CN211170521U - Recovery system of long-chain dibasic acid - Google Patents
Recovery system of long-chain dibasic acid Download PDFInfo
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- CN211170521U CN211170521U CN201922034597.2U CN201922034597U CN211170521U CN 211170521 U CN211170521 U CN 211170521U CN 201922034597 U CN201922034597 U CN 201922034597U CN 211170521 U CN211170521 U CN 211170521U
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Abstract
The utility model provides a recovery system of long chain dibasic acid can be used for retrieving remaining long chain dibasic acid after long chain dibasic acid crystallization mother liquor is concentrated, including discoloring device, first filter equipment, first crystallization device and second filter equipment. The decoloring device is used for decoloring the mixture containing the long-chain dicarboxylic acid; the first filtering device is connected with the decoloring device and used for filtering the decolored mixture containing the long-chain dicarboxylic acid to obtain a first filtrate; the first crystallizing device is connected with the first filtering device and is used for crystallizing the first filtrate; the second filtering device is connected with the first crystallizing device and used for filtering the product treated by the first crystallizing device to obtain a first crystallized wet product. Through above-mentioned decoloration device, first filter equipment, first crystallization device and the second filter equipment who connects gradually, can carry out recycle with the mixture that contains long chain dibasic acid, extract out the high long chain dibasic acid of purity, realized the recycle of waste resource.
Description
Technical Field
The utility model discloses relate to biological fermentation method production long chain binary acid technical field on the whole, particularly, relate to a recovery system of long chain binary acid.
Background
The long-chain dibasic acid (L ong chain dicarboxylic acids, L CDA) has the structural general formula of HOOC- (CH)2)n-COOH (n ═ 8-16) is an important organic intermediate, and is widely used in the fields of chemical industry, light industry, pesticides, medicines, new materials, and the like.
The most common method for preparing long-chain dicarboxylic acids at present is to ferment long-chain alkanes, fatty acids, fatty acid esters or fatty acid salts under specific strains. The crude long-chain dicarboxylic acid extracted from the fermentation broth of the long-chain dicarboxylic acid needs to be further refined to obtain a refined long-chain dicarboxylic acid. At present, the purpose of refining is usually realized by dissolving a crude long-chain dibasic acid product in a solvent at high temperature, cooling and crystallizing the solution, and separating out long-chain dibasic acid crystals. Most of impurities in the crude long-chain dicarboxylic acid can be dissolved in the solvent and separated from the target long-chain dicarboxylic acid through recrystallization. In the recrystallization process, the crude long-chain dicarboxylic acid is dissolved in the solvent, and then the solution is cooled and separated out, so that part of the long-chain dicarboxylic acid is dissolved in the crystallization mother liquor.
The solvent in the crystallization mother liquor of the long-chain dicarboxylic acid may be recovered by a solvent recovery apparatus such as a rectifying column. However, the residue after the solvent recovery, such as the residue generated in the distillation tower kettle while the solvent is recovered by the distillation tower, is often accumulated and cannot be effectively utilized, which wastes resources. The residue after the solvent is recovered from the crystallization mother liquor of the long-chain dibasic acid can contain other impurities besides the long-chain dibasic acid, and the impurities are partially denatured after high-temperature treatment in the solvent recovery process, so that the physicochemical properties are changed, and the technical difficulty of extracting and refining the long-chain dibasic acid from the impurities is increased.
Therefore, how to recycle the long-chain dibasic acid in the remainder and realize the recycling of resources becomes a problem to be solved.
SUMMERY OF THE UTILITY MODEL
The utility model discloses a main aim at overcomes above-mentioned prior art's at least defect, provides a recovery system of long chain dibasic acid to deposit the long chain dibasic acid sediment that the accumulation obtained to remainder or long chain dibasic acid sewage treatment workshop behind the crystallization mother liquor recovery most solvent of long chain dibasic acid and retrieve, extract long chain dibasic acid in the mixture that contains long chain dibasic acid from the aforesaid, realize the recycle of resource.
The mixture containing the long-chain dibasic acid may be in a solid-liquid mixture state, a liquid state or a solid state. For example, when a part of the solvent remains in the mixture containing the long-chain dibasic acid, the mixture containing the long-chain dibasic acid is in a liquid state or a solid-liquid mixture state.
In order to realize the purpose of the utility model, the utility model adopts the following technical scheme:
according to an aspect of the utility model, a recovery system of long chain dibasic acid is provided, include: the device comprises a decoloring device, a first filtering device, a first crystallizing device and a second filtering device. The decoloring device is used for decoloring the mixture containing the long-chain dicarboxylic acid; the first filtering device is connected to the decoloring device and is used for filtering the mixture containing the long-chain dibasic acid after decoloring to obtain a first filtrate; the first crystallization device is connected to the first filtering device and is used for crystallizing the first filtrate; and the second filtering device is connected with the first crystallizing device and is used for filtering the product treated by the first crystallizing device to obtain a first crystallized wet product.
It will be understood by those skilled in the art that, in the decoloring, a solvent may be optionally added to the mixture containing the long-chain dibasic acid to dissolve the long-chain dibasic acid, or may be not added.
According to some embodiments of the invention, the recycling system further comprises: the device comprises a dissolving device, a third filtering device, a second crystallizing device and a fourth filtering device. The dissolving device is connected with the second filtering device and is used for dissolving the first crystallized wet product to obtain a first solution, and whether a decoloring agent is added into the dissolving device for decoloring or not can be selected according to the condition of the first solution; the third filtering device is connected with the dissolving device and is used for filtering the first solution to obtain a second filtrate; the second crystallization device is connected to the third filtering device and is used for crystallizing the second filtrate; and the fourth filtering device is connected with the second crystallizing device and is used for filtering the product treated by the second crystallizing device to obtain a second crystallized wet product.
According to some embodiments of the present invention, the recovery system of the long-chain dicarboxylic acid further comprises a rectification device, and the rectification device is connected to the decolorization device.
The mixture comprising the long-chain dibasic acid can be residue in a rectification device, such as a rectification tower kettle. Namely, a rectifying device is used for recovering most of the solvent in the long-chain dicarboxylic acid crystallization mother liquor, and the remainder is the kettle residue.
According to some embodiments of the invention, the product after treatment with the fourth filtration device further comprises a third filtrate; the fourth filtering device is connected to the rectifying device to convey the third filtrate to the rectifying device. Thereby collecting the solvent in the third filtrate.
According to some embodiments of the present invention, the recycling system further comprises a drying device connected to the fourth filtering device for drying the second crystallized wet product.
According to some embodiments of the invention, the product after filtration by the second filtration device further comprises a fourth filtrate; the recycling system further comprises:
an evaporator connected to the second filtering device for evaporating the fourth filtrate to obtain a first gas;
and the temperature reduction device is connected with the evaporator and used for reducing the temperature of the first gas to obtain first liquid.
The cooling device can also be connected to the dissolving device, and the first liquid can be conveyed to the dissolving device by the cooling device.
According to some embodiments of the invention, the evaporator comprises a wiped film evaporator, an evaporation kettle or a multiple effect evaporator.
According to some embodiments of the invention, the mixture comprising the long chain dibasic acid produces a first solid after being treated by the decolorization means and the first filtration means in sequence. The first filtration device is further capable of washing the first solid and delivering a washed second solvent to the first crystallization device.
According to some embodiments of the present invention, the decolorization device uses a decolorizer, such as activated carbon or activated clay, in the decolorization process.
According to the above technical scheme, the utility model discloses a recovery system of long chain binary acid's advantage lies in with positive effect:
the utility model discloses a recovery system, through above-mentioned decoloration device, first filter equipment, first crystallization device and the second filter equipment that connects according to the preface, can carry out recycle with the mixture that contains long chain dibasic acid to extract the higher long chain dibasic acid of purity, realized the recycling of abandonment resource.
In addition, the decoloring device and the first filtering device are arranged in front of the first crystallizing device, so that the mixture containing the long-chain dibasic acid is decolored before crystallization, the purity of the crystallized long-chain dibasic acid is higher, and the condition that the decoloration is difficult in the subsequent steps due to crystallization without decoloring is avoided.
Drawings
The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings.
FIG. 1 is a flow diagram illustrating a system for recovering a long chain dibasic acid according to an exemplary embodiment.
FIG. 2 is a flow diagram illustrating a long chain diacid crystallization mother liquor recovery system in accordance with another exemplary embodiment.
Wherein the reference numerals are as follows:
1. rectifying device
2. Decoloration device
3. First filter device
4. First crystallization device
5. Second filter device
6. Dissolving device
7. Third filter device
8. Second crystallizing device
9. Fourth filter device
12. Drying device
13. Evaporator with a heat exchanger
14. Cooling device
Detailed Description
Example embodiments will now be described more fully with reference to the accompanying drawings. Example embodiments may, however, be embodied in many different forms and should not be construed as 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 concept of example embodiments to those skilled in the art. The same reference numerals in the drawings denote the same or similar structures, and thus their detailed description will be omitted.
Although relative terms, such as "upper" and "lower," may be used in this specification to describe one element of an icon relative to another, these terms are used in this specification for convenience only, e.g., in accordance with the orientation of the examples described in the figures. It will be appreciated that if the device of the icon were turned upside down, the element described as "upper" would become the element "lower". The terms "a," "an," "the," and "said" are used to indicate the presence of one or more elements/components/etc.; the terms "comprising" and "having" are intended to be inclusive and mean that there may be additional elements/components/etc. other than the listed elements/components/etc.; the terms "first," "second," "third," and "fourth," etc. are used merely as labels, and are not limiting as to the number of their objects.
It should be understood that the term "connected" as used herein may be directly connected or indirectly connected, and in the case of indirect connection, the connection may be achieved, for example, by means of an auger, a pipe, or a pump, so as to transfer the material to be transferred from the former device to the latter device.
In the refining process of the long-chain dicarboxylic acid, a crude long-chain dicarboxylic acid product is usually dissolved in a solvent, and then a cooling crystallization mode is performed to separate long-chain dicarboxylic acid crystals, wherein the remainder after crystal separation is called crystallization mother liquor. Since the long-chain dibasic acid cannot be completely separated out, the crystallization mother liquor also contains a certain amount of long-chain dibasic acid.
In the process of recovering the solvent from the crystallization mother liquor, a method of recovering the solvent by heating (such as 60-120 ℃) is often adopted, such as a rectifying tower is used for recovering the solvent. The inventor of the utility model finds, in research, that the remainder of the crystallization mother liquor of the long-chain dibasic acid after the solvent is recovered, on one hand, the remainder still contains the long-chain dibasic acid, and the remainder is directly stacked to cause resource waste; on the other hand, the remainder contains a small amount of other impurities such as cell tissues of fermentation microorganisms, pigments, proteins, sugars, inorganic salts and the like, and the impurities are partially denatured after high-temperature treatment in a solvent recovery device (such as a rectifying tower), so that the recovery process of the long-chain dibasic acid is difficult, and the purity of the recovered long-chain dibasic acid is affected.
The long-chain dibasic acid sediment obtained by long-term sediment accumulation in the long-chain dibasic acid sewage treatment workshop has complex components, and the recovery and the reutilization of the long-chain dibasic acid contained in the long-chain dibasic acid sediment are also difficult problems.
Based on this, an embodiment of the utility model provides a recovery system of long chain dibasic acid for retrieve the mixture that contains long chain dibasic acid, deposit the long chain dibasic acid that the accumulation obtained like remainder, long chain dibasic acid sewage treatment plant deposit behind the long chain dibasic acid crystallization mother liquor recovery solvent and deposit, retrieve long chain dibasic acid wherein, thereby realize the cyclic utilization of resource. The mixture containing the long-chain dicarboxylic acid is, for example, a residue remaining in the bottom of the rectifying column after most of the solvent in the crystallization mother liquor of the long-chain dicarboxylic acid is recovered by the rectifying column.
The recovery system comprises a decoloring device, a first filtering device, a first crystallizing device and a second filtering device. The decoloring device decolors a mixture containing long-chain dibasic acid; the first filtering device is connected with the decoloring device and is used for filtering the decolored mixture containing the long-chain dicarboxylic acid to obtain a first filtrate; the first crystallizing device is connected with the first filtering device and is used for crystallizing the first filtrate; and the second filtering device is connected with the first crystallizing device and is used for filtering the product treated by the first crystallizing device to obtain a first crystallized wet product.
The utility model discloses a recovery system, through above-mentioned decoloration device, first filter equipment, first crystallization device and the second filter equipment that connects according to the preface, can retrieve the long chain dibasic acid that contains in the mixture that contains long chain dibasic acid to extract the higher long chain dibasic acid of purity, realized the reuse of abandonment resource.
In addition, the decoloring device and the first filtering device are arranged in front of the first crystallizing device, so that the mixture containing the long-chain dibasic acid is decolored before crystallization, the purity of the crystallized long-chain dibasic acid is higher, and the condition that the decoloration is difficult in the subsequent steps due to crystallization without decoloring is avoided.
The following description is made in detail with reference to the accompanying drawings.
As shown in fig. 1, an embodiment of the present invention provides a system for recovering kettle residue generated in a refining process of a long chain dibasic acid, comprising a rectifying device 1, a decoloring device 2, a first filtering device 3, a first crystallizing device 4, a second filtering device 5, a dissolving device 6, a third filtering device 7, a second crystallizing device 8 and a fourth filtering device 9, which are connected in sequence.
The decoloring device 2 is connected to the rectifying device 1 and is used for decoloring the kettle residue so as to remove impurities such as pigment and the like in the kettle residue. Preferably, the decoloring apparatus 2 may employ an activated carbon decoloring tank. Of course, in other embodiments, the decoloring apparatus 2 may be a clay decoloring tank, an adsorbent resin decoloring tank, an oxidation decoloring tank, or the like. Wherein the activated carbon, the argil and the adsorption resin are decolorants used in the decoloration process.
The first filtering device 3 is used for filtering the decolored kettle residue to obtain a first filtrate. For example, when the decolorizing device 2 employs an activated carbon decolorizing tank, the first filtering device 3 filters impurities such as activated carbon particles or powder.
The first crystallization device 4 is used for crystallizing the first filtrate. For example, the first crystallization device 4 may crystallize the long-chain dicarboxylic acid in the first filtrate by cooling crystallization. The first filtrate is processed by the first crystallization device 4 to become a mixture of long-chain dicarboxylic acid crystals and liquid.
The second filtering device 5 is used for separating the mixture of the long-chain dicarboxylic acid crystals and the liquid to obtain a first crystallized wet product.
In this case, the first wet crystal product obtained is the purified long-chain dibasic acid, in other words, the long-chain dibasic acid is recovered from the residue remaining in the rectifying apparatus 1.
Of course, in order to obtain crystals of the long-chain dibasic acid with higher purity, secondary crystallization may be performed in addition to the above-described embodiments.
Specifically, with reference to fig. 1, the first crystallized wet product enters the dissolving device 6 for dissolving to obtain a first solution. The first crystallized wet product may be directly dissolved by using an organic solvent such as acetic acid. Or the long-chain dibasic acid in the first crystallized wet product can be converted into the long-chain dibasic acid salt by adding alkali liquor so as to be dissolved in the solution.
Then, the first solution enters a third filtering device 7 for filtering to obtain a second filtrate; the second filtrate passes through a second crystallization device 8, so that long-chain dicarboxylic acid crystals with higher purity are separated out. The second crystallization device 8 can crystallize and separate the long-chain dicarboxylic acid from the second filtrate by adopting a cooling crystallization or acidification crystallization mode. The second filtrate is processed by a second crystallization device 8 to form a mixture of long-chain dicarboxylic acid crystals and liquid.
The fourth filtering device 9 is used for filtering the product treated by the second crystallizing device 8 to obtain a second crystallized wet product.
Therefore, the utility model discloses an embodiment is through the rectifier unit 1, the decoloration device 2, first filter equipment 3, first crystallization device 4, second filter equipment 5, dissolving device 6, third filter equipment 7, second crystallization device 8 and the mutual cooperation of fourth filter equipment 9 that connect gradually, has retrieved the long chain dibasic acid in the cauldron is incomplete, has realized the recycling of abandonment resource. Meanwhile, the purity of the recovered long-chain dicarboxylic acid is higher through the sequential series connection of the devices.
As shown in fig. 1, in the present embodiment, the product treated by the fourth filtering device 9 includes the third filtrate in addition to the second crystallized wet product. The fourth filtration device 9 is connected to the rectification device 1 to deliver the third filtrate to the rectification device 1.
Since the second crystallized wet product and the third filtrate are a solid-liquid mixture after being treated by the second crystallization device 8, a small amount of the long-chain dibasic acid still remains in the third filtrate because crystals may not be completely precipitated. In this embodiment, it is specifically defined that the fourth filtering device 9 is connected to the rectifying device 1 so as to convey the third filtrate to the rectifying device 1 for further performing a recovery cycle, thereby recovering more long-chain dibasic acid and increasing the yield. And simultaneously collecting the solvent in the third filtrate.
With continued reference to fig. 1, in this embodiment, the fourth filtering device 9 is also capable of washing the second crystallized wet product, such as washing the filter cake with water, to obtain crystals with higher purity. In addition, since a small amount of the long-chain dibasic acid may remain in the eluate, the eluate is transferred to the rectifying apparatus 1 so as to be subjected to a recovery cycle, and further more long-chain dibasic acid is recovered.
As shown in fig. 1, in the present embodiment, the recycling system further includes a drying device 12 connected to the fourth filtering device 9 for drying the washed second crystallized wet product to obtain the long-chain dicarboxylic acid product.
Referring to fig. 1, in the present embodiment, the recycling system further includes an evaporator 13 and a temperature reducing device 14, the evaporator 13 is connected to the second filtering device 5, and the temperature reducing device 14 is connected to the evaporator 13. In another embodiment, as shown in fig. 2, the temperature reduction device 14 is further connected to the dissolution device 6.
In this embodiment, the recovery system further comprises an evaporator 13 and a temperature reduction device 14, which are in turn connected to the second filtering device 5. After the first filtrate passes through the first crystallizing device 4 and the second filtering device 5 in sequence, a first crystallized wet product is obtained, and a fourth filtrate is also obtained. The first crystallized wet product is fed to the dissolving device 6, and the fourth filtrate is fed to the evaporator 13. The evaporator 13 is configured to evaporate the fourth filtrate to obtain a first gas, and the first gas is cooled by the cooling device 14 to obtain a first liquid, so as to recover the solvent in the fourth filtrate. The first liquid can be transported from the temperature reduction device 14 to the dissolving device 6 for reuse.
Since the first wet crystallization product and the fourth filtrate are solid-liquid mixtures after being treated by the first crystallization device 4, there is a possibility that crystals are not completely precipitated, and a small amount of long-chain dibasic acid remains in the fourth filtrate. In this embodiment, the first liquid is sent to the rectifying apparatus 1 by the above-described design, so that the solvent in the mother liquid for crystallization is sufficiently recovered.
In an exemplary embodiment, the evaporator 13 is a wiped film evaporator. Because the first crystallization wet product and the fourth filtrate are solid-liquid mixtures processed by the first crystallization device 4, and the fourth filtrate may contain a small amount of long-chain dibasic acid, the wiped film evaporator has the advantages of low operation temperature, short heating time, high evaporation efficiency and the like, and coking and scaling of a liquid film on a heating surface are avoided. Of course, in other embodiments, other types may be used, and are not listed here.
As shown in fig. 1, in the present embodiment, the mixture containing the long-chain dibasic acid sequentially passes through the decoloring device 2 and the first filtering device 3 to generate a first solid, for example, activated carbon particles or powder in the decoloring device 2. Since a small amount of the long-chain dibasic acid may remain on the surface of the first solid, the first filtering device 3 can also wash the first solid, for example, wash the filter cake with water or acetic acid, and the eluent (containing the long-chain dibasic acid) is sent to the first crystallizing device 4 so as to recrystallize the eluent, thereby obtaining a larger amount of the long-chain dibasic acid and avoiding waste of resources.
It is worth mentioning that the various devices in the recycling system of the present invention are present, and the internal structure or construction of each device is well known to those skilled in the art, so that the present application is not described in detail.
It should be understood that the "mother liquid for crystallization" of the present invention may be a mother liquid for primary crystallization, a mother liquid for secondary crystallization, a mother liquid for tertiary crystallization, or a plurality of times, and the present invention is not particularly limited thereto.
To sum up, the utility model discloses a recovery system of long chain binary acid's advantage and beneficial effect lie in:
the utility model discloses a recovery system, through above-mentioned decoloration device 2, first filter equipment 3, first crystallization device 4 and the second filter equipment 5 that connects according to the preface, can carry out recycle with the mixture that contains long chain dibasic acid to extract out the higher long chain dibasic acid of purity, realized the recycle of abandonment resource.
In addition, the decoloring device 2 and the first filtering device 3 are arranged before the first crystallizing device 4, so that the mixture containing the long-chain dibasic acid is decolored before crystallization, the purity of the crystallized long-chain dibasic acid can be higher, and the condition that the decoloration is difficult in the subsequent steps due to crystallization without decoloring is avoided.
It should be noted here that the recovery system for long chain dibasic acids shown in the drawings and described in the present specification is only one example of the application of the principles of the present invention. It should be clearly understood by those skilled in the art that the principles of the present invention are not limited to any of the details or any of the components of the apparatus shown in the drawings or described in the specification.
It is to be understood that the invention is not limited in its application to the details of construction and the arrangement of components set forth in the description. The present invention is capable of other embodiments and of being practiced and carried out in a variety of ways. The foregoing variations and modifications fall within the scope of the present invention. It will be understood that the invention disclosed and defined in this specification extends to all alternative combinations of two or more of the individual features mentioned or evident from the text and/or drawings. All of these different combinations constitute various alternative aspects of the present invention. The embodiments set forth herein explain the best modes known for practicing the invention and will enable others skilled in the art to utilize the invention.
Claims (10)
1. A recovery system for long-chain dibasic acid, comprising:
a decoloring device for decoloring a mixture containing a long-chain dibasic acid;
the first filtering device is connected to the decoloring device and is used for filtering the mixture containing the long-chain dibasic acid after decoloring to obtain a first filtrate;
the first crystallization device is connected to the first filtering device and is used for crystallizing the first filtrate; and
and the second filtering device is connected with the first crystallizing device and is used for filtering the product treated by the first crystallizing device to obtain a first crystallized wet product.
2. The system for recovering long-chain dicarboxylic acid according to claim 1, wherein the mixture containing long-chain dicarboxylic acid is a residue after most of solvent is recovered from a crystallization mother liquor of long-chain dicarboxylic acid or a long-chain dicarboxylic acid precipitate accumulated in a long-chain dicarboxylic acid sewage treatment plant.
3. The recovery system of long-chain dibasic acid as claimed in claim 2, which comprises a rectification unit connected to the decolorization unit, wherein the mixture containing long-chain dibasic acid is the residue of the rectification unit.
4. The recovery system of long chain dibasic acid of claim 1, further comprising:
the dissolving device is connected to the second filtering device and is used for dissolving the first crystallized wet product to obtain a first solution;
a third filtering device connected to the dissolving device for filtering the first solution to obtain a second filtrate;
the second crystallization device is connected to the third filtering device and is used for crystallizing the second filtrate; and
and the fourth filtering device is connected with the second crystallizing device and is used for filtering the product treated by the second crystallizing device to obtain a second crystallized wet product.
5. The system for recovering long-chain dicarboxylic acid according to claim 4, wherein the product treated by the fourth filtering device further comprises a third filtrate.
6. The recovery system for long chain dibasic acid as claimed in claim 5, further comprising a drying device connected to the fourth filtering device for drying the second crystallized wet product.
7. The system for recovering long-chain dicarboxylic acid according to claim 1, wherein the product filtered by the second filtering device further comprises a fourth filtrate; the recycling system further comprises:
an evaporator connected to the second filtering device for evaporating the fourth filtrate to obtain a first gas;
and the temperature reduction device is connected with the evaporator and used for reducing the temperature of the first gas to obtain first liquid.
8. The recovery system of long chain dibasic acid of claim 7, wherein the evaporator comprises a wiped film evaporator, an evaporation kettle or a multiple effect evaporator.
9. The system for recovering a long-chain dicarboxylic acid according to claim 1, wherein the mixture comprising a long-chain dicarboxylic acid is sequentially treated by the decoloring device and the first filtering device to produce a first solid.
10. The system for recovering long-chain dicarboxylic acid according to claim 1, wherein the decoloring device comprises a decoloring agent.
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Effective date of registration: 20210826 Address after: Jining Chemical Industry Economic Development Zone, Huji Town, Jinxiang County, Jining City, Shandong Province Patentee after: KAISAI (JINXIANG) BIOMATERIAL Co.,Ltd. Patentee after: CATHAY R&D CENTER Co.,Ltd. Patentee after: CIBT USA Patentee after: Kaisai (Wusu) Biotechnology Co.,Ltd. Address before: 272200 Jining Chemical Industry Economic Development Zone, Huji Town, Jinxiang County, Shandong Province Patentee before: KAISAI (JINXIANG) BIOMATERIAL Co.,Ltd. Patentee before: CATHAY R&D CENTER Co.,Ltd. Patentee before: CIBT USA |