Summary of the invention
The object of the invention just provides the gelling gum that a kind of Determination of Residual Organic Solvents is low and gel-strength is high.
Another object of the present invention provides production technique of said gelling gum and uses thereof.
In first aspect of the present invention, a kind of gelling gum is provided, described gelling gum has following characteristic:
(a) the ethanol residual quantity is equal to or less than 200ppm;
(b) gel-strength is greater than 1000g/cm
2
In another preference, described gelling gum also has following characteristic:
(c) water-content is less than or equal to 15wt%;
(d) transmittance is more than or equal to 80%.
In another preference, the ethanol residual quantity≤100ppm of described gelling gum, more preferably≤and 50ppm or lower, like 30-50ppm.
In another preference, the transmittance of described gelling gum is more than or equal to 85%.
In another preference, the gel-strength of described gelling gum is more than or equal to 1050g/cm
2, more preferably be 1050-1800g/cm
2, be 1100-1500g/cm best
2
In another preference, the arsenic content of described gelling gum is less than 3ppm, and lead content is less than 2ppm.
In another preference, described gelling gum is with containing following method preparation of the present invention.
In second aspect present invention, a kind of method for preparing gelling gum is provided, described method comprises step:
(a) flocculation: gellan gum fermentation liquid and acidic conditions are stirred down, thereby make the flocculation of gelling gum composition, form the liquid stock that contains the gelling gum throw out, wherein said acidic conditions is pH 1.5-4;
(b) dehydration: the liquid stock to containing the gelling gum throw out dewaters (with optional decolouring), the gelling gum filter cake that obtains dewatering;
(c) homogenate:, form the homogenate mixture with the gelling gum filter cake and the water mixing homogenate of said dehydration.
(d) boil glue: to pH6-8, and heating boils glue with homogenate mixture pH regulator, thereby obtains to boil the glue mixture.
(e) filter: to boiling glue mixture filtered while hot, thereby obtain to contain the filtrating of gelling gum.
(f) gelation: for filtering the filtrating that contains gelling gum that the back obtains, reduce its temperature to 20-45 ℃, thereby make gelling gum generation gelation, form the feed liquid that contains the gel state gelling gum.
(g) press filtration: the feed liquid that contains the gel state gelling gum is carried out press filtration, thereby removes portion of water, is the gelling gum filter cake of 15-30wt% thereby obtain the gelling gum solid content.
(h) granulation and drying: for the gelling gum filter cake after the press filtration, granulation and drying obtain the exsiccant gelling gum.
In another preference, described method also comprises step:
(i) pulverize: exsiccant gelling gum material is pulverized, thereby obtained pulverous gelling gum.
In another preference, the condition of step (a) is pH1.5-4, and flocculation time is 10-40 minute.
In another preference, in the step (a), temperature is a normal temperature, as 4-30 ℃, and more preferably 15-25 ℃.
In another preference, in the step (a), regulate pH to acid with hydrochloric acid, sulfuric acid or its combination.
In another preference, in step (c), the consumption of water be said dehydration gelling gum filter cake weight 10-20 doubly.
In another preference, boil the glue step and comprise following three inferior steps:
(i) with the pH regulator of homogenate mixture to 6-8 (preferably 6.0-7.8),
(ii) be heated to 70-85 ℃, re-adjustment pH to 8.0-10 (preferably 8.1-10.0), insulation for some time (as 3-30 minute, preferably 5-15 minute),
(iii) regulate pH to 6-8 (preferably 6.0-7.8), obtain boiling the glue mixture.
In another preference, in boiling the glue step, the pH regulator agent comprises alkaline conditioner and acid regulator, and wherein alkaline conditioner is selected from: sodium hydroxide, Pottasium Hydroxide, calcium hydroxide or its combination.
Preferred alkaline conditioner is a sodium hydroxide.
Acid regulator is selected from: hydrochloric acid, sulfuric acid, acetic acid or its combination.
Preferred acid regulator is a hydrochloric acid.
In another preference, in step (e), the temperature maintenance of boiling the glue mixture is at 70-90 ℃.
In another preference, in step (e), be used in earlier and boil the flocculating aids that adds in the glue mixture, alkaline filter then.
In another preference, in boiling the glue mixture, add the 0.8-3.0wt% flocculating aids, filter then.
In another preference, in step (f), filtrating is cooled off with reverse-flow coil condenser.
In the third aspect of the invention, a kind of gelling gum with method for preparing is provided.
In fourth aspect of the present invention, a kind of goods are provided, it contains gelling gum of the present invention (like 0.001-99.0wt%).
In another preference, described goods are selected from down group:
(1) food: beverage, cake, jam, jelly, synthesised food, feed for pet, sugar-coat, frosting, milk food prod, bean product etc.;
(2) medicine: collyrium, soft or hard capsule, microcapsule, dressing etc.;
(3) makeup: personal care product, perfume etc.;
(4) Chemicals: film, tackiness agent, toothpaste, air aromatic etc.;
(5) agricultural prods: slow release fertilizer etc.;
(6) other products: mikrobe, plant tissue culture media etc.
Embodiment
The inventor is through deeply and extensive studies is optimized the aftertreatment technology of gellan gum fermentation liquid, developed first not with an organic solvent with acidic conditions under, with low cost, prepare the new production process of gelling gum expeditiously.Not only the organic solvent residue amount is very low for the gelling gum of novel process preparation of the present invention, and gel-strength is significantly increased.
As used herein, " gelling gum of the present invention " refer to Determination of Residual Organic Solvents low (like ethanol residual quantity≤200ppm, preferably≤100ppm, more preferably≤50ppm, best≤30ppm or lower) and gel-strength more than or equal to 1000g/cm
2(preferably gel-strength is more than or equal to 1050g/cm
2(like 1050-1800g/cm
2), more preferably gel-strength is more than or equal to 1100g/cm
2(like 1100-1500g/cm
2)) gelling gum.In addition, this term also comprises the gelling gum with above-mentioned low organic solvent residual quantity and high-gel strength characteristics with the inventive method preparation.
At first, the invention provides the method for producing gelling gum, it may further comprise the steps:
(a) flocculation:
Gellan gum fermentation liquid and acidic conditions are stirred down, thereby make the flocculation of gelling gum composition, form the liquid stock that contains the gelling gum throw out, wherein said acidic conditions is pH1.5-4.
Being applied to the not special restriction of acid of the present invention, can be organic acid or mineral acid, preferred mineral acid, especially hydrochloric acid, sulfuric acid or its combination.
A kind of preferred mode is that fermenation raw liquid is flowed the hydrochloric acid that adds 0.5wt%~3.4wt% concentration in whipping process, thereby makes the flocculation of gelling gum composition, forms the liquid stock that contains the gelling gum throw out.
(b) dehydration:
Liquid stock to containing the gelling gum throw out dewaters (with optional decolouring), the gelling gum filter cake that obtains dewatering.Wherein dewater and/or the available ordinary method of decolouring is carried out, for example carry out with water-removing press.
(c) homogenate:
With the gelling gum filter cake and a certain amount of water mixing homogenate of said dehydration, form the homogenate mixture.
In this step, the not special restriction of the water yield of adding, the 10-20 of the gelling gum filter cake weight of common said dehydration doubly also can add many slightly water.
Homogenate can be carried out with the conventional method and apparatus in this area.For example, use hollander,, form the homogenate mixture (being also referred to as the pasty liquid material) of pasty state the gelling gum filter cake and the water mixing homogenate of said dehydration.
(d) boil glue:
In this step, with homogenate mixture pH regulator extremely near neutral (pH6-8), and heat and boil glue, thereby obtain to boil the glue mixture.
In another preference, boil the glue step and comprise following three inferior steps:
(i) with the pH regulator of homogenate mixture to 6-8 (preferably 6.0-7.8),
(ii) be heated to 70-85 ℃, re-adjustment pH to 8.0-10 (preferably 8.1-10.0), insulation for some time (as 3-30 minute, preferably 5-15 minute),
(iii) regulate pH to 6-8 (preferably 6.0-7.8), obtain boiling the glue mixture.
This three-wave-length boils the gel-strength that the glue step helps further to improve gelling gum.
In boiling the glue step, the conventional various pH regulator agent in the available this area of pH regulator agent.
The representative example of alkaline conditioner comprises (but being not limited to): sodium hydroxide, Pottasium Hydroxide, calcium hydroxide or its combination.Preferred alkaline conditioner is a sodium hydroxide.
The representative example of acid regulator comprises (but being not limited to): hydrochloric acid, sulfuric acid, acetic acid or its combination.Preferred acid regulator is a hydrochloric acid.
(e) filter:
In this step, to boiling glue mixture filtered while hot, thereby obtain to contain the filtrating of gelling gum.
In this step, various usual manners in available this area and equipment filter.Because when temperature was low, gelling gum can solidify, the temperature of boiling the glue mixture when therefore filtering should keep comparatively high temps (being generally 70-90 ℃), in case gelling gum condenses and hinders filtration.
In addition, before filtering, also can be used on and boil an amount of flocculating aids of interpolation in the glue mixture.The example of flocculating aids commonly used comprises (but being not limited to): zeyssatite, perlite or its combination.
In a preference, in boiling the glue mixture, add the 0.8-3.0wt% flocculating aids, filter then.
(f) gelation
For filtering the filtrating that contains gelling gum that the back obtains, reduce its temperature to 20-45 ℃, thereby make gelling gum generation gelation, form the feed liquid that contains the gel state gelling gum.
In this step, the method for available routine reduces the filtrating temperature, thereby realizes gelation.A kind of preferred mode is to use coiled tube condenser, especially reverse-flow coil condenser.
In a preference, use reverse-flow coil condenser shown in Figure 1, liquid material (filtrating that promptly contains gelling gum) gets into condensing surface from the liquid material import of condensing surface top, after overcooling, flows out from the liquid material outlet of condensing surface below; Entrance of cooling water gets into and water coolant is from the below, from the cooling water outlet outflow of top.Use the reverse-flow type of cooling, can be so that the cooling of gelling gum filtrating to be more even, cooling performance is high.
(g) press filtration
In this step, the feed liquid that contains the gel state gelling gum is carried out press filtration, thereby removes portion of water, obtains the gelling gum filter cake.The gelling gum solid content is 15-30% in the common described filter cake.
The measuring method of solid content is measured with ordinary method, for example GB5009.3 weight loss on drying method.
In this step, can use the conventional press filtration device (like pressure filter) in this area to carry out press filtration.
(h) post-processing step such as granulation, drying
For the gelling gum filter cake after the press filtration, can carry out granulation with usual manner, form granular material.Granulation can be carried out with the conventional method and apparatus in this area, for example uses commercially available tablets press.
If desired, can carry out drying treatment (for example), thereby obtain the exsiccant gelling gum particulate state gelling gum material.Usually water ratio more preferably is 0.1-15wt% less than 15wt% in the exsiccant gelling gum.Dry can carrying out with the conventional method and apparatus in this area for example used commercially available various drying machines, especially the negative pressure drying machine.
If desired, also can pulverize, thereby obtain pulverous gelling gum dried material.Pulverizing can be carried out with the conventional method and apparatus in this area, for example uses commercially available various kibblers.In a preference, material is carried out low-temperature airflow pulverize.
Can make the gelling gum goods of various routines with gelling gum of the present invention, in these gelling gum goods, the content of gelling gum is the 0.01-99wt% of goods gross weight usually, more preferably is 0.1-50wt%.
Representational gelling gum goods comprise (but being not limited to):
(1) food: beverage, cake, jam, jelly, synthesised food, feed for pet, sugar-coat, frosting, milk food prod or bean product etc.;
(2) medicine: collyrium, soft or hard capsule, microcapsule or dressing etc.;
(3) makeup: personal care product or perfume etc.;
(4) Chemicals: film, tackiness agent, toothpaste or air aromatic etc.;
(5) agricultural prods: slow release fertilizer etc.;
(6) other products: mikrobe or plant tissue culture media etc.
The low acyl gelling gum that can make with the inventive method has high purity, high-content, low bacterium, and the technology cost is low.Major advantage of the present invention comprises:
(1) the omnidistance production process of low acyl gelling gum does not have any organic solvent and mixes, therefore so the organic solvent residual index is low for very.Particularly; Materials such as trace that itself contains in fermented liquid or small amount of ethanol can remain in the gelling gum product, do not have the adding of exogenous organic solvent, so organic solvent content are extremely low; For example the ethanol residual quantity is lower than 100ppm, more preferably is lower than 50ppm.This makes the security of gelling gum of the present invention improve greatly.
(2) flocculation step is carried out under acidic conditions, has avoided the negative impact of alkaline matter to the gelling gum gel-strength effectively, has effectively improved the gel-strength of gelling gum.Particularly, gelling gum is very responsive to alkalescence.Because the flocculation step of key in the deacylated tRNA operation of low acyl gelling gum adopts the nothing alkalization to handle, and gelling gum is made the transition under the not damaged condition, thereby make product not only on purity and content, all improve a lot, and on gel-strength, also be significantly increased.
(3) of the present inventionly boil the gel-strength that glue step (especially three-wave-length boils the glue step) helps further to improve gelling gum.
(4), energy consumption and cost have been reduced through press filtration.
(5) Determination of Residual Organic Solvents gelling gum low and that gel-strength is high makes its application surface more wide.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, usually according to the condition described in the normal condition, or the condition of advising according to manufacturer.Only if indicate in addition, otherwise per-cent and umber are calculated by weight.
Embodiment 1:
Gellan gum without organic solvent preparation technology No.1
Obtain to contain the fermenation raw liquid of gelling gum by ordinary method (like the 1 described method of embodiment in the one Chinese patent application 00125858.3).Press following prepared gelling gum:
1) flocculation: fermenation raw liquid flows the hydrochloric acid that adds 0.5%, 1% or 3% concentration in whipping process, make that pH is 2.5.
2) dehydration: the feed liquid after will flocculating pumps into the continuously dehydrating squeezing machine, gets about 15~30% filter cakes of water cut.
3) slurrying: filter cake and water are sent into hollander with 1: 15 ratio, and the pasty state feed liquid is delivered to and boiled the glue jar;
4) boil glue: the dirty sodium hydroxide solution that adds 2%, 5% or 9% concentration of whipped state reaches 6~8 to material liquid PH value.Feed liquid is heated to 70~85 ℃, and pH value transfers to 8~10.Insulation 5~15 clocks transfer to pH value again and reach 6~8.
5) filter: add 0.8~3% perlite, then 70~90 ℃ of high temperature feed liquids are filtered.
6) gel: the feed liquid after the filtration gets into the coil condenser (see figure 1), forms gel state material, discharging then at 20~45 ℃.
7) press filtration: the gel state thing is carried out press filtration with pressure filter, form the filter cake of solid content at 15%~30wt%.(wherein the measuring method of solid content is following: press GB5003.9 weight loss on drying method).
8) granulation: filter cake is got into tablets press by conveying belt, form granulous gelling gum gel;
9) drying: particulate materials input negative pressure drying machine, the exsiccant gelling gum of acquisition water ratio<15%.;
10) pulverize: the exsiccant gelling gum is sent into low-temperature airflow pulverize (depending on the circumstances or the needs of the situation), obtain pulverous gelling gum No.1 (about 80 orders).
Embodiment 2
Performance test
Gelling gum No.1 to preparation among the embodiment 1 measures its performance with ordinary method.
The result is as shown in table 1 below;
Table 1 sample detected result and measuring method:
Outward appearance | This white | Measuring method |
Granularity | 80 orders>99% | |
Weight loss on drying | <15% | GB5009.3 |
Transmittance | >85% | Relatively (detect) with pure water with the ultraviolet spectrometry protractor |
Gel-strength | >1120g/cm
2 | 0.5g gelling gum+99.5g water+2%CaCl
2Heat 80 ℃ of colloidal sols, be cooled to 20 ℃ of insulation 20h, detect with the gel-strength detector
|
PH | 4.5~6.5 | The PHs-2c precision acidity meter |
The organic solvent residual ethanol content | Do not detect | Standard addition method |
Ash content | <15% | |
Total metals | <20ppm | |
Arsenic | <3ppm | |
Plumbous | <2ppm | |
The bacterium number that always falls | <2600Cfu/g | |
Mould | <400Cfu/g | |
Intestinal bacteria | MPN/100g
* | |
*: be illustrated in the 100 gram gelling gums and do not detect intestinal bacteria.
Embodiment 3
Gellan gum without organic solvent preparation technology No.2
Repeat embodiment 1, it is following that difference is to boil glue step condition: homogenate mixture pH regulator to pH6-8, and is heated to 70-85 ℃, boiled glue 5-15 minute, thereby obtain to boil the glue mixture.
The result has obtained gelling gum No.2 equally.
By embodiment 2 same way as gelling gum No.2 is detected, the result shows that its characteristic and gelling gum No.1 are basic identical, and wherein the ethanol residual quantity can not detect (0ppm), and gel-strength is 1070g/cm
2
Embodiment 4
Gellan gum without organic solvent preparation technology No.3-5
Repeat embodiment 1, difference is that the flocculation step condition is following: add the hydrochloric acid of 1% concentration, make that pH2.0, pH are 3.0 or pH4.0.
The result has obtained gelling gum No.3-5 equally.
By embodiment 2 same way as gelling gum No.3-5 is detected, the result shows that its characteristic and gelling gum No.1 are basic identical, and wherein the ethanol residual quantity can not detect (0ppm), and gel-strength is 1050-1100g/cm
2Between.
Embodiment 5
Gellan gum without organic solvent preparation technology No.6-7
Repeat embodiment 1, difference is that the filtration step condition is following: do not add the flocculating aids perlite, add 2% zeyssatite as flocculating aids.
The result has obtained gelling gum No.6-7 equally.
By embodiment 2 same way as gelling gum No.6-7 is detected; The result shows; The filter effect when though the filter effect of interpolation flocculating aids is superior to not adding flocculating aids; But the gelling gum characteristic and the gelling gum No.1 that obtain are basic identical, and wherein the ethanol residual quantity can not detect (0ppm), and gel-strength is 1050-1100g/cm
2Between.
Embodiment 6
The gelling gum goods
With the gelling gum that makes among the embodiment 1, add in the raw material by ordinary method, making gelling gum content is 1-20wt% beverage product and jelly goods.
All documents in that the present invention mentions are all quoted as a reference in this application, are just quoted such as a reference separately as each piece document.Should be understood that in addition after having read above-mentioned teachings of the present invention, those skilled in the art can do various changes or modification to the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.