CN104755425B

CN104755425B - Accessible calcium and magnesium suspension

Info

Publication number: CN104755425B
Application number: CN201380056266.1A
Authority: CN
Inventors: 伯纳德·劳伦特
Original assignee: Lhoist Recherche et Developpement SA
Current assignee: Lhoist Recherche et Developpement SA
Priority date: 2012-10-25
Filing date: 2013-10-25
Publication date: 2016-11-30
Anticipated expiration: 2033-10-25

Abstract

A kind of calcium and magnesium waterborne suspension, comprises: in aqueous phase, concentration meets formula a Ca (OH) more than or equal to 200g/kg₂.b Mg(OH)₂.c the solid particle of MgO, wherein, a, b and c representation quality mark, their summation has the value of 90～100%；And be thinner and the additive of viscosity increase blocker, wherein, described additive is phosphonate or phosphonic acids. simultaneously.

Description

Accessible calcium and magnesium suspension

Technical field

The present invention relates to a kind of calcium-magnesium waterborne suspension, comprise: the concentration symbol more than or equal to 200g/kg in aqueous phase Close formula a Ca (OH)₂.b Mg(OH)₂.c the solid particle of MgO, wherein, a, b and c represent mass fraction, their summation tool There is the value of 90～100%；It is thinner and the additive of viscosity increase blocker simultaneously.

Background technology

For many years, various trials have been applied to reduce, by dispersant, the water yield used in calcium-magnesium waterborne suspension.

For meaning of the present invention, term " calcium-magnesium waterborne suspension " refers to that concentration is more than or equal in aqueous phase 200g/kg meets formula a Ca (OH)₂.b Mg(OH)₂.c the suspension of the solid particle of MgO, wherein, a, b and c represent matter Amount mark, their summation has the value of 90～100%.Granule contains as mass fraction 0～10% further and (represents whole Body per kilogram tens grams) material, this material is it is of course possible to containing impurity, i.e. from SiO₂、Al₂O₃、Fe₂O₃、MnO、P₂O₅ And/or SO₃Phase.These solid particles can also contain the calcium oxide as raw material not having during ripening with hydrate, And the calcium carbonate CaCO optionally combined with the form of dolime₃And/or magnesium carbonate MgCO₃.Therefore, lime cream will produce The particular case of application when the suspension of Calx, i.e. Mg (OH)₂Or the content of MgO is the lowest and is considered the formula of impurity Particular case.Above-mentioned formula can also be expressed as a Ca (OH)₂.b Mg(OH)₂.c (wherein d has as mass fraction MgO.d 0～the value of 10%).

Such calcium-magnesium waterborne suspension can pass through slaking quicklime, the quick lime containing dolomite, raw calcining Dolomite or quick lime are with (i.e. ratio obtains powder Calx (Calx of calcic, the Calx containing dolomite) than stoichiometry Required amount) mixture of water of much bigger amount obtains；Or by formula a Ca (OH) will be met₂.b Mg(OH)₂.c The solid particle of MgO is mixed in aqueous phase and obtains, and wherein, a, b and c represent mass fraction, their summation have 90～ The value of 100%.

Currently used various parameters can characterize calcium-magnesium waterborne suspension, and mainly viscosity, solid content, The granularity of these granules and the reactivity (i.e. rate of dissolution) of solid particle.

Viscosity is about application and the decisive attribute of process (pump, transport in the catheter ...) suspension.For this Individual purpose, rule of thumb can be derived that: the dynamic viscosity of suspension should be less than 2000mPa.s (US5616283), and preferable The dynamic viscosity (WO2007110401) being no more than 1500mPa.s.

Generally, viscosity increases when solid substance concentration increases and when the size of particle reduces.

The reactivity of calcium-magnesium waterborne suspension is to be determined by the rate of dissolution of granule.The reaction of calcium-magnesium waterborne suspension Property can by will a small amount of suspension inject a large amount of demineralitings water in measure.Time based on gained liquid phase electrical conductivity depends on Rely the record of property change, develop this measurement for monitoring reactivity (the v.Van Eckeren etc. of the lime cream softening drinking water People, " for softening the improvement lime cream of drinking water: the answer of leftover problem ", Aqua, 1994,43 (1) phases, page 1～10 (v.Van Eckeren et al.Improved milk-of-lime for softening of drinking water: the answer to the carry-over problem,in Aqua,1994,43(1),p.1-10)).Measure lime cream The more details of reactive process can be in " using conductance measurement solubility exponent " of § 6.11. standard EN 12485:2010 Obtain.

The reactivity of calcium-magnesium waterborne suspension also determines to neutralize or precipitation operation.

The rate of dissolution of the solid particle that known aqueous calcium-magnesium suspends is the fastest, because granule is small-sized.Enter one Step ground, the fabulous fineness of granule would generally reduce the precipitation of the solid phase of suspension.

Generally, economically it is beneficial that the concentration of lime cream can be increased to reduce the size (storage of cost of transportation and equipment Deposit tank, pump ...).

In mediation low viscosity, high concentration and suspension, the reduced size of difficulty of granule is intelligible.

Regrettably, although calcium-magnesium waterborne suspension has the dynamic viscosity less than 1500mPa.s at given time, but It is that the viscosity of these suspensions is known which are instability, and the fact that the most constantly increase still, this represents outstanding The major defect applied when the stirring of supernatant liquid becomes problem and when suspension is difficult to transport, because suspension can not keep pumpable Send and therefore undertake blocking and damage the danger of storage and transporting equipment.

In order to solve these stability problems, document is given and adds to wherein about such as additive or the most specifically select The information concentrating calcium-magnesium waterborne suspension of solid particle.

How to improve the concentration of lime cream by interpolation dispersant in the presence of a small amount of alkali metal hydroxide is (US 5616283) known.This preparation method is obtained in that dry substance concentration, and more than 40% and dynamic viscosity is less than 2000mPa.s It is even less than 1000mPa.s.But, use dispersant to be expensive and mismatch with some application.

When being there is the Calx of thicker particle size by incorporation or by ripening under conditions of promoting granule to grow Quick lime, such as by limit temperature during ripening increase, by add the additives such as such as sulfate limit viscosity increase Time big, increasing solid concentration in suspension is also known (BE1006655, US4464353).These lime cream be reactivity relatively Low, which has limited its application.And, without adding dispersant, then these suspensions settle faster.

By document EP 1663869, also know based on Calx or based on viscosity the lowest controlled lime compound Waterborne suspension, so as to be less than or equal to 10m having the specific surface area before suspending measured according to BET method²/ The suspension of the solid material particle of g increases solid material concentration and/or reduces particle size

Other family of dispersant is described, the derivant of such as soluble polysaccharide, the derivant of polyacrylate, poly- The derivant (US 4849128, US 4610801) of the derivant of amine and the polymer of diallyl ammonium chloride type.

By document EP 594332, EP592169 or US 4375526, other polymer dispersant is also known.

More specifically, file WO2007110401 discloses at the use elapsed in time with lime cream, application, the best of it By maintaining the flow behavior (such as dynamic viscosity, field stress or plastic viscosity) elapsed in time to come surely in the level that reason matches Determine lime cream.According to the teaching of the document, by add selected from carbohydrate or as by aoxidize these carbohydrates or This result is obtained by hydrogenating one or more additives of some their derivant obtained by these carbohydrates.

Additive described in this document more specifically monosaccharide, disaccharide, oligosaccharide and polysaccharide.

By document WO2006050567, by storing based on glucose and the combination of dispersant based on polycarboxylate Stablize during depositing, the waterborne suspension of low viscous Calx is also known.

Regrettably, these teachings need additive or the combination of specific Calx, or seek help from a large amount of and/or and Calx Some of breast applies unmatched additive；Or lime cream does not have in sufficiently long period (one day to a couple of days) intended Viscosity stability.

In order to solve this problem, provide the calcium-magnesium waterborne suspension according to the present invention described above according to the present invention, therefore It initially comprises the additive of the reagent increased simultaneously as thinner and retardance viscosity, i.e. can during preparation obtain little In the acceptable viscosity of 1500mPa.s, preferably smaller than 1200mPa.s, and can be in the period of storage calcium-magnesium waterborne suspension In and adding of increasing of the viscosity that slows down when the content of the additive relating to increasing blocker simultaneously as thinner and viscosity reduces Add agent.

Summary of the invention

For this purpose, it is characterised by according to the calcium-magnesium waterborne suspension of the present invention: described additive is phosphonate Or phosphonic acids, described phosphonate or phosphonic acids are selected from nitrogenous or unazotized organic phospho acid or their salt, more specifically select free ammonia Base alkylidene polyphosphonic acid (wherein said alkylidene contains 1 to 20 carbon atom), (wherein alkylidene radical contains hydroxyl alkylidene polyphosphonic acid 2 to 50 carbon atoms), (wherein alkane group contains 3 to 12 carbon atoms, and alkylphosphines acidic group to phosphonoalkane polycarboxylic polycarboxylic acid With the mol ratio of carboxylic acid group in the range of 1:2 to 1:4), their derivant of such as salt, and their mixture composition Group.

Therefore, can keep viscosity in acceptable value according to the calcium-magnesium waterborne suspension of the present invention, be derived from more While the lime cream being easily handled and storing, it is thus achieved that the higher solid of concentration of the solid particle that ratio conventional method obtains Grain.Therefore, under high solid particle concentration and the regulation of organic material provided with this solution compared with less feelings Under condition, it is flowing according to the calcium-magnesium waterborne suspension of the present invention.Mobility is determined by measuring viscosity.Term " flowing " refer to: modest viscosity, less than 1500mPa.s, particularly smaller or equal than 1200mPa.s, it is preferably lower than or equal to 1000mPa.s and more preferably less than or equal to 800mPa.s, it is advantageously less than or equal to 500mPa.s.

Present in calcium according to the present invention-magnesium waterborne suspension, phosphonate or phosphonic acids not only make calcium-magnesium aqueous suspension The modest viscosity of liquid, and viscosity in playing during storing, can be made to increase the effect stopped.

Therefore, benefiting from following two effect, i.e. playing the effect of thinner and play the viscosity increasing elapsed in time While adding the effect of blocker, the solid particle height according to the present invention can be prepared by adding phosphonate or interpolation phosphonic acids Calcium-magnesium waterborne suspension that degree concentrates.

In the sense of the present invention, term " viscosity increase blocker " refers to store at least 2 weeks under stirring or not stirring Afterwards, and preferably storage more than 1 month after, viscosity still less than or equal to 1500mPa.s, be preferably lower than or equal to 1200mPa.s, more preferably less than or equal to 1000mPa.s, it is advantageously less than or equal to 800mPa.s, more advantageously less than 500mPa.s。

Phosphonate or phosphonic acids are typically chelating agent, chelating agen, the multifunctional reagent active to metal ion.

The sour form or at least the one of its corresponding salt form combined with carbon atom is included according to definition, phosphonate or phosphonic acids Plant functional group PO₃ ^2-.The character of phosphonate is in particular from phosphorus-to-carbon bonds.These character are molten in strong anion (bearing) electric charge, water Stability in solution degree water-based system greatly, under the conditions of extreme temperature and pH, and the multiplicity of binding site.Therefore, phosphonate There are the multiple functions improving water-based system performance, it may be assumed that

Incrustation scale is formed by threshold effect suppression,

Isolation (complexation/chelating of metal ion),

The solid particle of dispersion suspension, especially reduces incrustation scale deposition,

Suppression electrochemical corrosion.

Their functional characteristic makes these reagent can apply in many fields.

In the sense of the present invention, term " phosphonic acids " or " phosphonate " include acid itself, or their conjugation salt or mixing Thing, this acid can be presented in the alkali compounds especially by such as NaOH or KOH partially or completely neutralizes.No matter Whether additive is the sour form partially or completely neutralized, and the concentration of phosphonate or phosphonic acids is indicated with " active acid " concentration.

It was shown that use phosphonate or phosphonic acids to make with commonly used in the art in aqueous calcium-magnesium according to the present invention Additive is compared additive level and is reduced, on the one hand, this additive level reduces the performance being able to maintain that calcium-magnesium waterborne suspension And effect；On the other hand, this additive level reduces can reduce COD (COD) and TOC (total organic carbon), and because of This reduces the environmental effect of the calcium and magnesium suspension used in some application, and rules and regulations limit use mainly in such applications Stably and therefore by organic additive rich in the suspension of carbon (such as sugar and/or polymer), the place of some liquid efflunent Manage the most this situation.Further, it is retained in solid phase in the major part by making additive and carries out liquid/solid and divide In the application of step, additive absorption tendentiousness on carrier reduces COD further.

And, according to the present invention, in calcium-magnesium suspension, the existence of phosphonate or phosphonic acids makes calcium-magnesium suspension play water The effect (threshold effect) of scale inhibitors, thus reduce the precipitation of calcium carbonate or calcium sulfate.This effect is by calcium and magnesium suspension It is applied to when processing liquid efflunent to increase the maximum calcium concentration that equipment scaling starts to occur.

According to the present invention, in fact it was surprisingly observed that, use phosphonate or phosphonic acids additive, it is possible to produce viscosity limited Calcium-magnesium suspension, the limited calcium-magnesium suspension of this viscosity especially inhibits this viscosity elapsed in time to increase, or very To reducing viscosity within some period, during the maturation phenomenon of calcium and magnesium suspension.Explanation according to the present invention is following thing Real: phosphonate fully absorbs at Ca (OH)₂And/or Mg (OH)₂Granule on, this reduce calcium and magnesium suspension maturation.Hydrate Grain is positively charged.Phosphate has strong anion (bearing) electric charge.Neutralizing Ca (OH)₂Afterwards, the phosphonate of additional quantity will make Charge reversal.The negative charge of phosphonate groups can repel each other, and this causes granule also to repel each other, thus reduces decant and foundation The probability of the interaction between them.Therefore, it is that there is less inclining according to the another advantage of the suspension of the present invention Analysis tendency.Finally, when the mobility of calcium and magnesium suspension is improved, the amount of water can reduce, and its concentration and/or it Fineness thus increase.

Certainly, in accordance with the present invention, it is preferred that have the alap decant elapsed in time, in order to keep suspension As far as possible uniformly without being subsequently agitated for, stirring usually forces calcium-magnesium suspension to be stored in the tank being provided with agitator.

Finally, by file JP57196748, by using water or using alkaline solution to carry out ripening cause quick lime system Standby lime cream is known.According to this document, add additive based on carboxylic acid, this base with the amount of 1～30 gram/tonne quick lime Additive in carboxylic acid can come from other additive mentioned, 2-phosphinylidyne butane-1,2,4-tricarboxylic acids.But, fail from This document is inferred about blocking the actual information that viscosity increases.The minimal amount of additive applied is for obtaining basis The calcium and magnesium suspension of the retardance viscosity of the present invention is actually priori deficiency.

In a preferred embodiment of the invention, described calcium-magnesium waterborne suspension comprises acid 2 to 8 of form, and preferably 2 To 6 " phosphonic acids " characteristic groups.

More specifically, described phosphonate or phosphonic acids select free amino group three (methylene phosphine) acid (ATMP)；1-hydroxy ethylidene-1, 1-di 2 ethylhexyl phosphonic acid (HEDP)；Ethylenediamine tetraacetic (methylene phosphine) acid (EDTMP)；Hexamethylene diamine four (methylene phosphine) acid (HDTMP)；Two sub-second Base triamine five (methylene phosphine) acid (DTPMP)；(2-hydroxyl) ethylamino-N, N-double (methylene phosphine) acid (HEMPA)；2-phosphono Base-1,2,4-butane tricarboxylic acid (PBTC)；6-amino-1-hydroxyhexylidene-N, N-di 2 ethylhexyl phosphonic acid (neridronic acid)；Double (the 3-of N, N'- Aminopropyl) ethylenediamine six (methylene phosphine) acid；Double (hexa-methylene triamine) five (methylene phosphine) acid；Amino three (methylene phosphine) Acid oxidase thing；The derivant of their such as salt and the group of their mixture composition.

According to the present invention, gross weight based on described solid particle, described phosphonate or phosphonic acids are more than with active acid content Or equal to 0.05 weight %, preferably greater than or equal to 0.1 weight %, more preferably equal to or greater than 0.5 weight % and the biggest In or equal to 0.8 weight % amount exist.

It addition, according to the present invention, gross weight based on described solid particle, described phosphonate or phosphonic acids are with active acid content Less than or equal to 5 weight %, preferably lower than or equal to 3 weight %, more preferably less than or equal to 2 weight % and especially less than or Exist equal to the amount of 1.5 weight %.

These concentration of additive are actually proved to be optimal.Actually, on the one hand, less than these concentration, to viscous The retardation that degree increases is insufficient.On the other hand, higher than these concentration, always observe that viscosity reduces, but to adding relatively The totle drilling cost of high additive level affect relative reduction.We recall, and must protect according to the calcium-magnesium suspension of the present invention Hold the most competitive, and they are generally not belonging to the chemical reagent that surcharge is the highest.

Advantageously, described solid particle concentration in aqueous phase is more than or equal to 300g/kg, is preferably greater than or equal to 350g/kg, more preferably equal to or greater than 400g/kg and particularly greater than or equal to 450g/kg.

In a preferred embodiment of the invention, described solid particle is to meet formula a Ca (OH)₂.b Mg(OH)₂.c The granule of the Calx of MgO, wherein, a is more than or equal to 90 weight %, preferably greater than or equal to 92 weight % and is more preferably greater than Or equal to 94 weight %.

According in the Advantageous embodiments of the present invention, described solid particle have according to BET method calculate between 4m²/ g and 25m²Specific surface area between/g.

In the embodiment that another is equally advantageous, described solid particle have by laser particle size method measure between D between 1 μm and 20 μm₅₀。

In the present invention, size d_x(it is d above₅₀) represent the diameter of granule so that the x%'s (being 50% above) of distribution Granule is that size is less.

Preferably making calcium-magnesium suspension, special lime cream, have following characteristics, thin particle size distribution is used for promoting to remain outstanding Supernatant liquid is the longest, and obtains more preferable chemical reactivity for simultaneously.In some embodiments, in order to ensure described Granularity, will experience grinding steps according to calcium-magnesium waterborne suspension of the present invention and optionally experience will screen step.

Mention other embodiment of calcium-magnesium waterborne suspension in the appended claims.

The invention still further relates to a kind of method for preparing calcium-magnesium waterborne suspension, described method includes: formation meets logical Formula a Ca (OH)₂.b Mg(OH)₂.c the solid particle of MgO suspension in the first aqueous phase, wherein, a, b and c representation quality Mark, their summation has the value of 90～100%, weight based on described suspension, and the concentration of described solid particle is more than Or equal to 200g/kg；And interpolation is the additive that thinner and viscosity increase blocker simultaneously.

The method according to the invention is characterised by: described additive is phosphonate or phosphonic acids, described phosphonate or phosphonic acids Selected from nitrogenous or unazotized organic phospho acid or their salt, more specifically select free amino alkylidenyl polyphosphonic acid (wherein alkylene Base contains 1 to 20 carbon atom), hydroxyl alkylidene polyphosphonic acid (wherein alkylidene radical contains 2 to 50 carbon atoms), phosphonoalkane polycarboxylic many (wherein alkane group contains 3 to 12 carbon atoms to carboxylic acid, and the mol ratio of alkylphosphines acidic group and carboxylic acid group is 1:2's to 1:4 In the range of), their derivant of such as salt and the group of their mixture composition.

According in only certain exemplary embodiments of this invention, the described step of the described suspension forming solid particle includes symbol Close formula a Ca (OH)₂.b Mg(OH)₂.c the solid particle of MgO and the mixing of described first aqueous phase, wherein, a, b and c are matter Amount mark, their summation has the value of 90%～100%, and it is thus possible, for instance corresponding to powder slaked lime solids granule With the suspension of aqueous phase or corresponding to comprising the powder solid phase of Calx granule and the mixture of aqueous phase.

In the alternative of the method according to the invention, the described step of the suspension forming solid particle includes using institute State the first aqueous phase and dilute the step concentrating slurry of the concentrated suspension liquid of described solid particle or described solid particle, and because of This, such as, corresponding to scenario described below, wherein, calcium lime cream or dolime lime cream will be used for the calcium-magnesium according to the present invention Suspension.

According in the further alternative of the present invention, form the described step bag of the described suspension of solid particle Include and meet logical with described first aqueous phase slaking quicklime, the optional quick lime containing dolomite or raw dolime with acquisition Formula a Ca (OH)₂.b Mg(OH)₂.c the step of the calcium of the solid particle of MgO-magnesium waterborne suspension, wherein, a, b and c are quality Mark, their summation has the value of 90%～100%.In this specific case, according to the calcium-magnesium suspension of the present invention it is Direct result with the compound such as quick lime of aqueous phase ripening life.

Advantageously, before, during or after forming the suspension of described solid particle, send out in described first aqueous phase Raw described phosphonate or the interpolation of phosphonic acids.

Therefore, in a preferred embodiment, will while phosphonate or phosphonic form be thinner and viscosity increase retardance The additive of agent add to the granule of Calx be added in the first aqueous phase therein, add in the first aqueous ripening mutually, Add in the first aqueous dilution mutually or add further in calcium-magnesium suspension formed according to the present invention.

According in the alternative of the present invention, described phosphonate or phosphonic acids add described quick lime or calcining white clouds to Stone, adds to and meets formula a Ca (OH)₂.b Mg(OH)₂.c the solid particle of MgO, wherein, a, b and c are mass fractions, it Summation there is the value of 90～100%, or add further to described concentrated suspension liquid or the concentrated pulp of described solid particle Material.

In the particular implementation of the method according to the invention, before adding phosphonate or phosphonic acids, regulate described the The pH of one aqueous phase is to guarantee total dissolubility of phosphonate or phosphonic acids.

In another particular implementation of the method according to the invention, described phosphonate or phosphonic acids are as solution or outstanding Supernatant liquid adds in the second aqueous phase.

Advantageously, before adding phosphonate or phosphonic acids, especially by alkalinity additive (especially NaOH, KOH, NH₄OH etc.) regulate the pH of described second aqueous phase to guarantee total dissolubility of phosphonate or phosphonic acids.

According in another alternative of the present invention, described phosphonate is added in solid form, particularly with Acid form or salt form are added.

Advantageously, according to the present invention, described phosphonate or phosphonic acids comprise 2 to 8 of acid form, preferably 2 to 6 " phosphines Acid " characteristic group.

More specifically, described phosphonate or phosphonic acids select free amino group three (methylene phosphine) acid (ATMP)；1-hydroxy ethylidene-1, 1-di 2 ethylhexyl phosphonic acid (HEDP)；Ethylenediamine tetraacetic (methylene phosphine) acid (EDTMP)；Hexamethylene diamine four (methylene phosphine) acid (HDTMP)；Two sub-second Base triamine five (methylene phosphine) acid (DTPMP)；(2-hydroxyl) ethylamino-N, N-double (methylene phosphine) acid (HEMPA)；2-phosphono Base-1,2,4-butane tricarboxylic acid (PBTC)；6-amino-1-hydroxyhexylidene-N, N-di 2 ethylhexyl phosphonic acid (neridronic acid)；Double (the 3-of N, N'- Aminopropyl) ethylenediamine six (methylene phosphine) acid；Double (hexa-methylene triamine) five (methylene phosphine) acid；Amino three (methylene phosphine) Acid oxidase thing；The derivant of their such as salt and the described phosphonate of group of their mixture composition or phosphonic acids select free amino group Three (methylene phosphine) acid (ATMP)；1-hydroxy ethylidene-1,1-di 2 ethylhexyl phosphonic acid (HEDP)；Ethylenediamine tetraacetic (methylene phosphine) acid (EDTMP)； Hexamethylene diamine four (methylene phosphine) acid (HDTMP)；Diethylenetriamines five (methylene phosphine) acid (DTPMP)；(2-hydroxyl) ethylamino- N, N-double (methylene phosphine) acid (HEMPA)；2-phosphono-1,2,4-butane tricarboxylic acid (PBTC)；6-amino-1-hydroxyl is sub-own Base-N, N-di 2 ethylhexyl phosphonic acid (neridronic acid)；N, N'-double (3-aminopropyl) ethylenediamine six (methylene phosphine) acid；Double (hexa-methylenes three Amine) five (methylene phosphine) acid；Amino three (methylene phosphine) acid oxidase thing；The derivant of their such as salt and their mixture The group of composition.

More specifically, described phosphonate or phosphonic acids are: amino alkylidenyl polyphosphonic acid, wherein, described alkylidene contains 1 to 12 Individual carbon atom；Hydroxy alkylidene phosphonic acids, wherein, described alkylene radical contains 2 to 12 carbon atoms and 2 phosphonyl groups； Or one or more phosphonoalkane polycarboxylic polycarboxylic acids, wherein, described alkane group contains 4 to 8 carbon atoms, and wherein, methyl The mol ratio of phosphonate group and carboxylic acid group is in the range of 1:2 to 1:4.

In a preferred embodiment, gross weight based on described solid particle, described phosphonate or phosphonic acids contain with active acid Amount is more than or equal to 0.05 weight %, preferably greater than or equal to 0.1 weight %, more preferably equal to or greater than 0.5 weight % and spy The amount not being greater than or equal to 0.8 weight % is added.

It addition, gross weight based on described solid particle, described phosphonate or phosphonic acids are less than or equal to 5 with active acid content Weight %, preferably lower than or equal to 3 weight %, more preferably less than or equal to 2 weight % and particularly smaller or equal than 1.5 weights The amount of amount % exists.

Advantageously, described solid particle concentration in described aqueous phase more than or equal to 300g/kg, preferably greater than or etc. In 350g/kg, more preferably equal to or greater than 400g/kg and particularly greater than or equal to 450g/kg.

In certain aspects of the present disclosure, the calcium obtained-magnesium suspension in controlling wet-type finishing machine decondensation to reach Desired granularity.It has surprisingly been observed that, according to the present invention, additive is not only to reduce what viscosity and slowing down elapsed in time Viscosity increases to target, it also have the additional advantage that it by mixed with water prepare calcium-magnesium suspension during carry further The incorporation (moistening of hydrate) of hyperhydrate and play the effect of grinding agent during wet lapping.

Mention other embodiment of the method according to the invention in the appended claims.

The invention still further relates to phosphonate or phosphonic acids as simultaneously for thinner and the viscosity increase resistance of calcium-magnesium waterborne suspension The application of the reagent of stagnant dose, described calcium-magnesium waterborne suspension is included in the first aqueous phase the concentration suspended more than or equal to 200g Solid particle/kg suspension meet formula a Ca (OH)₂.b Mg(OH)₂.c the solid particle of MgO, wherein, a, b and c are matter Amount mark, their summation has the value of 90%～100%, described phosphonate or phosphonic acids selected from nitrogenous or unazotized organic phosphine Acid or their salt, (wherein, to contain 1 to 20 carbon former for described alkylidene more specifically to select free amino alkylidenyl polyphosphonic acid Son), hydroxyl alkylidene polyphosphonic acid (wherein, alkylidene radical contains 2 to 50 carbon atoms), phosphonoalkane polycarboxylic polycarboxylic acid (wherein, alkyl Group is containing 3 to 12 carbon atoms, and the mol ratio of alkylphosphines acidic group and carboxylic acid group is in the range of 1:2 to 1:4), they The derivant of such as salt, and the group of their mixture composition.

Preferably, described phosphonate or phosphonic acids comprise 2 to 8 of acid form, preferably 2 to 6 " phosphonic acids " characteristic groups.

According in the advantageous applications of the present invention, gross weight based on described solid particle, described phosphonate or phosphonic acids with Active acid content is more than or equal to 0.05 weight %, preferably greater than or equal to 0.1 weight %, more preferably equal to or greater than 0.5 weight The amount of amount % and particularly greater than or equal to 0.8 weight % exists.

Advantageously, the concentration of the described solid particle of described aqueous phase is more than or equal to 300g/kg, is preferably greater than or equal to 350g/kg, more preferably equal to or greater than 400g/kg and particularly greater than or equal to 450g/kg.

The invention still further relates to the application as the additive of the decant reducing calcium-magnesium waterborne suspension of phosphonate or phosphonic acids, Described calcium-magnesium waterborne suspension be included in aqueous phase suspend concentration more than or equal to 200g/kg meet formula a Ca (OH)₂.b Mg(OH)₂.c the solid particle of MgO, wherein, a, b and c are mass fractions, and their summation has 90～100% Value.

Detailed description of the invention

According to the embodiment be given the most in a non-limiting manner, the present invention will preferably be described and be understood.Implementing In example 1 to 3 and 6 to 9, lime cream is prepared in the lab.In embodiment 4,5 and 11, lime cream is that industry manufactures.

Embodiment 1: phosphonate is for improving the application of the stability of the suspension of lime cream

During bench scale pilot, prepare lime cream (MoL) suspension according to following method.

First, it is being filled with the water of demineraliting and is being equipped with the 1dm of agitator of the rotor being provided with 4 blades³Hold Device dilutes phosphonate.Thus, prepare the whole water needed for lime cream with the phosphonate treatment added.

Then, under the stirring of 300rpm, by containing 95.9% the solid carbon dioxide from industrial site of calcium hydroxide Compound (Calx) is added gradually to mixture.After stirring at 10 minutes, lime cream is transferred to store in container and at 20 DEG C Deposit the scheduled time of up to 1 month.

The hydrate (solid material) concentration in suspension is 45 weight %, and uses after degassing at 190 DEG C The instrument of Micromeritics Tristar brand is 8m according to the specific surface area measured by BET method²/g。

The grading curve measured by the granulometry method of the laser with Beckman Coulter LS 13 320 instrument is produced Raw data below:

d₁₀₀=92 μm

d₉₈=54 μm

d₉₅=42 μm

d₉₀=27 μm

d₅₀=2.1 μm

d₂₅=1.3 μm.

Different tested phosphonates is following material:

1. ATMP, it is known that: it is abbreviated as ATMP, with the form of 50% activated acid solution of named AP5 Sold by Zschimmer and Schwarz.

2. diethylenetriamine pentamethylenophosphonic acid, it is known that: call as DTPMP, with 52% active acid of named D5012 The form of the solution that the form of sodium salt neutralizes with part is sold by Zschimmer and Schwarz.

3. phosphonobutane tricarboxylic acid, it is known that: it is abbreviated as PBTC, with the form of 50% activated acid solution of named P50 Sold by Zschimmer and Schwarz.

Oneself fork di 2 ethylhexyl phosphonic acid of 4.6-amino-1-hydroxyl, it is known that: call as neridronic acid, sold by Rhodia as powder.

Double (3-aminopropyl) the ethylenediamine hexa-methylene phosphonic acids of 5.N, N'-, with 30% activated acid solution of named D2086 Form sold by Thermphos.

In the present embodiment, weight based on hydrate (Calx), it is indicated with active acid, the ratio of phosphonate is 0.15% to 1%.With Brookfield DV III Ultra flow graph, use LV rotor to rotate with 100rpm, survey at 20 DEG C The viscosity that amount is indicated with mPa.s.No. 61 rotors are used for the viscosity of at most 60mPa.s；No. 62 rotors are between 60 Hes The viscosity of 300mPa.s；No. 63 rotors are used for the viscosity of at most 1200mPa.s.No. 64 rotors allow the survey of at most 6000mPa.s Amount.But, exceed certain value, measure and may often be such that instability.For that reason, the viscosity higher than 1200mPa.s is not had Have and carry out systematic survey.After preparation 1 hour (brand-new product) and after 1 week, 2 weeks, 3 weeks and 4 weeks, lime cream is suspended Liquid measures viscosity.Before every measurement, make lime cream uniform by mechanical agitation.In the case of there is no additive, have The viscosity of this lime cream of the solid material of 45% is more than 3000mPa.s, and this is too high viscosity number for accurately measuring. The result of the additive according to the present invention is shown in Table 1.

Table 1: by the lime cream viscosity of the solid material of the 450g/kg of the different additive process according to the present invention

As can be seen from the above table, in all cases, the stone according to the present invention carried out once the active acid adding 0.5% The initial viscosity of ash breast (brand-new MoL) is less than or equal to 1500mPa.s.For most of phosphonates, though less amount of interpolation Also it is enough.In addition to ATMP, dosage is 1% the least active acid, and viscosity elapses in time not to be increased too much.Extremely The most in some cases, the additive of 1% is used to be less than or equal to the viscosity of 1500mPa.s after being obtained in that 2 weeks, sometimes the most more Low.200mPa.s can be less than after 4 weeks with 1% some additive added.

Then, with the sucrose according to prior art and polymer (by the obtainable Tech of Chryso 646) and they The efficiency of phosphonate is compared in combination.These additives are generally known to those skilled in the art for lime cream fluidisation.With Mode as phosphonate adds sucrose, adds a polymer on ground suspension simultaneously.When sucrose and polymer In conjunction with time, the addition of additive reduces.

Unexpectedly, in the case of similar to DTPMP, individually with phosphonate energy compared with the additive of prior art It is enough that in the case of dosage is lower, acquisition mobile performance is higher and has the lime cream that passage viscosity increase in time is less.Cause This, will be obtained with the sucrose using 1.5% especially by the mobile performance adding the lime cream that the DTPMP of 1% is obtained The mobile performance of lime cream compare.Result is shown in Table 2.

Table 2: by the lime cream viscosity of the solid material of the 450g/kg of the different additive process according to prior art

Embodiment 2: DTPMP and/or neridronic acid are for improving the application wet type of the stability of lime cream soliquoid Situation about grinding

During bench-scale testing, prepare lime cream soliquoid according to following methods.First, be filled with distribution water and It is equipped with the 10dm of the agitator of anchoring type³Container dilutes phosphonate.Thus, prepare the whole water needed for lime cream all It is added with phosphonate.

Then, under the stirring of 150rpm, solid carbon dioxide compound (the ripe stone of the industrial source of the calcium hydroxide containing about 95% Ash) it is added gradually to mixture.After stirring for 30 minutes, lime cream is transferred to equipped with in the controlling wet-type finishing machine of bead.

After decondensation, with 150rpm combined lime breast 10 minutes, be subsequently poured in container and at 20 DEG C storage up to 1 The scheduled time of individual month.In lime cream, hydrate (dry substance) content is 45 weight %.

The granularity of the original Calx by measuring by the laser particle size method of Beckman Coulter LS 13 320 instrument Curve produces data below

d₁₀₀=257 μm

d₉₈=121 μm

d₉₅=81 μm

d₉₀=58 μm

d₅₀=9.3 μm

d₂₅=2.8 μm.

By using Micromeritics TRISTAR, according to the ratio of the hydrate that BET method is analyzed by N2 adsorption Surface area is 6m²/g.Adjust the disposal ability of grinding machine to obtain the d of 2.5～2.7 μm₅₀.Typical size after wet lapping is such as Under:

d₁₀₀=31 μm

d₉₈=11 μm

d₉₅=8.7 μm

d₉₀=7.3 μm

d₅₀=2.5 μm

d₂₅=1.4 μm.

The stone that average diameter is 2.5 μm with 45% solid material can not be produced in the case of there is no any additive Ash breast.This lime cream will block controlling wet-type finishing machine.

At 20 DEG C behind static 1 week, 2 weeks, 3 weeks and 4 weeks, decant kinetics with supernatant (lime water) relative to cumulative volume % calculate.The boundary of supernatant delimited by the border between suspension and lime aqueous solution.

Viscosity and decant result are shown in table 3 and table 3 attached middle school.

Table 3: by the lime cream viscosity of the solid of the 450g/kg of the additive treating according to the present invention after wet lapping

Table 3 is attached: the lime cream decant of the solid of the 450g/kg processed with the DTMP according to the present invention after wet lapping

As long as the dosage of additive more than or equal to 0.5% active acid, even if after 4 weeks viscosity again smaller than or be equal to 1200mPa.s, and passage in time does not increase too many compared with initial concentration, even reduces.For the activity of 0.75% Acid, within 4 weeks, viscosity is less than or equal to 400mPa.s, or even significantly lower.Even can with 0.75% neridronic acid to newly Product processed obtains the value of 78mPa.s, and after storing January, brand-new product does not significantly change.

Such as embodiment 1, compare phosphine with sucrose and polymer (Tech 646 obtained by Chryso) and combinations thereof The efficiency of hydrochlorate, and result is shown in table 4 and table 4 attached middle school.

Table 4: glue with the lime cream of the solid of the 450g/kg of the additive treating according to prior art after wet lapping Degree

Table 4 is attached: with the lime cream decant of the solid of the 450g/kg processed according to prior art after wet lapping

Unexpectedly, phosphonate is to combine, known to nowadays, the retardance that the viscosity elapsed in time much increases Agent.It can be seen that the combination of the Tech 646 of the sucrose+0.66% that the neridronic acid that content is 0.75% is than 1% is more preferable. Storage one week or longer after, be equally applicable to DTPMP.

As for decant, on the one hand table 3, table 3 echo on the other hand table 4, attached relatively the illustrating of table 4:

About sucrose+Tech 646 polymer (prior art), any dosage of additive increases the fall along with viscosity Low, but cause the increase of undesirable decant on the contrary；

About DTPMP (according to the present invention), any dosage of additive increases the reduction along with viscosity, and along with The reduction of favourable decant.

Embodiment 3: DTPMP (with the form of the D5012 of Zschimmer and Schwarz) is used for improving lime cream and suspends The application of the mobility of liquid has the situation of the Calx of different-grain diameter distribution

Repeat embodiment 1, except three kinds of tests hydrate (Calx) of industrial source have following characteristics.

By using Micromeritics Tristar, according to the specific surface area that BET method is analyzed by N2 adsorption it is 18m²/g。

The grading curve measured by the laser particle size method of Beckman Coulter LS 13 320 instrument is produced in table 5 The data illustrated.

Table 5: for preparing the particle size distribution of 3 industrial Calx of lime cream

The size of granule	Hydrate 1 (carefully)	Hydrate 2 (medium)	Hydrate 3 (slightly)
				d₁₀₀	194μm	257μm	257μm
d₉₈	73μm	129μm	137μm
				d₉₅	53μm	92μm	113μm
d₉₀	29.7	68μm	89μm
				d₅₀	5.3μm	6.5μm	12.2μm
d₂₅	2.8μm	2.8μm	2.8μm

Solid carbon dioxide compound contains the calcium hydroxide of about 95%.Relative to the weight of hydrate, in commercially available prod, the amount of D5012 is divided It is not expressed as 0.25%, 0.5%, 1% and 4.5%.This means that the amount of the active component represented with active acid is relative to hydration The quality representation of thing is 0.13%；0.26%；0.52% and 2.34%.The content of hydrate is 40 weight %.For variable DTPMP content, the result of flow behavior is shown in Table 6.

Table 6: with the Calx 1 of table 5, Calx 2 or the lime cream of Calx 3 of the 400g/kg that the DTMP according to the present invention processes Viscosity

For 3 kinds of Calx, even if due to the active acid of 0.13% dosage after 4 weeks, these suspensions also have acceptable Viscosity.In the case of latter two Calx, it is thus achieved that less than 400mPa.s, the most low-down viscosity, almost without with Any change of time passage.

Then, by the sucrose in water ratio efficiency compared with D5012.The flow-data obtained is shown in Table 7.

Table 7: by the lime cream viscosity of Calx 1, Calx 2 or the Calx 3 of the table 5 of the 400g/kg processed according to prior art

It can be seen that utilize DTMP, and compared with sucrose, it is possible to obtain the Calx that mobility is higher under lower dosage Breast.

Then, trying in the case of the suspension (MoL) (450g/kg and 500g/kg) more concentrated of No. 2 hydrates Test the efficiency of DTPMP.The flow-data obtained is shown in Table 8.

Table 8: by the lime cream viscosity of the Calx 2 of the table 5 of 450g/kg and 500g/kg processed according to the present invention

Hemihydrate content is that 45 weight % are to 50 weight %.It can be seen that have the D5012 energy of the active material of 0.26% Enough in 45 weight % maintenance lime cream mobility.

Lime cream when even it is expected to 50%, keeps viscosity less than 1500mPa.s the most after 4 weeks.

Embodiment 4:DTPMP is for improving answering of the stability of the suspension of the lime cream being produced on an industrial scale grinding With.

According to the industrially prepared lime cream soliquoid according to the present invention of method below.

The D5012 (DTPMP sold by Zschimmer and Schwarz) of 225kg is dissolved in and fills 13.5m³'s In the agitator tank of water.

After homogenizing, average diameter d of 11.3 tons₅₀Be 6.7 μm there is low specific surface area (8m²/ g) hydrate Gradually add 1/2 hour.

Then, the suspension of the thus obtained solid material (hydrate) with 45% solves solidifying in controlling wet-type finishing machine It is poly-, until it reaches the d of 3.2 μm₅₀With the d less than 10 μm₉₈.The result of viscosity measurement is shown in Table 9.

Table 9: by the viscosity of the commercial lime breast of the solid of the 450g/kg of the DTMP process according to the present invention

As finding out from laboratory scale test (embodiment 2, table 3), viscosity elapses reduction in time.Viscosity number with Laboratory scale is consistent, higher than embodiment 2 even for same treatment levels of viscosity.

With that prepare in a similar manner but use sucrose and the prior art of polymer (from the Tech 646 of Chryso) Suspension compare the efficiency of DTPMP.The result of viscosity measurement is shown in Table 10.

Table 10: by the viscosity of the commercial lime breast of the solid of the 405g/kg processed according to prior art

Observe, after 11 days, sucrose with 0.75% and the viscosity of the suspension of the polymer formulation of 0.4% from 270mPa.s increases to 605mPa.s.

Within the identical time, the viscosity of the identical suspension made with the DTPMP of 1.04% is reduced to from 520mPa.s 330mPa.s。

By slowing down, viscosity increases, and even with reducing viscosity, DTPMP has and can allow for the extra of higher initial viscosity Advantage.This has the effect reducing decant tendency.

Really, in the state of the art, in first day after manufacturing, i.e. when viscosity is minimum, generally go out Now reduce the effect of decant tendency.

Therefore, the viscosity of the lime cream manufactured with DTPMP elapses in time to reduce to have and reduces the most excellent of decant tendency Point.For brand-new product, the suspension prepared with DTPMP has higher initial viscosity compared with the suspension of prior art, This decant kinetics that will slow down.

Embodiment 5:DTPMP has the steady of the suspension of the particle mean size being produced on an industrial scale lime cream for raising Apply qualitatively.

Have 0.25% (to be indicated relative to hydrate) by Zschimmer and Schwarz sell The lime cream (MoL) of 40 tons of the solid material of the 40% of D5012 by water and have table 5, embodiment 3 have medium-grained The mixture manufacture of hydrate 2.

It is different from corresponding laboratory test, maintains commercial lime breast persistently to stir in its preparation tank.The result of viscosity It is shown in Table 11.

Table 11: there is the lime cream viscosity of the Calx 2 of the table 5 of 400g/kg

It can be seen that under persistently stirring, based on solid carbon dioxide compound represent only 0.13% DTPMP can be in more than one Viscosity is made to maintain 450mPa.s after Yue.

It is in static sample in the same period and there is the viscosity of 310mPa.s；I.e. it is similar in laboratory scale examination Test the value of the viscosity obtained in period table 6, embodiment 3.

Embodiment 6:DTPMP is for reducing the dynamic (dynamical) application of decant of the thick suspension of lime cream.

There is the decant power in the case of the solid material of 450g/kg in order to measure lime cream after wet lapping Learn, repeat the test of embodiment 2.

By have Beckman Coulter LS 13320 instrument laser particle size method measure grading curve produce with Lower data:

D₁₀₀=41 μm

D₉₈=13 μm

D₉₅=10 μm

D₉₀=8 μm

D₅₀=2.6 μm

D₂₅=1.3 μm.

At 20 DEG C behind static 1 day, 1 week, 2 weeks, 3 weeks and 4 weeks, decant kinetics with supernatant (lime water) based on totally Long-pending % measures.Viscosity and the decant result of the lime cream according to the present invention prepared with DTPMP are shown in table 12A and table 12B In.Table 12A shows the viscosity results consistent with the viscosity results of table 3.

Table 12A: the lime cream with the 450g/kg solid material of DTMP process according to the present invention glues after wet lapping Degree

Table 12B: the lime cream decant of 450g/kg solid processed with DTMP according to the present invention after wet lapping

As being found out by table 3, embodiment 2, increase DTPMP dosage and significantly reduce viscosity, but the most unexpectedly drop Low decant kinetics.

This phenomenon is unexpected in the sense that low viscosity is decant increase factor well known by persons skilled in the art 's.

Any reduction of decant reduces stirring at it to be needed, further allows for storing in fractional pack mode, promoting settling flux And say in the sense that causing less line clogging and obtained end user's accreditation.

The lime cream according to prior art prepared with sucrose and polymer (from the Tech 646 of Chryso) compares The efficiency of DTPMP.Result is shown in table 13A and table 13B.

Table 13A: by the lime cream viscosity of the solid material of the 450g/kg prepared according to prior art

Table 13B: with the lime cream decant of the solid of the 450g/kg prepared according to prior art

It can be seen that the lime cream initially produced with DTPMP produces less decant compared with the lime cream of prior art.

Answering of the stability of the suspension of the medium-grained lime cream that embodiment 7:DTPMP preserves at improving 45 DEG C With.

As described in table 6, embodiment 3, the hydrate 2 of table 5 prepare the lime cream soliquoid of 40%.In order to measure The ripening of suspension, under agitation stores these suspensions at 4 DEG C, 20 DEG C and 45 DEG C, known to those skilled in the art it lead to Excess temperature is accelerated.

Result is shown in Table 14.

Table 14:DTPMP is on the impact of the maturation of the lime cream of the 40% of storage at 45 DEG C

It can be seen that be able to maintain that, after 4 weeks, the viscosity of the suspension of ripening is far below at 45 DEG C with DTPMP 500mPa.s, does not has the identical suspension of any additive no longer to have acceptable viscosity simultaneously.

The application of the stability of the grinding suspension of the lime cream that embodiment 8:DTPMP preserves at improving 45 DEG C.

The sample experience of embodiment 6 tests identical test with described in embodiment 7.With sucrose and polymer (from The Tech 646 of Chryso) lime cream according to prior art prepared compares the efficiency of DTPMP.

Table 15:DTPMP is on the impact of the maturation grinding lime cream of the 45% of storage at 45 DEG C

It can be seen that initially with 1.04% or 1.56% DTPMP preparation lime cream will not at 45 DEG C aging；This is Do not meet the sucrose of 1% and the situation of the Tech 646 (table 16) of 0.6%.

Table 16: sucrose+polymer is on the impact of the maturation grinding lime cream of the 45% of storage at 45 DEG C

Embodiment 9:ATMP and PBTC are used for the application of the decant of the lime cream grinding suspension of suppression 45%.

By using DTPMP, ATMP and PBTC to prepare lime cream soliquoid according to the method for embodiment 2.

Viscosity results is shown in Table 17.

As table 1, embodiment 1 have shown that, ATMP and PBTC is not the phosphine that performance is best in terms of dropping low viscous efficiency Hydrochlorate.

On the other hand, under suitable dosage, ATMP with PBTC reaches to elapse the viscosity that slows down in time just as DTPMP Increase and even reduce viscosity.

Table 17:ATMP and the PBTC impact on the viscosity of the finer ground lime cream soliquoid of 45% solid material

As shown in table 18, for the emulsion processed with ATMP and PBTC, it is about 700mPa.s by making viscosity targets set To 800mPa.s, preferably for processing suspension acceptable, it is possible to make it elapse in time and be maintained at this level, and prevent Only any decant.

Table 18:ATMP and the PBTC impact on the decant of the finer ground lime cream soliquoid of 45% solid material

Herein again, it is seen that initially the lime cream with phosphonate preparation will not be aging；This be do not meet 1% sucrose Situation with the Tech 646 (table 19 and table 20) of 0.6%.

Table 19: the sucrose+polymer impact on the viscosity of the finer ground lime cream soliquoid of 45% solid material

Observe, initially rapider, particularly at initial several days with the suspension decant of sucrose+polymer formulation.

Table 20: the sucrose+polymer impact on the decant of the finer ground lime cream soliquoid of 45% solid material

Unexpectedly, when those skilled in the art agree to the decant considering to prevent lime cream, ATMP and PBTC, Lime cream inhibits any decant of 45% finer ground lime cream.

Suspension is introduced in the graduated cylinder that height is 35cm, a diameter of 6.5cm.Lime cream post is divided into aturegularaintervals 3 parts (high part, middle part and lower part).Each part characterizes with granularity, viscosity and dry extract.With being respectively provided with The characterization result of the ATMP+PBTC process table 17 of 0.5% active acid and the emulsion of table 18 is shown in Table 21.

It can be seen that after static storage 3 weeks, suspension be in concentration, granularity with glue on the whole post of 35cm at height The aspect of degree keeps uniformly.

Table 21: after adding 0.5%ATMP and 0.5%PBTC, in the sign of the suspension section that differing heights is collected

As a comparison, it can be seen that be added with the suspension of the sucrose of 1% and Tech 646 polymer of 0.26% 1 After week the most uniform.

Table 22: after adding 1% sucrose and 0.66%Tech 646 polymer, in the suspension portion that differing heights is collected The sign divided

Embodiment 10: the fineness of suspension and the dosage of additive are on viscosity and the impact of decant

The test of embodiment 2 is repeated, except adjusting the disposal ability of grinding machine to obtain 2.4 μm with the suspension of prior art Or 2.7 d of μm₅₀。

Decant kinetics is measured according to embodiment 6.

Table 23: the granularity shadow to the viscosity of the finer ground lime cream soliquoid of 45% solid material of prior art Ring

The content of table 24:Chryso Tech 646 polymer is finer ground to 45% solid material of prior art Lime cream soliquoid (d₅₀=2.9 μm) the impact of viscosity

With compositions sucrose+Tech 646 polymer of prior art, it can be seen that d₅₀It is changed to 2.4 μm from 2.7 μm draw Play the strong variations of viscosity.

Polymer content increases to 0.5% strong variations also causing viscosity from 0.4%.

Table 25:Chryso Tech 646 polymer content is finer ground to 45% solid material of prior art Lime cream soliquoid (d₅₀=2.9 μm) the impact of decant

In the case of according to the suspension of prior art, the granularity of the dosage of the polymer that commercial scale typically encounters Change cause the strong interference to decant subsequently.

In contrast, according to the present invention, it is thus achieved that have about three times of recommended dose (1%) of the suspension of acceptable viscosity The notable change of DTPM dosage will not cause the great change (being shown in Table 26) of any viscosity.

Because DTMP dosage is high, decant low and the lowest (being shown in Table 27).

Therefore, DTMP can be carried out under conditions of not producing change, and excess does not cause any decant to increase.

The table 26:DTMP content finer ground lime cream soliquoid (d to 45% solid material according to the present invention₅₀ =2.4 μm) the impact of viscosity

The table 27:DTMP content finer ground lime cream soliquoid (d to 45% solid material according to the present invention₅₀ =2.4 μm) the impact of decant

Embodiment 11: grind for the applicable industry manufacture obtaining the more constant finished product of feature according to the DTMP of the present invention The situation of the lime cream of mill.

Have the D5012's sold by Zschimmer and Schwartz of 3% (being indicated relative to hydrate) The lime cream of according to the present invention 20 tons of the solid material of 45% is prepared according to preparation principle similar to Example 2.

By changing the processing speed (4.6m in grinder³/ h to 5.2m³/ h) and the rotary speed (450rpm of grinder To 650rpm) adjust the granularity of lime cream.

Table 28: granularity is to the viscosity of the finer ground lime cream soliquoid of 45% solid material according to the present invention Impact

Wk=week

It can be seen that after 4 weeks, d₅₀Changing to 3.2 μm from 2.8 μm only makes viscosity change to from 425mPa.s 310mPa.s.Even if after 12 weeks, the viscosity in the case of first is not significantly higher than the viscosity in the case of second.

About decant, when with the results contrast table 29 of table 25, decant is the lowest.And, even if using thick suspension (3.2 μ The d of m₅₀), it is the least and the most limited that this decant elapses increase in time.

Table 29:DTMP content inclines to the finer ground lime cream soliquoid of 45% solid material according to the present invention The impact of analysis

Wk=week

Being best understood from, the present invention is never limited to above-mentioned embodiment；And without departing from appended claims In the case of scope, the present invention can be modified.

Claims

1. calcium-magnesium waterborne suspension, comprises: in aqueous phase concentration more than or equal to 200g/kg meet formula a Ca (OH)₂.b Mg(OH)₂.c the solid particle of MgO, wherein, a, b and c representation quality mark, their summation have 90%～ The value of 100%；And be thinner and the additive of viscosity increase blocker, it is characterised in that simultaneously

Described additive is phosphonate or phosphonic acids, the group of described phosphonate or phosphonic acids choosing freely following material composition:

Amino alkylidenyl polyphosphonic acid, wherein, described alkylidene contains 1 to 20 carbon atom；

Hydroxyl alkylidene polyphosphonic acid, wherein, alkylidene radical contains 2 to 50 carbon atoms；

Phosphonoalkane polycarboxylic polycarboxylic acid, wherein, alkane group contains 3 to 12 carbon atoms, and alkylphosphines acidic group is with carboxylic acid group's Mol ratio is in the range of 1:2 to 1:4；With

Their mixture.

Calcium the most according to claim 1-magnesium waterborne suspension, wherein, described phosphonate or phosphonic acids comprise acid form 2 to 8 " phosphonic acids " characteristic groups.

3. according to the calcium described in claim 1 or claim 2-magnesium waterborne suspension, wherein, described phosphonate or phosphonic acids are selected from By amino three (methylene phosphine) acid, the acid of 1-hydroxy ethylidene-1,1-di 2 ethylhexyl phosphonic acid, ethylenediamine tetraacetic (methylene phosphine), hexamethylene diamine four (methylene Base phosphine) acid, diethylenetriamines five (methylene phosphine) acid, (2-hydroxyl) ethylamino-N, N-double (methylene phosphine) acid, 2-phosphono Base-1,2,4-butane tricarboxylic acid, 6-amino-1-hydroxyhexylidene-N, N-di 2 ethylhexyl phosphonic acid, N, double (3-aminopropyl) ethylenediamine of N'- Six (methylene phosphines) sour, double (hexa-methylene triamine) five (methylene phosphine) acid, amino three (methylene phosphine) acid oxidase thing, and they Mixture composition group.

Calcium the most according to claim 1-magnesium waterborne suspension, wherein, gross weight based on described solid particle, described phosphine Hydrochlorate or phosphonic acids exist more than or equal to the amount of 0.05 weight % with active acid content.

Calcium the most according to claim 1-magnesium waterborne suspension, wherein, gross weight based on described solid particle, described phosphine Hydrochlorate or phosphonic acids exist less than or equal to the amount of 5 weight % with active acid content.

Calcium the most according to claim 1-magnesium waterborne suspension, wherein, described solid particle concentration in described aqueous phase More than or equal to 300g/kg.

Calcium the most according to claim 1-magnesium waterborne suspension, wherein, described solid particle is to meet formula a Ca (OH)₂.b Mg(OH)₂.c the Calx granule of MgO, wherein, a is more than or equal to 90 weight %.

Calcium the most according to claim 1-magnesium waterborne suspension, wherein, described solid particle has according to the calculating of BET method The specific surface area between 4m2/g and 25m2/g.

Calcium the most according to claim 1-magnesium waterborne suspension, wherein, described solid particle has by laser particle size method The d between 1 μm and 20 μm measured₅₀。

Calcium the most according to claim 1-magnesium waterborne suspension, wherein, storage at least 2 weeks after, have less than or etc. Viscosity in 1500mPa.s.

11. 1 kinds are used for the method preparing calcium-magnesium waterborne suspension, and described method includes: is formed and meets formula a Ca (OH)₂.b Mg(OH)₂.c the solid particle of MgO suspension in the first aqueous phase, wherein, a, b and c representation quality mark, they total With there is the value of 90%～100%, weight based on described suspension, the concentration of described solid particle is more than or equal to 200g/ kg；And interpolation is the additive that thinner and viscosity increase blocker simultaneously；

It is characterized in that, described additive is phosphonate or phosphonic acids, described phosphonate or phosphonic acids choosing freely following material composition Group:

Their mixture.

12. methods for preparing calcium-magnesium waterborne suspension according to claim 11, wherein, form solid particle The described step of described suspension includes meeting formula a Ca (OH)₂.b Mg(OH)₂.cMgO solid particle and described first water The mixing of phase, wherein, a, b and c are mass fractions, and their summation has the value of 90%～100%.

13. methods for preparing calcium-magnesium waterborne suspension according to claim 11, wherein, form solid particle The step of described suspension includes meeting formula a Ca with described first aqueous phase slaking quicklime or dolime to obtain (OH)₂.b Mg(OH)₂.c the step of the calcium of the solid particle of MgO-magnesium waterborne suspension, wherein, a, b and c are mass fractions, Their summation has the value of 90%～100%.

14. methods for preparing calcium-magnesium waterborne suspension according to claim 11, wherein, form solid particle The step of suspension includes diluting the concentrated suspension liquid of described solid particle or the dense of described solid particle with described first aqueous phase The step of contracting slurry.

15. preparation methoies according to claim 11, wherein, before forming the suspension of described solid particle, period Or afterwards, described first aqueous phase occurs the interpolation of described phosphonate or phosphonic acids.

16. preparation methoies according to claim 11, wherein, described phosphonate or phosphonic acids add quick lime to or calcining is white Marble, adds to and meets formula a Ca (OH)₂.b Mg(OH)₂.c the solid particle of MgO, wherein, a, b and c are mass fractions, Their summation has the value of 90～100%；Or add further to described concentrated suspension liquid or the concentration of described solid particle Slurry.

17. preparation methoies according to claim 11, wherein, before adding phosphonate or phosphonic acids, regulate described first The pH of aqueous phase is to guarantee total dissolubility of described phosphonate or phosphonic acids.

18. preparation methoies according to claim 11, wherein, described phosphonate or phosphonic acids add as solution or suspension In the second aqueous phase.

19. preparation methoies according to claim 18, wherein, before adding phosphonate or phosphonic acids, regulate described second The pH of aqueous phase, to guarantee total dissolubility of described phosphonate or phosphonic acids.

20. methods according to claim 11, wherein, described phosphonate adds as solid.

21. methods according to claim 11, wherein, described phosphonate or phosphonic acids comprise 2 to 8 " phosphonic acids " of acid form Characteristic group.

22. methods according to claim 11, wherein, described phosphonate or phosphonic acids select free amino group three (methylene phosphine) Acid, the acid of 1-hydroxy ethylidene-1,1-di 2 ethylhexyl phosphonic acid, ethylenediamine tetraacetic (methylene phosphine), hexamethylene diamine four (methylene phosphine) acid, diethylidene three Amine five (methylene phosphine) acid, double (methylene phosphine) acid of (2-hydroxyl) ethylamino-N, N-, 2-phosphono-1,2,4-butane tricarboxylic acid, 6-amino-1-hydroxyhexylidene-N, N-di 2 ethylhexyl phosphonic acid, N, double (3-aminopropyl) ethylenediamine six (the methylene phosphine) sour, double (six of N'- Trinitroso-trimethylene triamine) five (methylene phosphine) is sour, amino three (methylene phosphine) acid oxidase thing, and the group of their mixture composition.

23. methods according to claim 11, wherein, gross weight based on described solid particle, described phosphonate or phosphine Acid is added more than or equal to the amount of 0.05 weight % with active acid content.

24. methods according to claim 11, wherein, gross weight based on described solid particle, described phosphonate or phosphine Acid exists less than or equal to the amount of 5 weight % with active acid content.

25. methods according to claim 11, wherein, described solid particle concentration in described aqueous phase is more than or equal to 300g/kg。

26. phosphonates or phosphonic acids are as thinner and the reagent of viscosity increase blocker being calcium-magnesium waterborne suspension simultaneously Application, described calcium-magnesium waterborne suspension be included in the first aqueous phase suspend concentration more than or equal to 200g/kg meet formula a Ca(OH)₂.b Mg(OH)₂.c the solid particle of MgO, wherein, a, b and c representation quality mark, their summation has 90% ～the value of 100%,

The group of described phosphonate or phosphonic acids choosing freely following material composition:

Their mixture.

27. application according to claim 26, wherein, described phosphonate or phosphonic acids comprise 2 to 8 " phosphonic acids " of acid form Characteristic group.

28. application according to claim 26, wherein, described phosphonate or phosphonic acids select free amino group three (methylene phosphine) Acid, the acid of 1-hydroxy ethylidene-1,1-di 2 ethylhexyl phosphonic acid, ethylenediamine tetraacetic (methylene phosphine), hexamethylene diamine four (methylene phosphine) acid, diethylidene three Amine five (methylene phosphine) acid, double (methylene phosphine) acid of (2-hydroxyl) ethylamino-N, N-, 2-phosphono-1,2,4-butane tricarboxylic acid, 6-amino-1-hydroxyhexylidene-N, N-di 2 ethylhexyl phosphonic acid, N, double (3-aminopropyl) ethylenediamine six (the methylene phosphine) sour, double (six of N'- Trinitroso-trimethylene triamine) five (methylene phosphine) is sour, amino three (methylene phosphine) acid oxidase thing, and the group of their mixture composition.

29. application according to claim 26, wherein, gross weight based on described solid particle, described phosphonate or phosphine Acid exists more than or equal to the amount of 0.05 weight % with active acid content.

30. application according to claim 26, wherein, gross weight based on described solid particle, described phosphonate or phosphine Acid exists less than or equal to the amount of 5 weight % with active acid content.

31. application according to claim 26, wherein, described solid particle concentration in described aqueous phase is more than or equal to 300g/kg。

32. phosphonates or phosphonic acids are as the application of the additive of the decant ability reducing calcium-magnesium waterborne suspension, described calcium-magnesium Waterborne suspension be included in aqueous phase suspend concentration more than or equal to 200g/kg meet formula a Ca (OH)₂.b Mg (OH)₂.c the solid particle of MgO, wherein, a, b and c are mass fractions, and their summation has the value of 90～100%.