CN103752305B - A kind of catalyst, its preparation method and use the method for this Catalyst Production methyl acrylate co-production methyl methacrylate - Google Patents
A kind of catalyst, its preparation method and use the method for this Catalyst Production methyl acrylate co-production methyl methacrylate Download PDFInfo
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- CN103752305B CN103752305B CN201410022889.3A CN201410022889A CN103752305B CN 103752305 B CN103752305 B CN 103752305B CN 201410022889 A CN201410022889 A CN 201410022889A CN 103752305 B CN103752305 B CN 103752305B
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Abstract
The application relates to a kind of carbon monoxide-olefin polymeric, its preparation method by methyl acetate and formaldehyde synthesizing methyl acrylate co-production methyl methacrylate and uses this carbon monoxide-olefin polymeric to produce the method for methyl acrylate co-production methyl methacrylate.The carbon monoxide-olefin polymeric of the application is with SiO
2as catalyst carrier, also comprise the slaine of Cs and Zr, and the oxide of Sb.
Description
Technical field
The present invention relates to a kind of carbon monoxide-olefin polymeric, its preparation method and use this carbon monoxide-olefin polymeric to produce the method for industrial chemicals, be specifically related to a kind of for by methyl acetate and formaldehyde synthesizing methyl acrylate co-production methyl methacrylate carbon monoxide-olefin polymeric, its preparation method and use this carbon monoxide-olefin polymeric to produce the method for methyl acrylate co-production methyl methacrylate.
Background technology
Methyl acrylate is mainly used as organic synthesis intermediate, is also the monomer of synthesising macromolecule copolymer, for rubber, medicine, leather, papermaking, adhesive etc.The synthetic method of acrylic acid (ester) mainly contains: acrylonitrile hydrolysis method, oxidation of propylene and ketene process, and wherein applying more is oxidation of propylene.Adopt propylene oxidation to generate acrylic acid in industrial production, and then esterification generate corresponding ester method and has accounted for about 95%.
Along with the growing tension of petroleum resources, propylene feedstocks source is restricted, and the Coal Chemical Industry produce markets such as domestic acetic acid, formaldehyde are superfluous, most manufacturing enterprises utilization of capacity is not enough, and therefore exploitation Coal Chemical Industry raw material substitution process route synthesizing methyl acrylate and methyl methacrylate have great importance.
The research work that it is Material synthesis methyl acrylate that the many R&D institutions of recent domestic have also carried out with methyl acetate, formaldehyde.Qiqihar University Zhao Xin space etc., Harbin Institute of Technology Jing Tao, grand celebration China Tech and Daqing petrochemical Sun Wu sun and to lift a sail and Institutes Of Technology Of Taiyuan's Zhang Zhiqiang etc. is all studied at catalyst preparing and the application in methyl acetate and formaldehyde/methylal synthesis methyl acrylate.
Methyl methacrylate is mainly used in the production such as synthesis, PVC auxiliary agent, coating of lucite, is important Organic Chemicals.The production of methyl methacrylate mainly adopts ACH method both at home and abroad at present, but the method exists, and technological process is long, use hydrogen cyanide has the shortcomings such as severe toxicity.Other process routes have isobutene method, ethylene process, MGC method etc.Particularly, Lu Caite company improves ethylene process, proposes α technology, and this technology mainly comprises two courses of reaction: ethene and carbon monoxide, methyl alcohol react and generates methyl propionate under certain temperature and pressure; Methyl propionate and formolite reaction generate methyl methacrylate.
Can obtain a small amount of hydrogenation byproduct, i.e. methyl propionate in the process of methyl acetate and formaldehyde synthesizing methyl acrylate, but due to the specificity of catalyst, in the prior art, this part accessory substance is difficult to be applied.And thereby increase separation, the cost for purification of product, and the discharge of accessory substance, processing cost.In addition, because modern catalysts is of a great variety, expensive, mechanism is different, and therefore product complexity is various, therefore, also needs exploitation more, more targetedly, the carbon monoxide-olefin polymeric that customizes.
And there is not been reported in the research being raw material synthesizing methyl acrylate and methyl methacrylate simultaneously with methyl acetate and formaldehyde.
Summary of the invention
Therefore, an object of the present invention is to provide a kind of carbon monoxide-olefin polymeric, it can with methyl acetate and formaldehyde for raw material synthesizing methyl acrylate and methyl methacrylate simultaneously.
Another object of the present invention is to provide the preparation method of described carbon monoxide-olefin polymeric.
Another object of the present invention is to provide and uses described carbon monoxide-olefin polymeric with methyl acetate and the formaldehyde method for raw material synthesizing methyl acrylate and methyl methacrylate simultaneously.
According to an aspect of the present invention, which provide a kind of for the carbon monoxide-olefin polymeric by methyl acetate and formaldehyde synthesizing methyl acrylate and methyl methacrylate, said composition comprises catalyst carrier and active component, wherein, described active component comprises the slaine of Cs and Zr, and the oxide of Sb, based on the quality of described carrier, in the metallic element quality in slaine and oxide, this carbon monoxide-olefin polymeric comprises the Sb of the Zr of 0.01% ~ 0.5%, the Cs of 1% ~ 35% and 1% ~ 40%; Preferably include the Sb of the Zr of 0.02% ~ 0.4%, the Cs of 2% ~ 30% and 5% ~ 35%; More preferably the Sb of the Zr of 0.05% ~ 0.15%, the Cs of 5% ~ 25% and 10% ~ 30% is comprised;
Preferably, the slaine of described Cs is cesium carbonate, cesium nitrate, cesium chloride or cesium sulfate;
Preferably, described catalyst carrier is SiO
2, Al
2o
3or the composition of the two; Be preferably the microsphere particle that particle diameter is 50 ~ 100 microns;
Preferably, described carbon monoxide-olefin polymeric can comprise transition metal oxide further, and described transition metal oxide comprises the oxide etc. of Zn or Ni.
According to another aspect of the present invention, which provide the preparation method of described carbon monoxide-olefin polymeric, specifically comprise the following steps:
(1) Sb is taken
2o
3, be mixed with deionized water the colloidal solution that antimony molar concentration is 0.05 ~ 5mol/L;
(2) catalyst carrier is taken by the mass ratio in composition mentioned above, and stirring continuously and under 50 ~ 90 DEG C of conditions, making it mix with colloidal solution prepared in step (1), after dipping 5 ~ 24h, dry 2 ~ 5h at 80 ~ 130 DEG C;
(3) take the slaine of zirconium nitrate and caesium respectively by the mass ratio in composition mentioned above, being mixed with zirconium ion molar concentration is 0.005 ~ 0.5mol/L, and cesium ion molar concentration is the aqueous solution of 0.05 ~ 5mol/L;
(4) under continuous stirring and 50 ~ 80 DEG C of conditions, by the solids mixing prepared by solution prepared in step (3) and step (2), after dipping 5 ~ 24h, in 80 ~ 130 DEG C of drying 2 ~ 5h, then at 400 ~ 500 DEG C of roasting 3 ~ 5h, carbon monoxide-olefin polymeric is obtained.
Preferably, in step (3), make up water in solution by the salt (being generally the salt corresponding with the slaine of Cs) of transition metal Zn or Ni, wherein, the molar concentration of Zn or Ni ion is 0.01 ~ 2mol/L
Preferably, in above-mentioned steps (2), after drying at 400 ~ 500 DEG C of roasting 1 ~ 5h.
Preferably, in above-mentioned steps (2), the time of described dipping is 5 ~ 10 hours, and the temperature of described drying is 90 ~ 120 DEG C, and the time of described drying is 3 ~ 4 hours.
Preferably, in above-mentioned steps (4), the time of described dipping is 5 ~ 10 hours, and the temperature of described drying is 90 ~ 120 DEG C, and the time of described drying is 3 ~ 4 hours.
In above-mentioned preparation method, if dip time is too short, then catalyst active component can not load be on carrier fully, if dip time is oversize, then the support structures of " active component-carrier " may change, and uneconomical.
In above-mentioned preparation method, if baking temperature is too low or drying time is too short, then drying effect is insufficient, otherwise then uneconomical.
In above-mentioned preparation method, when described carbon monoxide-olefin polymeric comprises transition metal oxide further, then can further improve the selective of this carbon monoxide-olefin polymeric.
The invention provides the method using above-mentioned catalyst to be Material synthesis methyl acrylate and methyl methacrylate with methyl acetate and formaldehyde, the method comprises: with methyl acetate and formaldehyde for raw material, using methyl alcohol as the depolymerizing agent of formaldehyde, adopt atmospheric fixed bed reaction, wherein, loaded catalyst is 1 ~ 10g, preferably 1 ~ 5g, more preferably 2.0g, and described catalyst is above-mentioned carbon monoxide-olefin polymeric, with the N of 80ml/min flow
2as dispersed gas; Wherein, the mol ratio of raw material methyl acetate and formaldehyde is 1:2 ~ 8:1, and be preferably 1:1, the mol ratio of methyl alcohol and methyl acetate is 1:2 ~ 3:1, is preferably 1.5:1.Finally adopt gas chromatographic analysis product composition.
Through a large amount of experiments, applicant finds, when using the reaction of the catalyst of above-mentioned composition for methyl acetate and formaldehyde, and not only can with methyl acetate and formaldehyde for Material synthesis obtains two kinds of products, methyl acrylate and methyl methacrylate, thus accessory substance is converted into useful product; Meanwhile, also unexpectedly decrease the carbon deposition quantity of catalyst, have certain activation, palingenesis to catalyst, extend the service time of catalyst.
Study discovery through applicant, above-mentioned reaction can be represented by following equation:
CH
3COOCH
3+HCHO→CH
2=CHCOOCH
3+H
2O（1）
C+H
2O→H
2+CO（2）
CH
2=CHCOOCH
3+H
2→CH
3CH
2COOCH
3（3）
CH
3CH
2COOCH
3+HCHO→CH
2=CCH
3COOCH
3+H
2O；（4）
Reaction equation (1) and (4) represent the reaction obtaining methyl acrylate and methyl methacrylate product respectively, and are greatly reduced the carbon deposition quantity of catalyst by reaction (2) just.
Detailed description of the invention
Only illustratively, scope of the present invention is not limited to following embodiment to following examples, and when not departing from teachings of the present invention, alternate embodiment is included within technical scope of the present invention.
Embodiment one
(1) by 4.142gSb
2o
3be mixed in 50ml there-necked flask with 25ml deionized water, be heated with stirring to 75 DEG C, condensing reflux, add 2ml stabilizing agent triethanolamine, after 10min, be warming up to 85 DEG C, drip H
2o
23 ~ 4ml, continues to be stirred to solution clarification, obtains colloidal solution;
(2) SiO that 20.0g particle diameter is the microsphere particle of 50 ~ 100 microns is taken
2carrier, under 70 DEG C of conditions, by the colloidal solution that obtains in (1) and SiO
2carrier mixes, and after stirring dipping 8h continuously, in 90 DEG C of dry 2h, 450 DEG C of roasting 3h, obtain Sb/SiO
2;
(3) 0.1235gZr (NO3) is taken
45H
2o and 4.628gCsNO
3, be dissolved in 30ml deionized water;
(4) under 70 DEG C of conditions, by the mixed solution that obtains in (3) Sb/SiO with gained in (2)
2mixing, after stirring dipping 10h continuously, in 90 DEG C of dry 2h, 450 DEG C of roasting 3h, obtain SiO
2the Cs-Zr-Sb composite catalyst of upper load.
Adopt the catalyst of preparation to carry out synthesizing methyl acrylate and methyl methacrylate reaction evaluating, adopt atmospheric fixed bed reaction, wherein, loaded catalyst is 2.0g, with the N of 80ml/min flow
2as dispersed gas.
Wherein, the mol ratio of raw material methyl acetate and formaldehyde is 1:1, and the mol ratio of methyl alcohol and methyl acetate is 1.5:1, and reaction temperature is 350 DEG C, and Feed space velocities is 3h
-1.The evaluation result of this catalyst is: the conversion ratio of methyl acetate is 29.20%, and the selective of methyl acrylate is 78.98%, and the selective of methyl methacrylate is 12.57%.
Embodiment two:
Except in step (3), with 3.868gCs
2cO
3replace CsNO
3in addition, with the preparation method's Kaolinite Preparation of Catalyst composition described in embodiment one.
The condition described in embodiment one of employing carries out synthesizing methyl acrylate and methyl methacrylate reaction evaluating to this catalyst, evaluation result is: the conversion ratio of methyl acetate is 23.41%, the selective of methyl acrylate is 75.67%, and the selective of methyl methacrylate is 7.51%.
Embodiment three:
Except in step (1), by Sb
2o
3amount be increased to beyond 6.728g, with the preparation method's Kaolinite Preparation of Catalyst composition described in embodiment one.
The condition described in embodiment one of employing carries out synthesizing methyl acrylate and methyl methacrylate reaction evaluating to this catalyst, evaluation result is: the conversion ratio of methyl acetate is 32.75%, the selective of methyl acrylate is 74.27%, and the selective of methyl methacrylate is 15.62%.
Embodiment four:
Except in step (3), by CsNO
3amount be increased to beyond 7.287g, with the preparation method's Kaolinite Preparation of Catalyst composition described in embodiment one.
The condition described in embodiment one of employing carries out synthesizing methyl acrylate and methyl methacrylate reaction evaluating to this catalyst, evaluation result is: the conversion ratio of methyl acetate is 35.83%, the selective of methyl acrylate is 79.33%, and the selective of methyl methacrylate is 13.28%.
Embodiment five:
Except in step (3), replace CsNO with 3.997gCsCl
3in addition, with the preparation method's Kaolinite Preparation of Catalyst composition described in embodiment one.
The condition described in embodiment one of employing carries out synthesizing methyl acrylate and methyl methacrylate reaction evaluating to this catalyst, evaluation result is: the conversion ratio of methyl acetate is 22.31%, the selective of methyl acrylate is 80.56%, and the selective of methyl methacrylate is 10.37%.
Embodiment six:
Except in step (3), with 2.531gCs
2sO
4replace CsNO
3in addition, with the preparation method's Kaolinite Preparation of Catalyst composition described in embodiment one.
The condition described in embodiment one of employing carries out synthesizing methyl acrylate and methyl methacrylate reaction evaluating to this catalyst, evaluation result is: the conversion ratio of methyl acetate is 23.47%, the selective of methyl acrylate is 75.39%, and the selective of methyl methacrylate is 13.87%.
Embodiment seven:
The carbon monoxide-olefin polymeric that described in embodiment three prepared by preparation method is adopted to carry out synthesizing methyl acrylate and methyl methacrylate reaction evaluating, wherein, the mol ratio of raw material methyl acetate and formaldehyde is 2:1, the mol ratio of methyl alcohol and methyl acetate is 1:1, reaction temperature is 350 DEG C, and Feed space velocities is 3h
-1.The evaluation result of this catalyst is: the conversion ratio of methyl acetate is 22.17%, and the selective of methyl acrylate is 79.23%, and the selective of methyl methacrylate is 10.31%.
Embodiment eight:
The carbon monoxide-olefin polymeric that described in embodiment three prepared by preparation method is adopted to carry out synthesizing methyl acrylate and methyl methacrylate reaction evaluating, wherein, the mol ratio of raw material methyl acetate and formaldehyde is 1:1, the mol ratio of methyl alcohol and methyl acetate is 1:1.5, reaction temperature is 330 DEG C, and Feed space velocities is 3h
-1.The evaluation result of this catalyst is: the conversion ratio of methyl acetate is 21.84%, and the selective of methyl acrylate is 77.39%, and the selective of methyl methacrylate is 7.42%.
Embodiment nine:
The carbon monoxide-olefin polymeric that described in embodiment three prepared by preparation method is adopted to carry out synthesizing methyl acrylate and methyl methacrylate reaction evaluating, wherein, the mol ratio of raw material methyl acetate and formaldehyde is 1:1, the mol ratio of methyl alcohol and methyl acetate is 1:1.5, reaction temperature is 370 DEG C, and Feed space velocities is 3h
-1.The evaluation result of this catalyst is: the conversion ratio of methyl acetate is 33.74%, and the selective of methyl acrylate is 77.26%, and the selective of methyl methacrylate is 10.50%.
Embodiment ten:
The carbon monoxide-olefin polymeric that described in embodiment three prepared by preparation method is adopted to carry out synthesizing methyl acrylate and methyl methacrylate reaction evaluating, wherein, the mol ratio of raw material methyl acetate and formaldehyde is 1:1, the mol ratio of methyl alcohol and methyl acetate is 1:1.5, reaction temperature is 350 DEG C, and Feed space velocities is 5h
-1.The evaluation result of this catalyst is: the conversion ratio of methyl acetate is 23.49%, and the selective of methyl acrylate is 82.17%, and the selective of methyl methacrylate is 9.26%.
Embodiment 11:
Except among step (3), add 0.915gZn (NO further
3)
26H
2beyond O, with the preparation method's Kaolinite Preparation of Catalyst composition described in embodiment one.
The condition described in embodiment one of employing carries out synthesizing methyl acrylate and methyl methacrylate reaction evaluating to this catalyst, evaluation result is: the conversion ratio of methyl acetate is 28.73%, the selective of methyl acrylate is 85.21%, and the selective of methyl methacrylate is 11.37%.
Can find out according to above-described embodiment, when the catalyst with the present invention's composition is used for the reaction of methyl acetate and formaldehyde, with methyl acetate and formaldehyde for Material synthesis obtains two kinds of products, methyl acrylate and methyl methacrylate, thus accessory substance can be converted into useful product.
Claims (8)
1. a carbon monoxide-olefin polymeric, this carbon monoxide-olefin polymeric comprises catalyst carrier and active component, wherein, described active component comprises the slaine of Cs, and the oxide of Zr and Sb, based on the quality of described carrier, in the metallic element quality in slaine and oxide, this carbon monoxide-olefin polymeric comprises the Sb of the Zr of 0.01% ~ 0.5%, the Cs of 1% ~ 35% and 1% ~ 40%
Wherein, the slaine of described Cs is cesium carbonate, cesium nitrate, cesium chloride or cesium sulfate,
Wherein, described carbon monoxide-olefin polymeric comprises the oxide of Zn or Ni further, and wherein, based on the quality of described carrier, in the metallic element quality in oxide, this carbon monoxide-olefin polymeric comprises Zn or Ni of 0.5% ~ 20%.
2. carbon monoxide-olefin polymeric according to claim 1, wherein, based on the quality of described carrier, in the metallic element quality in slaine and oxide, this carbon monoxide-olefin polymeric comprises the Sb of the Zr of 0.02% ~ 0.4%, the Cs of 2% ~ 30% and 5% ~ 35%.
3. carbon monoxide-olefin polymeric according to claim 1, wherein, based on the quality of described carrier, in the metallic element quality in slaine and oxide, this carbon monoxide-olefin polymeric comprises the Sb of the Zr of 0.05% ~ 0.15%, the Cs of 5% ~ 25% and 10% ~ 30%.
4. the carbon monoxide-olefin polymeric according to any one of claim 1-3, wherein, described catalyst carrier is SiO
2, Al
2o
3or the composition of the two.
5. the preparation method of carbon monoxide-olefin polymeric according to any one of Claims 1 to 4, comprises the following steps:
(1) Sb is taken
2o
3, be mixed with deionized water the colloidal solution that antimony molar concentration is 0.05 ~ 5mol/L;
(2) take catalyst carrier, and stirring continuously and under 50 ~ 90 DEG C of conditions, making described catalyst carrier mix with colloidal solution prepared in step (1), after dipping 5 ~ 24h, dry 2 ~ 5h at 80 ~ 130 DEG C;
(3) take the slaine of zirconium nitrate and caesium, being mixed with zirconium ion molar concentration is 0.005 ~ 0.5mol/L, and cesium ion molar concentration is the aqueous solution of 0.05 ~ 5mol/L; Then make up water in solution by the salt of transition metal Zn or Ni further, wherein, the salt of described Zn or Ni is the salt corresponding with the slaine of described Cs, and the molar concentration of described Zn or Ni ion is 0.01 ~ 2mol/L;
(4) under continuous stirring and 50 ~ 80 DEG C of conditions, by the solids mixing prepared by solution prepared in step (3) and step (2), after dipping 5 ~ 24h, in 80 ~ 130 DEG C of drying 2 ~ 5h, then 400 ~ 500 DEG C of roasting 3 ~ 5h, obtain carbon monoxide-olefin polymeric
Wherein, the mass ratio of each component is identical with the mass ratio of each component of carbon monoxide-olefin polymeric according to any one of claims 1 to 3.
6. preparation method according to claim 5, wherein,
In described step (2), after drying at 400 ~ 500 DEG C of roasting 1 ~ 5h, and the time of described dipping be 5 ~ 10 hours, the temperature of described drying is 90 ~ 120 DEG C, and the time of described drying is 3 ~ 4 hours, and
In above-mentioned steps (4), the time of described dipping is 5 ~ 10 hours, and the temperature of described drying is 90 ~ 120 DEG C, and the time of described drying is 3 ~ 4 hours.
7. the method that is Material synthesis methyl acrylate and methyl methacrylate with methyl acetate and formaldehyde, the method comprises: with methyl acetate and formaldehyde for raw material, using methyl alcohol as the depolymerizing agent of formaldehyde, adopt atmospheric fixed bed reaction, wherein, loaded catalyst is 1 ~ 10g, and the carbon monoxide-olefin polymeric of described catalyst according to any one of claim 1-4, with the N of 80ml/min flow
2as dispersed gas, wherein, the mol ratio of raw material methyl acetate and formaldehyde is 1:2 ~ 2:1, and the mol ratio of methyl alcohol and methyl acetate is 1:2 ~ 3:1.
8. method according to claim 7, wherein,
Described loaded catalyst is 1 ~ 5g, and the mol ratio of raw material methyl acetate and formaldehyde is 1:1, and the mol ratio of methyl alcohol and methyl acetate is 1.5:1.
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| CN104275172A (en) * | 2014-09-10 | 2015-01-14 | 江苏金聚合金材料有限公司 | High-stability catalyst for synthesizing methyl acrylate and preparation method of high-stability catalyst for synthesizing methyl acrylate |
| CN104525176B (en) * | 2014-12-16 | 2017-05-17 | 旭阳化学技术研究院有限公司 | Preparation method of Cs-based catalyst microsphere, microsphere prepared by adopting preparation method, and method for synthesizing (methyl) acrylic acid methyl ester by utilizing microsphere |
| CN106423159B (en) * | 2016-09-08 | 2019-07-23 | 万华化学集团股份有限公司 | A kind of anti-carbon aldol condensation catalyst and preparation method thereof and method using the catalyst preparation methyl methacrylate |
| CN108097305B (en) * | 2016-11-25 | 2020-09-04 | 中国科学院大连化学物理研究所 | Regeneration method of catalyst for preparing acrylic acid and/or methyl acrylate |
| CN108097289B (en) * | 2016-11-25 | 2020-09-04 | 中国科学院大连化学物理研究所 | Regeneration method of catalyst for preparing acrylic acid and/or methyl acrylate |
| CN108097335A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of method that regeneration prepares the catalyst of unsaturated acids and/or unsaturated acid ester |
| CN107721855B (en) * | 2017-10-13 | 2021-01-19 | 北京博迩科技有限公司 | Method for preparing 3-methoxy methyl propionate |
| CN113713819B (en) * | 2020-05-26 | 2023-12-01 | 北京旭阳科技有限公司 | Catalyst composition and preparation method and application thereof |
| CN112221482B (en) * | 2020-11-03 | 2023-02-03 | 中触媒新材料股份有限公司 | Catalyst for synthesizing methyl acrylate or methyl methacrylate and application |
| CN112427031A (en) * | 2020-11-30 | 2021-03-02 | 中触媒新材料股份有限公司 | Preparation method and application of catalyst for synthesizing methyl acrylate/methyl methacrylate |
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Inventor after: Zhang Yingwei Inventor after: Zhang Lingwei Inventor after: Dang Weirong Inventor after: Wang Yaohong Inventor after: Wang Peng Inventor after: Sun Changjiang Inventor before: Zhang Yingwei Inventor before: Zhang Lingwei Inventor before: Wang Yaohong Inventor before: Wang Peng Inventor before: Sun Changjiang |
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Effective date of registration: 20180531 Address after: 061113 west side of Xu Yang Street, north of Bohai Road, Bohai New District, Hebei Patentee after: Cangzhou Xu Yang science and Technology Co., Ltd. Address before: 100070 building 21, zone 188, South Fourth Ring Road, Fengtai District, Beijing. Patentee before: Xuyang Chemical Technology Research Institute Co., Ltd. |
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Effective date of registration: 20190513 Address after: 100070 301, 3 floor, 21 building, 188 District, South Fourth Ring Road, Fengtai District, Beijing. Patentee after: BEIJING RISUN TECHNOLOGY CO., LTD. Address before: 061113 west side of Xu Yang Street, north of Bohai Road, Bohai New District, Hebei Patentee before: Cangzhou Xu Yang science and Technology Co., Ltd. |