publication Date
CN1201482A true CN1201482A (en) 1998-12-09

Family

ID=10782149

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 96197976 Pending CN1201482A (en) 1995-10-11 1996-10-10 agglomeration of mineral fines

Country Status (8)

Country Link
EP (1) EP0862605A1 (en)
CN (1) CN1201482A (en)
AU (1) AU7223096A (en)
BR (1) BR9610890A (en)
CA (1) CA2234705A1 (en)
GB (1) GB9520818D0 (en)
PL (1) PL326250A1 (en)
WO (1) WO1997013827A1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2330150B (en) * 1997-10-13 2001-11-14 Applied Ind Materials Uk Ltd Process for the agglomeration of petroleum coke fines
GB9826226D0 (en) * 1998-12-01 1999-01-20 Borden Chem Co Ltd Briquetting of powdered fuel
GB9914537D0 (en) * 1999-06-23 1999-08-25 Borden Chem Co Ltd Fuel briquetting composition and manufacture of fuel briquettes using it
US7655159B2 (en) 2003-04-09 2010-02-02 Graham Simpson Murray Conductive polymer, conductive polymer compositions and their use
GB0308135D0 (en) * 2003-04-09 2003-05-14 Bac2 Ltd Solid polymer electrolyte
US8333909B2 (en) 2003-04-09 2012-12-18 Bac2 Limited Conductive polymer, conductive polymer compositions and methods for their use
RU2467059C1 (en) * 2011-04-19 2012-11-20 Татьяна Викторовна Шевченко Resin binder for making coal briquettes
RU2467060C1 (en) * 2011-04-19 2012-11-20 Татьяна Викторовна Шевченко Complex binder for making coal briquettes
GB201613915D0 (en) * 2016-08-15 2016-09-28 Binding Solutions Ltd Briquettes

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1033255A1 (en) * 1982-03-25 1983-08-07 Липецкий политехнический институт Sand for manufacturing casting ceramic moulds and cores
GB8404595D0 (en) * 1984-02-22 1984-03-28 Foseco Int Foundry sand compositions
GB8608488D0 (en) * 1986-04-08 1986-05-14 Foseco Int Agglomeration of coal fines
AU605943B2 (en) * 1987-12-24 1991-01-24 Foseco International Limited Production of articles of bonded particulate material and binder compositions for use therein
GB2282387A (en) * 1993-09-07 1995-04-05 Hepworth Minerals & Chemicals Briquette and preparation of same

Also Published As

Publication number Publication date
MX9802789A (en) 1998-09-30
PL326250A1 (en) 1998-08-31
WO1997013827A1 (en) 1997-04-17
EP0862605A1 (en) 1998-09-09
GB9520818D0 (en) 1995-12-13
CA2234705A1 (en) 1997-04-17
AU7223096A (en) 1997-04-30
BR9610890A (en) 1999-12-21

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