CN101128264B - Modified amine-aldehyde resins and uses thereof in separation processes - Google Patents

Abstract

Amine-aldehyde resins are disclosed for removing a wide variety of solids and/or ionic species from the liquids in which they are suspended and/or dissolved. These resins are especially useful as froth flotation depressants in the separation of bitumen from sand and/or clay or in the beneficiation of clay (e.g., kaolin clay) from an impure clay-containing ore. The resins are also useful for treating aqueous liquid suspensions to remove solid particulates, as well as for removing metallic ions in the purification of water.

Description

The amine-aldehyde resins of modification and the application in separating technology thereof

The cross reference of related application

60/713,339 the priority that the application requires the U.S. Provisional Patent Application 60/638,143 that proposed on December 23rd, 2004 and proposed on September 2nd, 2005 is all introduced with for referencial use in full at this.

Technical field

The present invention relates to the modified resin for separating of technique, particularly Selective Separation solid and/or ionic species (for example metal cation) from water-bearing media.This technique comprises froth flotation (for example be used for ore dressing), separates drilling cuttings, clay and the dehydration of coal slurry material, sewage disposal, pulp mill and paper mill liquid waste processing, removes sand and water purification makes it suitable for drinking from pitch from the oil drilling fluid.Modified resin comprises base resin, and it is the product (for example Lauxite) of primary amine or secondary amine and aldehyde.In its preparation process or use thereafter coupling agent (as: silane of replacement) to carry out modification to this base resin.

Background technology

Froth flotation

Industrial, being used for purification suspension or dispersion (especially aqueous suspension or dispersion) is quite general with the technique of removing the solid particle that suspends.For example, froth flotation is a kind of separation process that has different combination tendencies based on various materials and rising bubble.Usually add additive to improve the selective of technique in froth flotation liquid.For example, " trapping agent " can be used for chemistry and/or Physical Absorption and treat the mineral (for example comprise useful metal those) of flotation to make them have better hydrophobicity.On the other hand, " inhibitor " that usually is combined with trapping agent makes other material (for example gangue mineral) less with the possibility of bubble incorporation, and the possibility that therefore is brought into foam concentrate is also less.

After this manner, some materials (for example valuable mineral or metal) show preferential affinity to bubble with respect to other material (for example gangue mineral), cause them to rise to the surface of aqueous slurry, they can be collected in foam concentrate at this.Realize thus separating degree.In particular cases, so-called anti-froth flotation, be gangue preferentially by flotation and in set of surfaces, required material is removed in the bottom.Although may comprise other mineral (such as fluorite, barite etc.), the gangue material is typically referred to as quartz, sand and clay silicate, and calcite.In some cases, material to be clean mainly comprises this material, and diffeential floatation amount impurity still less.For example, at the material of industrial extensive application---in kaolinic ore dressing, can isolate iron oxide and titanium oxide from impure ore argillaceous by flotation, stay the kaolin bottom product through purifying.

Although determine the mode that known trapping agent and inhibitor are realized its effect not yet fully, proposed at present several theories.For example inhibitor can prevent that gangue mineral from adhering on valuable mineral to be separated, and perhaps they can prevent that even trapping agent is absorbed on gangue mineral.Mechanism whatsoever, inhibitor improves optionally that ability can affect its economy highly beneficially in the froth flotation process.

Generally speaking, at multiple useful materials (for example mineral and metallic ore, even such as the high-molecular-weight hydrocarbons of pitch) ore dressing in, froth flotation is commonly used, in order to they and the unwanted impurity that inevitably extracts simultaneously from natural mineral reserve are separated.In the situation of solid mineral ore dressing, froth flotation generally includes the enough little disperse particles that tcrude ore is milled into valuable mineral or metal, and moisture " slurry " of the ore of then this being milled contacts with rising bubble, usually stirs simultaneously this slurry.Before froth flotation, tcrude ore can be carried out any amount of pre-treatment step, comprise selective crushing, screening, desliming, gravity separation, electric separation, low-temperature bake and magnetic differentiation.

Another kind of industrial important special foam floating process comprises separate bitumen from sand and/or clay, and they are ubiquity in those oil-sand mineral reserve of the vast Athabasca area discovery of for example Canadian Alberta.Pitch is considered to " semisolid " oil or contains the useful source of heavy hydrocarbons crude oil, can be processed into to comprise transport fuel such as gasoline or the many useful end product of petrochemicals even.The oil-sand mineral reserve of Alberta estimate to comprise 1.7 trillion barrels of bitumeniferous crude oil, surpass the reserves of whole Saudi Arabia.Therefore, recently paid huge effort in development for the economically viable operating aspect that reclaims pitch, mainly based on making the aqueous slurry that extracts oil-sand in froth flotation.For example " Clark technique " comprises the pitch that is recovered in foam concentrate, suppresses simultaneously sand and other solid impurity.

The multiple gangue inhibitor that separates for improvement of froth flotation known in the art, comprise sodium metasilicate, starch, tannic acid, dextrin, lignin sulfonic acid, carboxy methyl cellulose, cyanide salt and many other.Found that the synthetic polymer of recently determining is favourable in concrete ore dressing process.United States Patent (USP) Re.32 for example, 875 cascophens (for example cyanurotriamide modified linear novolaks) of having described phenolic aldehyde copolymer (for example phenol-formaldehyde A, linear novolaks) or modification are used as inhibitor, separate gangue from phosphate mineral (for example apatite).

United States Patent (USP) 3,990,965 described use water miscible low chain length prepolymer as inhibitor, optionally adhere to gangue and further polymerization obtain crosslinked insoluble resins, separation of oxygenated iron from bauxite.

United States Patent (USP) 4,078,993 solution of low-molecular-weight condensation product or the dispersions of having described aldehyde and the compound that contains 2-6 amine or amide group are used as inhibitor, the sulfide ore (for example pyrite, magnetic iron ore or zincblende) of separate sulfur compound or oxidation from metallic ore ore (for example copper, zinc, lead, nickel).

United States Patent (USP) 4,128,475 and 4,208,487 have described with conventional foaming agent (for example pine tar) in conjunction with (preferred alkyl) amine-aldehyde resins that can have free methylol group, separate the gangue material from mineral ore.

United States Patent (USP) 4,139,455 have described amines (for example polyamines) as inhibitor, the sulfide ore (for example pyrite, magnetic iron ore or zincblende) of separate sulfur compound or oxidation from metallic ore ore (for example copper, zinc, lead, nickel), in amines, at least 20% of the amido total amount being tertiary amine groups, and wherein quaternary ammonium group quantity is 1/3 of 0～no more than tertiary amine groups quantity.

United States Patent (USP) 5,047,144 have described and the Maranyl template have been combined active cationic surfactant (for example Organoalkyl amine) or active anion surfactant (for example alkylsulfonate of long-chain) with the active cation condensation product of formaldehyde as inhibitor, separation silicoide (for example feldspar) from ore (for example kaolinite).

Russ P 427,737 and 276,845 has been described with CMC and Lauxite, optionally and methacrylic acid-methacrylamide copolymer or starch suppress the clay sludge in conjunction with (' 845 patent).

Russ P 2,169,740,2,165,798 and 724,203 have described in potassium industry to have suppressed clay carbonate sludge from the ores that comprises sylvite (KCl-NaCl) ore deposit.Inhibitor used is the urea/aldehyde condensation products with the polyethylenepolyamine modification.In addition, use guanidine-urea formaldehyde (' 203 patent).

Markin, A.D. etc. have described in the flotation of potassium ore Lauxite as the application of carbonate clay inhibitor.Lauxite in the potassium ore deposit to the hydrophilic active research (Study of theHydrophilizing Action of Urea-Formaldehyde resins on Carbonate Clay Impuritiesin Potassium Ores) of carbonate clay impurity, Inst.Obshch.Neorg.Khim, USSR, Vestsi Akademii NavukBSSR, Seryya Khimichnykh Navuk (1980); The effect (Effect of Urea-Formaldehyde resins on the Flotation of Potassium Ores) of Lauxite in potassium ore deposit flotation, Khimicheskaya Promyshlennost, Moscow, Russian Federation (1980); And Lauxite is in the absorption (Adsorption of Urea-Formaldehyde resins onClay Minerals of Potassium Ores) of the clay mineral in potassium ore deposit, Inst.Obshch Neorg.Khim., Minsk, USSR, Doklady Akademii Nauk BSSR (1974).

As known in the art, can ore dressing/refining a variety of materials by froth flotation.Similarly, expectation very large with nature difference undesirable composition.This is because the chemical composition of these materials is different, and previous chemically treated kind is different with treatment step used.Therefore, the value volume and range of product of froth flotation inhibitor is relatively extensive.

And it is effectively same that the application of special inhibitor in a device (for example former potassium ore ore dressing) do not indicate that it is relating in the application of significantly different raw materials (for example bitumeniferous oil-sand).This is equally applicable to the relevant effectively application of inhibitor in froth flotation, and its any one separating solids impurity aspect from aqueous suspension of being described below of expectability is not all effectively (vice versa).Gu froth flotation and moisture liquid/separate the theoretical mechanism that produces are visibly different, the former process relies on hydrophobic difference, and the latter relies on several other possibilities (electric charge is unstable/neutralization, reunion, Subjective and Objective theoretical (comprising multiple tooth coordination), hsab theory, dipole-dipole-dipole interaction, the highest Gibbs free energy that takies molecular orbit-lowest unoccupied molecular orbital (HOMO-LUMO) interaction, hydrogen bond, key etc.).The inhibitor such as the guar gum that are used for the metallic ore ore dressing in froth flotation can not be used as dehydrating agent, perhaps even can not be as the inhibitor in the froth flotation of separated from bitumen.And, in the two kinds of application (dehydration of spent clay and coal) that are described below, do not have at present reagent to be used to improve solid/liquid separation.Generally speaking, although a large amount of depressing agents and dehydrating agent are arranged in this area, in many cases, even in the situation that froth flotation when using two or more continuous " slightly " and " essence " flotation thing, still is difficult to the degree of purification that reaches enough.Therefore need can be at the reagent that comprises froth flotation and effectively use in the large-scale separation process of separating solids impurity from suspension in this area.

Other separation

Be used for outside the foam-expelling flotation can comprising that from other technique of suspension separating solids impurity to make these suspension unstable or make impurity be condensed into the use of the additive of larger agglomerate.For example cohesion refer to by in and the electric charge of separate suspended solid particle, make them unstable.Flocculation refers to the solids bridge joint or reunites to becoming together piece or floccule, thereby according to the density of floccule with respect to liquid, impels their separation by precipitation or flotation.Can use in addition the means of filtering as separating larger floccule.

Above-mentioned additive especially flocculant is applied in usually, for example separates the solids of rock or drilling cuttings from oil well and gas well drilling fluid.In drilling technology because these drilling fluids of some reasons (usually also referred to as " drilling mud ") are important, these reasons comprise the Cooling and Lubricator drill bit, the generation liquid counterpressure prevents that the fluid that hydraulic oil, gas and/or water form from entering well too early, stops the borehole collapse that exposes.No matter be water base or oil base, drilling mud is also removed drilling cuttings from drilling well is regional, and they are transported to the surface.Flocculant such as acrylate copolymer is commonly used to make these bits to reunite on the surface of circulation drilling mud, thereby it is separated from drilling mud.

Other application of flocculant comprises the clays that are suspended in from a large amount of useless slurry effluents of phosphate production factory is reunited in solid/liquid separation.The flocculant that can mix with the fibrous material such as regenerated newsprint, natural or synthetic anionic polymer for example is through being usually used in this purpose.The moisture clay slurry that forms in the phosphate purifier has usually higher than 100,000 gallons of flow velocitys per minute, and usually comprises the solid that is less than 5wt.%.The dehydration (or precipitation) that makes water be able to recycling this spent clay is one of hard problem that is associated with recovery.The sedimentation basin that is used for this dehydration consists of approximately half mining area usually, and dewatering time may be that about some months was by several years.

Aspect separating solids from liquid, aqueous, industrial other important special application comprises filters coal (being the dehydration of coal slurry material) from aqueous slurry, dispose of sewage to remove impurity (for example mud) by sedimentation, and the processing of pulp mill and papermaking sewage is to remove the cellulosic solid that suspends.Being dehydrated into of coal is great industrial problem, reduces because the BTU value of coal increases with water content.Industry and city raw sewerage need huge disposal ability, for example be collected in sewerage system by the refuse of U.S. population generation and by every day the water of 14,000,000,000 gallons take away.The paper industry waste liquor stream is similarly and contains in a large number the liquid, aqueous of solid, and the waste water of a typical paper mill generation is common over 2,500 ten thousand gallons every day.As mentioned above, remove sand the extraction of oil-sand and processing subsequently from the moisture bituminous slurry that produces, proposing the huge challenge of another large-scale production aspect the purification of aqueous suspension.In addition, aspect water purification, for example in the preparation of drinking (namely drinkable) water, removing the solia particle that suspends is often the material particular that needs consideration.Synthetic polyacrylamide and the hydrocolloid polysaccharide such as alginates (copolymer of D-MANNOSE aldehydic acid and L-guluronic acid) and guar gum of natural formation are the flocculants in this device.

Therefore above application provides to relate to and has processed aqueous suspension to remove several object lessons of solia particle.Yet in a large amount of other techniques of mining, chemistry, industry and municipal waste, sewage disposal and paper industry and a variety of other water consumption industry, such separation is common.Thereby this area needs effectively to promote the additive of Selective Separation many kinds of solids impurity from liquid suspension.Advantageously, aspect the chemical interaction of solid impurity, such reagent should be optionally, by condensing, flocculate or other mechanism making the removal of these impurity be easy to realize.Especially expectation be can also the undesirable ionic species of complexing such as metal cation with the additive of same its removal of promotion.

Summary of the invention

All application

The present invention relates to for usually with selection mode from liquid remove suspend and/or be dissolved in wherein many kinds of solids and/or the modified resin of ionic species.These modified resin are particularly useful as many kinds of materials, comprise the froth flotation inhibitor in the ore dressing (for example kaolinic ore dressing) of mineral and metallic ore.This modified resin also can be used for processing the aqueous suspension (aqueous suspension that for example comprises sand, clay, coal and/or other solid, the cutting fluid of useless rig for example, and the process flow in the production process of phosphate and coal and waste liquor stream, sewage disposal, papermaking or bitumen recovery equipment), to remove solid particle and possible metal cation (for example in drinking water purification).This modified resin comprises coupling agent modified base resin, this coupling agent in conjunction with solid impurity particularly siliceous material (for example sand or clay) have the selective of height.

Froth flotation

Without being limited by theory, this coupling agent has the selective of height in particularly the froth flotation of siliceous gangue material (for example sand or clay) combination separates with gangue or required material (for example kaolin).And, because base resin has hydrophily, in foam floating process, at aqueous phase, effectively isolated with the material of coupling agent interaction or combination.Thereby, gangue material selectivity ground and valuable mineral (for example mineral, metal or pitch) or the argillaceous gangue (for example iron oxide and titanium oxide) that is isolated in foam concentrate can be separated.

Therefore, in one embodiment, the present invention is the method for ore beneficiation.The method comprises the slurry of processing ore particles with the inhibitor that comprises modified resin.This modified resin comprises base resin, and it is the product of primary amine or secondary amine and aldehyde, with coupling agent, this base resin is carried out modification.This ore slurry process can before froth flotation or during carry out.In one embodiment, this ore comprises sand or clay impurity, the ore that normally reclaims in phosphate or potassium ore deposit.In another embodiment, base resin is Lauxite.In another embodiment, the group of the silane that freely replaces of coupling agent choosing, silicate, silica, polysiloxanes and composition thereof composition.

In another embodiment, the present invention is the froth flotation inhibitor for the useful materials ore dressing, and described useful materials comprises mineral or useful metal ore.This inhibitor comprises solution or the dispersion of modified resin, and wherein resin solid content is the about 90wt.% of 30wt.%～approximately.Modified resin comprises base resin, and it is the product of primary amine or secondary amine and aldehyde.With coupling agent, this base resin is carried out modification.The content of this coupling agent is that resin solid content is the solution of the approximately 90wt.% of 30wt.%～approximately or the approximately 0.1wt.% of dispersion～approximately 2.5

wt.％。In another embodiment, this base resin is Lauxite, and it is urea and formaldehyde by formaldehyde: urea (F: U) mol ratio from approximately 1.75: 1 to the about product of 3: 1.In another embodiment; this coupling agent is substituted silane, is selected from the group that following material forms: urea groups (ureido) substituted silane, amino substituted silane, sulphur substituted silane, epoxy substituted silane, methacryl substituted silane, vinyl substituted silane, alkyl substituted silane, haloalkyl substituted silane.

In another embodiment, the present invention is a kind of for purify the method for clay from ore argillaceous, and this ore argillaceous comprises the impurity that is selected from metal, metal oxide, mineral and composition thereof.The method comprises with the inhibitor that comprises modified resin to be processed this ore slurry argillaceous, the froth flotation by impurity treatment step after or during reclaim the clay of purification, the content of at least a impurity is reduced in the clay of this purification.This modified resin comprises base resin, and it is the product of primary amine or secondary amine and aldehyde.With coupling agent, this base resin is carried out modification.In another embodiment, this ore argillaceous comprises kaolin.In another embodiment, this impurity comprises the mixture of iron oxide and titanium dioxide.In another embodiment, this impurity comprises coal.

In another embodiment, the present invention be a kind of from the bitumeniferous slurry that comprises sand or clay the method for purification pitch.The method comprises with the inhibitor that comprises modified resin as above processes this slurry, and treatment step after or during reclaim the pitch of purification by froth flotation, the content of sand or clay is reduced in the pitch of this purification.

Other separation

In another embodiment, the present invention is a kind of method that comprises the aqueous suspension of solid impurity for purification.The method comprises with above-mentioned modified resin treat liquid suspension, and after treatment step or during remove (1) and be rich in the liquid that at least part of solid impurity in the impurity part and/or (2) purify.In another embodiment, treatment step comprises and makes solid impurity (for example sand or clay) flocculation.In another embodiment, carry out this removal step by sedimentation, flotation or filtration.In another embodiment, suspension is well bore liquid, and the method comprises the drilling fluid that remove to purify, and makes it be reused for well bore.In another embodiment, aqueous suspension is the discharge slurry argillaceous from phosphate production factory, and the method comprises the water that remove to purify, and makes it be reused for phosphate production.In another embodiment, aqueous suspension is the moisture coal suspension liquid that contains, and the method comprises by filtration and removes the part that is rich in coal.In another embodiment, aqueous suspension comprises sewage, and the method comprises the water of removing purification by sedimentation.In another embodiment, aqueous suspension comprises the waste liquid in pulp mill or paper mill, and solid impurity comprises fibrous material, and the method comprises the water of removing purification.In another embodiment, aqueous suspension is comprise the intermediate of sand or clay in process for preparing asphalt or discharge slurry.In another embodiment, the liquid of purification is drinkable water.

In another embodiment, the present invention comprises the method for the water of metal cation for purification.The method comprises with above-mentioned modified resin processes water, and is removed to the small part metal cation by filtration, produces the water (for example, drinkable water) that purifies.In another embodiment, remove step and comprise membrane filtration.In another embodiment, metal cation selects free As ⁵⁺, pb ²⁺, Cd ²⁺, Cu ²⁺, Mn ²⁺, Hg ²⁺And composition thereof the group that forms.In another embodiment, with the further modification base resin of anionic functional group.

By following detailed description, these and other embodiment will be clearer.

Description of drawings

Fig. 1 shows milling performance in the flotation of potassium ore sample of the silane coupler modified Lauxite of molecular weight in 400～1200 g/mols of scopes.The resin of this performance and unmodified (namely not adding silane coupler) and the contrast of guar gum control sample provide.

The specific embodiment

All application

The modified resin that is used for separating technology of the present invention is to comprise base resin, and it is the product of primary amine or secondary amine and aldehyde.Owing to having the nitrogen-atoms (not being namely tertiary amine or quaternary amine part) that is not replaced fully, primary amine or secondary amine can with aldehyde reaction, form adduct.If as aldehyde, for example, adduct is the methylolation adduct with active methylol degree of functionality with formaldehyde.The typical primary amine and the secondary amine that are used to form base resin comprise the compound with at least two functionality amine or amide group, perhaps have at least a amidine compound in each these group.Such compound comprises urea, guanidine and melamine, and its amine nitrogen atom position separately can be replaced by aliphatic group or aryl, and wherein at least two nitrogen-atoms are not replaced fully.Usually use primary amine.Cheap and be convenient to buy due to urea, it is the representative of these primary amine.In the situation that use urea, if necessary, can (for example use ammonia, primary alkyl amine, silane alcohol base amine, polyamines, such as the alkyl primary diamines of ethylenediamine with such as the alkyl uncle triamine of diethylenetriamines), poly-alkanolamine, melamine or the substituted triazine of other amine, two cyanamide, (for example replace urea or ring urea, ethylidene-urea), the derivative of primary amine, secondary amine and alkylamine, quaternary amine and alkylamine, guanidine and guanidine (for example, cyanoguanidines and acetyl guanidine) substitutes its at least a portion.Aluminum sulfate, ring-type phosphate and annular phosphate, formic acid or other organic acid can also be used together with urea.If be attached to Substitute For Partial urea in resin, any amount in these components (if perhaps be used in combination, being the amount of their combinations) is generally the 20wt.% of the approximately 0.05wt.% of resin solid～approximately.The reagent that one skilled in the art will recognize that these types has aldehydes volatile quantity and other characteristic that improves hydrolytic resistance, flexibility, reduction.

The above-mentioned aldehyde that is used for primary amine or secondary amine reaction basis of formation resin can be formaldehyde, perhaps such as other aliphatic aldehydes of acetaldehyde and propionic aldehyde etc.Aldehyde also comprises aromatic aldehyde (for example, benzaldehyde and furfural), and other aldehyde, such as aldol, glyoxal and crotonaldehyde.Also can use the mixture of aldehyde.Normally, because it is convenient to purchase and relatively inexpensive, so use formaldehyde.

In the basis of formation resin process, it is known in the field forming adduct between initial amine and aldehyde.The substitution value that the speed of aldehyde addition reaction usually highly depends on pH and obtains.For example, formaldehyde it is estimated to be 9: 3: 1 with the ratio that the urea addition forms the speed of one, two and three methylol groups successively, and season methylol aldehyde usually can not produce with effective dose.Adduct forms reaction and usually carries out with favourable speed under alkali condition, thereby carries out having under suitable base catalyst (for example ammonia, alkali metal hydroxide or alkaline earth metal hydroxide) existence.What the most generally use is NaOH.

Under sufficiently high pH value, adduct forms reaction can be in the situation that there is no that the condensation reaction (namely making resin lifting (advance)) that increases the molecular resin amount by polymerization carries out.Yet for the further reaction by amine-aldehyde adducts forms the low-molecular-weight condensation resin, the pH value of reactant mixture remains on usually greater than 5, is generally approximately 5～approximately 9.If necessary, can add the acid such as acetic acid, help to control pH, thereby control the molecular weight of condensation speed and final condensation resin.Reaction temperature is generally the approximately 30 ℃～about scope of 120 ℃, is usually less than approximately 85 ℃, usually uses reflux temperature.In preparing low molecular weight amine-aldehyde condensation resin process by primary amine or secondary amine and aldehyde raw material, the reaction time adopted approximately 15 minutes～approximately 3 hours, was generally approximately 30 minutes～approximately 2 hours.

Before condensation reaction or during, can add various additives, in order to provide required performance for the amine-aldehyde resins of final modification.For example guar gum, carboxymethyl cellulose or other polysaccharide, for example alginates; Or polyalcohol, for example polyvinyl alcohol, pentaerythrite or Jeffol ^TMPolyalcohol (Hunstman Corporation, Salt Lake City, Utah, USA) can be used for changing viscosity and the denseness of amine-aldehyde resins, and when for the preparation of the amine-aldehyde resins of modification, it can improve the performance of froth flotation and other application.In addition, comprise diallyldimethylammonium chloride (or its analog, diallyl diethyl ammonium chloride for example) quaternary ammonium salt or comprise chloropropylene oxide (or its analog, epibromohydrin for example) alkylating agent can be used for improving the cationic charge of amine-aldehyde resins condensation product, when for the preparation of the amine-aldehyde resins of modification, it can improve the performance in following some solid/liquid separation (for example, clay dehydration).After this manner, and only compare with mixed with resin after preparation, such additive can more effectively react the amine-aldehyde resins that enters modification.

The condensation reaction products of above-mentioned amine-aldehyde, acid amides-aldehyde and/or amidine-aldehyde adducts comprises, for example by resulting those products of following mode: (i) form methylene bridge by silane alcohol base and amino reaction between ammonia nitrogen, (ii) reaction by two silane alcohol bases forms methylene ether link, (iii) remove subsequently formaldehyde by methylene ether link and form methene key, and (iv) remove water subsequently by silane alcohol base and formaldehyde forms methene key.

Usually, in preparation base resin process, aldehyde: the mol ratio of primary amine or secondary amine is approximately 1.5: 1～approximately 4: 1, it refers to during above-mentioned adduct formation and above-mentioned condensation reaction, no matter this reaction is carried out respectively or simultaneously, the ratio of the mole of all aldehyde of participation reaction preparation base resin and the mole of all amine, acid amides and amidine.Resin normally under atmospheric pressure prepares.The viscosity of reactant mixture is often used as the molecular weight that represents easily resin.Therefore, when after the sufficiently long time and when being in sufficiently high temperature and obtaining the viscosity of expectation, can stop condensation reaction.At this moment, can cooling and neutralization reaction mixture.Can remove water by vacuum distillation, make resin have required solid content.Can adopt for any of the multiple conventional method that makes primary amine and secondary amine and aldehyde component reaction, such as segmentation add monomer, segmentation is added catalyst, is controlled pH value, amine modification etc., but the invention is not restricted to any specific method.

The representative basis resin that is used for separating technology of the present invention is Lauxite.As mentioned above, can substitute a part of urea with other reactive amines and/or acid amides, and can substitute a part of formaldehyde with other aldehyde, various required performances are provided, and not break away from the base resin characteristic as Lauxite.When as base resin, Lauxite can or be prepared well known to a person skilled in the art mode by precondensate by urea and formaldehyde monomers.Usually, with approximately 1.75: the 1～about formaldehyde of 3: 1: urea (F: mol ratio U), usually with approximately 2: the 1～about formaldehyde of 3: 1: urea (F: mol ratio U), make urea and formolite reaction, in order to the methylolation material (for example dihydroxymethyl urea or trihydroxy methyl urea) of the confession resin crosslinks of abundance is provided.Usually, Lauxite is a kind of highly dispersion of water-dilutable, otherwise is exactly the aqueous solution.

In one embodiment, condensation is proceeded to a certain degree, makes the number-average molecular weight (Mn) of urea aldehyde radical plinth resin greater than approximately 300 g/mols, is generally approximately 400～approximately 1200 g/mols.As known in the art, the Mn value that has a polymer samples of molecular weight distribution is defined as

$M_n=\frac{\underset{i}{\mathrm{\Σ}}{N}_i{M}_i}{\underset{i}{\mathrm{\Σ}}{N}_i}$

N herein _iThe quantity with polymer of i repetitive, and M _iIt is the molecular weight with polymer of i repetitive.Number-average molecular weight uses gel permeation chromatography (GPC) to measure usually, and solvent used, standard and program are all known in those skilled in the art.

For example, also can be according to United States Patent (USP) 6,114,491 described method utilizations and preparation ring-type Lauxite.According to urea: formaldehyde: the mol ratio of ammonia is approximately 0.1～1.0: approximately 0.1～3.0: approximately 0.1～1.0 use urea, formaldehyde and ammonia react thing.With these reactants reaction vessel of packing into, keep simultaneously temperature lower than approximately 70 ℃ (160 °F), be generally approximately 60 ℃ (140 °F).Order of addition is not strict with, but importantly, owing to being exothermic reaction, (during perhaps adding formaldehyde to ammonia) is careful during adding ammonia to formaldehyde.In fact, due to violent heat release, preferably at first add formaldehyde and urea, add subsequently ammonia.This order of addition makes people be utilized the heat absorption that is added to the water and is caused by urea, improves the interpolation speed of ammonia.In whole digestion process, may need alkali to keep alkali condition.

In case all reactants are in reaction vessel, gained solution is heated to approximately (approximately 140～approximately 220 °F) between 60～105 ℃ under alkaline pH, be generally approximately 85～95 ℃ (approximately 185～205 °F), according to mol ratio and temperature, continue 30 minutes to 3 hours, perhaps until the reaction end.In case reaction finishes, the solution cool to room temperature is supplied to store.But gained solution is the storage-stable some months under environmental condition.PH is 5～11.

Productive rate is generally approximately 100%.The ring-type carbamide resin comprises at least 20% triazinone and the triazineon compounds of replacement usually.The ratio of ring-type urea and two replacements and trisubstituted urea and mono-substituted urea changes with the mol ratio of reactant.What for example, obtain in solution had 1.0: 2.0: 0.5U: F: the ring-type carbamide resin of A mol ratio passes through C ¹³-NMR characterizes, and comprises about 42.1% ring-type urea, 28.5% pair/trisubstituted urea, 24.5% mono-substituted urea and 4.9% free urea.What obtain in solution had 1.0: 1.2: 0.5U: F: the ring-type carbamide resin of A mol ratio passes through C ¹³-NMR characterizes, and comprises about 25.7% ring-type urea, 7.2% pair/trisubstituted urea, 31.9% mono-substituted urea and 35.2% free urea.

In addition, can prepare the ring-type Lauxite by for example United States Patent (USP) 5,674,971 described methods.By by at least two the step and be optionally three the step methods make urea and formolite reaction prepare the ring-type carbamide resin.The first step is carried out under basic reaction conditions, in the situation that exist ammonia with the F/U mol ratio of 1.2: 1～1.8: 1, makes urea and formolite reaction.By the amount supply ammonia that is enough to produce the ammonia/urea mol ratio of approximately 0.05: 1～1.2: 1.The mixture reaction forms ring-type triazinone/triazine or ring-type carbamide resin.

Can also be as United States Patent (USP) 2,641,584 and 4,778,510 is described by making urea, formaldehyde and primary amine reaction prepare water-soluble triazineon compounds.These patents have also been described suitable primary amine, such as but not limited to for example alkylamine of methylamine, ethamine and propylamine, and for example rudimentary hydroxylamine of monoethanolamine, for example cycloalkyl monoamine, ethylenediamine, hexamethylene diamine and the linear amine of cyclopentamine.Primary amine can be substituted or not be substituted.

In the situation that ring-type Lauxite or Lauxite, skilled professional can recognize urea and the formaldehyde that can buy many forms.Enough reactivities are arranged and any type of reactant and the product that external harmful part is introduced in the reaction of expecting can not be able to be used in the preparation of useful in the present invention Lauxite.For example, the general type of service of formaldehyde comprises polyformaldehyde (solid, the formaldehyde of polymerization) and formalin solution (formalin of 37%, 44% or 50% concentration of formaldehyde is sometimes with methyl alcohol).Can also obtain formaldehyde with gas form.In these forms, any all is applicable to prepare urea aldehyde radical plinth resin.Usually, formalin solution is originated as formaldehyde.In order to prepare resin of the present invention, can be with any (for example, glyoxal) all or part of instead of methanol in above-mentioned aldehyde.

Similarly, urea generally can obtain in a variety of forms.All can buy such as granular Solid urea and urea solution (being generally the aqueous solution).Any type of urea all is applicable in practice of the present invention.For example, can use the urea aldehyde solution of many industry preparations, comprise such as United States Patent (USP) 5,362 the urea aldehyde combination product of 842 and 5,389,716 urea-formaldehyde condensates (for example, UFC 85) that disclose.

In addition, can use the Resins such as Georgia Pacific, the Lauxite of Inc., Borden Chemical Co. and Neste Resins type that Corporation sells.These resins are made into the low-molecular-weight condensation product or comprise as mentioned above and can form the adduct of the active methylol group of resinous polymer through condensation, usually in aforementioned number average molecular weight scope.Resin generally comprises a small amount of unreacted urea and the formaldehyde of (namely dissociating), and ring-type urea, the urea of monomethylol and the urea of two methylolation and trihydroxy methyl.(formaldehyde used for example: the mol ratio of urea), the relative populations of these species may change according to preparation condition.The surplus of these resins is generally water, ammonia and formaldehyde.Can also comprise that the various additives of stabilizing agent, curing accelerator, filler, extender etc. add in base resin with known in the art.

Modified resin of the present invention is unwanted solid material to be separated in separation/process for purifying of the present invention (for example sand or clay) and/or ionic species (for example metal cation) are had height in conjunction with coupling agent optionally, foregoing base resin to be carried out modification and make by using.Without being limited by theory, in one embodiment, coupling agent is considered to improve the performance of base resin, it is normally cationic (namely generally with positive charge more than negative electrical charge), attract major part be generally anionic (namely generally with negative electrical charge more than positive charge) surface of clay.These differences on characteristic electron between base resin and clay can produce in a plurality of positions and attract each other, and even may shared electron form covalent bond.By several theoretical possible explanations make the clay particle attracted to base resin just-negative electrical charge interacts, such as Subjective and Objective theoretical (comprising multiple tooth coordination), soft-hard acid alkali theory, dipole-dipole-dipole interaction, the highest Gibbs free energy that takies molecular orbit-lowest unoccupied molecular orbital (HOMO-LUMO) interaction, hydrogen bond, key etc.

Coupling agent can be before the adduct of primary amine as above or secondary amine and aldehyde forms reaction, during or add afterwards.For example, coupling agent can be after amine-aldehyde adducts forms under alkali condition but adds before reducing the pH value of adduct (for example by adding acid) in order to realize condensation reaction.Usually, the reaction between the base resin reactive functional by coupling agent and the part of base resin forms covalent bond between coupling agent and base resin.

Coupling agent can also add after the condensation reaction that produces small molecular weight polymer.For example, coupling agent can add with after stopping condensation reaction the pH value that improves condensation product (for example by adding alkali).Advantageously, found to make the abundant modification of this base resin by introduce coupling agent when alkaline pH value (being that pH is greater than 7) in the resin condensation thing, can not improve the molecular weight of resin considerablely.Usually, the resin condensation thing be with the aqueous solution of resin or the form of dispersion exist.When using substituted silane as coupling agent, it can make the base resin modification effectively under normal temperature or high temperature under alkali condition.Forming relevant any temperature to adduct formation or condensation product in the preparation process of base resin as above all is applicable in conjunction with silane coupler with the modification base resin.Therefore, coupling agent can be in 100 ℃ of normal temperature～approximately join amine-aldehyde mixture, adduct or condensation product.Usually, with approximately 35 ℃～approximately the temperature of raising of 45 ℃ realizes the base resin reaction active groups of substituted silane and the required reaction rate between base resin itself.For the reaction of aforesaid resin condensation, the degree of this reaction is monitored in the rising of viscosity that can be by temporal evolution resin solution or dispersion.

Selectively, in some cases, for modification base resin at the scene, silane coupler can add in the liquid that comprises base resin to be clean (for example froth flotation slurry).

Can modification base resin of the present invention and impurity (for example sand, clay) and/or ionic species are had required combination representational coupling agent selective or affinity comprise substituted silane, it has base resin reaction active groups (for example organo-functional group) and can combine with unwanted impurity (particularly siliceous material) or interactional the second group (for example trimethoxy silane group).Without being limited by theory, process with modified resin, the second group can become these accumulation of impurities larger particle or flocculate (namely by flocculation).This is conducive to it and removes.In ore froth flotation separation case, the second group of coupling agent impels gangue impurity or required material (for example kaolin) to completely cut off at aqueous phase, and base resin may be dissolved in wherein or base resin has higher affinity to it.This impels by the flotation that utilizes gas (for example air) separates useful materials from aqueous phase.

the base resin reaction active groups of representational silane including, but not limited to: contain urea groups part (for example urea groups alkyl), contain amino part (for example aminoalkyl), sulfur-bearing part (for example mercaptoalkyl), contain epoxy radicals part (for example combining water glycerine oxygen base alkyl), contain methacryl base section (for example methacryl oxyalkyl), contain vinyl segment (for example vinyl benzene methylamino), contain moieties (for example methyl) or haloalkyl containing part (for example chloro alkyl).Therefore representational substituted silane coupling agent of the present invention comprises Carbamido substituted silane, amino substituted silane, sulphur substituted silane, epoxy substituted silane, methacryl substituted silane, vinyl substituted silane, alkyl substituted silane and haloalkyl substituted silane.

Silane coupler also can be replaced more than a base resin reaction active groups.For example, the tetravalence silicon atom in silane coupler can replace respectively two or three base resin reaction active groups as above.But the selection mode as a plurality of base resin reaction active groups replacements, perhaps in addition, this silane coupler also can have a plurality of silane functionals, to improve bond strength or the ability of coupling agent and gangue impurity (for example sand) or required material (for example kaolin).Can by for example adding extra silane group or this coupling agent is carried out crosslinked with the other silane monomer that contains in coupling agent, improve the silanization degree of silane coupler.The use of a plurality of silane functionals even can produce different orientation (affinity between a plurality of silane groups of surface of clay and coupling agent " sidepiece " for example, relative with the affinity between the single silane group of coupling agent " head ") between coupling agent and surface of clay.

Silane coupler also comprises the second group as above, it comprises the silane moiety of molecule as mentioned above, usually is selected from following group by one or more and replaces: alkoxyl (such as trimethoxy), acyloxy (such as acetoxyl group), alkoxyl alkoxyl (such as methoxy ethoxy), aryloxy group (such as phenoxy group), aryl acyloxy (such as benzoyloxy), heteroaryloxy (such as chaff oxygen base), halo aryloxy group (such as chlorophenoxy), heterocycle alkoxyl (such as tetrahydrochysene chaff oxygen base) etc.therefore, be used for making the representative silane coupler of having of base resin modification base resin reaction active groups as above and the second group (for example gangue active group) comprise the urea groups propyl trimethoxy silicane, the urea groups propyl-triethoxysilicane, TSL 8330, aminopropyltriethoxywerene werene, the aminopropyl methyldiethoxysilane, the aminopropyl methyl dimethoxysilane, the aminoethylamino propyl trimethoxy silicane, the aminoethylamino propyl-triethoxysilicane, aminoethylamino propyl group methyl dimethoxysilane, diethylidene triamido propyl trimethoxy silicane, diethylidene triamido propyl-triethoxysilicane, diethylidene triamido propyl group methyl dimethoxysilane, diethylidene triamido propyl group methyldiethoxysilane, the cyclohexyl TSL 8330, own diaminourea MTES, the anilino-MTMS, the anilino-MTES, diethylamino methyltriethoxy silane alkane, (diethylamino methyl) methyldiethoxysilane, the methylamino propyl trimethoxy silicane, two (triethoxysilylpropyltetrasulfide) tetrasulfide, two (triethoxysilylpropyltetrasulfide) disulphide, the sulfydryl propyl trimethoxy silicane, the sulfydryl propyl-triethoxysilicane, sulfydryl propyl group methyl dimethoxysilane, 3-sulphur cyanato propyl-triethoxysilicane, isocyanide acyl propyl triethyl silicane, glycidoxypropyltrimewasxysilane, the glycidoxypropyl triethoxysilane, the glycidoxypropyl methyldiethoxysilane, the glycidoxypropyl methyl dimethoxysilane, methacryloxypropyl trimethoxy silane, the methacryloxypropyl triethoxysilane, the methacryloxypropyl methyl dimethoxysilane, r-chloropropyl trimethoxyl silane, chloropropyl triethoxysilane, the chloromethyl triethoxysilane, the chloromethyl trimethoxy silane, the dichloromethyl triethoxysilane, vinyltrimethoxy silane, VTES, vinyl three (2-methoxy ethoxy) silane, vinyltriacetoxy silane, the alkyl methyl trimethoxy silane, vinyl benzene methylamino trimethoxy silane, (3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, aminopropyl triple phenoxyl silane, aminopropyl thribenzoyl silane, aminopropyl three chaff TMOSs, aminopropyl three (o-chlorophenoxy) silane, aminopropyl three (p-chlorophenoxy) silane, aminopropyl three (tetrahydrochysene chaff oxygen base) silane, ureido silane, mercaptoethyltriethoxysilane, and vinyl trichlorosilane, methacryloxypropyl three (2-methoxy ethoxy) silane.

Other representational silane coupler comprises oligomeric aminoalkyl silane, and its base resin active group is two or more aminoalkyls that repeat to be connected or alkylamino group.The example of this oligomeric aminoalkyl silane is Silane All06 solution, can obtain (GE Silicones-OSiSpecialties, Wilton, CT, USA) from trade mark Silquest, and it is considered to have general formula (NH ₂CH ₂CH ₂CH ₂SiO _1.5) _n, wherein n is 1～approximately 3.Also can use the amino silane of modification, as triamido solution of silane (for example SilaneAll28, can obtain from agreeing distributors with same trade mark).

Other representational silane coupler is Carbamido substituted as above and amino substituted silane.These special examples are urea groups propyl trimethoxy silicane, urea groups propyl-triethoxysilicane, TSL 8330 and aminopropyltriethoxywerene werene.

Can use polysiloxanes and polyorganosiloxane ramification as coupling agent as above, to improve the performance of modification base resin in solid/liquid separation.Polyorganosiloxane ramification comprises that those can mix the polysiloxane that obtains in conjunction with various functional groups (comprise urethanes, acrylate, epoxy radicals, vinyl and alkyl functional group) with therein by organic resin and polyorganosiloxane resin.

Also can use silica and/or silicate to be combined (for example as blending ingredients add) with modified resin of the present invention, with potential raising its to gangue impurity or desired substance (for example kaolin), siliceous material particularly comprises the affinity of sand and clay.Other reagent that can be used for improving the performance of modified resin in separating technology of the present invention comprises polysaccharide, polyvinyl alcohol, polyacrylamide and known flocculant (for example alginates).These reagent can use together with the Lauxite of modification equally, this Lauxite as previously mentioned, wherein at least a portion urea is replaced by foregoing ammonia or amine (such as primary alkyl amine, alkanolamine, polyamines etc.).In addition, this reagent also can use together with modified resin, and it is further by the modification of anionic functional group's (for example sulfonate radical) institute, or stablizes by the reaction with alcohol (for example methyl alcohol) as described below.

The silica of aqueous silica sol form for example can be with registration mark " Bindzil " available from AkzoNobel, or with registration mark " Ludox " available from DuPont.The colloidal sol that also can obtain to have various silica gel particle sizes and comprise other grade of various stabilizing agents.Can use alkali, for example hydroxide of sodium, potassium or lithium or quaternary ammonium hydroxide, perhaps water miscible organic amine, for example alkanolamine, carry out stabilisation to this colloidal sol.

In the preparation of modified resin, can also use silicate, for example alkali silicate and alkaline-earth-metal silicate (for example lithium metasilicate, sodium metasilicate, potassium silicate, magnesium silicate and calcium silicates) and ammonium silicate or silicic acid quaternary ammonium salt.In addition, as United States Patent (USP) 4,902,442 described stable silica colloidal-silicate admixtures or mixture are also available.

In separating technology of the present invention, when the amount of using coupling agent is approximately 30%～90% as solid content, be generally approximately the solution of 45%～approximately 70% base resin or the approximately 0.01wt.% of dispersion～when approximately 5wt.% prepares modified resin, found good especially effect.Usually, the coupling agent that adds less amount can not realized the obvious modification of base resin, and more amount is not enough to the raising of performance the cost of the coupling agent of offset increase.When using the coupling agent mixture, the gross weight of this mixture is usually in this scope.The addition that is particularly suitable for of coupling agent is the 2.5wt.% of the base resin solution of solid content in above-mentioned scope or the approximately 0.1wt.% of dispersion～approximately.

Selectively, no matter how many solid contents of base resin solution or dispersion is, usually the consumption of coupling agent is approximately 0.01%～approximately 17% of base resin solid weight, is generally approximately 0.1%～approximately 8.3%.The coupling agent that adds not only is applied to resin solution or dispersion based on these representative scopes of the own weight of base resin, and is applicable to have the modification base resin that seldom or not contains " pure " form of adding solvent or dispersant (for example water).When foregoing basis is that when reacting to each other the gross weight of the amine of basis of formation resin and aldehyde, these scopes also are suitable for usually.Usually, these amine and aldehyde component at least about 90wt.%, usually react at least about 95wt.%, to reduce free unreacted amine and the amount of aldehyde component, therefore it is more effectively utilized in the preparation process of base resin polymer, and the adverse effect relevant to the component of these free states (for example evaporating entered environment) minimized.As previously mentioned, modified resin also can be prepared by add coupling agent in the reactant mixture of the amine that is used to form base resin and aldehyde.The optimised quantity of coupling agent depends on many factors, comprise base resin solid content, base resin type and specific coupling agent, treat the purity of tcrude ore slurry or the liquid dispersion to be clean of ore dressing, etc.

The amine-aldehyde resins that is used for separating technology of the present invention comprises approximately 40%～approximately 100% resin solid or non-volatile matter usually, usually contains 55%～75% non-volatile matter.By about 105 ℃ of small samples with composition (for example 1-5 gram) heating approximately 3 hours, according to the weightless measurement non-volatile content.When use has on a small quantity or do not contain the modified resin of basic " pure " form of volatile component, pure resin (for example as viscous liquid, gel or such as the solid forms of powder) can be joined in froth flotation slurry or liquid dispersion to be clean, so that on-the-spot aqueous resin solution or the dispersion of forming.With dry technology such as the spray-drying of routine, can be by obtaining the modified amine-aldehyde resins of pure form in the solution of these resins or dispersion.

The aqueous solution of modified resin of the present invention or dispersion can be limpid liquid usually or have white or the liquid of yellow appearance.They will have usually from the Brookfield viscosity of about 75～approximately 500cps and about 6.5～approximately 9.5 pH value.Free formaldehyde content in Lauxite and free urea content are usually separately lower than 5%, and is common respectively lower than 3%, and often respectively lower than 1%.Owing to there being the health worry relevant to being exposed to the formaldehyde volatilization, usually obtain the formaldehyde of low content.If necessary, " formaldehyde trapping agent " that can add conventional known and free formaldehyde reaction is to reduce the levels of formaldehyde in solution.But due to difference, a small amount of free urea is also expected.without being limited by theory, because free formaldehyde itself can be by coupling agent modified (for example it can improve its affinity to siliceous material with the substituted silane reaction), do not think that free urea has essential molecular weight, (1) in froth flotation separates, " induce " material (for example clay) and the bubble phase mutual effect of rising of gangue impurity or expectation, (2) in the purification of liquid dispersion, make the solid impurity reunion of q.s be floccule, perhaps is removing ionic species from aqueous solution (3), these materials are combined with the molecule of enough large size, and hold back by filtration.Especially, found to have to show greater than the about resinous polymer of number-average molecular weight of 300 g/mols and promoted effectively to separate required quality.

Froth flotation

When selective due to its height, inhibitor in modified resin of the present invention separates as froth flotation, it is providing good result aspect addition saving.For example, when as the inhibitor of ore dressing, the material (for example ore argillaceous) that per metric ton will purify with froth flotation is based on the weight of resin solution or dispersion, the addition of modified resin is about 100～approximately 1000 grams, and typically from about 400～approximately 600 grams.Usually, those skilled in the art can easily determine the optimum addition of particular separation, and it depends on some factors, comprises kind and the quantity of impurity.

Modified resin of the present invention can be used for widely utility (for example mineral or metal, the for example hydrocarbon of phosphate, potash, lime, sulfate, gypsum, iron, platinum, gold, palladium, titanium, molybdenum, copper, uranium, chromium, tungsten, manganese, magnesium, lead, zinc, clay, coal and silver or HMW, for example pitch) froth flotation.Usually, raw material to be clean and that reclaim comprise sand or clay, and modified resin inhibitor described herein has special selective to it.

Although often be considered to impurity in common metal or mineral ore ore dressing medium clay soil, it also may occur with relatively large amount, as main component to be recycled.Some clays, for example kaolin is valuable mineral in some applications, for example in papermaking and rubber are made as mineral filler.Thereby, can use a kind of foam floating process of modified resin of the present invention to comprise from the argillaceous ore and separate clay.Impurity in such ore is generally metal and oxide thereof, and as iron oxide and titanium dioxide, it is through the froth flotation diffeential floatation.Other impurity of argillaceous ore comprises coal.The original impurity that is present in diffeential floatation in purification method of the present invention in most Georgia kaolin comprises titanium dioxide (iron-bearingtitania) and other common also mineral of iron content of iron content, as mica, ilmenite or tourmaline.

Thereby, optionally can separate recovery from metal, metal oxide and coal with the clay that amine-aldehyde resins of the present invention is combined.In the purification of clay, usually advantageously use a kind of anion-trapping agent, for example oleic acid; Flocculant, for example polyacrylamide, clay suspending agent, for example aliphatic acid or rosin acid and/or retinal are combined with to control foaming with modified resin of the present invention as inhibitor.

Other representative foam floating process of the present invention comprises phosphate or potash, and the ore dressing of aforementioned other useful metal and mineral, and wherein the removal of siliceous gangue material and other impurity is the key factor that realizes the good process economy.Potassium ore for example comprises the mineral intermixture except sylvite (KCl) usually, and sylvite needs to reclaim in foam concentrate.These comprise halite (NaCl), clay and do not allow carbonate mineral with water, for example alumina silicate, calcite, dolomite and anhydrite.

A kind of particularly method in ore argillaceous refining as described in more detail below comprises the further modification base resin with the anionic functional group.

Modified resin of the present invention also is advantageously used in separate bitumen in the sand that extracts altogether and/or clay from natural oil placer is hidden.At first pitch/the sand mixture that takes out oil-sand in the hundreds of foot of earth's surface or tar sand mineral reserve mixes with warm water or hot water usually, forms to have to be convenient to carry (for example using pipeline) to the low viscous oil-sand aqueous slurry that falls of processing in facility.All right steam injection and/or caustic solution are with the slurry of adjusting for froth flotation, and following many other purifying step.The inflation that comprises the bituminous slurry of sand and clay can cause the selective floation of pitch, makes pitch be recycled as purified product.By only stirring slurry to discharge bubble and/or this inflation can be realized in the bottom that air-source is incorporated into the separation chamber.Those skilled in the art easily determines the pitch of flotation expectation and can not take away too much solid impurity and required optimum air amount.

Therefore, the use of modified resin inhibitor of the present invention has advantageously promoted sand and/or clay impurity are retained in and has contained in water section, and this sand and/or clay impurity are removed from the bottom of froth flotation container.With respect to initial asphalt grout, (namely having higher concentration) sand and/or clay impurity are rich in this bottom.Whole purifications of pitch can rely on two or more FLOTATION SEPARATION stages.For example, the mid portion of primary flotation separation container can comprise a large amount of pitches, and it finally can be recovered in the secondary flotation of this " middle rank " part.

Usually, any according to foam floating process of the present invention in, reclaim at least 70% useful materials (for example pitch or kaolin) from raw material (for example ore argillaceous), its purity is 85wt.% at least.In addition, when modified resin of the present invention is used as inhibitor, can be combined with the known trapping agent of routine.These trapping agents comprise for example aliphatic acid (for example oleic acid, enuatrol, hydrocarbon ils), amine (for example dodecyl amine, octadecylamine, alpha-azyl aryl phosphonic acids and sodium sarcosinate) and xanthans salt.Similarly, conventional inhibitor known in the art also can be combined with the modified resin inhibitor.Conventional inhibitor comprises guar gum and other hydrocolloid polysaccharide, calgon etc.According to normal floating operation, the auxiliary conventional foaming agent (for example methyl isobutyl carbinol, pine tar and PPOX) that captures also can be combined with modified resin inhibitor of the present invention.

As those skilled in the art's understanding, in froth flotation separated, modified resin of the present invention can change according to concrete pending material as the pH value of the slurry that inhibitor adds.Usually, the pH value changes to strong basicity (for example pH 12) from neutral (pH 7).It is believed that, in some floatation systems, for example in the flotation of copper sulfide, high pH value (for example approximately 8～approximately 12.5) produces best result.

Usually in the froth flotation that is used for solid material (for example mineral or ore) ore dressing; usually at first tcrude ore to be selected is ground into the size of " breaking away from net (liberation mesh) "; the particle that contains useful material in this major part is all mineral or metallic particles or the salt crystal that separates, and is mixed with gangue (for example clay and/or sand) in these particles.With this material be attached in saline solution produce aqueous slurry before, this solid material can be ground to produce the particle of 1/8th inches of average diameters for example.After with material disintegrating and slurrying, can stir or stir slurry in " washing " technique, clay is decomposed into suspension as muddiness is retained in very trickle particle in salt solution.Before froth flotation, some in these clays can be washed off from ore particles, become aqueous suspension argillaceous or salt solution.In addition, as known in the art, before froth flotation, also can use respectively the pre-treatment step of any routine that comprises further pulverizing/screening, cyclonic separation and/or water decomposition step, the raw material granularity is reduced/classification, remove the salt solution of clay, and/or reclaim less solids from the salt solution of muddiness.

Before froth flotation or during, usually be easy to fully decentralized mode by inhibitor the modified resin of the present invention as inhibitor added in aqueous slurry.As mentioned above, can use conventional trapping agent to help the flotation of required useful materials.In foam floating process, the slurry that is approximately 10～50wt.% with common solid content is sent to one or more flotation cells.Air is passed into the bottom of these grooves, rising bubble is had select the relatively hydrophobic part of this material of affinity to rise to the surface (being foam), skim and be recovered at this.That hydrophilic bottom product also can be recovered with respect to foam concentrate.This technique can be with stirring.Use the further conventional steps that comprises separation (for example by centrifugation), dry (for example in gas burning kiln), size fractionation (for example screening) and refining (for example crystallization) through being everlasting after, can make commercial qualified product from the separating part that reclaims by this way.

Although be not like this all the time, froth flotation of the present invention can be included in flotation in " initial separatory cell ", then the concentrate of roughly selecting is carried out one or many and " makes with extra care ".Also can adopt two or more flotation step, at first reclaim a large amount of useful materials that comprise more than a kind of component, follow by selective flotation to separate these components.Modified resin of the present invention can advantageously be used for improving the selective recovery through the material of the expectation of froth flotation when the inhibitor in these steps arbitrarily.When using multistage froth flotation, modified resin once can be added before multistage flotation, perhaps in each flotation stage, they are added respectively.Other separation

Due to the compatibility of modified resin of the present invention to the solid impurity in suspension, they can be applicable to a variety of separation, particularly comprise those application of removing these impurity (as sand and/or clay) from the aqueous suspension of siliceous impurity or slurry.Therefore these aqueous suspensions or slurry can be processed with modified resin of the present invention, and at least a portion impurity can be separated from the liquid that purifies in the impurity enriched part." impurity enriched " part refer to suspension or the slurry of solid impurity enrichment part (namely be present at first suspension or slurry in solid impurity compare, comprise the solid impurity of higher percentage).Otherwise, to compare with the solid impurity in being present at first liquid suspension or slurry, the liquid of purification comprises the solid impurity of lower percentage.

Separating technology described herein is applicable to " suspension " and solids " slurry ".These terms implication sometimes are identical, but in the situation that " slurry " is based on adding at least some stirrings or energy to keep homogeneous, sometimes distinct.Because method of the present invention described herein can be widely used in separating solid particles from water-bearing media, in specification of the present invention and claims, term " suspension " can be replaced (vice versa) mutually with " slurry ".

Treatment step can comprise the modified resin that adds q.s, makes charge interaction and make solid impurity reunite or flocculate to be larger aggregate.Those skilled in the art can easily recognize according to some variablees (for example kind of impurity and concentration) can easily determine necessary amounts.In other embodiments, processing can comprise the fixed bed that makes suspension Continuous Contact solid state modification resin.

With during the modified resin suspension-treating or afterwards, remove and reunite or the solid impurity (can be for example larger agglomerated particles or floccule form now) of flocculation.Can realize removing by flotation (as the description of the relevant froth flotation in front, utilizing or do not utilize the bubble that rises) or sedimentation.The best approach of removing depends on relative density or the other factors of floccule.Increase also can improve for the treatment of the consumption of the modified resin of suspension the trend that floccule is floating rather than precipitate in some cases.No matter solia particle reunion floccule is on the top layer or in sediment, and filtration or coarse filtration can be also to remove their effective means.

The example of the suspension that can purify according to the present invention is included in the oil well that gathers rock (or drilling cuttings) solids between the normal operating period and the drilling fluid of gas well.Due to several reasons, these drilling fluids (often referring to " drilling mud ") are important in drilling process, comprise these drilling cuttings are transported to the surface from drilling area, and it is recycling that their removal is able to drilling mud.Modified resin of the present invention adds in well bore liquid especially water base (namely moisture) drilling fluid, make solid particle contamination effectively reunite or flocculate and be larger piece (or floccule), thereby promote them to separate by sedimentation or flotation.Modified resin of the present invention can be united for this application with known flocculant such as polyacrylamide or hydrocolloid polysaccharide.Usually, in the situation that water base oil well or gas well drilling fluid, the separation of solid impurity is enough to provide the drilling fluid of purification, for the drill-well operation recycling.

There is other waterborne suspension of actual benefit to comprise to follow and comprises above-mentioned those aqueous suspension argillaceous or the salt solution of ore refining technique.For example, produce the phosphate that purifies and usually rely on separating for several times solia particle from water-bearing media from the calcium phosphate rock of exploitation, can improve such separation with modified resin of the present invention thus.In whole technique, exploit out calcium phosphate from the underground approximately mineral reserve of mean depth of 25 feet.The initial phosphate rock that reclaims in the parent rock that contains sand and clay impurity.At first with parent rock and water mixed-shaped form slurry, after mechanical agitation, the screening slurry is to keep the phosphate gravel and to make the fine clay particle be able to pass through with large water gaging as the clay slurry effluent usually.

These effluents argillaceous have higher flow velocity usually, and usually carry the solid that is less than 10wt.%, and more generally only contain the approximately solid of 1wt.%～5wt.%.The dehydration (for example by sedimentation or filtration) of this spent clay of water circulation use has proposed great challenge to recovery.Yet, process the clay slurry effluent that obtains when producing phosphate with modified resin of the present invention, can reduce the required time of dehydration.The minimizing of clay sedimentation time can make in phosphate production operation by purifying waste water of obtaining of clay dehydration and effectively be reused.In a kind of embodiment of purification method, wherein suspension is the discharge slurry argillaceous from phosphate production factory, and after being less than the sedimentation or dewatering time of approximately 1 month, the liquid of purification comprises and is less than the approximately solid of 1wt.%.

Except the above-mentioned phosphate gravel and clay slurry effluent that keeps by screening, also obtained the mixture of sand and thinner phosphate particle in the initial management of the phosphate parent rock of exploitation.Be separated in sand and phosphate in this fluid by froth flotation, as mentioned above modified resin of the present invention can be improved this froth flotation as the inhibitor of sand.

In the de-watering of slurries zone, the Another Application of resin is to filter coal from aqueous slurry.The dehydration of coal is industrial important because increase with water content, the minimizing of BTU value and thus the quality of coal can reduce.Therefore, in one embodiment of the invention, before making coal dewatering by filtration, process moisture coal suspension liquid or the slurry of containing with modified resin.

Another important application of modified resin of the present invention is at sewage treatment area, and it refers to be responsible for removal from the various techniques of the impurity of industry and municipal wastewater.Purified waste water by such technique, provide to be fit to be discharged into purifying waste water and mud in environment (for example river, streams and ocean).Sewage refers to usually be collected in the aqueous waste that then sewerage system is transported to any type for the treatment of facility.Therefore, sewage comprises the municipal wastewater from toilet (being sometimes referred to as " filthy refuse ") and basin, bathroom, shower and kitchen (being sometimes referred to as " silting sewage up ").Sewage also comprises industry and business waste water (being sometimes referred to as " industrial wastewater ") and from the stormwater runoff in hardstanding regional (as roof and street).

The conventional treatment of sewage often comprises tentatively, the firsts and seconds treatment step.Coarse sand and gravel that preliminary treatment refers to filter or screen large solid such as wood, paper, chip etc. and usually damages pump.Then adopt coagulation subsequently, by sedimentation in tank, separate most of residual solids, reclaim the mud of enrichment solid from the bottom of these grooves and further process.The water that purifies also is recovered, and usually carries out two stage treatment through bioprocess technology.

Thereby in one embodiment of the invention, the sedimentation of sewage or precipitation can comprise with modified resin of the present invention disposes of sewage.This processing can be used for improving sedimentation operation (in batches or continuously), for example by minimizing realize assigned operation (for example based on the purity of purifying waste water and/or in mud the recovery percentage of solid) the required time of staying.In addition, for the sedimentation time of appointment, produce more highly purified purify waste water and/or mud in raising aspect the higher rate of recovery of solid be obvious.

After utilizing modified resin of the present invention to dispose of sewage and removing by precipitation the current that purify, modified resin can also be used for or introduce secondary treatment process and further purify waste water.Two stage treatment relies on the effect decomposition of organic material of spontaneous microorganism usually.Especially, aerobe technique makes to reclaim and substantially degrades from the biological content of purifying waste water of coagulation.Microorganism (for example bacterium and protozoan) consumes biodegradable solvable organic impurities (for example carbohydrate, fats and other organic molecule), and make many insoluble,practically parts be combined into floccule, thereby further promote the removal of organic material.

Two stage treatment depends on to aerobe " supply " oxygen and other nutrient, they is survived and consume organic impurities.Advantageously, nitrogenous modified resin of the present invention can be as " food " source of microorganism in two stage treatment, also might be as the extra flocculant of organic material.Therefore, in one embodiment of the invention, effluent purification method further comprises, remove by sedimentation and purify waste water (in the coagulation step) afterwards, having microorganism and modified resin exist under further treatment and purification water, the optionally additional quantity of the modified resin biochemical oxygen demand (BOD) of purifying waste water in order to reduction.Understand as this area, BOD is the important indicator of water quality, represents the oxygen by mg/l (perhaps ppm) by weight that microorganism oxidation organic impurities in 5 days is required.After processing with microorganism and modified resin, the BOD that purifies waste water generally is less than 10ppm, typically is less than 5ppm, and often is less than 1ppm.

Modified resin of the present invention can also be applied to the purification of the waste water in pulp mill and paper mill.These moisture waste stream comprise solid impurity (for example waste paper, bark or other timber composition, for example wood chip, wood strand, wood-fibred or the wood particle of fibrous material form usually; Perhaps string is as wheat straw fiber, rice fiber, switchgrass fiber, soybean rod fibers, bagasse fibre or cornstalk fiber; And the mixture of these impurity).The method according to this invention is processed the discharge currents that comprises cellulose solids impurity with modified resin of the present invention, in order to remove through sedimentation, flotation or filtration the water that purifies.

Separate bitumen from sand and/or clay impurity, can adopt various separating steps before or after the froth flotation of bituminous slurry as previously mentioned.These steps can comprise screening, filtration and sedimentation, wherein arbitrary step can be benefited from modified resin of the present invention and process oil-sand, remove subsequently the part of sand and/or clay impurity in impurity enriched part (for example bottom), perhaps remove the pitch part that purifies.As mentioned above, the relevant phosphate ores that usually comprises the solid clay particle is processed waste water, and treatment step can comprise makes these impurity flocculate to promote its removal (for example by filtering).Therefore waste water effluent from the bitumen treatment facility comprises sand and/or clay impurity equally, benefits from modified resin of the present invention and processes, and their is dewatered and/or partly remove at least a portion of these solid impurities in impurity enriched.The special process fluid of the concern that produces in the pitch extraction process is commonly referred to as " ripe smart mine tailing (mature fine tails) ", is the aqueous suspension that can benefit from the thin solia particle of dehydration.Usually, in the situation that from the asphalt production facility contain sand and/or slurry, decontaminating liquid or current that the separation of solid impurity is enough to make it possible to be recycled in pitch technique are recycled or remove.

In process for preparing asphalt, be not only limited to those techniques of the froth flotation of the moisture bituminous slurry of at least part of dependence with the modified resin various central fluid of processing of the present invention and effluent.As what those skilled in the art easily recognized, other technology (for example passing through the centrifugation of " synthetic crude process " (" Syncrude Process ")) that is used for the pitch purification can produce moisture central fluid and the accessory substance fluid that solid impurity is therefrom removed in expectation.

Modified resin of the present invention can be used for water purification (especially in order to make it drinkable), removes the solid particle that suspends, for example sand and clay.

And modified resin of the present invention also has the character of complexing metal cation (for example plumbous and mercury cation) in addition, and these unwanted impurity and solid particle are removed simultaneously.Therefore, modified resin of the present invention can be used for effectively processing the impure water that contains solid particle polluter and metal cation impurity.Be not limited by theory, still think electronegative part, for example the carbonylic oxygen atom on the Lauxite main polymer chain, with unwanted cation complexing, be convenient to it and remove.Usually, pH value occurs is approximately 7～approximately 9 greater than common its scope in about 5 water for this complexing.

The another kind of possible mechanism that metal cation is removed is based on the combination of itself and electronegative solid particle.Therefore the flocculation of these particles and remove at least to a certain extent and also can cause removing of metal cation.No matter mechanism how, in one embodiment, can realize according to the present invention processing and the removal of these impurity, produce drinkable water.

Mainly or even the only resource that the water that the removal of metal cation may represent to be realized by modified resin purifies is for example when the water of band purification comprises seldom or do not contain solid particle.Can use the modified resin of solid forms in continuous processing, the cationic impure water of containing metal passes through the fixed bed of this resin continuously thus.Selectively, the modified resin of the dissolved form that usually has lower molecular weight can be added, so that it is processed in impure water.Complex cation in this example can carry out hyperfiltration less than the perforated membrane (for example polysulfones) of modified resin molecular weight by weight shutoff value for example and remove.Method for purifying water described herein also can be combined with known method, and known method comprises counter-infiltration, UV irradiation etc.

In order to improve the efficient of modified resin and metal cation complexing, may need with one or more anionic functional groups, above-mentioned base resin to be carried out further modification.This modification is well known in the art, and required functional group (for example by with the sulfonation of sodium metabisulfite) is introduced in the reaction that can comprise this base resin or modified resin.Selectively, by add a kind of anionic copolymerization monomer (for example PAA) in base resin or crosslinking agent, (for example in condensation course) realizes further modification in the preparation process of base resin.For example, as mentioned above, can prepare the organopolysiloxane derivative as coupling agent by introduce another kind of organic resin functional group (for example acrylate) in coupling agent.Representational other functional group that can be used for modification base resin or modified resin (comprising Lauxite) comprises the anionic functional group, bisulfite, propylene acid group, acetate, carbonate, azido, acylamino-etc.The technique of using other functional group modification base resin is well known to a person skilled in the art.Also can realize introducing the anionic functional group in base resin in the separation of the purification that comprises the slurry that contains the solid clay particle (such as by froth flotation, flocculation etc.) (comprise above-mentioned those, for example in the purification of kaolin ore).Without being limited by theory, the sulfonation of base resin or other anionic functional group's introducing also can improve base resin and the Hydrogenbond between water on every side, with the condensation that suppresses base resin or improve on the contrary its stability.

Therefore, as mentioned above, in one embodiment, the present invention is a kind of method that purification comprises the water of metal cation, by with described herein and can further process water with the modified resin of anionic group modification.By in the fixed bed that holds it in modified resin or on the contrary its filtration is gone out the removal that can realize at least a portion metal cation.In the later case, the removal by filtering (for example membrane filtration) can directly be combined with modified resin or have the solid particle of affinity to realize indirect combination with modified resin by modified resin to it by metal cation.In indirectly in conjunction with situation, as previously mentioned, the flocculation of solid particle also can make a part of metal ion flocculation inevitably, therefore can be removed by flotation or the sedimentation of these particles.

Therefore modified resin of the present invention can be advantageously used in processing water, removes wherein those known metal cation that can cause health risk when taking in, for example arsenic, lead, cadmium, copper and mercury.Therefore these cations comprise As ⁵⁺, pb ²⁺, Cd ²⁺, Cu ²⁺, Hg ²⁺And composition thereof.Usually, the removal degree of realization makes to purify waste water and substantially do not contain one or more of above-mentioned metal cation after processing." do not contain substantially " that the concentration that refers to one or more metal cations of paying close attention to is reduced to the concentration that is considered to safety (for example management organization is assert, for example U.S. Environmental Protection Agency) or under this concentration.Therefore, in various representational embodiments, the middle approximately As5 of 10ppb that will comprise at the most purifies waste water ⁺, the about pb of 15ppb at the most ²⁺, the about Cd of 5ppb at the most ²⁺, the about Cu of 1.3ppm at the most ²⁺And/or the about Hg of 2ppb at the most ²⁺That is, generally at least a, at least two kinds usually, often all above-mentioned anion are all these limting concentrations of purifying waste water or under this concentration.

In described any application, can make modified resin stabilisation of the present invention by the reaction (being etherification) with alcohol herein.Bound by theory not, we think that the etherificate of silane alcohol base functional group of suspention can suppress the further condensation (for example condensation of Lauxite self) of base resin.This can finally hinder or prevent the precipitation of base resin in the long term storage process, makes the non-etherified resin corresponding with it compare, and the resin of etherificate can have larger molecular weight, and can its stability of corresponding loss.

Therefore etherificate comprises the reaction of amine-aldehyde adducts or condensation product or modified resin even as above and alcohol.In one embodiment, with coupling agent to urea aldehyde radical plinth resin modified before, with the alcohol that contains 1～8 carbon atom, Lauxite is carried out etherificate.The representational alcohol that is used for etherificate comprises methyl alcohol (for example being used for methylating), ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol and isobutanol.In the exemplary preparation of etherificate base resin, amine-aldehyde adducts or condensation reaction products under existing, alcohol are heated to the approximately 70 ℃～about temperature of 120 ℃, until etherificate fully.Can with alcohol reaction before or during, add acid, for example sulfuric acid, phosphoric acid, formic acid, acetic acid, nitric acid, alum, iron chloride or other acid.Usually use sulfuric acid or phosphoric acid.

All documents that this specification is quoted include but not limited to all U.S., the world and foreign patent and patent application, and in all summaries and this specification of the whole introducing of paper spare (such as journal of writings, magazine etc.) as a reference.List of references discussion herein only is used for summing up the opinion that its author makes, and does not think that any list of references has consisted of prior art.The applicant keeps the right to the correctness of citing document and appropriateness query.Due to the above, can see that advantages more of the present invention are achieved, and have obtained other favourable result.

Make various changes owing to can not departing from the scope of the present invention in said method and composition, therefore all the elements that comprise in the application, comprise above-mentioned theoretical mechanism and/or interaction mode, all be appreciated that and only play illustration, and be used for limiting never in any form the scope of claims.

Following embodiment is proposed as representative of the present invention.These embodiment also are not used in circumscription of the present invention in this, and with reference to this specification and claims, other suitable embodiment will become apparent.

Froth flotation

Embodiment 1

Prepare various Lauxites as low-molecular-weight condensation resin, at first form methylolated urea addition product under alkali condition, then form this condensation product under acid condition.Stop this condensation reaction by the pH value that improves the condensation reaction mixture.Other preparation condition as mentioned above.Listed these base resins in following table 1 corresponding in g/mol molecular weight (Mol.Wt.), and about standardization percentage by weight of the urea (Di/Tri) of the urea (Mono) of free urea, ring-type urea part (ring-type urea), monomethylol and combination two/trihydroxy methyl.In each example, the resin solid content in the solution of base resin place is 45～70%, and viscosity is 500cps or lower, and free formaldehyde content is lower than 5wt.%.

Table 1---urea aldehyde radical plinth resin

IDMol.Wt. ^a Free urea The ring-type urea Mono Di/Tri

Resin A 406 8 39 30 23

Resin B ^*997 5 50 22 23

Resin C and C ' ^*500 6 46 25 23

Resin D and D ' ^{* *}131 4 32 13 06

Resin E 578 0 18 10 72

Resin F 1,158 1 44 11 44

Resin G 619 0 26 3 71

^*Resin B is a kind of highly stable Lauxite, has higher ring urea content.United States Patent (USP) 6,114 is described this resin in 491.

^*Resin C ' is by except silane #1 (as described below), and the diethylenetriamines and the 2wt.% dicyano diamides that add 2wt.% in the resin preparation process in urea and formaldehyde mixture form.

^{* *}Resin D ' forms by the annular phosphate that adds 0.75wt.% in the resin preparation process in the mixture of urea and formaldehyde.This resin has lower molecular weight, has the free urea of high-load, does not substantially contain free formaldehyde, and the non-volatile matter of high level (approximately 70% solid).

^aUse is with appropriate size PLgel ^TMThe gel permeation chromatography of post (GPC) (PolymerLaboratories, Inc., Amherst, MA, USA) measuring number-average molecular weight, be mobile phase with 0.5% glacial acetic acid/oxolane under 1500psi, and polystyrene, phenol and bisphenol-A is as measurement standard.

Urea-formaldehyde resin solution as above is carried out modification with silane coupler, to prepare resin inhibitor of the present invention.Silane coupler #1, the #2 that uses in the preparation of these modified resin and #3 are the substituted silanes defined in following table 2.

Table 2---silane coupler

ID Type The source

Silane #1 base propyl trimethoxy silicane Silane A1160 ^↑

The oligomeric aminoalkyl silane of silane #2 Silane A1106 ^↑

Silane #3 aminopropyltriethoxywerene werene Silane A1100 ^↑

^↑Can obtain (GE Silicones-OSi Specialties, Wilton, CT, USA) by trade mark Silquest

Embodiment 2

According to abovementioned steps, carry out modification with the above-mentioned urea aldehyde radical plinth resin described in silane coupler #1, the #2 described in table 2 and #3 his-and-hers watches 1.That is: as mentioned above, at the low-molecular-weight condensation product that forms, then add after alkali improves the pH value and termination condensation reaction of solution, silane coupler is added in base resin solution, its addition is approximately 0.1～2.5% of resin solution weight.Then the alkaline mixt of base resin and silane coupler is heated to approximately the temperature approximately 0.5～4 hour of 35～45 ℃, until reach the approximately viscosity of 350～450cps.

Embodiment 3

To represent unmodified resin or as mentioned above with the various Lauxites of silane coupler modified resin and contrast inhibitor in laboratory size ore dressing research, remove selectively testing of siliceous sand and clay impurity from the potash ore by froth flotation.In each test, per unit weight treat pH value, the per unit volume slurry of solid content, the slurry of amount, the ore slurry of the inhibitor that the ore of ore dressing is used air velocity, phosphate purity and the various condition of ore all represents industrial operation before ore dressing.In each test, the ore that reclaims by flotation is 90wt.% pure phosphoric acid salt material at least.Use commercially available guar gum as the inhibitor control sample.

In these trials, measure the performance of each inhibitor according to the amount of the potash that can reclaim with certain pure (being flotation).This amount provide each inhibitor with the combination of unwanted gangue material in selective.In other words, inhibitor selectively higher can be just larger by the amount of 90% pure phosphoric acid salt of flotation.Obtain following data, as shown in table 3 below.

The performance of table 3---inhibitor in phosphate reclaims

Inhibitor Flotation〉grams of 90% potassium

Contrast 1-guar gum 212

Resin A. with silane #1 modification 230

Resin A. unmodified 85

Resin B. with silane #1 modification 226

Resin B. unmodified 97

Resin C. silane #1 modification 172

Resin C '. with silane #1 modification 158

Resin D. silane #1 modification 82 (2 testing means)

Resin D '. unmodified 100

Resin E. silane #1 modification 215

Resin E. silane #2 modification 232 (2 testing means)

Resin E. silane #3 modification 226 (2 testing means)

Resin F. silane #1 modification 229

Resin F. silane #2 modification 231

Resin F. silane #3 modification 225

Resin G silane #1 modification 223

Resin G silane #2 modification 228

Resin G silane #3 modification 224

Based on the above results, use silane coupler modified urea aldehyde radical plinth resin (preferably passing through covalent bond) can significantly improve resin as the performance of the inhibitor in froth flotation.And along with the molecular weight rising of base resin, the performance advantage relevant with using silane coupler becomes more and more obvious.Especially, molecular weight has obtained good performance higher than the about base resin of 300 g/mols before modification.This is shown in Figure 1, has shown the Performance Ratio of silane coupler modified resin and unmodified resin, and the molecular weight of these resins is approximately 400～approximately 1200 g/mols.And, the Lauxite in this molecular weight ranges can not be subject to base resin other modifier (such as diethylenetriamines, dicyano diamides, phosphate etc.) use and be affected.

It is better that the silane coupler modified resin that Fig. 1 also shows the molecular weight that has approximately 400～approximately 1200 g/mols and its unmodified homologue are compared performance, usually than well known in the art for bonding clay and talcum but obviously the performance of more expensive guar gum is better.In addition, compare with guar gum, inhibitor of the present invention shows flotation to the raw phosphoric acid salt particle and has much higher selective.In the phosphate of the purification that flotation obtains in the test of guar gum, the amount of subparticle is relatively large, and it has obviously increased dry with the downstream and screening operates to produce the expense of salable product.

Embodiment 4

The character that the performance of modified resin inhibitor sample of the present invention in potash ore dressing factory and the guar gum that is used as the commercial inhibitor of gangue material at present in this factory are compared.The inhibitor of the present invention that is used for this test is the resin F described in above-described embodiment 1-3, by silane #2 modification.

For contrast test, the pH value of the amount for the treatment of the inhibitor that flotation of ores is used of per unit weight, the solid content of ore slurry, slurry, the air velocity of per unit volume slurry, phosphate purity and other conditions of ore all represents industrial operation before ore dressing.Measure the performance of each inhibitor according to the amount of the potash that can reclaim with certain pure (being flotation).This amount provide each inhibitor with the combination of unwanted gangue material in selective.In other words, inhibitor selectively higher can be just larger by the amount of the potash of flotation with certain pure.

Compare with guar gum, inhibitor of the present invention has improved approximately 19% to the productive rate that purifies potash.In addition, use silane coupler modified Lauxite, make the coarse grained productive rate of required potash (potassium chloride) mineral obtain improving fully.Due to reason as above, this raising of the productive rate of thick material reduced energy requirement to drying relevant and in the further refining required expense of being correlated with total processing time of before sales.

Embodiment 5

Silane coupler modified urea aldehyde (UF) resin as above is tested by the ability that filtration reduces the dewatering time that is suspended in the various solid impurities in aqueous slurry.In each test, with the solid impurity sample of 25 grams and 0.01 mole of KNO of 100 grams ₃Evenly blend together slurry.Measure the pH value of slurry.Then the qualitative #1 filter paper of the Buchner funnel device of Application standard 12.7cm diameter and 11.0cm diameter Whatman carries out vacuum filtration to this slurry.Dewatering time in each embodiment is exactly to reclaim the required time of 100ml filtrate by filter paper.

Each solid impurity for test, carry out check experiment, then carry out same test, difference only is that (1) add the silane-modified UF resin of 0.5～1 gram in slurry, and under agitation mixed slurry other one minute after forming uniform sizing material (2) again again.The results are shown in following table 4.

(25 gram solid impurities are at 100 gram 0.01M KNO for the dewatering time of table 4---aqueous slurry ₃In)

Solid contrast contrast+0.5～1 silane-modified UF resin of gram

Geltone ^*13.1 second 8.2

(slurry pH value) (8.1) (8.5)

Bentonite 5.3 2.3

(slurry pH value) (8.8) (8.8)

Graphite 8.1 5.2

(slurry pH value) (4.4) (4.5)

Kaolin 10.5 5.4

(slurry pH value) (3.3) (3.7)

Talcum (＜10 microns) 2.0 1.3

(slurry pH value) (8.8) (8.9)

^*The brand name of montmorillonitic clay

The above results shows that silane-modified UF resin even when a small amount of the use, still has the ability that can obviously reduce the dewatering time of many solid particles.

Claims (44)

1. the method for a purification clay from ore argillaceous, the method comprises:

The ore argillaceous that comprises clay and one or more organic or inorganic impurity is provided;

The aqueous slurry of this ore argillaceous is contacted with the inhibitor that comprises amine-aldehyde resins and silane coupler;

Wherein this amine-aldehyde resins is base resin, and it is the product of primary amine or secondary amine and aldehyde; With

Wherein this base resin is by silane coupler modified; And

By the froth flotation of at least a impurity, the clay of separating-purifying from this ore argillaceous.

2. method as claimed in claim 1, wherein these one or more organic or inorganic impurity are selected from metal, metal oxide, mineral, coal, pitch or its any combination.

3. method as claimed in claim 1, wherein said ore argillaceous comprises kaolinton, wherein one or more organic or inorganic impurity are selected from iron oxide, titanium dioxide or its combination.

4. the method for the pitch of purifying comprises:

The aqueous slurry that will comprise pitch and one or more impurity contacts with the inhibitor that comprises amine-aldehyde resins and silane coupler;

Wherein this amine-aldehyde resins is base resin, and it is the product of primary amine or secondary amine and aldehyde; With

Wherein this base resin is by silane coupler modified; And

By froth flotation separate bitumen from this aqueous slurry,

Wherein, with respect to aqueous slurry, foam comprises at least a or plurality of impurities of lower concentration.

5. method as claimed in claim 4, wherein one or more solvable or soluble impurity comprise sand or clay.

6. method of purifying waste water comprises:

The Aquo-composition that comprises water and one or more impurity is provided;

This Aquo-composition is contacted with the inhibitor that comprises amine-aldehyde resins and silane coupler, to form resin-impurity complex compound;

Wherein this amine-aldehyde resins is base resin, and it is the product of primary amine or secondary amine and aldehyde; With

Wherein this base resin is by silane coupler modified; And

Separation resin from this Aquo-composition-impurity complex compound is to provide the water of purification.

7. method as claimed in claim 6, wherein said separating step c) comprise sedimentation, flotation, filtration or its any combination.

8. method as claimed in claim 7, wherein said filtration is membrane filtration.

9. method as claimed in claim 6, wherein these one or more solvable or soluble impurity is selected from As ⁵⁺, Pb ²⁺, Cd ²⁺, Cu ²⁺, Mn ²⁺, Hg ²⁺Compound or its any combination.

10. method as claimed in claim 6, Aquo-composition solvable comprising one or more or soluble impurity is the discharge slurry that comprises sand or clay of water base well bore liquid, the discharge slurry argillaceous from phosphate production factory, the intermediate product that contains coal suspension liquid, sewage, pulp mill or paper mill waste liquid, process for preparing asphalt or process for preparing asphalt.

11. method as claimed in claim 6, wherein separation resin-impurity complex compound comprises that the water that shifts out purification is used for reusing in phosphate production from this Aquo-composition.

12. method as claimed in claim 6, wherein the method further comprises steps d): under existing, microorganism and amine-aldehyde resins process the water of described purification, with the biochemical oxygen demand (BOD) of the water that reduces described purification.

13. method as claimed in claim 6, wherein said Aquo-composition are water base well bore liquid, wherein separation resin-impurity complex compound comprises that the drilling fluid that shifts out purification is used for reusing in well bore from this Aquo-composition.

14. method as claimed in claim 6, wherein said Aquo-composition are to contain coal suspension liquid, wherein separation resin-impurity complex compound comprises by filtration and shifts out the part that is rich in coal from this Aquo-composition.

15. method as claimed in claim 6, wherein one or more solvable or soluble impurity are clay, sand or fibrous material.

16. the beneficiation method of an ore comprises:

The ore that comprises valuable mineral and one or more impurity is provided;

The aqueous slurry of this ore is contacted with the inhibitor that comprises amine-aldehyde resins and silane coupler;

Wherein this amine-aldehyde resins is base resin, and it is the product of primary amine or secondary amine and aldehyde; With

Wherein this base resin is by silane coupler modified; And

Separate valuable material from this aqueous slurry by froth flotation.

17. as the method for claim 16, wherein valuable material is selected from: phosphate, potash, lime, sulfate, gypsum, iron, platinum, gold, palladium, titanium, molybdenum, copper, uranium, chromium, tungsten, manganese, magnesium, lead, zinc, silver, coal or its any combination.

18. as the method for claim 16, wherein one or more impurity are selected from titanium dioxide, mica, ilmenite, tourmaline, alumina silicate, calcite, dolomite, anhydrite or its combination of sand, clay, iron oxide, titanium oxide, iron content.

19. as the method for claim 16, wherein this amine-aldehyde resins is the product of primary amine and formaldehyde.

20. as the method for claim 16, wherein this amine-aldehyde resins comprises having solution or the dispersion that resin solid content is 30wt.%～90wt.%, wherein the amount of this silane coupler is the 0.01wt.%-5wt.% of this amine-aldehyde resins solution or dispersion.

21. as the method for claim 16, wherein take the amount of scope as ore 100-1000 donaxine-urea formaldehyde per ton, come to process this ore slurry with this amine-aldehyde resins.

22. as the method for claim 16, wherein the method reclaims the valuable material of 70wt.% at least from this ore, wherein the purity of valuable material is 85wt.% at least.

23. as the method for claim 16, wherein the solid content of this amine-aldehyde resins is 40%～100%.

24. as the method for claim 16, wherein this amine-aldehyde resins is pure basically, and is viscous liquid, colloid or pressed powder.

25. as claim 1-18 and the described method of 20-24 any one, wherein this amine-aldehyde resins is the product of primary amine or secondary amine and aldehyde, wherein this silane coupler is selected from substituted silane, silica, silicate, polysiloxanes or its any combination.

26. as the described method of claim 1-24 any one, wherein this amine-aldehyde resins comprises Lauxite, wherein silane coupler comprises substituted silane.

27. as the described method of claim 1-24 any one, wherein this amine-aldehyde resins be aldehyde and amine take mol ratio as 1.5: 1-4: 1 product.

28. as the described method of claim 1-24 any one, wherein this amine-aldehyde resins comprises Lauxite, this Lauxite is that formaldehyde and urea are take the product of mol ratio as 1.75: 1～3: 1.

29. as the described method of claim 1-24 any one; wherein this silane coupler comprises Carbamido substituted silane, amino substituted silane, sulphur substituted silane, epoxy substituted silane, methacryl substituted silane, vinyl substituted silane, alkyl substituted silane, haloalkyl substituted silane or its any combination.

30. as the described method of claim 1-24 any one, wherein this silane coupler is selected from urea groups alkyltrialkoxysilaneand, aminoalkyl trialkoxy silane, oligomeric aminoalkyl silane or its any combination.

31. as the described method of claim 1-24 any one, wherein this silane coupler is selected from the urea groups propyl trimethoxy silicane, the urea groups propyl-triethoxysilicane, TSL 8330, aminopropyltriethoxywerene werene, the aminopropyl methyldiethoxysilane, the aminopropyl methyl dimethoxysilane, the aminoethylamino propyl trimethoxy silicane, the aminoethylamino propyl-triethoxysilicane, aminoethylamino propyl group methyl dimethoxysilane, diethylidene triamido propyl trimethoxy silicane, diethylidene triamido propyl-triethoxysilicane, diethylidene triamido propyl group methyl dimethoxysilane, diethylidene triamido propyl group methyldiethoxysilane, the cyclohexyl TSL 8330, own diaminourea MTES, the anilino-MTMS, the anilino-MTES, diethylamino methyltriethoxy silane alkane, (diethylamino methyl) methyldiethoxysilane, the methylamino propyl trimethoxy silicane, two (triethoxysilylpropyltetrasulfide) tetrasulfide, two (triethoxysilylpropyltetrasulfide) disulphide, the sulfydryl propyl trimethoxy silicane, the sulfydryl propyl-triethoxysilicane, sulfydryl propyl group methyl dimethoxysilane, 3-sulphur cyanato propyl-triethoxysilicane, isocyanide acyl propyl triethyl silicane, glycidoxypropyltrimewasxysilane, the glycidoxypropyl triethoxysilane, the glycidoxypropyl methyldiethoxysilane, the glycidoxypropyl methyl dimethoxysilane, methacryloxypropyl trimethoxy silane, the methacryloxypropyl triethoxysilane, the methacryloxypropyl methyl dimethoxysilane, r-chloropropyl trimethoxyl silane, chloropropyl triethoxysilane, the chloromethyl triethoxysilane, the chloromethyl trimethoxy silane, the dichloromethyl triethoxysilane, vinyltrimethoxy silane, VTES, vinyl three (2-methoxy ethoxy) silane, vinyltriacetoxy silane, the alkyl methyl trimethoxy silane, vinyl benzene methylamino trimethoxy silane, (3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, aminopropyl triple phenoxyl silane, aminopropyl thribenzoyl silane, aminopropyl three chaff TMOSs, aminopropyl three (o-chlorophenoxy) silane, aminopropyl three (p-chlorophenoxy) silane, aminopropyl three (tetrahydrochysene chaff oxygen base) silane, ureido silane, mercaptoethyltriethoxysilane, and vinyl trichlorosilane, methacryloxypropyl three (2-methoxy ethoxy) silane or its any combination.

32. as the described method of claim 1-24 any one, wherein this amine-aldehyde resins further comprises the anionic functional group.

33. as the described method of claim 1-24 any one, wherein this amine-aldehyde resins has the concentration of free formaldehyde less than 5%.

34. as the described method of claim 1-24 any one, wherein the number-average molecular weight of this amine-aldehyde resins (Mn) is greater than 300 g/mols.

35. as the described method of claim 1-24 any one, wherein this treatment step further comprises with silica, silicate, polysiloxanes, polysaccharide, polyvinyl alcohol, polyacrylamide, flocculant or the processing of its any combination.

36. an inhibitor that comprises amine-aldehyde resins and silane coupler,

Wherein this amine-aldehyde resins is base resin, and it is the product of primary amine or secondary amine and aldehyde; With

Wherein this base resin is by silane coupler modified.

37. as the inhibitor of claim 36, wherein this amine-aldehyde resins comprises Lauxite, the number-average molecular weight of this Lauxite (Mn) is greater than 300 g/mols.

38. as the inhibitor of claim 36, wherein this amine-aldehyde resins comprises Lauxite, this Lauxite has the concentration of free formaldehyde less than 5%.

39. as the inhibitor of claim 36, wherein this amine-aldehyde resins comprises Lauxite, wherein this silane coupler comprises substituted silane.

40. as the inhibitor of claim 36, wherein this amine-aldehyde resins is that aldehyde and amine are take the product of mol ratio as 1.5: 1～4: 1.

41. as the inhibitor of claim 36, wherein this amine-aldehyde resins comprises Lauxite, this Lauxite is that formaldehyde and urea are take the product of mol ratio as 1.75: 1～3: 1.

42. as the inhibitor of claim 36, wherein this silane coupler comprises Carbamido substituted silane, amino substituted silane, sulphur substituted silane, epoxy substituted silane, methacryl substituted silane, vinyl substituted silane, alkyl substituted silane, haloalkyl substituted silane or its any combination.

43. as the inhibitor of claim 36, wherein this silane coupler is selected from urea groups alkyltrialkoxysilaneand, aminoalkyl trialkoxy silane, oligomeric aminoalkyl silane or its any combination.

44. as the inhibitor of claim 36, wherein this silane coupler is selected from the urea groups propyl trimethoxy silicane, the urea groups propyl-triethoxysilicane, TSL 8330, aminopropyltriethoxywerene werene, the aminopropyl methyldiethoxysilane, the aminopropyl methyl dimethoxysilane, the aminoethylamino propyl trimethoxy silicane, the aminoethylamino propyl-triethoxysilicane, aminoethylamino propyl group methyl dimethoxysilane, diethylidene triamido propyl trimethoxy silicane, diethylidene triamido propyl-triethoxysilicane, diethylidene triamido propyl group methyl dimethoxysilane, diethylidene triamido propyl group methyldiethoxysilane, the cyclohexyl TSL 8330, own diaminourea MTES, the anilino-MTMS, the anilino-MTES, diethylamino methyltriethoxy silane alkane, (diethylamino methyl) methyldiethoxysilane, the methylamino propyl trimethoxy silicane, two (triethoxysilylpropyltetrasulfide) tetrasulfide, two (triethoxysilylpropyltetrasulfide) disulphide, the sulfydryl propyl trimethoxy silicane, the sulfydryl propyl-triethoxysilicane, sulfydryl propyl group methyl dimethoxysilane, 3-sulphur cyanato propyl-triethoxysilicane, isocyanide acyl propyl triethyl silicane, glycidoxypropyltrimewasxysilane, the glycidoxypropyl triethoxysilane, the glycidoxypropyl methyldiethoxysilane, the glycidoxypropyl methyl dimethoxysilane, methacryloxypropyl trimethoxy silane, the methacryloxypropyl triethoxysilane, the methacryloxypropyl methyl dimethoxysilane, r-chloropropyl trimethoxyl silane, chloropropyl triethoxysilane, the chloromethyl triethoxysilane, the chloromethyl trimethoxy silane, the dichloromethyl triethoxysilane, vinyltrimethoxy silane, VTES, vinyl three (2-methoxy ethoxy) silane, vinyltriacetoxy silane, the alkyl methyl trimethoxy silane, vinyl benzene methylamino trimethoxy silane, (3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, aminopropyl triple phenoxyl silane, aminopropyl thribenzoyl silane, aminopropyl three chaff TMOSs, aminopropyl three (o-chlorophenoxy) silane, aminopropyl three (p-chlorophenoxy) silane, aminopropyl three (tetrahydrochysene chaff oxygen base) silane, ureido silane, mercaptoethyltriethoxysilane, and vinyl trichlorosilane, methacryloxypropyl three (2-methoxy ethoxy) silane or its any combination.

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