CN104229851B - The preparation method of a kind of eggshell ultramicro active calcium carbonate - Google Patents
The preparation method of a kind of eggshell ultramicro active calcium carbonate Download PDFInfo
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- CN104229851B CN104229851B CN201410448258.8A CN201410448258A CN104229851B CN 104229851 B CN104229851 B CN 104229851B CN 201410448258 A CN201410448258 A CN 201410448258A CN 104229851 B CN104229851 B CN 104229851B
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- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
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Abstract
The present invention discloses the preparation method of a kind of eggshell ultramicro active calcium carbonate, it comprises the following steps: the eggshell after shell membrane sepn is crushed to micro-powder that granularity is 0.1��10 ��m, then the ratio that micro-for eggshell powder and water and polysaccharide are 100: 50��200: 0.5��3 by weight is mixed, fully disperse postlyophilization, lyophilized powder reacts 3��5 days at 50��100 DEG C, remove unreacted polysaccharide with distillation washing after having reacted, dry, obtain eggshell ultramicro active calcium carbonate. The present invention adopts edible polysaccharide as Hydrophilic modification agent, ultrafine calcium carbonate is activated, owing to polysaccharide has extremely strong water-absorbent, therefore make the ultrafine calcium carbonate after activating effectively to be scattered in aqueous phase solution, food, cosmetics of everyday use, medicine and other fields can be widely used in.
Description
Technical field
The present invention relates to the preparation method of activated Calcium carbonate, the preparation method of especially a kind of eggshell ultramicro active calcium carbonate.
Background technology
Eggshell after birds, beasts and eggs are edible not only rotten expense of resource after being abandoned as domestic refuse, and contaminate environment. Eggshell main component is calcium carbonate, and containing a small amount of organic matter, how to make full use of eggshell Calcium Carbonate resource, play its maximum economic worth, be the difficult problem faced at present. Ultramicro active calcium carbonate is a kind of high value added product, as the high-grade weighting agent of high filler loading capacity, has been widely used in the industries such as rubber, high grade paint, tire, sole. The preparation method of current ultramicro active calcium carbonate is mainly chemical synthesis, ore generates unslaked lime through calcining, lead to after hot water digests and carry out carbonization into carbonic acid gas, when the carbonization of strict control, generate the calcium carbonate granule that granularity is suitable, with activator, its surface is carried out moditied processing again, thus obtain ultramicro active calcium carbonate. The method complex process, highly energy-consuming, equipment requirements height, condition are wayward.
As biological calcium carbonate resource, eggshell contains a small amount of organic matter (about 2%), can be the functional group that its modifying and decorating provides more polymorphic type, and this makes the ultramicro active calcium carbonate prepared by eggshell may possess some new characteristics. Simultaneously, eggshell calcium carbonate has the features such as natural, safe, there is range of application more widely, as as food ingredient or foodstuff additive, not only can be used for improving Food Quality or characteristic, also can improve the content of calcium in food simultaneously, make it to become nourishing reinforced food or functional food, it is to increase added value. But eggshell is prepared ultramicro active calcium carbonate and also be there are some difficult problems, such as the selection etc. of shell membrane sepn, Carbonate Particle Size control, modifier, the solution that the present invention is these problems improves a kind of perfect technical scheme.
Summary of the invention
The present invention is directed to some problems in current ultramicro active calcium carbonate Synthesis and applications, make full use of eggshell biological calcium carbonate resource, prepare ultrafine calcium carbonate, and select modifier it to be activated, while making full use of eggshell resource, expand the purposes of ultramicro active calcium carbonate.
For achieving the above object, present invention employs following technical scheme:
The preparation method of a kind of eggshell ultramicro active calcium carbonate, it comprises the following steps: the eggshell after shell membrane sepn is crushed to micro-powder that granularity is 0.1��10 ��m, then the ratio that micro-for eggshell powder and water and polysaccharide are 100: 50��200: 0.5��3 by weight is mixed, fully disperse postlyophilization, lyophilized powder reacts 3��5 days at 50��100 DEG C, removes unreacted polysaccharide with distillation washing after having reacted, and dries, obtain eggshell ultramicro active calcium carbonate
Described polysaccharide be selected from pectin, pecticoligosaccharide, chitosan, oligochitosan, dextran, konjac glucomanna, starch, dextrin one or more.
Preferably, the weight ratio of the micro-powder of described eggshell and water and polysaccharide is 100: 100: 1.5.
Preferably, by the eggshell micronizing after shell membrane sepn to granularity it is micro-powder of 1��3 ��m.
Preferred further, the method of described shell membrane sepn comprises the following steps: cleaned by discarded eggshell, crushed after being dried becomes meal, in eggshell meal, add the polymer colloidal solution that 2��5 times of concentration are 0.1��5% by weight, ultrasonic agitation 5��15 minutes, filter, precipitation with water wash once, dry, to obtain final product
Described polymer colloid be selected from polyoxyethylene glycol, pectin, carboxymethyl cellulose, dextran one or more.
The invention has the beneficial effects as follows:
(1) use edible polysaccharide as Hydrophilic modification agent, ultrafine calcium carbonate is activated, start the Application Areas that activated Calcium carbonate is new. Traditional active carbon acid calcium is applied in rubber, plastics mainly as weighting agent, for improving its dispersion in organic materials, the oil loving group of many employings carries out modifying activation, such as oleic acid, stearic acid etc., these modification groups are reacted by the hydroxyl of carboxyl and calcium carbonate granule surface, thus are attached to calcium carbonate granule surface. Containing a small amount of organic matter (albumen, polypeptide etc. in the ultrafine calcium carbonate prepared by eggshell in the present invention, content is about 2%), the activation that carboxyl in these organic molecules, amino are ultrafine calcium carbonate provides dissimilar decorating site, in a heated condition, polysaccharide can with the protein molecule generation Maillard reaction in eggshell, thus be fixed on calcium carbonate granule surface. Above-mentioned modifier molecule safety non-toxic, can eat, there is extremely strong water-absorbent simultaneously, therefore make the ultrafine calcium carbonate after activating effectively to be scattered in aqueous phase solution, such as, add in egg-white powder, the hydrogel intensity enhancing 45% that egg-white powder is formed can be made. Eggshell ultramicro active calcium carbonate prepared by the present invention can be widely used in food, cosmetics of everyday use, medicine and other fields, has filled up the blank of traditional active carbon acid calcium in above-mentioned Application Areas.
(2) improve the efficiency of shell membrane sepn, improve separating effect, saved and used water. Under ultrasonic effect, eggshell accelerates to be separated with egg shell membrane; Meanwhile, polymer colloidal solution replaces the aqueous solution, adds soltion viscosity so that departs from the egg shell membrane chip after eggshell and suspends better in the solution, in stratification process, facilitates the layering of precipitation with solution, avoids the sedimentation of egg shell membrane chip. In addition, a small amount of polymer colloid remained in eggshell powder after separation, evenly adheres to calcium carbonate granule surface in mechanical milling process, for follow-up activation provides more surface charge, makes the efficiency of activation higher more thorough. The shell membrane separating method of the present invention is compared with traditional aqueous solution partition method, the shell membrane sepn time shortened to 5 minutes by 20 minutes, when in guarantee eggshell powder, the residual rate of egg shell membrane is 0.2��0.3%, the eggshell rate of recovery reaches 96.5%, improve about 3 percentage points, in addition, the eggshell water of separation phase homogenous quantities is only 1st/1st to six/3rd of traditional method, and effect is remarkable.
Accompanying drawing explanation
Fig. 1 is the degree of activation of the ultramicro active calcium carbonate sample prepared by embodiment 1��3.
Fig. 2 is microscopic appearance and the structure of ultramicro active calcium carbonate sample.
Fig. 3 is that various different ultrafine calcium carbonate is on the impact of egg white gellifying property.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1
(1) shell membrane sepn. Discarded eggshell is cleaned, and crushed after being dried becomes meal, takes eggshell meal, and preparation weight concentration is the polyglycol solution of 5%, adds the polyglycol solution of 2 times by weight, ultrasonic agitation 15 minutes in eggshell meal, filters, precipitation with water wash once, dry.
(2) micronizing. Adopt ball milled to carry out micronizing in the eggshell powder after the shell membrane sepn obtained in step 1, taking agate pearl as grinding element, eggshell powder is ground to micro-powder that granularity is 3 ��m.
(3) activation is modified. It it is the micro-powder of eggshell according to weight ratio: water: the ratio mixing of oligochitosan=100:100:1.5, fully disperseing postlyophilization, lyophilized powder reacts 3 days at 100 DEG C, removes the oligochitosan not combined after having reacted with distillation washing, dry, obtain eggshell ultramicro active calcium carbonate.
Embodiment 2
(1) shell membrane sepn. Discarded eggshell is cleaned, and crushed after being dried becomes meal, takes eggshell meal, and preparation weight concentration is the pectin solution of 0.5%, adds the pectin solution of 5 times by weight, ultrasonic agitation 5 minutes in eggshell meal, filters, precipitation with water wash once, dry.
(2) micronizing. Adopt ball milled to carry out micronizing in the eggshell powder after the shell membrane sepn obtained in step 1, taking agate pearl as grinding element, eggshell powder is ground to micro-powder that granularity is 1 ��m.
(3) activation is modified. It it is the micro-powder of eggshell according to weight ratio: water: the ratio mixing of pectin=100:50:0.5, fully disperseing postlyophilization, lyophilized powder reacts 4 days at 70 DEG C, removes the pectin not combined after having reacted with distillation washing, dry, obtain eggshell ultramicro active calcium carbonate.
Embodiment 3
(1) shell membrane sepn. Discarded eggshell is cleaned, and crushed after being dried becomes meal, takes eggshell meal, preparation weight concentration is the cmc soln of 0.1%, adds the cmc soln of 4 times by weight, ultrasonic agitation 8 minutes in eggshell meal, filter, precipitation with water wash once, dry.
(2) micronizing. Eggshell powder after the shell membrane sepn obtained in step 1 is crushed to micro-powder that granularity is 10 ��m.
(3) activation is modified. Being the micro-powder of eggshell according to weight ratio: water: the ratio mixing of dextrin=100:200:3, fully disperse postlyophilization, lyophilized powder react 5 days at 50 DEG C, and with distilling the pectin washed and go not combine after react, oven dry, obtains eggshell ultramicro active calcium carbonate.
The qualification of embodiment 4 eggshell ultramicro active calcium carbonate
(1) mensuration of degree of activation
Protein in eggshell calcium carbonate granule has amino, and polyose modification molecule is combined with it by Maillard reaction, therefore measures the free amine group content on calcium carbonate granule surface before and after activation, can assess degree of activation. Free amine group assay adopts o-phthalaldehyde(OPA) (OPA) method.
The preparation of OPA reagent: take 40.0mgOPA and be dissolved in 1.0mL deionized water, add sodium laurylsulfonate (SDS) solution (20% successively, w/w) 2.5mL, borax soln (0.1mol/L) 25.0mL, beta-mercaptoethanol 100uL, is finally settled to 50mL with deionized water.
Sample determination: getting the eggshell ultrafine calcium carbonate sample 0.25g before and after activation respectively, the OPA reagent of preparation fresh in 5mL mixes, is placed in water-bath concussion reaction 2min, the quick centrifugal 1min of 35 DEG C, gets supernatant liquor and measure its light absorption value at 340nm place. Using Methionin as standard substance drawing standard curve, calculate free amine group content and degree of activation.
As shown in Figure 1, the degree of activation of embodiment 1��3 gained sample, all more than 80%, shows that polysaccharide has been combined in calcium carbonate granule surface effectively to result.
(2) microscopic appearance is observed
Using JSM-6390LV scanning electronic microscope, shape looks and microtexture to obtained sample are observed. Sample spray gold, thickness about 10nm, acceleration voltage is 20KV, and bundle spot is 30, and operating distance is 17mm. Magnification is that 15000 �� lower observation is taken pictures.
Result is as shown in Figure 2, compared with (Fig. 2 A) before activation, after activation, the eggshell calcium carbonate granule particle diameter of (Fig. 2 B��D is followed successively by the sample obtained by embodiment 1��3) obviously increases, surface turns into smooth from loosening simultaneously, shows that the modifiers such as polysaccharide have been fixed on calcium carbonate granule surface effectively.
Embodiment 5 effect comparative example
Eggshell ultramicro active calcium carbonate prepared by the present invention is added in egg-white powder, investigates it to the impact (A group) of egg white gelation. With super micro-eggshell calcium carbonate (B group) of not activating and commercially available ultramicro active calcium carbonate (sad modification, C group) for experiment contrast group, the pure egg-white powder not adding calcium carbonate is blank group (CK).
The preparation of egg white gel:
Being mixed with the ratio of 9:1:90 with calcium carbonate, water by egg-white powder, in 80 DEG C of water-baths 30 minutes after fully stirring, ice-water bath 20 minutes immediately after taking-up, measure the intensity of the gel formed.
Gel-strength measures:
By the TPA pattern of Texture instrument, selecting the probe of P0.5, measure and sample is carried out the stress time curve in compression process, before surveying, speed is 5mm/s, test speed is 2mm/s, and rear flank speed is 5mm/s, and extruding distance is 10mm, trigger force is 5g, and every sample replication 3 times, averages; Calibration weight is 1000g, and calibrated altitude is 5cm, and reply speed is 10mm/s.
Measurement result:
Experimental result is as shown in Figure 3, the egg white gel-strength that A group is formed is compared with commercially available lipophilicity ultramicro active calcium carbonate group (C group) with blank (CK), non-active set (B group), improve 45%, 32% and 69% respectively, show that the eggshell ultramicro active calcium carbonate prepared by the present invention can be scattered in aqueous phase solution effectively, and the gellifying property that solution is formed is had certain promoter action, obtain good effect.
Claims (4)
1. the preparation method of an eggshell ultramicro active calcium carbonate, it is characterized in that comprising the following steps: the eggshell after shell membrane sepn is crushed to micro-powder that granularity is 0.1��10 ��m, then the ratio that micro-for eggshell powder and water and polysaccharide are 100: 50��200: 0.5��3 by weight is mixed, fully disperse postlyophilization, lyophilized powder reacts 3��5 days at 50��100 DEG C, removes unreacted polysaccharide with distillation washing after having reacted, and dries, obtain eggshell ultramicro active calcium carbonate
Described polysaccharide be selected from pectin, chitosan, oligochitosan, dextran, konjac glucomanna, starch, dextrin one or more.
2. the preparation method of eggshell ultramicro active calcium carbonate as claimed in claim 1, it is characterised in that: the weight ratio of the micro-powder of described eggshell and water and polysaccharide is 100: 100: 1.5.
3. the preparation method of eggshell ultramicro active calcium carbonate as claimed in claim 1, it is characterised in that: it is micro-powder of 1��3 ��m by the eggshell micronizing after shell membrane sepn to granularity.
4. such as the preparation method of the eggshell ultramicro active calcium carbonate of claims 1 to 3 as described in any one, it is characterized in that: the method for described shell membrane sepn comprises the following steps: cleaned by discarded eggshell, crushed after being dried becomes meal, in eggshell meal, add the polymer colloidal solution that 2��5 times of concentration are 0.1��5% by weight, ultrasonic agitation 5��15 minutes, filter, precipitation with water wash once, dry, to obtain final product
Described polymer colloid be selected from polyoxyethylene glycol, pectin, carboxymethyl cellulose, dextran one or more.
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| CN105962315A (en) * | 2016-05-10 | 2016-09-28 | 孙洋平 | Edible calcium carbonate |
| US11434347B2 (en) * | 2017-04-05 | 2022-09-06 | Alterwaste Ltd | Processing method and products produced thereby |
| CN108384550B (en) * | 2018-01-22 | 2020-11-03 | 南京林业大学 | Preparation method of soil conditioner |
| CN113040285A (en) * | 2021-04-23 | 2021-06-29 | 青岛中晨康地农牧发展有限公司 | Antibiotic-free fermented suckling pig feed and storage process thereof |
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| EP1165441A1 (en) * | 1999-03-31 | 2002-01-02 | Minerals Technologies Inc. | Process for the preparation of discrete particles of calcium carbonate |
| CN101967000B (en) * | 2010-07-14 | 2013-04-24 | 山东海泽纳米材料有限公司 | Method for preparing high-solid-content and low-viscosity suspended nano calcium carbonate slurry |
| KR101243610B1 (en) * | 2011-03-25 | 2013-03-14 | (주)에센트론 | Manufacturing method of precipitated calcium carbonate using egg shell |
| CN103253692A (en) * | 2013-05-03 | 2013-08-21 | 广西大学 | Organic matter modified calcium carbonate and production method thereof |
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