Disclosure of Invention
In order to solve the problem that the viscosity number fluctuation of the bio-based long carbon chain polyamide resin produced by the traditional polymerization process is too large, and the post-processing and the performance are influenced, the inventor of the application can control the viscosity number fluctuation of the long carbon chain polyamide resin to be less than 15mL/g, even less than 6mL/g by optimizing the polymerization process, including controlling polymerization raw materials and regulating and controlling reaction conditions.
The invention provides a long carbon chain polyamide resin, which comprises the following structural formula:
-NH-(CH2)5-NH-CO-R-CO-
wherein R is an alkylene group having 8 to 10 carbon atoms. Preferably, R is a C8 alkylene group or a C10 alkylene group.
The long carbon chain polyamide resin of the present invention has a viscosity number fluctuation of less than 15mL/g, preferably a viscosity number fluctuation of less than 10mL/g, more preferably a viscosity number fluctuation of less than 6 mL/g.
The viscosity number of the long carbon chain polyamide resin is 120-300mL/g, preferably 125-220 mL/g.
The content of the terminal amino group in the long-carbon-chain polyamide resin of the present invention is 11 to 39mol/ton, preferably 13 to 35mol/ton, and more preferably 15 to 33 mol/ton.
The raw materials for producing the long-carbon-chain polyamide resin comprise 1, 5-pentanediamine (namely pentanediamine or cadaverine and pentamethylene diamine), long-carbon-chain dibasic acid and a blocking agent.
The long carbon chain dibasic acid is aliphatic long carbon chain dibasic acid, and the pentanediamine and/or the aliphatic long carbon chain dibasic acid is/are prepared by a biological method. Biological production as used herein includes production of products (e.g., pentanediamines, long chain diacids, etc.) from bio-based feedstocks via bioconversion processes (e.g., fermentation, enzymatic conversion); or producing products (such as long chain dibasic acids) from petroleum-based raw materials by a biotransformation process; or chemically producing products (e.g., sebacic acid, etc.) using bio-based feedstocks. Alternatively, the pentanediamine and/or the aliphatic long carbon chain diacid contains a renewable source of organic carbon that meets ASTM D6866 standard.
The aliphatic long carbon chain dibasic acid is preferably any one or a combination of sebacic acid, undecanedioic acid and dodecanedioic acid, and more preferably sebacic acid or dodecanedioic acid.
The blocking agent comprises any compound which reacts with a terminal amino group and a terminal carboxyl group, preferably a carboxyl group-containing compound, and more preferably either or both of acetic acid and adipic acid.
The mass of the end-capping agent accounts for less than 2 percent, preferably less than 1 percent of the total mass of the pentanediamine and the dibasic acid which are raw materials for producing the long carbon chain polyamide resin.
The raw material for producing the long carbon chain polyamide resin may further include an additive, and the mass of the additive is 40% or less, preferably 20% or less of the total mass of the raw material for producing the long carbon chain polyamide resin.
The invention also provides a preparation method of the long carbon chain polyamide resin, which comprises the following steps:
1) under the protection of nitrogen or inert gas, adding reaction raw materials into a reaction container to prepare a polyamide salt aqueous solution;
2) transferring the polyamide salt aqueous solution obtained in the step 1) to a polymerization kettle for polycondensation reaction.
The pH value of the polyamide salt aqueous solution in the step 1) is 6.60-8.75, preferably 6.70-7.42, and more preferably 6.80-7.15 when the concentration of the polyamide salt aqueous solution is 10 wt%.
Preferably, the pH of the aqueous polyamide salt solution is adjusted with pentanediamine or a long carbon chain diacid.
The preparation of the polyamide salt aqueous solution in the step 1) further comprises adding an end-capping agent.
Preferably, the end capping agent in the step 1) is one or two of acetic acid and adipic acid, and the adding amount of the end capping agent is less than 2%, preferably less than 1% of the total mass of the pentanediamine and the dibasic acid of the raw materials for producing the long carbon chain polyamide resin.
The preparation of the polyamide salt aqueous solution in step 1) further comprises the addition of additives.
Preferably, the additive in step 1) is an antioxidant.
The mass concentration of the polyamide salt aqueous solution in the step 1) is 30-80%, and the preferred mass concentration is 40-70%.
The polymerization process listed in the step 2) is a conventional polycondensation process, and the reaction conditions are as follows: heating until the pressure in the reaction vessel rises to 0.5-3.0 MPa, starting to exhaust and keeping the pressure, gradually reducing the pressure in the reaction vessel to normal pressure when the temperature of the system rises to 200-320 ℃, and continuing to react for 25-120 min, preferably 40-80 min.
Preferably, the step 2) further comprises a step of reducing the pressure after the pressure in the reaction vessel is reduced to normal pressure.
More preferably, the pressure in the reaction vessel is reduced to normal pressure in step 2), and the pressure is increased to normal pressure again after the pressure is reduced.
The reduced pressure is in the range of-0.01 to-0.1 MPa (gauge pressure).
Due to the adoption of the scheme, the invention has the beneficial effects that:
the invention adopts raw materials of 1, 5-pentanediamine, aliphatic long carbon chain dibasic acid, a terminating agent and various additives to obtain the bio-based long carbon chain polyamide resin with viscosity fluctuation less than 15mL/g through an optimized polymerization process. Overcomes the defect of large viscosity number fluctuation of the long carbon chain bio-based polyamide resin prepared by the traditional polymerization process. Too large viscosity fluctuation can cause a plurality of problems in the processing process, such as unsmooth feeding, broken filaments in spinning, poor mechanical property of products, no film formation and the like.
In addition, one or more of the raw materials used in the invention are derived from renewable plants, belong to environment-friendly materials on the whole, relieve the dependence on non-renewable energy sources, and are beneficial to building a circulating society.
Detailed Description
The long carbon chain polyamide resin of the present invention comprises the following structural formula:
-NH-(CH2)5-NH-CO-R-CO-
wherein R is an alkylene group having 8 to 10 carbon atoms. Preferably, R is a C8 alkylene group or a C10 alkylene group.
The long carbon chain polyamide resin of the present invention has a viscosity number fluctuation of less than 15mL/g, preferably a viscosity number fluctuation of less than 10mL/g, and more preferably a viscosity number fluctuation of less than 6 mL/g.
The viscosity number fluctuation refers to that a plurality of samples are randomly taken from the same batch of slices or the packaging bag, and the viscosity numbers and the maximum difference of the viscosity numbers among the random samples are respectively detected. Viscosity number fluctuation of long carbon chain polyamide obtained by polymerization of pentanediamine and long carbon chain dibasic acid by using a traditional polymerization process can be more than 20mL/g, the viscosity number fluctuation range can seriously influence the use of the long carbon chain polyamide in downstream processing, and if the long carbon chain polyamide is not smoothly fed on a screw, molten drops are generated in the spinning process, the long carbon chain polyamide can not be processed into a film, and meanwhile, the product performance can be seriously influenced. The viscosity number fluctuation of the bio-based long carbon chain nylon obtained by the method can be controlled below 15mL/g, even below 6mL/g, and the requirements of downstream customers on processability and mechanical properties are completely met.
The viscosity number of the long carbon chain polyamide resin is 120-300mL/g, preferably 125-220 mL/g.
The viscosity number is an indicator of the molecular weight, and a higher viscosity number indicates a higher molecular weight of the polymer, and a higher molecular weight indicates a higher strength of the polyamide. This is because if the molecular weight is higher, the smaller the amount of molecular chain terminals present per unit, the fewer defects that may be fibers. Meanwhile, because the molecular chains are longer, each molecular chain interacts with more molecular chains (such as physical entanglement, hydrogen bonds, van der waals forces and the like) to uniformly transfer various stresses, and therefore, the molecular chains are uniformly oriented in the processing process. On the other hand, the viscosity number in sulfuric acid is preferably kept in a suitable range, and since an excessively high viscosity number may result in a decrease in the fluidity of the solution, affecting the appearance and processing efficiency of the sample, the viscosity number is more preferably 125-220 mL/g.
The long carbon chain polyamide resin of the present invention may have an amino group-terminated content of 11 to 39mol/ton, preferably 13 to 35mol/ton, and more preferably 15 to 33 mol/ton. The reason is as follows: we find that when the content of the terminal amino group is low, the viscosity number fluctuation range of the product is small, and the viscosity number of the obtained polyamide resin is improved due to the fact that the content of the terminal amino group is too low, so that the long carbon chain polyamide resin with applicable value cannot be obtained.
The raw materials for producing the long carbon chain polyamide resin comprise 1, 5-pentanediamine, long carbon chain dibasic acid and a blocking agent.
Pentanediamine (i.e., 1, 5-pentanediamine or cadaverine, pentamethylenediamine) may be prepared biologically or chemically and may contain a renewable source of organic carbon in accordance with ASTM D6866. As is known to those skilled in the art, the removal of carboxyl groups at both ends of lysine or lysine salt by lysine decarboxylase (EC 4.1.1.18) produces pentanediamine. For example, "the lysine decarboxylase property and application research" (Jiangli, Nanjing university, Master thesis) discloses a specific biological method for preparing pentanediamine. For example, the research on the transformation of L-lysine into cadaverine by microorganisms (ZhuJing, Tianjin science and technology university, Master's paper, 2009.3) also discloses a specific biological method for preparing pentanediamine.
The dibasic acid is aliphatic long carbon chain dibasic acid. The aliphatic long carbon chain dibasic acid may also be prepared biologically or chemically, and may also contain a renewable source of organic carbon that meets ASTM D6866 standard. Provided that at least one of the pentanediamine and the aliphatic long carbon chain dibasic acid is a bio-based product.
The aliphatic long carbon chain dibasic acid can be any one or combination of sebacic acid, undecanedioic acid and dodecanedioic acid, and is preferably sebacic acid or dodecanedioic acid.
The blocking agent includes any compound which reacts with the terminal amino group and the terminal carboxyl group, preferably a carboxyl group-containing compound, and more preferably acetic acid and adipic acid.
The mass of the end-capping reagent accounts for less than 2 percent of the total mass of the pentanediamine and the dibasic acid which are raw materials for producing the long carbon chain polyamide resin. In experiments, the end-capping agent is found to be capable of effectively controlling the viscosity number fluctuation of the long-carbon-chain polyamide resin, but the viscosity number of the long-carbon-chain polyamide resin is too low to lose the application value after the end-capping agent is added too much, so that the content of the end-capping agent is preferably below 1%.
The raw material for producing the long carbon chain polyamide resin of the present invention may further include an additive, and the mass of the additive accounts for 40% or less, preferably 20% or less of the total mass of the raw material for producing the long carbon chain polyamide resin.
The additive can be any one or the combination of several of an antioxidant, a heat-resistant stabilizer, a weather-resistant agent, a pigment, a gloss enhancer, a dye, a crystal nucleating agent, a delustering agent, a plasticizer, an antistatic agent and a flame retardant.
Among them, the heat stabilizer includes, but is not limited to, hindered phenol-based compounds, hydroquinone-based compounds, thiazole-based compounds, phosphorus-based compounds (e.g., phenylphosphonic acid), imidazole-based compounds (e.g., 2-mercaptobenzimidazole) and substitution products thereof, copper halide and iodine compounds, and the like.
Weathering agents include, but are not limited to, resorcinol, salicylates, benzotriazoles, benzophenones, hindered amines, and the like.
Pigments include, but are not limited to, cadmium sulfide, phthalocyanines, carbon black, and the like.
Gloss enhancers include, but are not limited to, titanium oxide and calcium carbonate, among others.
Dyes include, but are not limited to nigrosine and nigrosine, and the like.
Crystal nucleating agents include, but are not limited to talc, silica, kaolin, clay, and the like.
Plasticizers include, but are not limited to, octyl paraben, N-butylbenzenesulfonamide, and the like.
Antistatic agents include, but are not limited to, alkyl sulfate type anionic antioxidants, quaternary ammonium type cationic antistatic agents, nonionic antistatic agents (such as polyoxyethylene sorbitan monostearate), and betaine-based amphoteric antistatic agents, and the like.
Flame retardants include, but are not limited to, melamine cyanurate, hydroxides (such as magnesium hydroxide or aluminum hydroxide), ammonium polyphosphate, brominated polystyrene, brominated polyphenylene oxide, brominated polycarbonate, brominated epoxy resins, combinations of any bromine-based flame retardant with antimony trioxide, and the like.
The invention also discloses a method for preparing the long-carbon-chain polyamide resin, which comprises the following steps:
1) under the protection of nitrogen or inert gas, adding reaction raw materials into a reaction container to prepare a polyamide salt aqueous solution;
2) transferring the polyamide salt aqueous solution obtained in the step 1) to a polymerization kettle for polycondensation reaction. The preparation of the polyamide salt aqueous solution in the step 1) further comprises adding an end-capping agent. In experiments, the viscosity number of the long carbon chain polyamide resin is found to fluctuate greatly under the condition that no end-capping agent is added, and even if various process parameters are adjusted, the viscosity number is not easy to control in a small fluctuation range, because the end-capping agent reduces a polymerization end point platform, a polymerization system can reach an equilibrium state quickly, however, the viscosity number of the long carbon chain polyamide is too low and the industrial application value is lost due to excessive addition of the end-capping agent, and therefore, the addition amount of the end-capping agent needs to be accurately controlled in a proper range.
Preferably, the end-capping reagent in step 1) can be acetic acid or adipic acid, and the addition amount of the end-capping reagent is less than 2 percent, preferably less than 1 percent of the total mass of the pentanediamine and the dibasic acid which are raw materials for producing the long carbon chain polyamide resin.
The method also comprises the step of adjusting the pH value of the solution to 6.60-8.75 by using pentanediamine or long carbon chain dibasic acid after the polyamide salt aqueous solution is obtained in the step 1). Too high and too low pH values can cause end group imbalance and affect the viscosity and mechanical properties of the polyamide.
Preferably, the pH value of the solution is 6.70-7.42, more preferably 6.80-7.15, the pH value of the initial polyamide salt aqueous solution has a large influence on the viscosity number fluctuation of the long carbon chain polyamide resin, and at a higher pH value, the viscosity number can be controlled within a small fluctuation range by adding the end capping agent, but the control range is not large, probably because the long carbon chain polyamide 5X has the polymerization capability of the super-conventional nylon, and if the pH value is not seriously lower, the polymerization process cannot be slowed down, so that the pH value of the long carbon chain polyamide with smaller viscosity number fluctuation is required to be lower than that for preparing the conventional polyamide. However, the pH value is too low, the mechanical properties of the resulting long carbon chain polyamide resin are affected, probably due to the low degree of polymerization, and therefore, by precisely controlling the pH value, the viscosity number fluctuation can be controlled to a smaller range.
In order not to introduce other impurities, the pH value of the polyamide salt aqueous solution can be adjusted by selecting pentanediamine or long carbon chain dibasic acid.
The preparation of the aqueous polyamide salt solution in step 1) may also comprise the addition of additives.
Preferably, the additive in step 1) is an antioxidant.
The mass concentration of the polyamide salt aqueous solution in step 1) is 30-80%, preferably 40-70%, because the concentration is limited by the upper limit of solubility, and the concentration is preferably 30-80% because the energy consumption is high due to too low concentration.
The polymerization process listed in the step 2) is a conventional polycondensation process, and the reaction conditions are as follows: heating until the pressure in the reaction vessel rises to 0.5-3.0 MPa, starting to exhaust and keeping the pressure, gradually reducing the pressure in the reaction vessel to normal pressure when the temperature of the system rises to 200-320 ℃, and continuing to react for 25-120 min, preferably 40-80 min.
Preferably, the step 2) further comprises a step of reducing the pressure after the pressure in the reaction vessel is reduced to normal pressure.
More preferably, the pressure in the reaction vessel is reduced to normal pressure in step 2), and the pressure is increased to normal pressure again after the pressure is reduced.
The reduced pressure is in the range of-0.01 to-0.1 MPa (gauge pressure).
We find that the viscosity fluctuation of the product can be effectively reduced by carrying out the polymerization for a certain time under reduced pressure or firstly carrying out the polymerization under reduced pressure and then carrying out the polymerization under normal pressure after the polymerization system is reduced to normal pressure. Through analysis, the polymerization pressure is considered to determine a polymerization rate and a reaction end point platform, the decompression process is favorable for improving the polymerization rate, the end point pressure is determined by a system moisture platform and the reaction end point platform, and the more the end point pressure is close to the normal pressure, the more the reaction end point platform is easy to reach, so the process of decompressing firstly and then pressurizing secondly is the most preferable. In addition, the polymerization system can reach the reaction end point platform by prolonging the post-polymerization time.
The present invention will be further described with reference to examples and comparative examples.
The following examples were used to characterize the properties of long carbon chain polyamide resins using the following characterization methods:
(1) viscosity number
Concentrated sulfuric acid method by Ubbelohde viscometer: a dried sample of polyamide resin (e.g., PA510) is accurately weighed by the 0.25 viscometer method of concentrated sulfuric acid: adding 50mL of concentrated sulfuric acid (96%) for dissolution, measuring and recording the flowing time t of the concentrated sulfuric acid in a constant-temperature water bath at 25 DEG C0And the time t for the solution to flow through the polyamide resin sample (e.g., PA 66).
Viscosity number calculation formula: viscosity number VN ═ t/t0-1)/C;
t1 solution flow time;
t0-the time of solvent flow;
concentration of agent C Polymer (g/mL).
(2) Terminal amino group
1g of polyamide resin chips were dissolved at 30 ℃ in 50ml of a phenol/ethanol mixed solution (phenol/ethanol ═ 80/20) with shaking, and the solution was neutralized and titrated with 0.02mol/L hydrochloric acid. The amount of 0.02mol/L hydrochloric acid used was determined. The above phenol/ethanol mixed solvent was titrated with 0.02mol/L hydrochloric acid for a blank, and the amount of 0.02mol/L hydrochloric acid was determined. From the difference between the amounts, the content of terminal amino groups per 1 ton of polyamide sample was obtained.
(3) pH value
The polyamide salt solution was diluted to 10 wt% and measured at 30 ℃ using a pH meter.
Example 1 Polyamide 510
1) A100-liter polymerization kettle (K/SY166-2007 type) is used for replacing air with nitrogen, 15kg of pure water is added into the reaction kettle, 11.75kg (115.2mol) of pentanediamine (containing organic carbon of renewable source meeting the ASTM D6866 standard) is added, after stirring, 23.25kg (115.2mol) of sebacic acid is added, the pH value is adjusted to 8.71 by small amounts of pentanediamine and sebacic acid (the salt solution at 30 ℃ is diluted to 10% of detection result), 350g of adipic acid is added, and 25g of antioxidant H10 is added, so that a polyamide salt water solution is prepared.
2) And (2) gradually increasing the oil bath temperature to 289 ℃ under a nitrogen environment, starting to exhaust when the pressure in the polymerization kettle is increased to 1.7MPa, gradually reducing the pressure in the reaction container to normal pressure when the temperature in the kettle reaches 240 ℃, keeping the temperature in the kettle to 262 ℃, and continuously reacting for 38min under the normal pressure to obtain the polyamide 510.
Example 2 Polyamide 510
1) A100 liter polymerization vessel (type K/SY 166-2007) was purged with nitrogen, 20kg of pure water was added to the reaction vessel, 11.75kg (115.2mol) of pentamethylenediamine (containing a renewable organic carbon meeting ASTM D6866 standard), after stirring, 23.25kg (115.2mol) of sebacic acid was added, the pH was adjusted to 8.21 with a small amount of pentamethylenediamine and sebacic acid (30 ℃ saline solution was diluted to 10% test result), and 175g of adipic acid was added to prepare a polyamide saline solution.
2) And under the nitrogen environment, gradually increasing the oil bath temperature to 285 ℃, starting to exhaust when the pressure in the polymerization kettle is increased to 1.5MPa, gradually reducing the pressure in the reaction container to normal pressure when the temperature in the kettle reaches 245 ℃, keeping the vacuum degree to 268 ℃, vacuumizing to-0.07 MPa, and keeping the vacuum degree for 28min to obtain the polyamide 510.
Example 3 Polyamide 510
1) A100 liter polymerization vessel (type K/SY 166-2007) was purged with nitrogen, 15kg of pure water was added to the reaction vessel, 11.75kg (115.2mol) of pentamethylenediamine (containing a renewable organic carbon meeting ASTM D6866 standard), after stirring, 23.25kg (115.2mol) of sebacic acid was added, the pH was adjusted to 7.42 with a small amount of pentamethylenediamine and sebacic acid (30 ℃ saline solution was diluted to 10% test result), and 35g of adipic acid was added to prepare a polyamide salt aqueous solution.
2) And under the nitrogen environment, gradually increasing the oil bath temperature to 293 ℃, starting to exhaust when the pressure in the polymerization kettle is increased to 1.7MPa, gradually reducing the pressure in the reaction container to normal pressure when the temperature in the kettle reaches 238 ℃, vacuumizing to-0.06 MPa when the temperature in the kettle reaches 265 ℃, and keeping the vacuum degree for 55min to obtain the polyamide 510.
Example 4 Polyamide 511
1) A100-liter polymerization kettle (K/SY166-2007 type) is used for replacing air with nitrogen, 15kg of pure water is added into the reaction kettle, 11.75kg (115.2mol) of pentanediamine (containing organic carbon of renewable origin meeting the ASTM D6866 standard) is added, 24.865kg (115.2mol) of undecanedioic acid is added after stirring, the pH value is adjusted to 7.29 by a small amount of pentanediamine and undecanedioic acid (the salt solution at 30 ℃ is diluted to 10% of detection result), 35g of acetic acid is added, and 20g of antioxidant H10 is added, so that a polyamide salt water solution is prepared.
2) And (2) gradually increasing the oil bath temperature to 286 ℃ in a nitrogen environment, starting to exhaust when the pressure in the polymerization kettle is increased to 1.7MPa, gradually reducing the pressure in the reaction vessel to normal pressure when the temperature in the kettle reaches 235 ℃, vacuumizing to-0.08 MPa, keeping the vacuum degree for 28min, then filling nitrogen to normal pressure, and continuously stirring for 20min to obtain the polyamide 511.
Example 5 Polyamide 512
1) A100-liter polymerization kettle (K/SY166-2007 type) was purged with nitrogen, 25kg of pure water was added to the reaction kettle, 11.75kg (115.2mol) of pentamethylenediamine (containing a renewable organic carbon meeting ASTM D6866 standard), 26.47kg (115.2mol) of dodecanedioic acid was added after stirring, the pH was adjusted to 6.96 with a small amount of pentamethylenediamine and dodecanedioic acid (10% detection result by dilution with a 30 ℃ saline solution), 3.5g of adipic acid was added, and 50g of antioxidant H10 was added to prepare a polyamide salt aqueous solution.
2) And (2) gradually increasing the oil bath temperature to 290 ℃ in a nitrogen environment, starting to exhaust when the pressure in the polymerization kettle is increased to 1.5MPa, gradually reducing the pressure in the reaction vessel to normal pressure when the temperature in the kettle reaches 245 ℃, vacuumizing to-0.07 MPa when the temperature in the kettle reaches 272 ℃, keeping the vacuum degree for 36min, then filling nitrogen to normal pressure, and continuously stirring for 30min to obtain the polyamide 512.
Comparative example 1 Polyamide 510
1) A100 liter polymerization vessel (type K/SY 166-2007) was purged with nitrogen, 15kg of pure water was added to the reaction vessel, 11.75kg (115.2mol) of pentamethylenediamine (containing a renewable organic carbon meeting ASTM D6866 standard) was then added, and after stirring, 23.25kg (115.2mol) of sebacic acid was added, and the pH was adjusted to 7.89 with a small amount of pentamethylenediamine and sebacic acid (30 ℃ C. salt solution was diluted to 10% of the test result), to prepare a polyamide salt aqueous solution.
2) And under the nitrogen environment, gradually increasing the oil bath temperature to 285 ℃, starting to exhaust when the pressure in the polymerization kettle is increased to 1.7MPa, vacuumizing to-0.06 MPa when the temperature in the kettle reaches 262 ℃, and keeping the vacuum degree for 30min to obtain the polyamide 510.
After the polyamide resin is prepared, nitrogen is filled into a polymerization kettle to the pressure of 0.4MPa, melting and discharging are started, a granulator is used for granulation, samples are taken every 8kg in the granulation process, four samples are taken in total, and the viscosity number fluctuation is the maximum difference value between any two viscosity numbers in the four samples. Drying at 110 deg.C for 24 hr, and packaging. The slice detection results are shown in table 1.
TABLE 1 data for sample testing of each example
The data in table 1 show that the viscosity number fluctuation of the bio-based long carbon chain polyamide obtained by the method is obviously smaller than that of the bio-based long carbon chain nylon prepared by the traditional polymerization process, the pH value of nylon salt in the polymerization process, the addition of a terminating agent and the selection of polycondensation vacuum conditions are very important for controlling the viscosity number, and the bio-based polyamide is suitable for downstream processing, has excellent performance and huge market prospect.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.