CN109154029A - Solid composite for sugar purifying - Google Patents
Solid composite for sugar purifying Download PDFInfo
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- CN109154029A CN109154029A CN201780032571.5A CN201780032571A CN109154029A CN 109154029 A CN109154029 A CN 109154029A CN 201780032571 A CN201780032571 A CN 201780032571A CN 109154029 A CN109154029 A CN 109154029A
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- quaternary ammonium
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- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
- C13B20/00—Purification of sugar juices
- C13B20/14—Purification of sugar juices using ion-exchange materials
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/64—Quaternary ammonium compounds having quaternised nitrogen atoms bound to carbon atoms of six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
- C13B20/00—Purification of sugar juices
- C13B20/02—Purification of sugar juices using alkaline earth metal compounds
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Distillation Of Fermentation Liquor, Processing Of Alcohols, Vinegar And Beer (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
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- Paper (AREA)
Abstract
For removing the solid composite of the foreign pigment in liquid glucose or syrup and the application method of the solid composite, wherein the solid composite includes at least quaternary ammonium compound and phosphorus compound.
Description
This application claims the excellent of the PCT International Patent Application PCT/CN2016/083428 submitted on May 26th, 2016
It first weighs, is for all purposes incorporated herein the full content of the application by quoting mode.
Technical field
The present invention relates to a kind of solid composites for sugar purifying.The solid composite can remove in liquid glucose or syrup
Foreign pigment.The solid composite includes quaternary ammonium compound and phosphorus compound.
Background technique
Refined sugar be usually pass through purifying raw sugar or syrup obtain.For example, raw sugar can be by purifying, flashing to concentrated sugar slurry
And the process crystallized is obtained from syrup.Then crystallized product can be dissolved in water to obtain liquid glucose.Then, liquid glucose
It can be further purified and process to obtain the refined sugar with acceptable purity rubric.Alternatively, it is obtained from syrup
Syrup can be subjected to crystallisation step of the purification process without raw sugar.
The whiteness of refined sugar is an important sugared quality standard.The purpose is to reduce coloured miscellaneous by one of liquid glucose or syrup purification
Matter, so that purified sugar product has desired whiteness.For reducing the various sides of foreign pigment during sugared purification process
Method is known in the art.Method known to a kind of is phosphating process, is intended to generate phosphorus using phosphorus compound and lime
Sour calcium flocculate passes through addition polymer as flocculant progress flocculation step later.To a kind of heavy of the phosphating process
Modify is to apply color precipitating reagent, such as certain quaternary ammonium compounds.Property is that the quaternary ammonium compound of cation can improve yin
The precipitating of ion high molecular weight foreign pigment, these impurity can be removed more easily as flotation dross.
Routinely, quaternary ammonium compound and phosphorus compound are added to individual stream containing in sugared mixture.For example, in the U.S.
In the patent No. 3,698,951, disclose for by adding, quaternary ammonium compound, addition phosphoric acid to be coloured in liquid glucose to remove later
The method of impurity.Reagent it is independent addition be laborious and such method be also required to high capital cost (carpex cost),
Energy and maintenance cost.Usually it is diluted in water before quaternary ammonium compound is added to liquid glucose or syrup.However, quaternary ammonium
Compound solution tends to have relatively high viscosity, this influences addition efficiency and there may come a time when that equipment is caused to block.In order to
This problem is solved, needs high dilution factors so as to the level that makes the viscosity of quaternary ammonium compound solution reach sufficiently low.This can wave
Water wasting and cost.
Summary of the invention
It has been found that the above problem can solve through the invention.
In the first aspect of the present invention, a kind of solid composite is provided, it is especially a kind of for removing liquid glucose or syrup
In foreign pigment solid composite, include at least quaternary ammonium compound and phosphorus compound；Wherein, the quaternary ammonium compound with should
The weight ratio of phosphorus compound is in the range of 1: 1 to 1: 5.
Preferably, the weight ratio of the quaternary ammonium compound and the phosphate compounds is in the range of 1: 1 to 1: 3.
In particular, the quaternary ammonium compound has following general formula:
[N+(R1)(R2)(R3)(R4)]yX- (I)
Wherein:
R1、R2、R3And R4, it can be identical or different, indicate the saturation or unsaturation, straight chain with from 1 to 30 carbon atom
Or branched aliphatic group or aromatic group；
X is anion；
Y is the chemical valence of X.
Preferably, which has following general formula:
[N+(R5)2(R6)(R7)]yX- (II)
Wherein:
R5It is alkyl or hydroxyalkyl containing from 8 to 22 carbon atoms；
R6It is alkyl or hydroxyalkyl containing from 1 to 4 carbon atom；
R7It is R5Or R6；
X is anion；
Y is the chemical valence of X.
The quaternary ammonium compound can have following general formula:
[N+((CH2)n-T-R8)m(R9)4-m]yX- (III)
Wherein:
R8Independently selected from C1-C24Alkyl or hydroxyalkyl；
R9Independently selected from C1-C4Alkyl or hydroxyalkyl；
T is-C (=O)-O- ,-O-C (=O)-,-NR10- C (=O)-or (C=O)-NR10, wherein R10It is hydrogen, C1-C6Alkane
Base or C1-C6Hydroxyalkyl；
N is from 0 to 5 integer；
M is selected from 1,2 and 3；
X is anion；
Y is the chemical valence of X.
The quaternary ammonium compound can have following general formula:
[N+(R11)(R12)(R13)((CH2)z-Ph)]yX- (V)
Wherein:
R11And R12, it can be identical or different, indicate the linear or branched alkyl group or hydroxyalkyl with from 1 to 24 carbon atom；
R13It is linear or branched alkyl group or hydroxyalkyl with from 1 to 8 carbon atom；
Z=0 or integer of 1 to 3；
Ph indicates phenyl；
X is anion；
Y is the chemical valence of X.
Preferably, which is selected from the group being made of the following terms: C14-C18Alkyl dimethyl ammonium compounds, two
Ammonium chloride compound, two palmityl dimethyl compounds, di-cetyl dimethyl ammonium compounds, double octadecyls
Dimethyl ammonium compounds, two oleyl dimethyl ammonium compounds, dihydro rapeseed alkyl dimethyl ammonium compounds (di
Hydrogenated rapeseed alkyl dimethyl ammonium compound) and its mixture.
Preferably, which is phosphoric acid.
In the second aspect of the present invention, provide a kind of for reducing foreign pigment in liquid glucose or syrup in the following manner
Method: quaternary ammonium compound and phosphorus compound are added in the liquid glucose or syrup；Wherein, the quaternary ammonium compound and the phosphatization are closed
The weight ratio of object is in the range of 1: 1 to 1: 5.
In particular, providing a kind of method for reducing the foreign pigment in liquid glucose or syrup, this method includes following step
It is rapid:
(1) aqueous solution or dispersion of solid composite according to the first aspect of the invention are provided；And
(2) aqueous solution or dispersion are added in the liquid glucose or syrup.
Preferably, this method further includes steps of
(a) lime based compound and flocculant are added in the liquid glucose or syrup, to form the cotton-shaped of these foreign pigments
Sediment；
(b) flocky precipitate is separated from the liquid glucose or syrup.
Preferably, which is polyacrylamide.
Preferably, the quaternary ammonium compound is to be the amount from 100 to 500ppm based on the weight of sugar cube in liquid glucose or syrup
In the presence of.
In the third aspect of the present invention, solid composite according to the first aspect of the invention is provided for reducing liquid glucose
Or the purposes of the foreign pigment in syrup.
In the fourth aspect of the present invention, a kind of solid group being used to prepare comprising quaternary ammonium compound and phosphorus compound is provided
The method for closing object；Wherein, this method includes the steps that mixing the quaternary ammonium compound with the phosphorus compound, the quaternary ammonium compound with
The weight ratio of the phosphorus compound is in the range of 1: 1 to 1: 5.
Specific embodiment
Throughout this explanation, including claims, term " include/kind (comprising one) " or " include
(comprising a) " be understood as with term " comprising at least one/kind " it is synonymous, unless otherwise specified, and " ...
Between " it is understood to include limiting value.
It should be noted that any specific upper concentration, weight ratio or amount can be with when specifying any concentration, weight ratio or amount range
It is associated with any specific least concentration, weight ratio or amount.
As used herein, term " alkyl " means that is be saturated can be straight chain, branch or cricoid alkyl, for example, first
Base, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl, amyl, n-hexyl, cyclohexyl.
As used herein, term " hydroxyalkyl " means the alkyl group being optionally substituted by a hydroxyl group, such as methylol, ethoxy, hydroxyl
Propyl and hydroxy decyl.
As used herein, term " aryl " means the monovalent undersaturated alkyl containing one or more six-membered carbon rings,
Wherein degree of unsaturation can be represented by three conjugated double bonds, can be by hydroxyl, alkyl, alkene on one or more carbon of the ring
Base, halogen, alkylhalide group or amino replace, such as, phenoxy group, phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, trimethylphenyl, chlorine
Phenyl, trichloromethyl phenyl, aminophenyl.
As used herein, term " aralkyl " means the alkyl replaced by one or more aryl, such as phenyl first
Base, phenylethyl, trityl group.
It is especially a kind of for reducing the foreign pigment in liquid glucose or syrup the present invention provides a kind of solid composite
Solid composite includes at least quaternary ammonium compound and phosphorus compound；Wherein, the weight of the quaternary ammonium compound and the phosphorus compound
Than being in the range of 1: 1 to 1: 5.Foreign pigment in liquid glucose or syrup especially include phytochrome, melanoidin, caramel and
The basic degradation products of fructose.The solid composite has good storage stability and can provide excellent decoloration effect
Rate.
As used herein, term " solid composite " refer in as powder, particle, aggregate, thin slice, pellet, spherolite,
Tablet, brick, paste, block (such as the block of molding), the solid form of unit dose object or those skilled in the art
The composition of known another kind solid form.Term " solid " refers under the storage of the composition and the anticipated conditions that use
The state of the composition.In general, it is expected that the composition will keep being in solid form under environment temperature (about 25 DEG C).
When referring to paste discernablely, it is intended that the solid composite will not flow, and in middle iso-stress or pressure or only weigh
Its shape will be kept substantially under power, such as example, when being removed from the molds the shape of mold, such as shape when being squeezed out from extruder
At product shape etc..
As used herein, term " quaternary ammonium compound " (also known as " quaternary ammonium salt ") means quaternized containing at least one
Nitrogen compound, wherein the nitrogen-atoms is attached on four organic groups.The quaternary ammonium salt may include one or more quaternary ammoniums
The nitrogen-atoms of change.Preferably, which includes the quaternized nitrogen-atoms of only one.
Term " liquid glucose or syrup " as used herein means any liquid or syrup containing sugar or fusing raw sugar.It is typical
Ground, which derives from plant origin, such as sugarcane, beet and corn." raw sugar " means to process and contain by bottom line solvable
The sugar of property and insoluble impurities.The raw sugar can be starched by purifying, flashing to concentrated sugar and the process crystallized is obtained from syrup.
Then crystallized product can be dissolved in water to obtain liquid glucose, which is also referred to as " melt ".Alternatively, from syrup
The syrup of acquisition can be used as the raw material of sugar refining process.
According to the present invention, which can have following general formula:
[N+(R1)(R2)(R3)(R4)]yX-(I)
Wherein:
R1、R2、R3And R4, it can be identical or different, indicate the saturation or unsaturation, straight chain with from 1 to 30 carbon atom
Or branched aliphatic group or aromatic group (such as aryl or aralkyl)；
X is anion, such as halogen ion such as Cl or Br, sulfate radical, alkyl sulfate, nitrate anion or acetate, it is preferable that X is
Chloride ion or methylsulfate；
Y is the chemical valence of X.
If the aliphatic group defined in logical formula (I) may include hetero atom, such as oxygen, nitrogen, sulphur and halogen.Optionally
Ground, the aliphatic group include at least ester or amide functional group.
Advantageously, which is alkyl quaternary ammonium salts, with following general formula:
[N+(R5)2(R6)(R7)]yX-(II)
Wherein:
R5It is alkyl or hydroxyalkyl containing from 8 to 22 carbon atoms, such as C8H17、C10H21、C12H25、C14H29、C16H33、C18H37,
Preferably, R5Contain from 12 to 20 carbon atoms；
R6It is alkyl or hydroxyalkyl containing from 1 to 4 carbon atom, such as methyl, ethyl and propyl, preferably R6It is methyl；
R7It is R5Or R6；
X is anion, such as halogen ion such as Cl or Br, sulfate radical, alkyl sulfate, nitrate anion or acetate, it is preferable that X is
Chloride ion or methylsulfate；
Y is the chemical valence of X.
In particular, being dialkyl dimethyl quaternary ammonium salt according to the quaternary ammonium salt of logical formula (II).Quaternary ammonium salt with logical formula (II)
Example includes C14-C18Alkyl dimethyl ammonium compounds (DHT21 such as sold by Su Wei company (Solvay Company)), two
Tallow alkyl dimethyl ammonium compounds, distearyl dimethyl ammonium compounds, two palmityl dimethyl compounds, double hexadecyl
Dimethyl ammonium compounds, double octadecyldimethyl ammonium compounds, two oleyl dimethyl ammonium compounds, dihydro rapeseed alkyl
Dimethyl ammonium compounds.
Advantageously, which has following general formula:
[N+((CH2)n-T-R8)m(R9)4-m]yX-(III)
Wherein:
R8Independently selected from C1-C24Alkyl or hydroxyalkyl；
R9Independently selected from C1-C4Alkyl or hydroxyalkyl；
T is-C (=O)-O- ,-O-C (=O)-,-NR10- C (=O)-or-(C=O)-NR10, wherein R10It is hydrogen, C1-C6Alkyl
Or C1-C6Hydroxyalkyl；
N is from 0 to 5 integer；
M is selected from 1,2 and 3；
X is anion, such as halogen ion such as Cl or Br, sulfate radical, alkyl sulfate, nitrate anion or acetate, it is preferable that X is
Chloride ion or methylsulfate；
Y is the chemical valence of X.
Preferably, if the m defined in logical formula (III) is 2.Therefore, which can have following general formula:
[N+((CH2)n-T-R8)2(R9)2]yX- (IV)
R8、R9, T, n, X and y be as defined in the logical formula (III).
The example of quaternary ammonium salt with logical formula (III) includes:
TET: two (tallow base carboxyethyl) hydroxyethyl methyl methylsulfuric acid ammoniums,
TEO: two (oil base carboxyethyl) hydroxyethyl methyl methylsulfuric acid ammoniums,
TES: distearyl hydroxyethyl methyl methylsulfuric acid ammonium,
TEHT: two (tallow base-carboxyethyl of hydrogenation) hydroxyethyl methyl methylsulfuric acid ammoniums,
TEP: two (palmityl carboxyethyl) hydroxyethyl methyl methylsulfuric acid ammoniums
DEEDMAC: bis- [2- [(the 1- oxo octadecyl) oxygroup] ethyl] ammonium chlorides of dimethyl.
Advantageously, which has following general formula:
[N+(Ru)(R12)(R13)((CH2)z-Ph)]yX- (V)
Wherein:
R11And R12, it can be identical or different, indicate the straight chain with from 1 to 24 carbon atom, preferably from 8 to 24 carbon atoms
Or branched alkyl or hydroxyalkyl；
R13It is linear or branched alkyl group or hydroxyalkyl with from 1 to 8 carbon atom, preferably from 1 to 3 carbon atom；
Z=0 or integer of 1 to 3, preferably z=1；
Ph indicate phenyl, the phenyl can on any available position have at least one be selected from by halide, nitrous acid ester,
And the substituent group of the group of sulfuric ester composition；
X is anion, such as halogen ion such as Cl or Br, sulfate radical, alkyl sulfate, nitrate anion or acetate, it is preferable that X is
Chloride ion or methylsulfate；
Y is the chemical valence of X.
The example of quaternary ammonium salt with logical formula (V) includes distearyl methylbenzyl ammonium compounds, two tallow alkyl methyl
Benzyl ammonium compounds, two palmityl methylbenzyl compounds, double hexadecyl methylbenzyl ammonium compounds, double octadecyl methyls
Benzyl ammonium compounds.
It should be understood that the solid composite may include the mixture of single quaternary ammonium salt or more than one quaternary ammonium salt.
According to the present invention, phosphorus compound can be phosphoric acid or phosphate compounds.Suitable phosphate compounds include but
It is not limited to tripolyphosphate, pyrophosphate, hexametaphosphate, tertiary sodium phosphate, sodium dihydrogen phosphate, calcium dihydrogen phosphate, biphosphate
Ammonium, disodium hydrogen phosphate, diammonium hydrogen phosphate, or the water-soluble phosphorus of expected any pH that will not substantially reduce syrup or liquid glucose
Hydrochlorate is within the scope of the invention.Preferably, which is phosphoric acid.
The solid composite can further include water and organic solvent, such as ethyl alcohol and isopropanol.
The solid composite can further include polycationic polymer.Suitable polycationic polymer includes diene
The copolymer of diallyidimethylammonium chloride (DADMAC) and acrylamide, the copolymer of DADMAC and sodium acrylate, DADMAC, third
The copolymer of acrylamide and sodium acrylate, the copolymer of dimethylamine-epichlorohydrin.
The solid composite is further included in the oxidant that can be used in sugar purifying.Suitable oxidant includes peroxide
Change hydrogen and hypochlorite.
According to the present invention, the weight ratio for including quaternary ammonium salt and phosphorus compound in the solid composite is 1: 1 to 1: 5
(include: 1: 1,1: 1.1,1: 1.2,1: 1.3,1: 1.4,1: 1.5,1: 1.6,1: 1.8,1: 2,1: 2.2,1: 2.4,1: 2.6,1:
2.8, all values and subrange between 1: 3,1: 4,1: 5 etc. and described value, as clearly write out) in the range of.It is preferred that
Ground, the weight ratio are in the range of 1: 1 to 1: 3, more preferably in the range of 1: 1.2 to 1: 3.In context of the invention
In, which is what the weight based on active constituent calculated.
The solid composite can by via any mixed media well known to those skilled in the art by quaternary ammonium salt component
It is blended with phosphorus compound component to prepare.Therefore, the present invention also provides one kind to be used to prepare comprising quaternary ammonium compound and phosphatization
The method for closing the solid composite of object；Wherein, this method includes the steps that mixing the quaternary ammonium compound with the phosphorus compound, should
The weight ratio of quaternary ammonium compound and the phosphorus compound is in the range of 1: 1 to 1: 5.Typically, by the way that quaternary ammonium salt to be heated to
Temperature (such as from about 65 DEG C) higher than its fusing point makes its fusing, then can under stiring preferably under heating add phosphorus compound
It is added in the quaternary ammonium salt.Then, which can be cooled to environment temperature to solidify the composition.
On the other hand, the present invention provides a kind of for reducing foreign pigment in liquid glucose or syrup in the following manner
Method: quaternary ammonium compound and phosphorus compound are added in the liquid glucose or syrup；Wherein, the quaternary ammonium compound and the phosphorus compound
Weight ratio be in the range of 1: 1 to 1: 5.Quaternary ammonium compound and phosphorus compound can be added in liquid glucose or syrup simultaneously
Or it premixes and is added as blend.
The present invention also provides one kind for being reduced in liquid glucose or syrup by using solid composite described herein
Foreign pigment method.In particular, method includes the following steps:
(1) aqueous solution or dispersion of the solid composite are provided；And
(2) solution or dispersion are added in the liquid glucose or syrup.
The solid composite can be dissolved or dispersed in water, optionally use organic solvent.Preferably, in such solution or
The concentration of quaternary ammonium salt in dispersion is from 5wt% to 30wt%, more preferably from 10wt% to 20wt%.
The solution containing quaternary ammonium salt and phosphorus compound or dispersion can be added to reaction with metering pump and agitating device
In liquid glucose or syrup in slot, contact the quaternary ammonium salt with foreign pigment.In particular, the reaction 70 DEG C -90 DEG C, preferably 80 DEG C -
It is carried out at a temperature of 85 DEG C.The sediment formed in this reaction is initially very finely divided, and with the naked eye can hardly
It observes；But its presence can be disclosed by measuring the optical characteristics of liquid, such as by using spectrophotometer measurement
Optical density (OD) at 420nm.An exemplary embodiment according to the present invention, such thin sediment can be used with sufficiently small
The filter medium of porosity is removed by filtration.
It is one advantage of the present invention that it allows quaternary ammonium salt and phosphorus compound being conveniently added to liquid glucose or sugar with single stream
In slurry, this can save time and cost.In addition, under identical quaternary ammonium salinity, it, should compared with the solution for containing only quaternary ammonium salt
The viscosity of the dilution aqueous solution of solid composite is lower.This is particularly advantageous, because the dilution aqueous solution is lower viscous
Degree allows the quick of quaternary ammonium salt and liquid glucose or syrup and is sufficiently mixed, and reacting between quaternary ammonium salt and foreign pigment can be improved in this
Efficiency.In addition, the fusing point of the solid composite is lower than the fusing point of quaternary ammonium salt solid, and therefore, when melting color sediment, by
In needing lower temperature and shorter heating time, energy can be saved by using the solid composite.
The effective dose of the solid composite can be readily determined by those skilled in the art.Generally, it is based on the sugar
The weight of sugar cube in liquid or syrup, the dosage of the solid composite are from about 200ppm to about 2000ppm.It is preferably based on
The weight of sugar cube in the liquid glucose or syrup, the dosage of the solid composite are from about 400ppm to about 1000ppm.
According to the present invention, the method may further comprise the step of:
(a) lime based compound and flocculant are added in the liquid glucose or syrup, to form the cotton-shaped of these foreign pigments
Sediment；
(b) flocky precipitate is separated from the liquid glucose or syrup.
In particular, the flocky precipitate is calcium phosphate.
Term " lime based compound " as used herein refers to calcium containing compound, can be used for neutralizing solution acidity and in sugar
The insoluble calcium phosphate of precipitating is formed in liquid or syrup with phosphorus compound.Suitable lime based compound includes but is not limited to hydrogen-oxygen
Change calcium, as any in the slurry (milk of lime) and lime succinate (lime succrate) with water.It can be by the lime
Based compound is added in liquid glucose or syrup with enough amounts, by the pH of the liquid glucose or syrup improve between 6 and 8, preferably
Between 6.8 and 7.2.
Flocculant can be added to the size for increasing sediment dross in liquid glucose or syrup, which includes
Most of calcium phosphate coagulation and other foreign pigments precipitated and in conjunction with quaternary ammonium salt.
Preferably, which is Anionic polyelectrolytes, such as polyacrylate, polyacrylamide, preferably polypropylene
Amide.Based on the weight of sugar cube in the liquid glucose or syrup, the polyacrylamide of the amount of about 5ppm to about 30ppm may include.
It is preferably based on the weight of sugar cube in the liquid glucose or syrup, polyacrylamide exists with the amount of about 10ppm to about 25ppm.
Polyacrylamide used in the present invention preferably has being averaged for from 12,000,000 to 30,000,000 dalton
Molecular weight.It is highly preferred that the average molecular weight that the polyacrylamide has for 22,000,000 dalton.
After flocculation, can by include floatation (such as air flotation), filtering physical separation method will likely
It is removed from liquid glucose or syrup in the flocky precipitate containing foreign pigment of float scum form.For of the invention preferred
Separation method is air-flotation methods, for this method, there is additional micro- aerating step before the step of adding flocculant.
Micro- aeration can be carried out to generate liquid glucose or syrup through being aerated.This step can carry out in the reactive tank with agitating device
Or it is carried out using air compressor.It may then pass through skimming device (such as scaler) and swim in liquid glucose from liquid surface removing
Or the dross captured by air in syrup.
Generally, by using method of the invention, the color value of sugar product can be reduced to 15-100 ICUMSA unit,
More typically, 20-50 ICUMSA unit.
The present invention is described referring now to many specific examples, these examples are not considered as limiting claimed
The range of invention.
If by the disclosure content of quoting any patent, patent application and publication that mode is incorporated herein with
The application's illustrates mutually to conflict to may cause the unclear degree of term, then this explanation should be preferential.
Example
Material
Dialkyl quats salt: DHT21；C14-C18Alkyl dimethyl ammonium chloride (CAS 68002-59-5)；From Su Wei company
Monoalkyl quaternary ammonium salts: octadecyltrimethylammonium chloride (CAS 112-03-8)；From Su Wei company
Benzyl quaternary ammonium salt: two C14-C18Alkyl methyl benzyl ammonium chloride (CAS 61789-73-9)；From Su Wei company
Phosphoric acid: 85wt%
Decoloration performance test
Sample preparation
Solids blend is prepared by mixing DHT21 (coming from Su Wei company) with phosphoric acid, wherein the DHT21 and the phosphoric acid exist
Weight ratio in such sample is shown in table 1 below.These solids blends are melted at 60 DEG C and then dilute in the hot water
It releases to obtain the concentration with DHT21 as the solution of 10wt% (activity).It will be obtained by simple lime treatment from sugar-cane juice
Raw sugar dissolution in the hot water to obtain the liquid glucose of 60-65 Brix Scale.The liquid glucose has the sugar of 500-1500 ICUMSA unit
Value.
Phosphatization processing
Liquid glucose is heated to 80 DEG C -85 DEG C, then the weak solution of blend is added in the liquid glucose and is stirred 15 minutes.It is based on
The weight of sugar cube in the liquid glucose, the dosage of quaternary ammonium salt are 300ppm.Then lime succinate is added under stiring mixed
It closes in object, so that the pH value of the mixture reaches 6.9-7.0.
Flotation
Then, liquid glucose is transferred in separatory funnel and PAM solution (0.1wt%) is added in the liquid glucose (based on sugar cube
Content, the dosage of PAM are 15ppm-20ppm).It shakes the liquid glucose and immerses the separatory funnel in boiling water bath 10 minutes.Contain
The sediment of foreign pigment floats to the top of liquid glucose.The clarifying sugar liquid for collecting 40ml from funnel bottom is tested for color value.
Color value test
Collected liquid glucose is diluted to (sugared ultimate density is 35-40 Brix Scale) in water.By using diluted HCl or
The pH value of the solution is adjusted to 7.0 by NaOH solution.Then, which is used in combination with (porous having a size of the 0.45 μm) filtering of filter paper
UV/Vis spectrometer detects absorption of the solution at 420nm.
Calculate color value (COL) according to the following formula:
Wherein:
A420 is expressed as absorbance of the liquid glucose under 420nm wavelength；
B is that (detection of the Brix Scale of liquid glucose is with Abbe refractometer (Abbe- to Brix Scale of the liquid glucose at 25 DEG C
Refractometer it) carries out, unit is a ° Bx)；
L is the length of absorption cell；
ρ is the density of liquid glucose.
Percent of decolourization is calculated according to the following formula:
Percent of decolourization=(COLStoste-COLFlotation)/COLStoste* 100%
Percent of decolourization result is shown in table 1 below:
Table 1
Another group of experiment is carried out according to the above method, the difference is that the DHT21 in solids blend is by benzyl season
Ammonium salt, that is, two C14-C18Alkyl methyl benzyl ammonium chloride (obtaining from Su Wei company) replaces.
Table 2
As shown in Table 1 and Table 2, the decolorizing efficiency of solid composite is influenced by the weight ratio of quaternary ammonium salt and phosphorus compound.When
When the weight ratio is not less than 1: 1, solid composite is more effective in terms of reducing foreign pigment.
Stability test
Solids blend of the preparation containing DHT21 and phosphoric acid as described above.By the solids blend in 54 DEG C of baking oven
It incubates 4 weeks.The content of DHT21 and phosphoric acid are titrated before incubation and after incubating respectively.The titration that phosphoric acid is carried out using NaOH, is used in combination
Phenolphthalein is as color indicator.The program of such titration is well-known to those skilled in the art.According in China national mark
The titration of the progress of method described in quasi- GB/T 5174-2004 DHT21.As a result it is shown in the following table 3:
Table 3
| DHT21 content (%) | H3PO4Content (%) | |
| 0 week | 49.5 | 35.7 |
| 4 weeks | 49.9 | 36.1 |
Solid composite according to the present invention can incubate at 50 DEG C as the result is shown for up to keeps its component after 4 weeks
Stability.There are the slight decreases of DHT21 content, this should be the evaporation due to organic solvent.
Viscosity test
The solids blend of solid DHT21 or DHT21 and phosphoric acid are dissolved in water, wherein various DHT21 concentration such as exist
It is shown in the following table 4.Then by using Brookfield LVT viscosimeter, (rotor #S2) is measured under the shear velocity of 100rpm
The viscosity of solution.It is measured at environment temperature, 40 DEG C and 60 DEG C respectively.The unit of viscosity is cP.S.As a result it is shown in the following table 4
In:
Table 4
As the result is shown compared with the solution for only including quaternary ammonium salt, the solution comprising quaternary ammonium salt and phosphoric acid shows significant lower
Viscosity (quaternary ammonium salt content keep identical).
The decoloration performance of different quarternary ammonium salt compounds is tested
Solids blend is prepared according to program as described above and according to the formula in the following table 5.Use dialkyl quats salt
(DHT21) or monoalkyl quaternary ammonium salts (1831 70).Evaluation decoloration performance as described above.As a result it is shown in down
In table 5:
Table 5
As the result is shown compared with monoalkyl quaternary ammonium salts, when being prepared in solids blend with phosphoric acid, dialkyl group season
Ammonium salt generates higher decolorizing efficiency.
Flotation rate test
Solids blend is prepared according to program as described above and according to the formula in the following table 6.Use dialkyl quats salt
(DHT21) or monoalkyl quaternary ammonium salts.The weight ratio of quarternary ammonium salt compound and phosphoric acid is 1: 1 (w/w) in solids blend.
These solids blends are melted at 60 DEG C and are then diluted in the hot water to obtain the concentration with quaternary ammonium salt
For the solution of 10wt% (activity).The raw sugar obtained by simple lime treatment from sugar-cane juice is dissolved in the hot water to obtain
The liquid glucose of 60-65 Brix Scale.The liquid glucose has the sugar value of 500-1500 ICUMSA unit.
Liquid glucose is set to be subjected to phosphatization processing as described above.Then, liquid glucose is transferred in separatory funnel and by PAM solution
(0.1wt%) is added in the liquid glucose (based on solid sugared content, the dosage of PAM is 15ppm-20ppm).It shakes the liquid glucose and incites somebody to action
The separatory funnel immerses in boiling water bath 10 minutes.Sediment containing foreign pigment floats to the top of liquid glucose.The liquid separation is leaked
Bucket immerses after boiling water bath, measures flotation rate in different time points.In order to determine flotation rate, estimate to tie by visual inspection
Fruit, and flotation rate passes through the amount that will float to the flocky precipitate of liquid glucose top surface divided by cotton-shaped heavy present in liquid glucose
The total amount of starch indicates.As a result it is shown in the following table 6.
Table 6
Be highly desirable to, the flocky precipitate containing foreign pigment once occur can quickly float and with clarification
Liquid glucose separation.This is even more important in commercial scale sugar purification process, because flotation rate can lead to the technique faster
Higher efficiency.As the result is shown compared with monoalkyl quaternary ammonium salts, when preparing in solids blend, dialkyl quats salt is generated more
Fast flotation efficiency.
Claims (15)
1. a kind of solid composite includes at least quaternary ammonium compound and phosphorus compound；Wherein, the quaternary ammonium compound and the phosphatization
The weight ratio for closing object is in the range of 1: 1 to 1: 5.
2. solid composite according to claim 1, wherein the weight ratio of the quaternary ammonium compound and the phosphate compounds
It is in the range of 1: 1 to 1: 3.
3. solid composite according to claim 1 or 2, wherein the quaternary ammonium compound has following general formula:
[N+(R1)(R2)(R3)(R4)]yX- (I)
Wherein:
R1、R2、R3And R4, can be identical or different, indicate to have the saturation of from 1 to 30 carbon atom or unsaturation, straight chain or
Branched aliphatic group or aromatic group；
X is anion；
Y is the chemical valence of X.
4. solid composite according to any one of claim 1 to 3, wherein the quaternary ammonium compound has following general formula:
[N+(R5)2(R6)(R7)]yX- (II)
Wherein:
R5It is alkyl or hydroxyalkyl containing from 8 to 22 carbon atoms；
R6It is alkyl or hydroxyalkyl containing from 1 to 4 carbon atom；
R7It is R5Or R6；
X is anion；
Y is the chemical valence of X.
5. solid composite according to any one of claim 1 to 3, wherein the quaternary ammonium compound has following general formula:
[N+((CH2)n-T-R8)m(R9)4-m]yX- (III)
Wherein:
R8Independently selected from C1-C24Alkyl or hydroxyalkyl；
R9Independently selected from C1-C4Alkyl or hydroxyalkyl；
T is-C (=O)-O- ,-O-C (=O)-,-NR10- C (=O)-or-(C=O)-NR10, wherein R10It is hydrogen, C1-C6Alkyl
Or C1-C6Hydroxyalkyl；
N is from 0 to 5 integer；
M is selected from 1,2 and 3；
X is anion；
Y is the chemical valence of X.
6. solid composite according to any one of claim 1 to 3, wherein the quaternary ammonium compound has following general formula:
[N+(R11)(R12)(R13)((CH2)z-Ph)]yX- (V)
Wherein:
R11And R12, it can be identical or different, indicate the linear or branched alkyl group or hydroxyalkyl with from 1 to 24 carbon atom；
R13It is linear or branched alkyl group or hydroxyalkyl with from 1 to 8 carbon atom；
Z=0 or integer of 1 to 3；
Ph indicates phenyl；
X is anion；
Y is the chemical valence of X.
7. solid composite according to any one of claim 1 to 4, wherein the quaternary ammonium compound is selected from by following
The group of item composition: C14-C18Alkyl dimethyl ammonium compounds, distearyl dimethyl ammonium compounds, two palmityl dimethyl chemical combination
Object, di-cetyl dimethyl ammonium compounds, double octadecyldimethyl ammonium compounds, two oleyl dimethyl ammonium compounds, two
Hydrogenate rapeseed alkyl dimethyl ammonium compounds and its mixture.
8. solid composite according to any one of claim 1 to 7, wherein the phosphorus compound is phosphoric acid.
9. a kind of method for reducing foreign pigment in liquid glucose or syrup in the following manner: quaternary ammonium compound and phosphatization are closed
Object is added in the liquid glucose or syrup；Wherein, the weight ratio of the quaternary ammonium compound and the phosphorus compound is the model 1: 1 to 1: 5
In enclosing.
10. a kind of method for reducing foreign pigment in liquid glucose or syrup, method includes the following steps:
(1) aqueous solution or dispersion of solid composite according to any one of claim 1 to 8 are provided；And
(2) aqueous solution or dispersion are added in the liquid glucose or syrup.
11. method according to claim 9 or 10, wherein this method further includes steps of
(a) lime based compound and flocculant are added in the liquid glucose or syrup, to form the cotton-shaped of these foreign pigments
Sediment；
(b) flocky precipitate is separated from the liquid glucose or syrup.
12. method described in 0 or 11 according to claim 1, wherein the flocculant is polyacrylamide.
13. the method according to any one of claim 9 to 12, wherein the weight based on sugar cube in the liquid glucose or syrup
Amount, the quaternary ammonium compound exist with the amount from 100ppm to 500ppm.
14. solid composite according to any one of claim 1 to 8 is used to reduce the foreign pigment in liquid glucose or syrup
Purposes.
15. a kind of method for being used to prepare solid composite, which includes quaternary ammonium compound and phosphorus compound；Its
In, this method includes the steps that mixing the quaternary ammonium compound with the phosphorus compound, the quaternary ammonium compound and the phosphorus compound
Weight ratio is in the range of 1: 1 to 1: 5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNPCT/CN2016/083428 | 2016-05-26 | ||
| CN2016083428 | 2016-05-26 | ||
| PCT/CN2017/085456 WO2017202289A1 (en) | 2016-05-26 | 2017-05-23 | A solid composition for sugar purification |
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| Publication Number | Publication Date |
|---|---|
| CN109154029A true CN109154029A (en) | 2019-01-04 |
Family
ID=60411040
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780032571.5A Pending CN109154029A (en) | 2016-05-26 | 2017-05-23 | Solid composite for sugar purifying |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN109154029A (en) |
| BR (1) | BR112018074072A2 (en) |
| WO (1) | WO2017202289A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11787967B2 (en) | 2020-07-13 | 2023-10-17 | Advansix Resins & Chemicals Llc | Branched amino acid surfactants for inks, paints, and adhesives |
| US11857515B2 (en) | 2020-07-13 | 2024-01-02 | Advansix Resins & Chemicals Llc | Branched amino acid surfactants for use in healthcare products |
| US11897834B2 (en) | 2020-07-09 | 2024-02-13 | Advansix Resins & Chemicals Llc | Branched amino acid surfactants |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3698951A (en) * | 1967-09-29 | 1972-10-17 | Tate & Lyle Ltd | Sugar refining |
| CN101812546A (en) * | 2010-04-23 | 2010-08-25 | 广西大学 | Preparation of phosphoric acid composite decolorizer and application method thereof |
| CN103210095A (en) * | 2009-11-11 | 2013-07-17 | 卡博Ua有限公司 | Compositions and processes for improving phosphatation clarification of sugar liquors and syrups |
-
2017
- 2017-05-23 BR BR112018074072A patent/BR112018074072A2/en not_active Application Discontinuation
- 2017-05-23 WO PCT/CN2017/085456 patent/WO2017202289A1/en active Application Filing
- 2017-05-23 CN CN201780032571.5A patent/CN109154029A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3698951A (en) * | 1967-09-29 | 1972-10-17 | Tate & Lyle Ltd | Sugar refining |
| CN103210095A (en) * | 2009-11-11 | 2013-07-17 | 卡博Ua有限公司 | Compositions and processes for improving phosphatation clarification of sugar liquors and syrups |
| CN101812546A (en) * | 2010-04-23 | 2010-08-25 | 广西大学 | Preparation of phosphoric acid composite decolorizer and application method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11897834B2 (en) | 2020-07-09 | 2024-02-13 | Advansix Resins & Chemicals Llc | Branched amino acid surfactants |
| US11787967B2 (en) | 2020-07-13 | 2023-10-17 | Advansix Resins & Chemicals Llc | Branched amino acid surfactants for inks, paints, and adhesives |
| US11857515B2 (en) | 2020-07-13 | 2024-01-02 | Advansix Resins & Chemicals Llc | Branched amino acid surfactants for use in healthcare products |
Also Published As
| Publication number | Publication date |
|---|---|
| BR112018074072A2 (en) | 2019-03-06 |
| WO2017202289A1 (en) | 2017-11-30 |
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