CN113428868B - Method for recycling perlite from carrageenan residues - Google Patents
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- CN113428868B CN113428868B CN202110666238.8A CN202110666238A CN113428868B CN 113428868 B CN113428868 B CN 113428868B CN 202110666238 A CN202110666238 A CN 202110666238A CN 113428868 B CN113428868 B CN 113428868B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
- B01J20/106—Perlite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
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Abstract
The invention discloses a method for recycling perlite from carrageenan residues, which comprises the following steps: adding water into the dried carrageenan residues, precooking for 0.5-3.5 h and then performing filter pressing; adding hydrogen peroxide into the carrageenan residues treated in the previous step, precooking for 0.5-3.5 h and then performing filter pressing; adding hydrochloric acid into the carrageenan residues treated in the previous step, precooking for 0.5-3.5 h, and then performing filter pressing to obtain perlite; and drying the perlite, crushing and sieving for later use. Therefore, the algae residues in the perlite pores are degraded by a chemical method, the perlite-collecting pores are effectively opened, the substances such as residual gum, cellulose and the like in the carrageenan residues are degraded, the pollution of the residues to the environment is reduced, and the recovered perlite can be subjected to carrageenan extraction; the carrageenan extraction residue is reused in the carrageenan extraction process, so that the pollution of the carrageenan solid waste to the environment is reduced, and the recovery and the utilization of perlite in the carrageenan residue are realized.
Description
Technical Field
The invention relates to the technical field of carrageenan treatment, in particular to a method for recycling perlite from carrageenan residues.
Background
Perlite is a substance formed by volcanic eruptions, mainly consisting of aluminium silicates. The perlite used in industry is a white solid powder made from natural perlite ore through high temperature expansion processing. Based on the presence of interconnected drainage-aid pores in the interior between perlite particles, which are widely used in modern industry, often in the form of filter aids, such as sugar, beer, pharmaceuticals, agar and carrageenan; moreover, the perlite filter aid has the characteristics of low production cost, high filtering speed, high transparency, small using amount and the like, so that the perlite filter aid has wider application compared with filter aids such as diatomite and the like.
According to the marketing condition of carrageenan in China, the carrageenan residues generated in the carrageenan extraction process are increased from 3.19 ten thousand tons in 2012 to 6.53 ten thousand tons in 2018, about 70 percent of perlite is contained in the carrageenan residues, and most of the carrageenan residues become stacked solid wastes except a small amount of recycled perlite in a fertilizer plant, so that environmental pollution and resource waste are caused.
Disclosure of Invention
In order to solve the problems, the invention provides a method for recycling perlite from carrageenan residues, which degrades the substances such as residual gum, cellulose and the like in the carrageenan residues by a chemical treatment means, reduces the pollution of the residues to the environment and realizes the recycling of the perlite in the carrageenan residues.
In order to achieve the above objects, embodiments of the present invention in one aspect propose a method for recycling perlite from carrageenan residue, comprising the steps of:
(1) Adding water into the dried carrageenan residues, precooking for 0.5-3.5 h and then performing filter pressing;
(2) Adding hydrogen peroxide into the carrageenan residues treated in the step (1), precooking for 0.5-3.5 h and then carrying out filter pressing;
(3) Adding hydrochloric acid into the carrageenan residues treated in the step (2), pre-boiling for 0.5-3.5 h, and then performing filter pressing to obtain perlite;
(4) And drying the perlite, crushing and sieving for later use.
According to the method for recycling the perlite from the carrageenan residues, disclosed by the embodiment of the invention, the algal residues in the perlite pores are degraded through a chemical method, the perlite collecting pores are effectively opened, the substances such as residual gum, cellulose and the like in the carrageenan residues are degraded, the pollution of the residues to the environment is reduced, the recycled perlite can reach the low-speed perlite standard in the standard JC/T849-2012 perlite filter aid, and the carrageenan can be extracted; therefore, the method reuses the carrageenan extraction residues in the carrageenan extraction process by a reverse recovery technology, thereby reducing the pollution of the carrageenan solid waste to the environment and realizing the recovery and utilization of perlite in the carrageenan residues.
Optionally, in the step (4), the perlite is dried, crushed and sieved, and then added into the carrageenan solution to be filtered, and the filtered carrageenan solution and carrageenan residues are obtained through pressure filtration; salting out, freeze-dehydrating, drying, crushing and sieving the filtered carrageenan solution to obtain a carrageenan sample; and (4) repeating the steps (1) to (4) on the carrageenan residues. Therefore, the permeability of the recycled perlite is larger than 0.3Darcy, the flow rate of the filtrate is larger than 0.3mL/s, the recycling effect is stable, the recycled perlite can reach the standard of slow perlite in the JC/T849-2012 perlite filter aid, and carrageenan extracted by the perlite recycled at different stages meets the standard of GB 1886.169-2016.
Optionally, in the step (1), water is added into 150g of the dried carrageenan residues according to the solid-to-liquid ratio of 1:5-1, namely, 20, and the mixture is pre-boiled in a water bath kettle at 75-100 ℃ for 0.5-3.5 hours and then is subjected to filter pressing by a filter bag plate frame.
Optionally, in the step (2), adding 0.5-3% hydrogen peroxide into the carrageenan residue treated in the step (1) according to a solid-liquid ratio of 1:5-1.
Optionally, in the step (3), adding hydrogen peroxide with a concentration of 0.1 mol/L-0.5 mol/L into the carrageenan residue treated in the step (2) according to a solid-liquid ratio of 1:5-1.
Optionally, in the step (4), the perlite is dried at 105 ℃ to constant weight, and is sieved by a 60-mesh sieve after being crushed.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a graph comparing the effects of the products of example 1 according to the present invention and comparative example 1;
FIG. 2 is a scanning electron microscope image of thermal field emission according to an embodiment of the invention;
figure 3 is a graph of the results of the properties of carrageenan extracted according to the example of the invention.
Detailed Description
The technical solution of the present invention is illustrated by specific examples below. It is to be understood that one or more method steps mentioned in the present invention do not exclude the presence of other method steps before or after the combination step or that other method steps may be inserted between the explicitly mentioned steps; it should also be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
In order to better understand the above technical solutions, exemplary embodiments of the present invention are described in more detail below. While exemplary embodiments of the invention are shown, it should be understood that the invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The test materials adopted by the invention are all common commercial products and can be purchased in the market.
Wherein, the test of the recycled perlite adopts:
step 1: accurately weighing the dried and cooled sample (to the accuracy of 0.01 g) at the room temperature (20 +/-3) DEG C, pouring the sample into a beaker, adding about 50mL of distilled water into the beaker, uniformly stirring the mixture, then pouring the mixture into a 1 'test bottle, washing the beaker and a stirring rod by using the distilled water, and pouring the washed substance into the 1' test bottle.
Step 2: starting a vacuum pump, and controlling the vacuum degree to be (7.6 +/-0.1) kPa [ (775 +/-10) mm water column ] until a filter cake is formed and no filter liquor is generated.
And step 3: and (3) closing the vacuum pump, emptying the 2 'test bottle, adding 50mL-60mL of distilled water along the bottle wall of the 1' test bottle (directly impacting a filter cake is avoided), starting the vacuum pump again, and filtering under the vacuum degree of (7.6 +/-0.1) kPa, wherein the volume of the filtrate is about 40 mL. The corresponding filtration time t and filtrate volume V are accurately recorded.
And 4, repeating the step 3 three times. Immediately after the third completion, the filter cake thickness was accurately determined.
The filtrate flow is calculated according to the formula (1):
in the formula:
q-filtrate flow in milliliters per second (mL/s);
v-volume of filtrate in milliliters (mL) over the filtration time t;
t is the filtration time in seconds(s).
The average of the three test results of the same experiment is taken as the test result.
The permeability is calculated according to the formula (2)
In the formula:
k-permeability, in Darcy;
a-filtration area in square centimeters (cm) 2 )；
Q-filtrate flow in milliliters per second (mL/s);
eta-viscosity coefficient, in centipoise (cP), according to the temperature of the distilled water at the time of the test, found in appendix A of standard JC/T849-2012 perlite filter aids;
h-cake thickness in centimeters (cm);
p-vacuum, in Pa (Pa).
Wherein, the test of carrageenin property adopts:
viscosity: 300mL of carrageenan solution with the mass fraction of 1.5% is prepared, the carrageenan solution is poured into a beaker in equal quantity, the temperature is kept for 30min in a water bath kettle at the temperature of 75-100 ℃, a viscometer uses a s61 rotor, and the viscosity is measured at a certain rotating speed, wherein the unit is mPa.
Transparency: preparing a carrageenan solution with the mass fraction of 1.5%, pouring the carrageenan solution into a cuvette while the carrageenan solution is hot (higher than 85 ℃), scanning the cuvette by using an ultraviolet spectrophotometer between 400 and 800nm, determining the maximum absorption wavelength of 750nm, and determining the light transmittance (T) of a sample at the maximum absorption wavelength.
Gel strength: putting a carrageenan sample sieved by a 80-mesh sieve into a beaker, preparing 300mL of compound glue solution with the mass fraction of 1.5%, pouring the mixture into 3 100mL beakers in equal quantity, cooling, covering a surface dish after gel is formed, placing the beakers in an inverted mode at room temperature for 15h, measuring the gel strength on a gel strength measuring instrument, wherein the gel strength is measured by the mass (g) of the compound colloid (dry basis) with the mass fraction of 1.5% and the anti-fracture code mass (g) of the gel in 15-20s and the surface area (cm) of the lower end of a device rod 2 ) The ratio is expressed in g cm -2 。
Whiteness: the carrageenan samples were sieved through an 80 mesh standard sieve and the whiteness was measured by a whiteness meter.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
Extracting carrageenan by primary recovery of perlite:
(1) Weighing 150g of air-dried primary carrageenan residues (extracted from factory pure perlite) in a 2000mL beaker, pre-boiling the primary carrageenan residues in a water bath kettle at 100 ℃ for 2h according to a solid-to-liquid ratio of 1.
(2) Preparing H with the concentration of 2% 2 O 2 Adding the solution into the carrageenan treated in the step (1) according to the solid-to-liquid ratio of 1And pre-boiling the residue in a water bath kettle at 100 ℃ for 2 hours, and performing filter pressing by using a filter bag plate frame.
(3) And (3) preparing 0.3mol/L HCl solution, adding the HCl solution into the carrageenan residues treated in the step (2) according to the solid-to-liquid ratio of 1.
(4) Drying the primarily recovered perlite at 105 ℃, crushing and sieving the perlite with a 60-mesh sieve, adding the perlite into a carrageenan solution to be filtered in an adding amount of 2.0g/L, performing plate-and-frame filter pressing to obtain a filtered carrageenan solution and secondary carrageenan residues, salting out the filtered carrageenan solution with a 5% KCl solution, taking out the solution, performing freeze dehydration, drying, crushing and sieving with a 80-mesh sieve to obtain a carrageenan sample.
In the embodiment, the flow rate of the filtrate of the primary recovered perlite is 0.290-0.344 mL/s, and the permeability is 0.351-0.418 Darcy. The whiteness of the carrageenan is 63.62% -70.94%, the viscosity is 6.05 mPa.s-7.92 mPa.s, the transparency is 67.50% -82.10%, and the gel strength is 491.40 g-cm -2 ～560.60g·cm -2 。
Example 2
Extracting carrageenan from the secondary recovered perlite:
(1) Weighing 150g of air-dried secondary carrageenan residues (obtained in example 1) in a 2000mL beaker, pre-boiling the beaker in a water bath kettle at 90 ℃ for 2h according to the solid-to-liquid ratio of 1.
(2) Preparing H with the concentration of 2% 2 O 2 And (2) adding the solution into the carrageenan residues treated in the step (1) according to the solid-to-liquid ratio of 1.
(3) And (3) preparing 0.5mol/L HCl solution, adding the HCl solution into the carrageenan residues treated in the step (2) according to the solid-to-liquid ratio of 1.
(4) Drying the perlite recovered for the second time at 105 ℃, crushing and sieving the perlite with a 60-mesh sieve, adding the crushed perlite into a carrageenan solution to be filtered according to the addition amount of 1.5g/L, performing plate-and-frame filter pressing to obtain a filtered carrageenan solution and third carrageenan residues, salting out the filtered carrageenan solution with a 5% KCl solution, taking out the solution, performing freeze dehydration, drying, crushing and sieving with a 80-mesh sieve to obtain a carrageenan sample.
In the embodiment, the flow rate of the filtrate of the secondary recycled perlite is 0.321-0.368 mL/s, and the permeability is 0.367-0.421 Darcy. The whiteness of the carrageenan is 62.83% -5% -63.63% -5%, the viscosity is 11.30 mPa & s-11.50 mPa & s, the transparency is 68.60% -69.20%, and the gel strength is 720.20g & cm -2 ～782.20g·cm -2 。
Example 3
Extracting carrageenan by recycling perlite for the third time:
(1) 150g of air-dried tertiary carrageenan residue (obtained in example 2) was weighed into a 2000mL beaker, pre-cooked in a 75 ℃ water bath for 3.5h at a solid-to-liquid ratio of 1.
(2) Preparing H with the concentration of 3% 2 O 2 And (3) adding the solution into the carrageenan residues treated in the step (1) according to the solid-to-liquid ratio of 1.
(3) And (3) preparing 0.1mol/L HCl solution, adding the HCl solution into the carrageenan residues treated in the step (2) according to the solid-to-liquid ratio of 1.
(4) Drying the perlite recovered in the third time at 105 ℃, crushing and sieving the perlite with a 60-mesh sieve, adding the crushed perlite into a carrageenan solution to be filtered in an adding amount of 1.5g/L, performing plate-and-frame filter pressing to obtain a filtered carrageenan solution and four-time carrageenan residues, salting out the filtered carrageenan solution with a 5% KCl solution, taking out the solution, performing freeze dehydration, drying, crushing and sieving with a 80-mesh sieve to obtain a carrageenan sample.
In the embodiment, the flow rate of the filtrate of the three times of recovered perlite is 0.311-0.390 mL/s, and the permeability is 0.334-0.419 Darcy. The whiteness of the carrageenan is 62.19% -63.19%, the viscosity is 4.90-5.20 mPa.s, the transparency is 47.90% -48.10%, and the gel strength is 820.40 g.cm -2 ～854.00g·cm -2 。
Example 4
And (3) recovering perlite for four times to extract carrageenan:
(1) 150g of air-dried carrageenan residue (obtained in example 3) was weighed out and placed in a 2000mL beaker in a solid-to-liquid ratio of 1.
(2) Preparing H with the concentration of 3% 2 O 2 And (3) adding the solution into the carrageenan residues treated in the step (1) according to the solid-to-liquid ratio of 1.
(3) And (3) preparing 0.5mol/L HCl solution, adding the HCl solution into the carrageenan residues treated in the step (2) according to the solid-to-liquid ratio of 1.
(4) Drying the perlite recovered for four times at 105 ℃, crushing and sieving the perlite by a 60-mesh sieve, adding the perlite into a carrageenan solution to be filtered in an adding amount of 2.0g/L, carrying out plate-and-frame filter pressing to obtain a filtered carrageenan solution and five-time carrageenan residues, salting out the filtered carrageenan solution by using a 5% KCl solution, taking out the solution, and carrying out freeze dehydration, drying, crushing and sieving by a 80-mesh sieve to obtain a carrageenan sample.
In the embodiment, the filtrate flow rate of the four times of recycled perlite is 0.303mL/s to 0.310mL/s, and the permeability is 0.336Darcy to 0.344Darcy. The whiteness of the carrageenan is 58.87% -59.81%, the viscosity is 29.90 mPa.s-30.10 mPa.s, the transparency is 41.40% -42.90%, and the gel strength is 929.80 g-cm -2 ～950.80g·cm -2 。
Comparative example 1
Extraction of carrageenin from pure perlite
Adding commercial pure perlite into a carrageenan solution to be filtered in an adding amount of 2.0g/L, performing plate-and-frame filter pressing to obtain the filtered carrageenan solution, salting out the filtered carrageenan solution by using a 5% KCl solution, taking out the filtered carrageenan solution, and performing freeze dehydration, drying, crushing and sieving to obtain a carrageenan sample.
In this comparative example, the filtrate flow rate of the perlite in the sample was 0.647mL/s to 0.710mL/s, and the permeability was 1.070 to 1.176Darcy. The whiteness of carrageenan is 6431 to 70.22 percent, the viscosity is 9.15 to 9.50 mPa.s, the transparency is 62.17 to 67.20 percent, and the gel strength is 631.80 g.cm -2 ～716.07g·cm -2 。
Comparative example 2
Extraction of carrageenan without adding perlite
Directly performing plate-and-frame filter pressing on carrageenan solution to be filtered to obtain filtered carrageenan solution, salting out the filtered carrageenan solution by using 5% KCl solution, taking out the carrageenan solution, and performing freeze dehydration, drying, crushing and sieving to obtain a carrageenan sample.
In this example, the flow rate of the filtrate of the carrageenan extraction residue was 0.062mL/s to 0.065mL/s, and the permeability was 0.064Darcy to 0.067Darcy. The whiteness of the carrageenan is 54.64% -54.93%, the viscosity is 16.60-16.80 mPa.s, the transparency is 55.00-56.80%, and the gel strength is 613.40 g-cm -2 ～629.60g·cm -2 。
To sum up, with reference to the above examples 1 to 4, comparative examples 1 and 2, and fig. 2 and fig. 3, when the carrageenan residues are subjected to hot water leaching treatment, hydrogen peroxide treatment, and hydrochloric acid treatment, the permeability of the recovered perlite is greater than 0.3Darcy, the filtrate flow rate is greater than 0.3mL/s, the recovery effect is stable, and the recovered perlite obtained after the carrageenan extraction residue treatment can reach the slow perlite standard in the standard JC/T849-2012 perlite filter aid, and can meet the production requirements. The whiteness, viscosity and transparency of the extracted carrageenan are not greatly different compared with pure pearl and carrageenan extracted without adding perlite, but the gel strength shows a remarkable rising trend along with the increase of the recovery times, and reaches 950.80g cm -2 It is possible that ions accumulated continuously in the perlite recovery process play a role in enhancing the gel strength, and the carrageenan extracted by the perlite recovered at different stages meets the GB1886.169-2016 standard.
Therefore, according to the method for extracting carrageenan by continuously recovering perlite disclosed by the embodiment of the invention, the algal residue in the perlite pores is degraded by a chemical method, the perlite pores are effectively opened, the substances such as residual gum, cellulose and the like in the carrageenan residues are degraded, the pollution of the residues to the environment is reduced, and the recovered perlite is subjected to carrageenan extraction, so that the reutilization of the perlite in the carrageenan residues is realized.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not to be understood as necessarily referring to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples described in this specification can be combined and combined by those skilled in the art.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that changes, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (6)
1. A method for recycling perlite from carrageenan residues is characterized by comprising the following steps:
(1) Adding water into the dried carrageenan residues, precooking for 0.5 to 3.5 hours, and then carrying out filter pressing;
(2) Adding hydrogen peroxide into the carrageenan residues treated in the step (1), pre-boiling for 0.5 to 3.5 hours, and then carrying out filter pressing;
(3) Adding hydrochloric acid into the carrageenan residues treated in the step (2), precooking for 0.5 to 3.5 hours, and performing filter pressing to obtain perlite;
(4) Drying the perlite, crushing and sieving, adding the perlite into a carrageenan solution to be filtered, and performing filter pressing to obtain a filtered carrageenan solution and carrageenan residues; wherein, the filtered carrageenan solution is subjected to salting out, freeze dehydration, drying, crushing and sieving to obtain a carrageenan sample.
2. The process according to claim 1, wherein in step (4), the carrageenan residue is treated by repeating steps (1) to (4).
3. The method according to claim 1, wherein in the step (1), water is added into the dried 150g carrageenan residues according to a solid-to-liquid ratio of 1 to 5 to 1, the mixture is pre-boiled in a water bath kettle at a temperature of 75 to 100 ℃ for 0.5 to 3.5 hours and then is subjected to filter pressing by using a filter bag frame.
4. The method according to claim 1, wherein in the step (2), hydrogen peroxide with the concentration of 0.5-3% is added into the carrageenan residues treated in the step (1) according to the solid-liquid ratio of 1-5-1.
5. The method according to claim 1, wherein in the step (3), hydrochloric acid with the concentration of 0.1 mol/L-0.5 mol/L is added into the carrageenan residues treated in the step (2) according to the solid-liquid ratio of 1 to 5 to 1 and 20, and the mixture is placed in a water bath kettle at 75-100 ℃ for precooking for 0.5 to 3.5 hours and then is subjected to filter pressing by a plate and frame filter bag.
6. The method of claim 2, wherein in step (4), the perlite is dried to constant weight at 105 ℃, crushed and sieved through a 60-mesh sieve.
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| DK1458764T3 (en) * | 2001-12-28 | 2007-10-01 | Cp Kelco Aps | Process for the preparation and fractionation of two-component pliers of gelatin and non-gelatinized carrageenans |
| PT1458763E (en) * | 2001-12-28 | 2009-07-20 | Cp Kelco Aps | A heterogenous carrageenan manufacturing process with recovery of alkali |
| CN1301269C (en) * | 2005-06-08 | 2007-02-21 | 江南大学 | Process for extracting Iota-type carrageenin |
| EP2750685A4 (en) * | 2011-09-02 | 2015-03-25 | Fmc Corp | Process for making and using cellulose-containing seaweed residue and products made therefrom |
| CN105432358A (en) * | 2015-11-23 | 2016-03-30 | 嘉兴大印农业科技有限公司 | Seedling culture medium |
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