CN86100669A - The synthetic organic polymers that is used for selective flocculating floatation of titanium and iron ores - Google Patents
The synthetic organic polymers that is used for selective flocculating floatation of titanium and iron ores Download PDFInfo
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Abstract
A kind of unit cell is equivalent to general formula
Polymer or copolymer with the flocculant of making titanium ore is carried out selective flocculation flotation.R wherein
1And R
2(can be identical or different) have been represented-O-CHR
5-O-abutment, or two hydroxyls that also can exist with its ether or ester derivant form.In this chemical formula, symbol R
3, R
4Or R
5Be equivalent to atomic group in the polymerization series that on the position of substitution different spatial, contains.
Description
The present invention relates to a class and be used for the optionally synthetic organic polymers of flocculating floatation of titanium and iron ores.
More particularly, the present invention relates to organic polymer or the copolymer that a class is suitable for the ore that is suspended in the what is called " ultra-fine grain " in the water is carried out selective flocculation flotation, and said flocfloatation effect has high productive rate.
People are well understood to, and so far, selective flocculation flotation is used in once in a while to be handled some kinds of limited ores, and its reason is to lack suitable flocculating compound.Yet, because its potential advantage, in fact flucculation process is just in paid more and more attention,, this method can make us reclaim ore valuable in a large number, to disperse less than the particle form of 20um, but this is impossible or be not suitable for an obtaining target in the past.
It should be noted that, so tiny particle not only with implement the prior art process in a large amount of waste materials of producing relevant, and it is relevant with the whole ore body of giving, former mineral aggregate wherein has the interpenetrative miniature composite construction of the very fine grained that is equivalent to different ores, thereby these ore bodies are ground into fine grained in advance and can be gathered, on the other hand, handle fine grain conventional method (comprising floatation process) and also do not have a kind of particle mensuration of granularity that can be used to handle less than above institute how, by way of exception be that this selection flocculation-floatation successfully is used in to handle on the taconite (sees D.W.Frommer, A.E.Colombo, J.W.Vjllar; With the elaboration of people such as G.A.Dawe on Min.Cong.J magazine 61 volumes in 1975 40 pages (1975); The United States Patent (USP) 3,292,780 on December 20th, 1966; Chemical abstracts the 66th volume 58118y in 1967) still, the application of said method has been subjected to very big restriction owing to lacking suitable synthetic flocculant.
At present in some cases, though said flocculant because their attribute of animal or plant can be changed or be improved the existing material that obtains in various uses or bought by experiment obtains.But also there is not a kind of safe and reliable standard that shows its composition, structure or usefulness in advance.
In order to satisfy said can be used for titanium iron ore, requirement synthetic, selective flocculant, we find in former experiments that their type of action can be described on the basis of lucky three basic parameters:
With the mutual chemical action of ore particles,
The hydrophobic and the binding effect of chemistry, and
Effect with as the chemical relationship of the water of solvent has, for example can be by the water-wet behavior of a kind of outside agent modification or " modulation ".Be necessary to point out, can prepare the polymer of good flocculant or very of inferior quality dispersant according to external condition (for example pH value) to the suitable selection of last a kind of effect.All these has very important advantage, for example can reduce to minimum to the unwanted refuse of physically introducing, and perhaps EQUILIBRIUM CONDITION improves selectivity by setting up more between particle and polymer.
On the above basis of giving, we have been surprised to find the purpose flocculant as the present invention, they have the selectivity to titanium iron ore, said flocculant is made up of polymer and copolymer, and these polymer and copolymer contain the monomer that is equivalent to following general formula (I) in the form of monomer whose unit.
Wherein, R
1And R
2On behalf of molecular formula, (identical or different each other) be
-O-CHR
′-O-
Abutment, perhaps represented also the hydroxyl that can exist with its ether or ester derivant form, and symbol R
3, R
4Or R
5Be equivalent at the atomic radical that contains a polymerizable series on the different locus of the position of substitution, other group can identical or differently be hydrogen atom, alkyl, aryl, hydroxyl, alkoxyalkyl, hydroxy alkyl, alkoxyl, haloalkyl, carbonyl, carboxyl, ester, acylamino-, nitrilo-, sulfo group, halogen atom or nitro each other.Said polymerizable series is preferably a kind of to be suitable for the activated alkene series of polymerisation.
The monomeric compound that is equivalent to general formula (I) is in that contain from the different separations place of polymerizable double bond can be to the active part of mineral particle generation effect, its reason is the activity that has influenced compound from the distance of polymeric chain under following two kinds of situations, a kind of situation is that this distance is the structure that only contains carbon atom and hydrogen atom, and another kind of situation is that it is the structure that contains assorted element.
More satisfactoryly be, said copolymer is that monomer is formed by monomeric unit that is equivalent to general formula (I) and alkene hydroxyl, and they contain the group that its water-wet behavior changes with pH value.
In said monomer beneficially the acrylic acid methacrylate, what preferentially select for use is 4-vinyl benzoic acid or their hydroxy methacrylate or amino ethyl ester, vinyl benzoic acid, acrylamide, N-vinyl acetamide, aminoalkyl vinethene, vinylphenol or their ether or ester or vinylpyridine, what preferentially select for use is 4-vinylpridine, vinylpyridine-N-oxide, acryloyl morpholine, vinyl morpholine, vinyl pyrrole, vinyl pyrazoles, vinyl imidazole, vinylquinoline or N-vinyl lactam.
The monomer of general formula (I) prepares by various method, and this is because R
1, R
2, R
3, R
4And R
5And all ingredients on the market availability determined.Here given example has been showed some adopted methods.But, following this point also is rational, promptly, general known organic chemical reactions is changed over be fit to special circumstances discussed herein, thereby the possibility of same substance is easily prepared in expectation by additive method from same reactant or other materials.
Because sometimes; chemical action and the initiator of polyreaction or the applied incompatible polymerizatino of monomer in the general formula (I); said monomer just is produced and uses with chemoprotectant form; when polymer or copolymer are obtained, so desirable chemical action just has been released.The preparation of copolymer is normally carried out under the conversion ratio of low copolyreaction, its objective is in order to prevent large-scale composition different, but 0%～100% conversion ratio all is attainable unlimitedly.Polymer is purified out from monomer, oligomer then is cleaned out through precipitation by different solvents, the classified separation of they palpuses, specifically be to be precipitated out at leisure a kind of by adding " non-solvent " weak solution under keeping constant temperature, so just can obtain some samples, its molecular weight was enough to play the effect of molecular weight usefulness when these samples were used to carry out floc test.
According to the present invention, the mean molecule quantity of the flocculant of the usefulness of making the non-crosslinked material described here changes in several thousand to 1,000,000 such scopes, still, does not also foreclose up to the material of millions of more macromolecules.The influence that force of flocculation is not changed by molecular weight usually.Copolymer is made up of two or more component, for example is 3 kinds of components, but copolymer preferably contains the monomer shown in 10%～30% the general formula (I), yet the more substantial monomer that is equivalent to chemical formula (I) is not discharged outside yet.A kind of flocculation ability of copolymer generally is to depend primarily on copolymer originally in forming with quantitative copolymerization qualitatively.
Have to be noted that containing 100% the polymer that is equivalent to general formula (I) is not excluded outside scope of the present invention.
In addition, we can also recall, and said polymer and copolymer have the saturated hydrocarbon chain of deriving out from the polymerisation of the olefin-based of activity.Polymerisation and copolyreaction for simplicity; normally free radical type initator carries out, but also can successfully adopt and the chemical usefulness polymerisation compatible or become any other compatible type by suitable chemoproection that is present in the monomer.
Because demonstrate the existence that contains oxygen or nitrogenous usefulness of significant acidity or alkalescence, thereby have water-soluble and force of flocculation as the flocculant of the present invention's purpose, the two all depends on pH value significantly.So they are good flocculants under certain given pH value, and with different therewith pH value under they are of inferior quality flocculants or often demonstrate dispersiveness.This feature can obtain by the comonomer of suitably selecting above indication, this selection is to carry out in demonstrating the simplest and prevailing comonomer of hydrophily with the pH value variation, so this class reagent can be used as the processing and the condition of the more balance of mineral dispersion and form, pH value when the flocculant in the aqueous solution begins is to make flocculant itself more solvable, till pH value being adjusted to the optimum value of flocfloatation then, while said pH value is to determine by stirring the experiment that adds inorganic acid or alkali under each special situation always.
Stirring, temperature and mineral are dispersed in the concentration of adjusting time in the flocculant solution and this solution and density that mineral disperse all is to come by experiment to determine under each situation, but can not determine in advance, because Properties of Objects is experience basically; Yet the shear stress of agitating device is generally avoided, so that help the formation of big flocculus during the time in room temperature and the adjusting adopted 1 minute to several hours.The productive rate of flocfloatation generally depends on the concentration of polymeric flocculant in the solution to a great extent.Concentration is too high to be disadvantageous, and optium concentration is generally 10PPm～100PPm, but the concentration value beyond this scope can not be excluded.
Coagulating agent as the present invention's purpose is selectively in the flocfloatation of the ultra-fine dispersion of water of titanium iron ore.Field trash in the mineral ore is for example quartzy not to flocculate.Exist mineral and said mineral ore field trash not to change the possibility of the flocfloatation of the mineral that can be flocculated basically in the time of can be by flocfloatation separated.The flocfloatation that the mineral that can be flocculated are carried out can be very high productive rate (about 100%) carry out.
Flocculant of the present invention can flocculate especially rutile, ilmenite and bloodstone, but do not get rid of other mineral yet.
Pointed out as above, existing flocculant is selectively to iron ore, for example to taconite, but must remember, existing flocculant is to obtain from the polymerizate of natural polymer amount, so they are what to be different from as the flocculant of the present invention's purpose fully.On the contrary, the selectively high or low-molecular-weight flocculant that is used for titanium ore just is known seldom.
For the present invention being described better and in order more easily to use, below shown the example of some explanations, but said example is not considered to the restriction to purpose of the present invention and scope.
Force of flocculation in these examples can calculate by the following relationship formula:
P
f= (P0-P)/(P0) ×100
Wherein, P
fBe force of flocculation, P
0Be when no flocculant, to be in 70% the contained mineral quantity in decentralized photo top that its volume is a cumulative volume, and P is the weight that is in the contained mineral of same section of decentralized photo under similarity condition when having flocculant to exist, and can obtain the maximum P of force of flocculation when P=0
f=100%.At P＞P
0The time, P
fPresent a negative value, polymer plays dispersant in other words.In this case, dispersion force (P
d) can calculate by following routine relational expression:
P
d= (P
0-P)/(P
0) ×100
P wherein
pBe equivalent to enter decentralized photo mineral weight 70%.Work as P=P
pThe time, can obtain maximum dispersion power (P
d=100%)
Embodiment 1
Chemical formula is
Monomeric compound synthetic.
Place the process stirred mixture of 15.90 gram catechols of 115 milliliters of dichloro-benzenes at room temperature to handle with 22.84 gram 3-chloropropionic acid chlorine, 3-chloropropionic acid chlorine is drop by drop to add in about 10 minutes time, this mixture is heated to 50 ℃ and turned to up to complete homogeneous phase in about 30 minutes and to end then, then be cooled to room temperature again, and in about 1 hour, be subjected to 41.0 the gram AlCl, batch processing, and then be heated to 110 ℃ about 3 hours, with the ice of 300 grams and 150 milliliters dense HCl cooled mixture is hydrolyzed, the solid of so separating after filtration, and with the benzene processing of seething with excitement, and then be subjected to Crystallization Separation.So just can obtain 8.00 the gram its boiling points be 138～140 ℃ 3,4-dihydroxy phenyl-2 '-chloroethene ketone.Water after filtration, through with carrying out drying with anhydrous sodium sulfate again after the extracted with diethyl ether and removing and desolvate, so just further provided 2.42 products that restrain.The compound exhibits that purifies from the mixture of chloroform-methanol by crystallization goes out 143.5 ℃ fusing point.
8.10 restrain 3,4-dihydroxy phenyl-2 '-chloroethene ketone, aceticanhydride and a concentrated sulfuric acid of 28 milliliters at room temperature is stirred 40 hours, and be introduced into then in 400 milliliters the water, and further stirred 7 hours.Like this solid that forms, after filtration and use P
2O
5After the drying, just obtained 3 of 10.42 grams, 4-diacetoxyl phenyl-2 '-chloroethene ketone, its boiling point is 94～97 ℃, it just no longer further purifies and can use.
Put 11.38 grams 3 in 133 milliliters of purified petroleum benzin, 4-diacetoxyl phenyl-2 '-while the solution of chloroethene ketone is stirred the triethylamines that drop by drop added 6.75 grams, processing time is 12 minutes, at room temperature stirred then 4.25 hours, till chloride reagent disappears, and then with 50 milliliter 1: 10HCl is hydrolyzed to this solution.Water carries out extract and separate with METHYLENE CHLORIDE.Then, extract is added into and washes with water then in the organic facies till this mixture is neutrality, and is after this in addition dry to this mixture with anhydrous sodium sulfate again, removes from mixture and desolvates.Be that 40～60 ℃ benzinum extracts product with boiling point again.Extract has provided 6.98 grams 3,4-diacetoxyl phenyl vinyl one monomers behind evaporating solvent concentrated.By under-53 ℃ from ether after purging by crystallization is come out, this compound exhibits 70～72 ℃ fusing point.
Embodiment 2
Chemical formula is
Monomeric compound synthetic
According to embodiment 1 preparation be dissolved in 3 of the gram of 9.42 in 450 milliliters of absolute ethers, 4-dihydroxy phenyl-2 '-chloroethene ketone is subjected to the processing of 12 milliliters of triethylamines, at room temperature accepts 24 hours stirring then under 0 ℃.Then this reactant mixture is hydrolyzed, and extract with ether with 300 milliliters of HCl of 1: 10.Residual water after the extraction is subjected to the processing of salt and accepts extraction once more.Then, ether is collected mutually and carries out drying with anhydrous sodium sulfate, and except that after desolvating, they have just provided 3 of 5.00 grams, the semifinished product of 4-dihydroxy phenyl vinyl ketone, shown fusing point was 114～117 ℃ after it crystallized out from ether at low temperatures again.
Embodiment 3
Chemical formula is
Monomeric compound synthetic
Handle being dissolved in the gram of 11.70 in 20 milliliters of pure toluenes piperonyl ethanol with 4.5 gram sodium carbonate and 0.32 gram stannous chloride, in about 10 minutes and under the condition of stirring, the solution of the acryloyl chloride that contains 7.66 grams in 20 milliliters of pure toluenes is joined in this mixture then.Through accepting to filter and be subjected to the washing of toluene after 5 hours the backflow heating again, under low pressure accepting distillation again except that after desolvating then.Provided 3 of 11.62 grams at 97～100 ℃/0.01 torr collected fraction, 4-methylenedioxy benzyl acrylate, its purification is to be undertaken by low-pressure distillation in the presence of as the tert-butyl-catechol of stabilizing agent.
Embodiment 4
Chemical formula is
Monomeric compound synthetic
8.308 the solution that the oxolane of gram 4-chlorostyrene and 64 milliliters is formed is drop by drop stirred in blanket of nitrogen in the solution that the anhydrous tetrahydro furan that joins 1.474 magnesium that restrain and 11 milliliters forms on one side, thereby the natural back flow of accelerated solvent.Then, after this mixture is also at room temperature stirred 3 hours through 30 minutes backflow heating, this mixture is carried out 20 minutes processing with the 7.16 piperonyl aldehyde solution that restrain that are dissolved in 30 milliliters anhydrous tetrahydro furan again, thereby this mixture is remained under the slight counterflow condition naturally, at room temperature be stirred again then and reach 1.5 hours, then be hydrolyzed and extract with ether with the aqueous solution of 100 milliliter of 10% ammonium sulfate.Water washs till they neutralizations extract, and carries out drying and make it to break away from solvent with anhydrous sodium sulfate, so just obtained a kind of must be through the oil of the chromatographic isolation on 70～230 order Merck (Merck) silicagel columns (is eluent with the chloroform).Said chromatographic isolation has provided 3 of 12.03 grams, 4-methylenedioxyphenyl-4 '-styryl carbinol it with just-hexane demonstrates 55～56 ℃ fusing point after the crystallization again.
Embodiment 5
Chemical formula is
Monomeric compound synthetic
15.3 the mixture of gram Pyridinium chlorochromate on silica gel, 50 gram anhydrous methylene chlorine and the crushed 4A molecular sieve of 19 grams was subjected to 12.0 grams 3 in the clock time at 5 minutes, 4-methylenedioxyphenyl-4 '-processing of the solution of styryl carbinol (being in 50 milliliters of METHYLENE CHLORIDEs), so keep a slight backflow.At room temperature through after 2 hours the stirring, the solid that filters out washs with METHYLENE CHLORIDE, is that eluent is accepted chromatographic isolation with the METHYLENE CHLORIDE on synthetic silicic acid magnesium carrier post just through the solution after concentrating then.
Said chromatography has provided the solid 3 of 8.95 grams, 4-methylenedioxyphenyl base-4 '-styryl ketone.Said compound carries out just having demonstrated 83～84 ℃ fusing point after the crystallization with ether under-40 ℃.
Embodiment 6
Chemical formula is
Monomeric compound synthetic
9.89 restrain 3, the solution of 4-two (methoxymethoxy) benzaldehyde (being in 50 milliliters of anhydrous tetrahydro furans) is added into the solution of 4-styryl magnesium chloride (being in the oxolane) (according to the preparation of the method for embodiment 4, since 1.474 gram magnesium) in, condition is blanket of nitrogen and stirring.At room temperature this mixture is carried out 2 hours stirring then, the aqueous solution with 10% ammonium sulfate is hydrolyzed to this mixture again, and extracts with ether again.Then, water washs extract, with anhydrous sodium sulfate it is carried out drying again then, remove just provided after desolvating 13.44 grams by 3,4-two (methoxymethoxy) phenyl-4 '-oil that styryl carbinol is formed, then should oil on 230～400 order Merck (Merek) silicagel columns, be that eluent is accepted chromatographic isolation again with the chloroform.
Embodiment 7
Chemical formula is
Monomeric compound synthetic
Be dissolved in 3 of the gram of 8.43 in 50 milliliters of METHYLENE CHLORIDEs according to embodiment 6 preparation, 4-two (methoxymethoxy) phenyl-4 '-styryl carbinol, accept oxidation according to the method identical with embodiment 5, specifically be that this solution is splashed in the mixture of 8.25 gram pyridine chlorine chromium phenates, 50 milliliters of METHYLENE CHLORIDEs and 1.00 gram sodium acetates, and at room temperature this mixture carried out 2 hours stirring.This reactant mixture is added in 500 milliliters the ether and accepts filtration then, then reduces its volume, and is that eluent is accepted chromatographic isolation with the ether on synthetic silicic acid magnesium carrier post.NaOH with 3% is to containing 3,4-two (methoxymethoxy) phenyl-4 '-the ether cut of styrene ketone washs, wash then till they are neutrality, and then carry out drying with anhydrous sodium sulfate, so just provided the products of 7.96 grams afterwards by removing to desolvate, be that eluent is carried out product after further post chromatography purifies with benzinum (boiling point is 40～60 ℃)-ethyl acetate on 230～400 order Merck (Merck) silicagel columns, just the form with slightly yellow edible vegetable oil (6.54 restrain) is collected.
Embodiment 8
Chemical formula is
Monomeric compound synthetic
According to 12.12 grams 3 of embodiment 7 preparation, 4-two (methoxymethoxy) phenyl-4 '-styrene ketone is subjected to 200 milliliters of ethanol and 200 milliliter 1: the processing of the mixture of 10HCl was heated to 100 ℃ then between 15 minutes.Then this mixture that contains the solid precipitation is carried out 3 extractions with ether.Then, this mixture is subjected to the dry of anhydrous sodium sulfate and removes after the moisture content, has just provided 3,3 of 8.80 grams, and 4-dihydroxy phenyl styrene ketone through after twice crystallization more repeatedly, just demonstrates 157～159 ℃ fusing point with benzene.
Embodiment 9
3, the preparation of 4-methylenedioxy benzyl acrylate/acrylic copolymer.
4 milliliters of no peroxide De dioxs, 5.124 gram acrylic acid, 1.639 restrain 3, the not end that is in the blanket of nitrogen that it is good that the homogeneous mixture of the azodiisobutyronitrile (AIBN) of 4-methylenedioxy benzyl acrylate and 69 milligrams is added into prior drying has in the phial of tail shaped, this phial is sealed by flame then, and in thermostat, being heated to 60 ℃ while stirring, be 90 minutes heat time heating time.Then the material in the phial is introduced in the benzene, and solid just is filtered through post precipitation, is dissolved in then and also accepts precipitation in a spot of diox once more in benzene.Through further filtering and in the baking oven of 30 ℃ of vacuum, just obtained after the dried overnight copolymer of 5.193 grams, the solution that contains 1% this copolymer then in the Zai diox with preparation carries out classification to this copolymer to be separated, and with very low speed benzene is drop by drop joined in the said solution under stirring condition and to go, and remain under 25 ℃ the constant temperature.After filtration three kinds of fraction collections are got up, they are equivalent to a spot of light fraction, useful midbarrel and a large amount of tailings.2.86 midbarrel interior viscosity in dioxanes in the time of 25 ℃ of gram is 82.1 milliliters/gram, its mean molecule quantity that obtains by osmometry is 35,000 dalton.
Interior viscosity in the time of 25 ℃ in the Zai diox is 77.9 milliliters/gram and is 33 through the mean molecule quantity of osmometry, 000 daltonian copolymer can be obtained equally, its yield is 70%, and it is that same monomeric compound with 1.59: 1 this weight rates is an initial substance.
After the same method, under the situation that does not have solvent to exist, being initial substance with the same monomeric compound of 1: 1.23 weight rate, can to prepare interior viscosity in 25 ℃ dioxanes be 76.3 milliliters/gram and be 33,000 daltonian copolymers through the mean molecule quantity of osmometry through 62% conversion.
Embodiment 10
3, the preparation of 4-methylenedioxy benzyl acrylate/methacrylic acid copolymer.
According to the same quadrat method among the embodiment 9 this copolymer is prepared with classification and separates, still, the solvent that is used for the classification separable programming is a methyl alcohol, and non-solvent is a METHYLENE CHLORIDE.
In the presence of 113 milligrams of azodiisobutyronitriles (AIBN), 3 of 6 milliliters of De dioxs, 3.150 acrylic acid that restrain and 8.124 grams, 4-methylenedioxy benzyl acrylate, through 210 minutes later copolymers that just provided 3.674 grams, the classified after separating of this copolymer has just provided the heart cut of 2.226 grams, its interior viscosity in the Zai diox in the time of 25 ℃ is 125.0 milliliters/gram, and the mean molecule quantity that obtains through osmometry is 54,000 dalton.
Same monomeric compound with 3.92: 1 part by weight is an initial substance, make after the same method a kind of in the time of 25 ℃ the interior viscosity in the methyl alcohol be 208.7 milliliters/gram copolymer, its conversion ratio is 54%
Embodiment 11
3.4-the preparation of methylenedioxy benzyl acrylate/4-vinyl benzoic acid copolymer.
17.505 gram 4-vinyl benzoic acid, 6.106 restrain 3,4 methylenedioxy benzyl acrylate, the mixture of 14 milliliters of no peroxide De dioxs and 238 milligrams of azobis isobutyronitriles (AIBN), according to method given among the embodiment 9, in 60 ℃ phial, accept 135 minutes copolyreaction, so just provided the copolymer of 3.217 grams, just obtained the heart cut of 2.189 grams after the mixture classification fractionation through Yong diox/benzene, its interior viscosity in the Zai diox in the time of 25 ℃ is 17.6 milliliters/gram, and the mean molecule quantity that obtains through osmometry is 100.000 dalton.
Embodiment 12
3, the preparation of 4-methylenedioxy benzyl acrylate/4-vinylpridine copolymer.
In 60 ℃ phial, 7.027 gram 4-vinylpridines, 4.162 are restrained 3 according to the method for being set forth among the embodiment 9, the mixture of 4-methylenedioxy benzyl acrylate, 10 milliliters of no peroxide De dioxs and 112 milligrams of azobis isobutyronitriles (AIBN) is accepted 280 minutes copolyreaction, so obtain the copolymer of 2.718 grams, after classification is isolated from 1% METHYLENE CHLORIDE solution by the benzene that slowly adds 25 ℃ the time, just provided the heart cut of 2.513 grams, its interior viscosity in METHYLENE CHLORIDE in the time of 25 ℃ is 69.4 milliliters/gram.
Embodiment 13
3, the preparation of 4-methylenedioxy benzyl-4-styrene ketone/acrylic copolymer.
According to method given among the embodiment 9, under 60 ℃ temperature, restrain 3 to 4.054,4-methylenedioxyphenyl-4 '-styrene ketone, 28 milliliters no peroxide De diox, 4.625 the mixture of gram acrylic acid and 11 milligrams of azodiisobutyronitriles (AIBN) is implemented 750 minutes copolyreaction, thereby obtain the copolymer of 2.670 grams, this copolymer is after 25 ℃ of following Yong diox/benzol mixtures carry out the classification separation, just provided the heart cut of 2.300 grams, interior viscosity in its Zai diox in the time of 25 ℃ is 78.3 milliliters/gram, and the mean molecule quantity that obtains through osmometry is 70.000 dalton.
After the same method, be initial substance with the same monomer of 1: 5.33 part by weight, can make in the time of 25 ℃ in viscosity be the copolymer of 74.94 milliliters/gram, its conversion ratio is 50%.
Embodiment 14
3,4-methylenedioxyphenyl-4 '-preparation of styrene methyl alcohol/acrylic copolymer.
Method according to embodiment 9, under 60 ℃ temperature, restrain 3 to 3.933,4-methylenedioxyphenyl-4 '-mixtures of styrene methyl alcohol, 29 milliliters of no peroxide De dioxs, 4.518 gram acrylic acid and 9 milligrams of azodiisobutyronitriles (AIBN) carry out 1970 minutes copolyreaction, thereby obtain the copolymer of 3.805 grams, this copolymer 25 ℃ down through carry out with/diox/benzol mixture/the classification after separating just obtains the heart cuts of 3.369 grams, its interior viscosity in the Zai diox in the time of 25 ℃ be 99.2 milliliters/restrain.
Embodiment 15
3, the preparation of 4-diacetoxyl phenyl ketenes/acrylic copolymer.
Method according to embodiment 9, under 60 ℃ temperature, restrain 3 to 2.471,4-diacetoxyl phenyl ketenes, 6 milliliters of no peroxide De dioxs, 2.872 the mixture of gram acrylic acid and 21 milligrams of azodiisobutyronitriles (AIBN) carries out copolyreaction, reaction time is 340 minutes, so obtain the copolymer of 4.015 grams, carry out the heart cut that the classification after separating has just obtained 3.080 grams at 25 ℃ of following Yong diox/benzol mixtures, its interior viscosity in the Zai diox in the time of 25 ℃ is 52.5 milliliters/gram, and the mean molecule quantity that obtains through osmometry is 41.000 dalton.
Embodiment 16
3, the preparation of 4-dihydroxy benzenes ethyl ketene/acrylic copolymer.
According to the method for being set forth among the embodiment 15, prepare 3 of 2.703 grams, 4-diacetoxyl phenyl ketenes/acrylic copolymer, its interior viscosity in the Zai diox in the time of 25 ℃ is 52.5 milliliters/gram.Divide four parts in 7 hours and under the condition of 40～45 ℃ temperature continuous stirring, 100 milliliters of De dioxs to be handled with 1 milliliter concentrated hydrochloric acid.Resulting copolymer like this has not shielded phenolic hydroxyl group, and it is partly separated with the form of oil and a same part can obtain reclaiming Cong dioxane solution by evaporating solvent.Copolymer is dissolved in the oxolane, accepts precipitation in the METHYLENE CHLORIDE by with low rate this solution being injected into then.Its weight is 2.451 grams after 25 ℃ of dryings under vacuum.
Embodiment 17
3,4-dihydroxy benzenes ethyl ketene/3, the preparation of 4-methylenedioxy benzyl acrylate/acrylic acid ternary polymerization compound.
According to embodiment 9 described methods, under 60 ℃ temperature, restrain 3 to 1.308,4-dihydroxy benzenes ethyl ketene, 3.522 restrain 3,4-methylenedioxy benzyl acrylate, 32 milliliters of no peroxide De dioxs, 6.071 the mixture of gram acrylic acid and 12 milligrams of azodiisobutyronitriles (AIBN) carries out 96 hours copolyreaction, thereby 2.979 gram copolymers have been provided, through carrying out the classification after separating at 25 ℃ of following Yong diox/benzol mixtures, just obtained the heart cut of 2.020 grams, its interior viscosity in the Zai diox in the time of 25 ℃ is 21.0 milliliters/gram, and the mean molecule quantity that obtains through osmometry is 105.000 dalton.
Embodiment 18
3,4-dihydroxy phenyl-4 '-preparation of styrene ketone/acrylic copolymer.
According to the method described in the embodiment 9, under 27 ℃ temperature, restrain 3 to 5.380,4-dihydroxy phenyl-4 '-styrene ketone, 55 milliliters of no peroxide De dioxs, 6.923 gram acrylic acid and 35 milligram three (just-butyl) mixture of monoborane carries out 27 hours copolyreaction, thereby provide the copolymer of 4.353 grams, just obtained 2.520 heart cuts that restrain with oxolane/METHYLENE CHLORIDE compound through the classification after separating down at 25 ℃ then, its interior viscosity in dioxanes in the time of 25 ℃ is 60.3 milliliters/gram.
Embodiment 19
3,4-dimethoxy methoxyl group-phenyl-4 '-preparation of styrene ketone/acrylic copolymer.
According to embodiment 9 described methods, under 60 ℃ temperature, restrain 3 to 4.250,4-dimethoxy methoxyphenyl-4 '-mixture of the azodiisobutyronitrile (AIBN) of styrene ketone, 35 milliliters of no peroxide De dioxs, 3.890 acrylic acid and 3 milligrams carries out 22 hours copolyreaction, thereby obtain the copolymer of 3.460 grams, carry out the heart cut that the classification after separating has just obtained 2.595 grams at 25 ℃ of following Yong diox/benzol mixtures then, its interior viscosity in the Zai diox in the time of 25 ℃ is 22.20 milliliters/gram.
Embodiment 20
With 3,4-methylenedioxy benzyl acrylate/acrylic copolymer carries out dispersion treatment to rutile.
Purity is 98%, the powder particle size is the rutile of≤20um.
Employed material:
A kind of as embodiment 9 described copolymerizations, its interior viscosity in diox in the time of 25 ℃ is 82.1 milliliters/gram.
The aqueous solution of NaOH and HCl.
Experiment is undertaken by following approach:
Be in the processing of the ores of about 2 grams in 100 milliliters of graduated cylinders (its height that can effectively be used is 185 millimeters) and the copolymer that 70 milliliters water is subjected to aequum (be in pH value and be 12 the aqueous solution in), this mixture was by shake 5 minutes then, and be adjusted to required pH value, again at a high speed after again by shake 15 minutes, after this, it is allowed to be placed in the graduated cylinder that is in vertical position, the time of placing during its PH=3.5 is 2 ' 30 "; be 20 the standing time during PH=7.5 ' and standing time during PH=9.5 also is 20 ' (time is to determine on the basis of previous test; because not in the presence of flocculant; the ore weight that is contained in the upper volume of 70 milliliters of liquid should be about 1 gram; for example, employed in the experiment is 50%).So the top volume in 70 milliliters of decentralized photos just is removed by siphon pipe, and be evaporated dry till constant weight.
According to the equation that is used for determining flocculation or force of flocculation, have that contained mineral weight is equivalent to P in the top 70 milliliters of liquid volumes of existence of copolymer; Do not have that contained mineral weight is equivalent to P in the top 70 milliliters of liquid volumes that copolymer exists
o; Do not have contained mineral weight in the bottom 30 milliliters of liquid volumes that solvent exists, add P
oValue multiply by 0.7 then and just is equivalent to PP
oBottom 30 ml volumes of decentralized photo also are evaporated dry till constant weight.
Flocculate forms under acid pH value at last, and at this moment flocculation sediment is very fast.
When the concentration of flocculant is 10PPm, and final pH value is as already pointed out, and the result is exactly so: PH=3.5, P
f=76; PH=7.5, P
d=59; PH=9.5, P
d=47.
When the concentration of flocculant is 50PPm, consequently: PH=3.5, P
f=89; PH=7.5, P
d=78; PH=9.5, P
d=77.
When the concentration of flocculant is 100PPm consequently: PH=3.5, P
f=78; PH=7.5, P
d=85; PH=9.5, P
d=80.
Embodiment 21
With 3,4-methylenedioxy benzyl acrylate/acrylic copolymer carries out dispersion treatment to rutile.
Prepare according to embodiment 9 that the interior viscosity in the Zai diox is the copolymer of 77.9 milliliters/gram 25 ℃ the time.Experimentize according to embodiment 20.
When the concentration of flocculant was 10PPm, its result was: PH=3.5, P
f=70; PH=7.5, P
f=53; PH=9.5, P
d=67.
When the concentration of flocculant was 50PPm, its result was: PH=3.5, P
f=91; PH=7.5, P
d=74; PH=9.5, P
d=87.
When the concentration of flocculant was 100PPm, its result was: PH=3.5, P
f=89; PH=7.5, P
f=7; PH=9.5, P
d=100.
Embodiment 22
With 3,4-methylenedioxy benzyl acrylate/acrylic copolymer carries out dispersion treatment to rutile.
Prepare according to embodiment 9 that the interior viscosity in the Zai diox is the copolymer of 76.3 milliliters/gram 25 ℃ the time.
Test according to embodiment 20.
When the concentration of flocculant was 10PPm, its result was: PH=3.5, P
f=58; PH=7.5, P
f=1; PH=9.5, P
f=0.
When the concentration of flocculant was 50PPm, its result was: PH=3.5, P
f=85; PH=7.5, P
d=18; PH=9.5, P
d=20.
When the concentration of flocculant was 100PPm, its result was: PH=3.5, P
f=80; PH=7.5, P
d=74; PH=9.5, P
d=86.
Embodiment 23
With 3,4-methylenedioxy benzyl acrylate/A-vinylpyridine copolymer carries out dispersion treatment to rutile.
The interior viscosity in METHYLENE CHLORIDE 25 ℃ time the according to embodiment 12 preparation is the copolymer of 69.4 milliliters/gram.
Test according to embodiment 20, but some exception is arranged, promptly copolymerization is added in the aqueous solution of PH=2.
When the concentration of flocculant was 50PPm, its result was: PH=3, P
d=100; PH=7, P
f=41; PH=9, P
f=12.
Embodiment 24
With 3,4-methylenedioxy benzyl acrylate/acrylic copolymer carries out dispersion treatment to bloodstone.
Prepared according to embodiment 9 that the interior viscosity in the Zai diox is the copolymer of 77.9 milliliters/gram 25 ℃ the time.
Test according to embodiment 20.
When the concentration of flocculant was 10PPm, its result was: PH=3, P
f=80; PH=7, P
f=65; PH=9, P
f=55.
When the concentration of flocculant was 50PPm, its result was: PH=3, P
f=98; PH=7, P
f=70; PH=9, P
f=18.
When the concentration of flocculant was 100PPm, its result was: PH=3, P
f=87; PH=7, P
d=82; PH=9, P
d=26.
Embodiment 25
With 3,4-methylenedioxy benzyl acrylate/acrylic copolymer carries out dispersion treatment to ilmenite.
Prepared according to embodiment 9 that the interior viscosity in the Zai diox is the copolymer of 77.9 milliliters/gram 25 ℃ the time.
Test according to embodiment 20.
When the concentration of flocculant was 10PPm, its result was: PH=3, P
f=52; PH=7, P
f=64; PH=9, P
f=98.
When the concentration of flocculant was 50PPm, its result was: PH=3, P
f=52; PH=7, P
f=22; PH=9, P
d=11.
When the concentration of flocculant was 100PPm, its result was: PH=3, P
f=44; PH=7, P
f=2; PH=9, P
d=17.
Embodiment 26
With 3,4-methylenedioxy benzyl acrylate/acrylic copolymer carries out dispersion treatment to quartz.
Prepared according to the method for embodiment 9 that the interior viscosity in the Zai diox is the copolymer of 82.1 milliliters/gram 25 ℃ the time
Test by the method described in the embodiment 20.
When the concentration of copolymer was 50PPm, its result was: PH=3, P
d=43; PH=7, P
f=3; PH=9, P
d=13.
Embodiment 27
With 3,4-methylenedioxy benzyl acrylate/methacrylic acid copolymer carries out dispersion treatment to rutile.
Prepared according to the method described in the example 10 that the interior viscosity in the Zai diox is the copolymer of 125.0 milliliters/gram 25 ℃ the time.
Test according to the method among the embodiment 20.
When the concentration of polymer was 10PPm, its result was: PH=3.5, P
d=33; PH=7.5, P
f=0; PH=9.5, P
d=3.
When the concentration of polymer was 50PPm, its result was: PH=3.5, P
d=3; PH=7.5, P
d=29; PH=9.5, P
d=3.
When the concentration of polymer was 100PPm, its result was: PH=3.5, P
d=18; PH=7.5, P
d=33; PH=9.5, P
d=20.
Embodiment 28
With 3,4-dihydroxy benzenes ethyl ketene/acrylic copolymer carries out dispersion treatment to rutile.
Prepared copolymer according to the method that provides among the embodiment 16.
Method according to embodiment 21 is tested.
When polymer concentration was 10PPm, its result was: PH=3, P
d=59; PH=7, P
f=35; PH=11, P
d=20.
When polymer concentration was 50PPm, its result was: PH=3, P
d=100; PH=7, P
d=72; PH=11, P
d=100.
When polymer concentration was 100PPm, its result was: PH=3, P
d=100; PH=7, P
d=100; PH=11, P
d=100.
Embodiment 29
With 3,4-dihydroxy benzenes ethyl ketene/acrylic copolymer carries out dispersion treatment to ilmenite.
Prepared copolymer according to the method among the embodiment 16.
Test according to the method among the embodiment 20.
When the concentration of polymer was 10PPm, its result was: PH=3, P
f=58; PH=7, P
d=18; PH=9, P
d=15.
When the concentration of polymer was 50PPm, its result was: PH=3, P
f=79; PH=7, P
d=6; PH=9, P
d=34.
When the concentration of polymer was 100PPm, its result was: PH=3, P
f=58; PH=7, P
f=6; PH=9, P
d=45.
Embodiment 30
With 3,4-methylenedioxyphenyl-4 '-styryl carbinol/acrylic copolymer carries out dispersion treatment to rutile.
Prepared according to the method among the embodiment 14 that the interior viscosity in the Zai diox is the copolymer of 99.2 milliliters/gram 25 ℃ the time.
Test according to the method among the embodiment 20.
When the concentration of polymer was 10PPm, its result was: PH=3, P
d=63; PH=7, P
d=74; PH=9, P
d=98.
When the concentration of polymer was 50PPm, its result was: PH=3, P
d=2; PH=7, P
d=76; PH=9, P
f=11.
When the concentration of polymer was 100PPm, its result was: PH=3, P
d=2; PH=7, P
d=75; PH=9, Pd=78.
Embodiment 31
With 3,4-methylenedioxyphenyl-4 '-styryl carbinol/acrylic copolymer carries out dispersion treatment to ilmenite.
Prepared according to the method among the embodiment 14 that the interior viscosity in the Zai diox is the copolymer of 99.2 milliliters/gram 25 ℃ the time.
Test according to the method among the embodiment 20.
When the concentration of polymer was 10PPm, its result was: PH=3, P
f=58; PH=7, P
f=1; PH=9, P
d=21.
When the concentration of polymer was 50PPm, its result was: PH=3, P
f=64; PH=7, P
f=15, PH=9, P
d=32.
When the concentration of polymer was 100PPm, its result was: PH=3, P
d=5; PH=7, P
f=10; PH=9, P
d=30.
Embodiment 32
With 3,4-methylenedioxy benzyl acrylate/methacrylic acid copolymer carries out dispersion treatment to ilmenite.
Prepared according to the method among the embodiment 10 that the interior viscosity in methyl alcohol is the copolymer of 208.7 milliliters/gram 25 ℃ the time.
Test according to the method among the embodiment 20.
When polymer concentration was 10PPm, its result was: PH=3, P
f=76; PH=7, P
f=86; PH=9, P
d=21.
When polymer concentration was 50PPm, its result was: PH=3, P
d=4; PH=7, P
d=28; PH=9, P
d=83.
When polymer concentration was 100PPm, its result was: PH=3, P
d=12; PH=7, P
d=32; PH=9, P
d=44.
The present invention has passed through more effective especially specific embodiments are disclosed in conjunction with detailed explanation, but must understand, can introduce the present invention to some modifications and variations, this can not depart from the essence and the scope of the priority of the present patent application patent.
Claims (8)
1, a kind of unit cell is equivalent to general formula
Polymer or copolymer with the flocculant of making titanium iron ore is carried out selective flocculation flotation, wherein R
1And R
2On behalf of molecular formula, (each other can be identical or different) be
-O-CHR
5The abutment of-O-, or the hydroxyl that can exist with its ether or ester derivant form, in above-mentioned general formula, symbol R
3, R
4Or R
5Be equivalent to atomic radical, and some other group (each other can be identical or different) can be hydrogen atom, alkyl, aryl, hydroxyl, alkoxyl, hydroxy alkyl, alkoxyalkyl, haloalkyl, carbonyl, carboxyl, ester, acylamino-, nitro, sulfo group, halogen atom or nitrilo-nitro in the polymerizable series that on the different spatial of the position of substitution, contains.
2, the selective flocculant that is used for titanium iron ore according to claim 1, it is characterized in that said polymerizable series be applicable to polymerisation through overactivation alkene series.
3, according to claim 1 and 2 described selective flocculants, it is characterized in that said copolymer is made up of the monomeric unit that is equivalent to general formula (I) monomer, these monomers are olefinic monomers that a class contains the group that its hydrophily changes with pH value.
4, the selective flocculant of flocculating floatation of titanium and iron ores according to claim 3 is characterized in that said monomeric compound belongs to this class, and they are acrylic acid, methacrylate, 4-vinyl benzoic acid, 4-vinylpridine.
5,, it is characterized in that in several thousand to 1,000,000 such scopes, to change as the molecular weight of the said flocculant of non-crosslinked material according to the selective flocculant of any described flocculating floatation of titanium and iron ores of claim 1-4.
6, according to any described selective flocculant of claim 1-5, it is characterized in that copolymer comprises two or more component, for example three kinds, said copolymer preferably contains the represented monomeric compound of general formula (I) of 10%-30%.
7, according to any described selective flocculant that is used for flocculating floatation of titanium and iron ores of claim 1-6, it is characterized in that their concentration in solution is 10-100PPm.
8, described according to above any claim to flocculating floatation of titanium and iron ores flocculant selectively, they in the above by substantially open and explanation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 86100669 CN86100669A (en) | 1986-01-20 | 1986-01-20 | The synthetic organic polymers that is used for selective flocculating floatation of titanium and iron ores |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP86830014A EP0232679B1 (en) | 1986-01-20 | 1986-01-20 | Synthetic organic polymers for the selective flocculation of titanium and iron ores |
| CN 86100669 CN86100669A (en) | 1986-01-20 | 1986-01-20 | The synthetic organic polymers that is used for selective flocculating floatation of titanium and iron ores |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN86100669A true CN86100669A (en) | 1987-08-05 |
Family
ID=25742171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 86100669 Pending CN86100669A (en) | 1986-01-20 | 1986-01-20 | The synthetic organic polymers that is used for selective flocculating floatation of titanium and iron ores |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN86100669A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100388983C (en) * | 2006-01-23 | 2008-05-21 | 攀枝花钢铁有限责任公司钛业分公司 | Collector for flotation collecting ilmenite and its preparation method |
| CN107638956A (en) * | 2017-09-30 | 2018-01-30 | 江苏闽江矿业有限公司 | A kind of method that dual liquid flotation method removes iron in silica sand |
-
1986
- 1986-01-20 CN CN 86100669 patent/CN86100669A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100388983C (en) * | 2006-01-23 | 2008-05-21 | 攀枝花钢铁有限责任公司钛业分公司 | Collector for flotation collecting ilmenite and its preparation method |
| CN107638956A (en) * | 2017-09-30 | 2018-01-30 | 江苏闽江矿业有限公司 | A kind of method that dual liquid flotation method removes iron in silica sand |
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