CN102787519B - Method for preparing soluble kelp cellulose - Google Patents

Method for preparing soluble kelp cellulose Download PDF

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Publication number
CN102787519B
CN102787519B CN201210312647.9A CN201210312647A CN102787519B CN 102787519 B CN102787519 B CN 102787519B CN 201210312647 A CN201210312647 A CN 201210312647A CN 102787519 B CN102787519 B CN 102787519B
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kelp
fiber element
solubility
add
preparation
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CN102787519A (en
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缪锦来
李友海
李健
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QINGDAO HENGSHENG BIOLOGICAL PHARMACEUTICAL TECHNOLOGY DEVELOPMENT Co Ltd
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QINGDAO HENGSHENG BIOLOGICAL PHARMACEUTICAL TECHNOLOGY DEVELOPMENT Co Ltd
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Abstract

The invention discloses a method for preparing soluble kelp cellulose. The method includes the steps: firstly, preparing kelp dietary fibers from kelp residues by means of flocculation, decalcifying, bleaching, washing and the like; secondly, performing steam explosion to obtain insoluble kelp cellulose, then adding low-temperature cellulase into the insoluble kelp cellulose, and performing enzymolysis in water bath at the temperature of 25 DEG C-35 DEG C to obtain the soluble kelp cellulose with the content of 90.14+/-1.09wt% and the yield of 50-60%. When the soluble kelp cellulose is prepared, the low-temperature cellulase is used, enzymolysis is performed at the normal temperature, enzymolysis conditions are moderate, only macromolecules are sensitive to the cellulose, and macromolecules in kelp are easily decomposed while micromolecules are relatively stable and not easily further decomposed, so that the obtained soluble kelp cellulose is uniform in molecular weight and high in yield, cellulose content, water-holding capacity and expansibility. Moreover, the enzymolysis temperature is low, so that production energy consumption and operability are reduced.

Description

A kind of preparation method of solubility Kelp fiber element
Technical field
The present invention relates to the reutilization technology field of sea-tangle trade waste, be specifically related to a kind of preparation of solubility Kelp fiber element.
Background technology
Sea-tangle is a kind of large-scale brown alga, China coast all extensively distribute, but mainly originate in China Shandong and Liaoning etc. economize coastal.Output and the scale of China's sea-tangle plantation all occupy first place in the world, and within 2009, China's sea-tangle Dried product reaches 6.0 × 10P 5Pt, accounts for the more than 50% of Gross World Product.Sea-tangle contains abundant algin, cellulose, hemicellulose, vitamin and mineral matter etc., and except for directly edible, sea-tangle is one of main raw material of brown alga industry.In China, sea-tangle processing has formed the industrial system taking algin, sweet mellow wine, iodine as major product at present.Due to Market competition, because added value of product is low, production technology water consumption large, it is large, seriously polluted to consume energy, cause production cost high in recent years simultaneously.On the other hand, in sea-tangle industrial processes, produce a large amount of sea-tangle trade wastes.The industrial utilization rate of sea-tangle only approximately 30%, also has more 50% composition to become discarded object.The discarded object that is rich in a large number organic and nutritive salt is disposed in water body, become the latency that eutrophication and red tide bring out, bring to sea fishery economy and ecology and destroy and impact, not only wasted a large amount of natural resourcess, but also brought a series of problem of environmental pollutions.The main component of these trade wastes is celluloses.For a long time, sea-tangle trade waste fails to be utilized effectively, and not only causes the waste of resource, also environment is formed to huge pollution simultaneously.Select the kelp processing waste taking cellulose as main component to prepare Kelp fiber element, not only can realize the twice laid of sea-tangle industrial wood waste, solve problem of environmental pollution, can also realize the efficient utilization of renewable resource.At present, although the extraction of Kelp fiber element is had to known extractive technique in sea-tangle and kelp residue, but generally use cellulase or protease to carry out above high temperature enzymolysis at 50 DEG C, when high temperature enzymolysis, in sea-tangle, do not need the little molecule of enzymolysis can be degraded because enzymatic hydrolysis condition is fierce yet, therefore cause that in extract, Kelp fiber cellulose content is low, extract yield is low, and the molecular weight heterogeneity of Kelp fiber element, affects Kelp fiber quality amount.
Along with improving constantly of living standards of the people, meticulous food variety increases gradually, meat and vegetarian diet disequilibrium gradually, the intake of dietary fiber reduces just increasingly, the ciril disease (obesity, high blood pressure, diabetes etc.) that meals imbalance causes occurred, this situation is particularly serious in the relatively advanced coastal cities of economy.
Because kelp dietary fiber has very strong retentiveness, be 249.33% left and right through its retention ability of measuring.After its water suction, intestinal contents volume is increased, the deliquescing that fluffs of defecating, can be more smooth and easy more laborsaving during by enteron aisle.Meanwhile, kelp dietary fiber can stimulate contraction and the wriggling of enteron aisle as foreign body in intestine, accelerates stool excretion, plays effect for the treatment of constipation.Dietary fiber affiliated food additives associating evaluation committee of food and agricultural organization of united state and the World Health Organization is regarded as food additives, uses in a large number, as reducing blood sugar, improving gastrointestinal function use in (health care) food industry is produced.
Though Kelp fiber element is made up of glucose, but human body can not digest β type glucose, its caloric value is zero, so Kelp fiber element only moves together with food in human body, not by human body is absorbed, it can help digest and reach the object that reduces or prevent disease of digestive system.
Summary of the invention
Technical problem to be solved by this invention is: for the deficiency of prior art existence, provide the preparation method of the solubility Kelp fiber element that a kind of Kelp fiber cellulose content is high, yield is high, cellulosic molecule weight range is concentrated.
For solving the problems of the technologies described above, technical scheme of the present invention is:
The preparation method of solubility Kelp fiber element, comprises the following steps:
(1) extraction of kelp dietary fiber: add calcium chloride solution until kelp residue is all flocculated in the muddy glue of kelp residue, leave standstill and collect flocculate, described flocculate is added to water dilution acid adding decalcification, then centrifugal or filtration is collected, add appropriate sodium carbonate liquor to neutral filtrate, collection is filtered dry thing, add sodium hypochlorite bleaching that in solution, mass concentration is 8~12% more than 24 hours, suction filtration, washing, then use suction filtration after the alcohol flushing of 70~80wt%, 45~55 DEG C of vacuumizes, pulverize and obtain kelp dietary fiber.
(2) preparation of solubility Kelp fiber element: the kelp dietary fiber that step (1) is obtained, add the NaOH solution of 1~3wt% with the mass ratio of 1:15~30, more than soak at room temperature 48h, be washed to neutrality, add water, at >=121 DEG C, under the condition of >=0.14MPa, carry out steam blasting 20~30min, obtain insoluble Kelp fiber element, then in insoluble Kelp fiber element suspension, add low-temperature cellulase, in the water-bath of 25 DEG C~35 DEG C more than enzymolysis 24h, drying, it is 90.14 ± 1.09wt% that pulverizing obtains content, yield is 50~60% solubility Kelp fiber element.
Preferably, in step (1), in described when flocculation, adds the calcium chloride solution of 8~12wt% until kelp residue is all flocculated, and standing 0.5h~1h, collects flocculate.
Preferably, in step (1), when described decalcification, in described flocculate, add distilled water by the weight ratio of 1:8~10, and add the HCl of 0.1~0.2mol/L, 40~50 DEG C add thermal agitation 0.5h more than, then centrifugal or filter collect.
Improve as one, described decalcification step repeats twice.
Improve as one, in step (2), described low-temperature cellulase is the gelled pill of immobilization low-temperature cellulase.Described immobilization low-temperature cellulase is low-temperature cellulase to be fixed on the carriers such as sodium alginate, makes the gelled pill that can reuse.
Preferably, when described enzymolysis, the addition of low-temperature cellulase is 20~30U/g.
Preferably, in step (2), when described steam blasting, add water to carry out again steam blasting with the ratio of 1:20~30.
Preferably, in step (2), described dry employing vacuum freeze drying, described pulverizing adopts ball mill grinding.
The present invention investigates and analyzes drying process
Investigate respectively electric heating forced air drying, vacuumize, the impact of vacuum freeze drying on solubility Kelp fiber element product whiteness and moisture.Result is as shown in table 1.Can be found out by experimental result, the solubility Kelp fiber element of preparing under vacuum freeze drying condition has better whiteness, and lower moisture is best drying process.
The white degree of solubility Kelp fiber and moisture result under table 1 different dry drying process
Investigate item Whiteness Moisture
Electric heating forced air drying 79.9% 2.61%
Vacuumize 80.7% 2.45%
Vacuum freeze drying 89.1% 2.26%
Disintegrating process is investigated and is analyzed
Disintegrating process on solubility Kelp fiber element product fineness to affect result as shown in table 2.Can be found out by experimental result, ball mill grinding can obtain thinner solubility Kelp fiber element.
The do not sieve amount of solubility Kelp fiber element of table 2
Owing to having adopted technique scheme, the invention has the beneficial effects as follows:
1, the present invention prepares insoluble Kelp fiber element taking kelp residue as raw material, prepare solubility Kelp fiber element through further enzymolysis, in the time of preparation solubility Kelp fiber element, first by kelp dietary fiber at >=121 DEG C, under the condition of >=0.14MPa, carry out steam blasting 20~30min, obtain insoluble Kelp fiber element, then in insoluble Kelp fiber element suspension, add low-temperature cellulase, in the water-bath of 25 DEG C~35 DEG C more than enzymolysis 24h, then drying, it is 90.14 ± 1.09wt% that pulverizing obtains content, yield is 50~60% solubility Kelp fiber element, the present invention uses low-temperature cellulase in the time of enzymolysis, enzymolysis under normal temperature condition, because hydrolysis temperature is low, enzymatic hydrolysis condition is gentleer, only large molecule is to cellulase sensitivity, large molecule in Kelp fiber element is easily decomposed, small molecular phase is to more stable, be difficult for being further decomposed, the molecular weight of the solubility Kelp fiber element therefore obtaining is compared with homogeneous, yield is high, content of cellulose is high, the content of solubility Kelp fiber element of the present invention is 90.14 ± 1.09wt%, and retention ability is 260.33 ± 1.15%, and expansive force is 34.23 ± 0.31ml/g, and because hydrolysis temperature of the present invention is low, has reduced energy consumption and operability.
2, the gelled pill that the low-temperature cellulase that the present invention uses in the time of enzymolysis is immobilization low-temperature cellulase, described immobilization low-temperature cellulase is low-temperature cellulase to be fixed on the carriers such as sodium alginate, make the gelled pill that can reuse, therefore low-temperature cellulase can reuse, and has reduced production cost.
3, the present invention adopts vacuum freeze drying in the time that solubility Kelp fiber element is dried, pulverize and adopt ball mill grinding, confirm through experiment, adopting moisture content in the Kelp fiber element after vacuum freeze drying is 2.26wt%, whiteness 89.1%, compare other drying modes, there is higher whiteness and lower moisture content.
4, the solubility Kelp fiber element molecular weight of preparing due to the present invention is compared with homogeneous, and content of cellulose is high, and retention ability and expansive force are high, therefore,, in food additives, not only can reduce blood sugar but also to improving gastrointestinal function, improve constipation and there is better effect in food industry applications.
Detailed description of the invention
Further set forth the present invention below in conjunction with specific embodiment.
Embodiment 1
The extraction of kelp dietary fiber: add calcium chloride solution until kelp residue is all flocculated in the muddy glue of kelp residue, leave standstill and collect flocculate, in described flocculate, add distilled water, and add hydrochloric acid solution decalcification, then centrifugal collection, repeat above decalcification step once, add appropriate sodium carbonate liquor to neutral filtrate, collection is filtered dry thing, add the sodium hypochlorite bleaching 24 hours that in solution, mass concentration is 10%, suction filtration, washing, then use suction filtration after the alcohol flushing of 75wt%, 50 DEG C of vacuum freeze dryings, pulverize and obtain kelp dietary fiber.
The preparation of solubility Kelp fiber element: the kelp dietary fiber that step (1) is obtained, add the NaOH solution of 2wt% with the mass ratio of 1:20, soak at room temperature 48h, be washed to neutrality, ratio with 1:20 adds water, at 121 DEG C, under the condition of 0.14MPa, carry out steam blasting 20min, obtain insoluble Kelp fiber element, then in insoluble Kelp fiber element suspension, add low-temperature cellulase, the addition of low-temperature cellulase is 20U/g, enzymolysis 24h in the water-bath of 30 DEG C, through vacuum freeze drying, it is 91.14wt% that ball mill grinding obtains content, yield is 58%, retention ability is 261.43%, expansive force is the solubility Kelp fiber element of 34.43ml/g.
Embodiment 2
The extraction of kelp dietary fiber: to add in the muddy glue of kelp residue 8wt% calcium chloride solution until kelp residue all flocculate, leave standstill 1h, collect flocculate, in described flocculate, add distilled water by the weight ratio of 1:8, and add the HCl of 0.1mol/L, add thermal agitation 0.6h at 40 DEG C, then centrifugal collection, add appropriate sodium carbonate liquor to neutral filtrate, collection is filtered dry thing, add the sodium hypochlorite bleaching 24 hours that in solution, mass concentration is 8%, suction filtration, washing, then use suction filtration after the alcohol flushing of 70wt%, 45 DEG C of vacuumizes, pulverizing obtains kelp dietary fiber.
The preparation of solubility Kelp fiber element: the kelp dietary fiber that step (1) is obtained, add the NaOH solution of 1wt% with the mass ratio of 1:15, soak at room temperature 48h is washed to neutrality above, ratio with 1:20 adds water, at 121 DEG C, under the condition of 0.14MPa, carry out steam blasting 20min, obtain insoluble Kelp fiber element, then in insoluble Kelp fiber element suspension, add the gelled pill that low-temperature cellulase is fixed to the immobilization low-temperature cellulase of making on the carriers such as sodium alginate, the addition of low-temperature cellulase is 25U/g, enzymolysis 24h in the water-bath of 25 DEG C DEG C, through vacuum freeze drying, it is 90.85wt% that ball mill grinding obtains content, yield is 55% solubility Kelp fiber element.
Embodiment 3
The extraction of kelp dietary fiber: to add in the muddy glue of kelp residue 12wt% calcium chloride solution until kelp residue all flocculate, leave standstill 0.5h, collect flocculate, in described flocculate, add distilled water by the weight ratio of 1:10, and add the HCl of 0.2mol/L, add thermal agitation 0.5h at 50 DEG C, then filter and collect, repeat above decalcification step once, add appropriate sodium carbonate liquor to neutral filtrate, collection is filtered dry thing, add the sodium hypochlorite bleaching 24 hours that in solution, mass concentration is 12%, suction filtration, washing, then use suction filtration after the alcohol flushing of 80wt%, 55 DEG C of vacuumizes, pulverizing obtains kelp dietary fiber.
The preparation of solubility Kelp fiber element: the kelp dietary fiber that step (1) is obtained, add the NaOH solution of 3wt% with the mass ratio of 1:30, soak at room temperature 48h, be washed to neutrality, ratio with 1:30 adds water, at 121 DEG C, under the condition of 0.14MPa, carry out steam blasting 25min, obtain insoluble Kelp fiber element, then in insoluble Kelp fiber element suspension, add the gelled pill that low-temperature cellulase is fixed to the immobilization low-temperature cellulase of making on the carriers such as sodium alginate, the addition of low-temperature cellulase is 20U/g, enzymolysis 24h in the water-bath of 35 DEG C, through vacuum freeze drying, it is 91.09wt% that ball mill grinding obtains content, yield is 56%, retention ability is 261.23%, expansive force is the solubility Kelp fiber element of 34.45ml/g.
Embodiment 4
The extraction of kelp dietary fiber: to add in the muddy glue of kelp residue 10wt% calcium chloride solution until kelp residue all flocculate, leave standstill 0.8h, collect flocculate, in described flocculate, add distilled water by the weight ratio of 1:9, and add the HCl of 0.15mol/L, add thermal agitation 0.8h at 45 DEG C, then centrifugal collection, repeat above decalcification step once, add appropriate sodium carbonate liquor to neutral filtrate, collection is filtered dry thing, add the sodium hypochlorite bleaching 26 hours that in solution, mass concentration is 10%, suction filtration, washing, then use suction filtration after the alcohol flushing of 75wt%, at 48 DEG C of freeze-day with constant temperature, pulverizing obtains kelp dietary fiber.
The preparation of solubility Kelp fiber element: the kelp dietary fiber that step (1) is obtained, add the NaOH solution of 2wt% with the mass ratio of 1:20, soak at room temperature 50h, be washed to neutrality, ratio with 1:25 adds water, at 121 DEG C, under the condition of 0.14MPa, carry out steam blasting 25min, obtain insoluble Kelp fiber element, then in insoluble Kelp fiber element suspension, add and low-temperature cellulase is fixed to the immobilization low-temperature cellulase of making on the carriers such as sodium alginate, the addition of low-temperature cellulase is 22U/g, enzymolysis 25h in the water-bath of 32 DEG C, through vacuum freeze drying, it is 91.05wt% that ball mill grinding obtains content, yield is 58.5%, retention ability is 261.15%, expansive force is the solubility Kelp fiber element of 34.50ml/g.
Kelp fiber cellulose content is measured
Content of cellulose is one of important indicator to cellulose products quality investigation.Content of cellulose is higher, shows that the purity of product is higher.Kelp residue is prepared to extract has been the kelp residue cellulose that obtains high-purity, high-quality, is the preparation of supplying raw materials of preparation kelp residue microcrystalline cellulose.
Get dry product cellulose 0.125g, put in conical flask, 25ml adds water, it (is to get base weight potassium chromate 4.903g that precision adds potassium bichromate solution, add water and make in right amount to dissolve and be diluted to 200ml) 50ml, mix, carefully add sulfuric acid 100ml, be heated to rapidly boil, let cool to room temperature, move in 250ml measuring bottle, be diluted with water to scale, shake up, precision measures 50ml, add 3 of Phen indicator solutions, with iron ammonium sulfate titrating solution (0.1mol/L) titration, and the result of titration is proofreaied and correct with blank test.Every 1ml iron ammonium sulfate titrating solution (0.1mol/L) is equivalent to the cellulose of 0.675mg.
The mensuration of content of ashes
Cellulosic ash content is mainly mineral matter, inorganic salts or other impurity.After the organic matter calcination oxidation in cellulose sample, remaining whiteness is weighed at a certain temperature, obtain ash content weight.The mensuration of content of ashes is with reference to GB/T 742-1989.
The mensuration of retention ability, expansive force
Retention ability and expansive force are the important investigation indexs of cellulose products performance.The retention ability of separate sources fiber and expansive force are also different, have also determined the difference of cellulose performance.
Take 1g kelp residue cellulose powder and put into beaker, add 20 DEG C of water appropriate, shake up, at 20 DEG C of temperature, soak 1h, waterishlogged fiber is poured on filter paper funnel and filtered, after water droplet is dry, the fiber that combines water is all transferred in surface plate and weighed, by the retention ability of formula calculating below.
Take 1g kelp residue cellulose powder and put into graduated cylinder, read the milliliter number of fiber dust, then according to the expansive force of dietary fiber, add 20 DEG C of water appropriate, shake up, at 20 DEG C of temperature, place 24h, read the milliliter number after fibre material imbibition in graduated cylinder, finally the fibre material volume after expanding is deducted to dry fibre material volume, to obtain final product.

Claims (8)

1. a preparation method for solubility Kelp fiber element, is characterized in that comprising the following steps:
(1) extraction of kelp dietary fiber: add calcium chloride solution until kelp residue is all flocculated in the muddy glue of kelp residue, leave standstill and collect flocculate, described flocculate is added to water dilution acid adding decalcification, then centrifugal or filtration is collected, add appropriate sodium carbonate liquor to neutral filtrate, collection is filtered dry thing, adding mass concentration is that 8~12% liquor natrii hypochloritis bleaches more than 24 hours, suction filtration, washing, then use suction filtration after the alcohol flushing of 70~80wt%, 45~55 DEG C of vacuumizes, pulverize and obtain kelp dietary fiber;
(2) preparation of solubility Kelp fiber element: the kelp dietary fiber that step (1) is obtained, add the NaOH solution of 1~3wt% with the mass ratio of 1:15~30, more than soak at room temperature 48h, be washed to neutrality, add water, at >=121 DEG C, under the condition of >=0.14MPa, carry out steam blasting 20~30min, obtain insoluble Kelp fiber element, then in the suspension of insoluble Kelp fiber element, add low-temperature cellulase, in the water-bath of 25 DEG C~35 DEG C more than enzymolysis 24h, drying, it is 90.14 ± 1.09wt% that pulverizing obtains content, yield is 50~60% solubility Kelp fiber element.
2. the preparation method of solubility Kelp fiber element as claimed in claim 1, is characterized in that: in step (1), described when flocculation adds the calcium chloride solution of 8~12wt% until kelp residue is all flocculated, and standing 0.5h~1h, collects flocculate.
3. the preparation method of solubility Kelp fiber element as claimed in claim 1, it is characterized in that: in step (1), when described decalcification, in described flocculate, add distilled water by the weight ratio of 1:8~10, and add the HCl of 0.1~0.2mol/L, 40~50 DEG C add thermal agitation 0.5h more than, then centrifugal or filter collect.
4. the preparation method of solubility Kelp fiber element as claimed in claim 3, is characterized in that: described decalcification step repeats twice.
5. the preparation method of solubility Kelp fiber element as claimed in claim 1, it is characterized in that: in step (2), described low-temperature cellulase is the gelled pill of immobilization low-temperature cellulase, described immobilization low-temperature cellulase is low-temperature cellulase to be fixed on the carriers such as sodium alginate, makes the gelled pill that can reuse.
6. the preparation method of solubility Kelp fiber element as claimed in claim 1, is characterized in that: in step (2), when described enzymolysis, the addition of low-temperature cellulase is 20~30U/g.
7. the preparation method of solubility Kelp fiber element as claimed in claim 1, is characterized in that: in step (2), when described steam blasting, add water to carry out steam blasting with the ratio of 1:20~30 again.
8. the preparation method of solubility Kelp fiber element as claimed in claim 1, is characterized in that: in step (2), and described dry employing vacuum freeze drying, described pulverizing adopts ball mill grinding.
CN201210312647.9A 2012-08-29 2012-08-29 Method for preparing soluble kelp cellulose Expired - Fee Related CN102787519B (en)

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