CN103172761B - Energy-saving and emission-reducing production method of high-quality sodium alginate - Google Patents
Energy-saving and emission-reducing production method of high-quality sodium alginate Download PDFInfo
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- CN103172761B CN103172761B CN201310138593.3A CN201310138593A CN103172761B CN 103172761 B CN103172761 B CN 103172761B CN 201310138593 A CN201310138593 A CN 201310138593A CN 103172761 B CN103172761 B CN 103172761B
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000000661 sodium alginate Substances 0.000 title claims abstract description 55
- 235000010413 sodium alginate Nutrition 0.000 title claims abstract description 55
- 229940005550 sodium alginate Drugs 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000605 extraction Methods 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 239000000648 calcium alginate Substances 0.000 claims description 19
- 235000010410 calcium alginate Nutrition 0.000 claims description 19
- 229960002681 calcium alginate Drugs 0.000 claims description 19
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 239000008399 tap water Substances 0.000 claims description 9
- 235000020679 tap water Nutrition 0.000 claims description 9
- 238000002203 pretreatment Methods 0.000 claims description 8
- 235000010443 alginic acid Nutrition 0.000 claims description 7
- 229920000615 alginic acid Polymers 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000029087 digestion Effects 0.000 claims description 6
- 239000008213 purified water Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 108010059892 Cellulase Proteins 0.000 claims description 5
- 108091005804 Peptidases Proteins 0.000 claims description 5
- 239000004365 Protease Substances 0.000 claims description 5
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims description 5
- 229940106157 cellulase Drugs 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229940072056 alginate Drugs 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000010865 sewage Substances 0.000 abstract description 3
- 241000512259 Ascophyllum nodosum Species 0.000 abstract 1
- 238000004134 energy conservation Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 230000001131 transforming effect Effects 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 229960001126 alginic acid Drugs 0.000 description 3
- 239000000783 alginic acid Substances 0.000 description 3
- 150000004781 alginic acids Chemical class 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 235000021050 feed intake Nutrition 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229940088598 enzyme Drugs 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses an energy-saving and emission-reducing production method of sodium alginate. The method is characterized by transforming non-sodium alginate components which are insoluble in water in kelp to substances which are soluble in the water through a biological pretreatment way and dissolving out the most of the components during the pretreatment process so as to reduce impurities existing in a subsequent sodium alginate extraction process step, be conductive to the extraction process of the sodium alginate and improve the extraction efficiency. Through a way of reusing process water, the consumption of water resources and the emission of sewage are reduced, and energy conservation and emission reduction are realized; and compared with a traditional process, by using the method disclosed by the invention, water can be saved by 90%.
Description
Technical field
The present invention relates to a kind of production method of high-quality sodium alginate energy-saving and emission-reduction, belong to marine alga comprehensive utilization and energy-saving and emission-reduction field.
Background technology
Sea-tangle is a kind of important economical alga.China's sea-tangle aboundresources take sea-tangle as deep processed products such as raw material production sodium alginate, iodine and N.F,USP MANNITOL is the main path that sea-tangle fully utilizes.In recent decades, the extraction process of sodium alginate has achieved very large improvement, and application is also more and more extensive, extracts sodium alginate and mainly adopts following several method: (1) acid cure-acidization from sea-tangle; (2) calcium coagulates-acidization; (3) calcium coagulates-ion exchange method; (4) enzymolysis process; Enzymolysis process technique, belongs to a kind of relatively mild method, can not destroy the structure of polysaccharide, and can large-scale application in suitability for industrialized production, but enzymolysis process extract research start late, research report less, there is no the application of actual scale operation at present.But, the current technology of current industrial abstract sodium alginate is complicated, production cost is higher, product degraded is serious, viscosity and yield general lower, more importantly production technique water loss is very large, often produce one ton of sodium alginate and approximately produce 1000 tons of waste water, the mostly discharge after simply processing of these waste water, not only waste water resource, and it is high to consume energy, severe contamination.
Occupy first place in the world in the sea-tangle output of China, study more effective, low power consuming, clean, energy-saving and emission-reduction and the comprehensive utilization of the sodium alginate of production high-quality cleans technique will have prior economy, society and Significance for Environment.
Summary of the invention
For solving the technical problem existed in prior art, the object of this invention is to provide a kind of production method of high-quality sodium alginate energy-saving and emission-reduction, the method raw material sources are wide, the sodium alginate stay in grade of producing, viscosity are higher, production technique water is compared traditional technology and is reduced 90%, achieves energy-saving and emission-reduction, reduces discharge of wastewater, reduces environmental pollution.
In order to achieve the above object, the technical solution adopted in the present invention is: a kind of production method of high-quality sodium alginate energy-saving and emission-reduction, and its step comprises:
Step one, pre-treatment: pulverized by sea-tangle, regulate solid-to-liquid ratio to be 1: 6 ~ 10, soaking at room temperature 2-3h with fresh tap water, soaked to be placed in hollander and pulled an oar; Then the water-bath of 55 DEG C is placed in, the pH regulating stock liquid is 5 ~ 9, add cellulase and the compound protease enzymolysis 2 ~ 5h of 0.01 ~ 0.5%, enzymolysis process constantly stirs, after enzymolysis terminates, be warmed up to 80-90 DEG C and keep 20min, carry out enzyme-deactivating, then centrifugation, obtains pretreated sea-tangle;
The extraction of step 2, sodium alginate and separation: by obtain in step one 0.5 ~ 2% of pretreated sea-tangle weight ratio 1: 10 ~ 20 sodium carbonate solution, in 55-60 DEG C of water-bath, carry out digestion 1 ~ 3h, filtered by 250 ~ 400 object tulles; Filtered liquid adds the hydrogen peroxide of volume ratio 0.1 ~ 0.3%, and at 50-60 DEG C of decolouring 0.5 ~ 2h, be then warmed up to 90 DEG C of constant temperature 10 ~ 30min, filter with 300 ~ 500 object tulles, filtrate slowly adds the CaCl of volume ratio 20 ~ 50mL 10%
2solution, is converted into calcium alginate and separates out, filter after leaving standstill 0.5 ~ 2h by sodium alginate wherein, with CaCl residual in fresh tap water cleaning calcium alginate fiber
2solution and other impurity; The HCl solution of calcium alginate 5-15M regulates pH to be 3 ~ 5, makes calcium alginate wherein be converted into alginate gel completely, then filters, Lalgine gel adds the purified water of 3 ~ 5 times of volumes, NaOH solution with 10% regulates pH to be 7 ~ 9, then uses alcohol settling, obtains sodium alginate.
Step 3, finished product: sodium alginate step 2 obtained obtains finished product through dehydration, oven dry, pulverizing.
Further, add the ethanol of 95% in sodium alginate step 2 obtained in described step 3, sodium alginate solid is fully dewatered, in 60 DEG C of baking ovens, dry 4h, pulverize and obtain sodium alginate solid articles.
Beneficial effect of the present invention is: carry out pre-treatment through compound bio enzyme process to sea-tangle, make the sea-tangle impurity component entering digestion operation extraction sodium alginate relatively less, be beneficial to the extraction of sodium alginate and the raising of quality: technique is simple simultaneously, compared with existing industrialized producing technology, water saving more than 90%, greatly reduce consumption and the quantity of wastewater effluent of water resources, reduce environmental pollution.
Embodiment
Embodiment 1
A production method for high-quality sodium alginate energy-saving and emission-reduction, its step comprises:
Step one, pre-treatment: by sea-tangle 30g, shred, then 270mL fresh tap water is added, soaking at room temperature 3h, then carries out homogenate with hollander by sea-tangle, is put in the water-bath of 55 DEG C and heats, regulate pH=6.5, then add the cellulase of sea-tangle weight 0.1% and the compound protease of 0.05%, 55 DEG C of enzymolysis 4h, enzymolysis process constantly stirs; After enzymolysis terminates, be warmed up to 90 DEG C and keep 20min, carry out enzyme-deactivating, then centrifugation, obtain pretreated sea-tangle.
The extraction of step 2, sodium alginate and separation: by the pretreated sea-tangle obtained in step one, add the Na of 500gl%
2cO
3solution, stirs, and at 60 DEG C of water-soluble middle digestion 1.5h, filters with 300 order tulles; 4mL H is added in the filtrate of clarification
2o
2, decolour 30min in 50 DEG C of water-baths, is then warmed up to 90 DEG C, and constant temperature 10 ~ 30min removes wherein residual H
2o
2, filter with 400 object tulles more while hot, in filtrate, add the CaCl of 10mL 10%
2solution, sodium alginate is wherein converted into calcium alginate to separate out, filter after leaving standstill 0.5 ~ 2h, calcium alginate fiber precipitation is extracted, add the purified water of 200mL again, then regulate pH=4 with the HCl solution of 5M, calcium alginate is wherein converted into alginic acid precipitation, after ion-exchange 2h, alginic acid is squeezed in, add the purified water of 300mL, regulate pH=8 with the NaOH of 5M, object makes alginic acid be converted into sodium alginate, until all dissolve, then slowly add the ethanol of 2 times of volumes 95%, constantly stir, sodium alginate is separated out and extracts.
Step 3, finished product: the ethanol being added certain volume 95% in the sodium alginate that step 2 is obtained, makes sodium alginate solid fully dewater, in 60 DEG C of baking ovens, dry 4h, obtain sodium alginate solid 5.78g, the extraction yield of sodium alginate is 19.3%.
Embodiment 2
Carry out industrialization production in Better (Yantai) Marine Bio-Technology Co., Ltd., feed intake 10 tons of sea-tangles,
Step one, pre-treatment: pulverized by sea-tangle, regulate solid-to-liquid ratio to be 1: 6, soaking at room temperature 2h with fresh tap water, be then placed in hollander and pull an oar; Then the water-bath of 55 DEG C is placed in, the pH regulating stock liquid is 5 ~ 9, add cellulase and the 0.15% compound protease enzymolysis 5h of 0.25%, enzymolysis process constantly stirs, after enzymolysis terminates, be warmed up to 80-90 DEG C and keep 20min, carry out enzyme-deactivating, then centrifugation, obtains pretreated sea-tangle;
The extraction of step 2, sodium alginate and separation: by less suddenly a kind of pretreated sea-tangle weight ratio 1: 20 obtained 2% Na
2cO
3solution, carries out digestion 3h in 55 DEG C of water-baths, is filtered by 250 object tulles; Filtered liquid adds the H of volume ratio 0.1%
2o
2at 50 DEG C of decolouring 1.5h, then 90 DEG C of constant temperature 20min are warmed up to, filter with 500 object tulles, filter slowly adds the CaCl2 solution of 10% of volume ratio 50: 1 night, sodium alginate is wherein converted into calcium alginate to separate out, filters after leaving standstill 2h, with CaCl residual in fresh tap water cleaning calcium alginate fiber
2solution and other impurity; The HCl solution of calcium alginate 5-15M regulates pH to be 3 ~ 5, makes calcium alginate wherein be converted into alginate gel completely, then filters, Lalgine gel adds the purified water of 5 times of volumes, NaOH solution with 10% regulates pH to be 7 ~ 9, then uses alcohol precipitation, obtains sodium alginate.
Step 3, finished product: sodium alginate step 2 obtained obtains finished product through dehydration, oven dry, pulverizing.
Consume 750 tons of water altogether, obtain sodium alginate 1.95 tons, the yield of sodium alginate reaches 19.5%, and water consumption is less than original 10%.Whole set process is because of pre-treatment, and subsequent disposal is relatively simple, can reduce water loss, realize water saving more than 90%, reduces sewage discharge.
Embodiment 3
Carry out industrialization production in Better (Yantai) Marine Bio-Technology Co., Ltd., feed intake 1 ton of sea-tangle,
Step one, pre-treatment: shredded by sea-tangle, regulate solid-to-liquid ratio to be 1: 10, soaking at room temperature 2.5h with fresh tap water, be then placed in hollander and pull an oar; Then the water-bath of 55 DEG C is placed in, the pH regulating stock liquid is 5 ~ 9, add cellulase and the 0.15% compound protease enzymolysis 5h of 0.25%, enzymolysis process constantly stirs, after enzymolysis terminates, be warmed up to 80-90 DEG C and keep 20min, carry out enzyme-deactivating, then centrifugation, obtains pretreated sea-tangle;
The extraction of step 2, sodium alginate and separation: by the Na of 2% of a kind of for step pretreated sea-tangle weight ratio 1: 20 obtained
2cO
3solution, carries out digestion 3h in 55 DEG C of water-baths.Filtered by 250 object tulles; Filtered liquid adds the H of volume ratio 0.1%
2o
2, at 50 DEG C of decolouring 1.5h, be then warmed up to 90 DEG C of constant temperature 20min, filter with 500 object tulles, filtrate slowly adds the CaCl of 10% of volume ratio 50: 1
2solution, is converted into calcium alginate and separates out, filter after leaving standstill 2h by sodium alginate wherein.With CaCl residual in fresh tap water cleaning calcium alginate fiber
2solution and other impurity; The HCl Ji liquid of calcium alginate 5-15M regulates pH to be 3 ~ 5, makes calcium alginate wherein be converted into alginate gel completely, then filters, Lalgine gel adds the purified water of 5 times of volumes, NaOH solution with 10% regulates pH to be 7 ~ 9, then uses alcohol precipitation, obtains sodium alginate.
Step 3, finished product: sodium alginate step 3 obtained obtains finished product through dehydration, oven dry, pulverizing.
Consume 73 tons of water altogether.Obtain sodium alginate 0.21 ton, the yield of sodium alginate reaches 21%, and water consumption is less than original 10%.Whole set process is because of pre-treatment, and subsequent disposal is relatively simple, can reduce water loss, realize water saving more than 90%, reduces sewage discharge.
Above-described embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; do not departing under the present invention designs spiritual prerequisite; the various distortion that those skilled in the art make technical solution of the present invention and improvement, all should fall in protection domain that claims of the present invention determine.
Claims (2)
1. the production method of high-quality sodium alginate energy-saving and emission-reduction, it is characterized in that, step comprises: step one, pre-treatment: pulverized by sea-tangle, regulates solid-to-liquid ratio to be 1: 6 ~ 10 with fresh tap water, soaking at room temperature 2-3h, has soaked to be placed in hollander and has pulled an oar; Then the water-bath of 55 DEG C is placed in, the pH regulating stock liquid is 5 ~ 9, add cellulase and the compound protease enzymolysis 2 ~ 5h of 0.01 ~ 0.5%, enzymolysis process constantly stirs, after enzymolysis terminates, be warmed up to 80-90 DEG C and keep 20min, carry out enzyme-deactivating, then centrifugation, obtains pretreated sea-tangle; The extraction of step 2, sodium alginate and separation: by obtain in step one 0.5 ~ 2% of pretreated sea-tangle weight ratio 1: 10 ~ 20 sodium carbonate solution, in 55 ~ 60 DEG C of water-bath, carry out digestion 1 ~ 3h, filtered by 250 ~ 400 object tulles; Filtered liquid adds the H of volume ratio 0.1 ~ 0.3%
2o
2, at 50-60 DEG C of decolouring 0.5 ~ 2h, be then warmed up to 90 DEG C of constant temperature 10 ~ 30min, filter with 300 ~ 500 object tulles, filtrate slowly adds the CaC1 of 10% of volume ratio 50: 1
2solution, is converted into calcium alginate and separates out, filter after leaving standstill 0.5 ~ 2h by sodium alginate wherein, with CaC1 residual in fresh tap water cleaning calcium alginate fiber
2solution and other impurity; The HCl solution of calcium alginate 5-15M regulates pH to be 3 ~ 5, calcium alginate is wherein made to be converted into alginate gel completely, then filter, Lalgine gel adds the purified water of 3 ~ 5 times of volumes, NaOH solution with 10% regulates pH to be 7 ~ 9, then use alcohol settling, obtain sodium alginate; Step 3, finished product: sodium alginate step 2 obtained obtains finished product through dehydration, oven dry, pulverizing.
2. according to the production method of the high-quality sodium alginate energy-saving and emission-reduction described in claim 1, it is characterized in that: in sodium alginate step 2 obtained in described step, add the ethanol of 95%, sodium alginate solid is fully dewatered, in 60 DEG C of baking ovens, dry 4h, pulverize and obtain sodium alginate solid articles.
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| CN104341535B (en) * | 2013-08-07 | 2018-09-14 | 青岛博研达工业技术研究所(普通合伙) | A kind of high-valued extracting method of Enteromorpha |
| CN104341537A (en) * | 2013-08-08 | 2015-02-11 | 青岛博研达工业技术研究所(普通合伙) | Method for arsenic removal and extraction of nutrient substances in sargassum fusiforme |
| CN104341233A (en) * | 2013-08-08 | 2015-02-11 | 青岛博研达工业技术研究所(普通合伙) | Method for high-efficiency extraction of nutrient substances in undaria pinnatifida sporophyll |
| CN104341536A (en) * | 2013-08-08 | 2015-02-11 | 青岛博研达工业技术研究所(普通合伙) | Method for high-efficiency extraction of nutrient substances in seaweed |
| CN103665183A (en) * | 2013-12-18 | 2014-03-26 | 青岛福创环境科技有限公司 | Producing method of sodium alginate with ultralow viscosity |
| WO2015128963A1 (en) * | 2014-02-26 | 2015-09-03 | Ｉｇａバイオリサーチ株式会社 | Method for extracting and purifying polysaccharide from organism containing polysaccharides |
| CN104610463B (en) * | 2015-02-04 | 2017-01-11 | 山东洁晶集团股份有限公司 | Method for industrial production of sodium alginate by adopting South Africa great kelps |
| CN104910293A (en) * | 2015-06-24 | 2015-09-16 | 雷邦斯生物技术（北京）有限公司 | Process for producing alginic acid |
| CN105440154A (en) * | 2015-12-09 | 2016-03-30 | 江苏明月海洋科技有限公司 | Method for extracting alginate in brown algae |
| CN107324415A (en) * | 2017-08-01 | 2017-11-07 | 天津中瑞水处理剂有限公司 | A kind of heavy metal-polluted water treatment agent |
| CN109796541A (en) * | 2018-12-27 | 2019-05-24 | 青岛海之林生物科技开发有限公司 | A kind of meat products specific complex alginates cleanly production technique |
| CN110922501A (en) * | 2019-10-24 | 2020-03-27 | 浙江工业大学 | A process for extracting sodium alginate by ultrasonic-assisted-complex enzyme |
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| JP4882088B2 (en) * | 2007-05-21 | 2012-02-22 | 日本オプネクスト株式会社 | Tunable laser device and wavelength control method therefor |
| CN102321191B (en) * | 2011-08-31 | 2013-09-18 | 山东洁晶集团股份有限公司 | Enzymolysis-chemistry combined method for producing sodium alginate |
| CN102718884B (en) * | 2011-11-29 | 2015-09-02 | 青岛聚大洋藻业集团有限公司 | A kind of method adopting fresh Sargassum fusiforme to extract algin |
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