CN102586032A - Production method for biodiesel - Google Patents
Production method for biodiesel Download PDFInfo
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- CN102586032A CN102586032A CN201210035500XA CN201210035500A CN102586032A CN 102586032 A CN102586032 A CN 102586032A CN 201210035500X A CN201210035500X A CN 201210035500XA CN 201210035500 A CN201210035500 A CN 201210035500A CN 102586032 A CN102586032 A CN 102586032A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000003225 biodiesel Substances 0.000 title abstract 4
- 238000000034 method Methods 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002028 Biomass Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 11
- 239000000194 fatty acid Substances 0.000 claims abstract description 11
- 229930195729 fatty acid Natural products 0.000 claims abstract description 11
- 238000007670 refining Methods 0.000 claims abstract description 10
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- -1 triglyceride fatty acid Chemical class 0.000 claims abstract description 6
- 238000004061 bleaching Methods 0.000 claims abstract description 5
- 230000036571 hydration Effects 0.000 claims abstract description 5
- 238000006703 hydration reaction Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000001179 sorption measurement Methods 0.000 claims abstract description 5
- 239000003921 oil Substances 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 19
- 239000002551 biofuel Substances 0.000 claims description 15
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 7
- 150000002194 fatty esters Chemical class 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 238000005809 transesterification reaction Methods 0.000 claims description 4
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 4
- 239000006200 vaporizer Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000010865 sewage Substances 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000003729 cation exchange resin Substances 0.000 abstract 1
- 125000004185 ester group Chemical group 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 230000009965 odorless effect Effects 0.000 abstract 1
- 238000005292 vacuum distillation Methods 0.000 abstract 1
- 239000012535 impurity Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 3
- 238000005815 base catalysis Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 210000001161 mammalian embryo Anatomy 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108010048734 sclerotin Proteins 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 229940088594 vitamin Drugs 0.000 description 2
- 229930003231 vitamin Natural products 0.000 description 2
- 235000013343 vitamin Nutrition 0.000 description 2
- 239000011782 vitamin Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012075 bio-oil Substances 0.000 description 1
- 238000010364 biochemical engineering Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Liquid Carbonaceous Fuels (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention belongs to the technical field of chemical biodiesel, and particularly relates to a production method for biodiesel. The production method for the biodiesel comprises the following steps of: (1) physically and chemically refining biomass oil: refining raw biomass oil into colorless, odorless and transparent triglyceride fatty acid mixture through filtration, hydration degumming, adsorption bleaching and a solvent dewaxing process; and (2) producing fatty acid ester of different carbon chain lengths: adding the refined biomass obtained after treatment and the low carbon alcohol into a catalytic refining tower according to a molar ratio of 1-6:1, wherein AlCl3-loaded strong-acid cation exchange resin is used as a catalyst bed in the catalytic refining tower; diatomite is used as an inertial layer of the catalyst bed; the refined biomass oil and the low carbon alcohol are subjected to catalytic ester exchange reaction under the conditions of reaction temperature of 50-120 DEG C and the reaction pressure of normal pressure for the reaction time of 2-3.5 hours to obtain fatty acid ester; and the fatty acid ester is added into an evaporator to perform vacuum distillation, separation and purification. A method adopted by the invention has a simple and feasible technological line; a product is easily separated from a catalyst; the catalyst can be repeatedly used; the application cost of the catalyst is saved; and meanwhile, a large amount of sewage is not produced so as not to cause environmental pollution.
Description
Technical field
The invention belongs to the technical field of chemical industry biofuel, relate to a kind of working method of biofuel particularly.
Background technology
Along with the sustained and rapid development of Chinese national economy, the equilibrium of supply and demand problem of diesel oil has become the focus of China's oil market development.In recent years; Although oil refining enterprise makes bavin/vapour than progressively improving through employing new technology; But still can not satisfy growing diesel oil demand, and can produce a large amount of oxysulfide, oxynitride and carbon soot particles behind the diesel combustion, enter and can cause serious environmental to pollute in the atmosphere.Biofuel is the renewable energy source of cleaning, is fine petroleum diesel substitute, greatly develops biofuel to sustainable economic development, alleviates environmental stress, and the control urban atmospheric pollution is significant.
The production of the biofuel of prior art, the main employing adds alkali and handles with depickling in carrying out, to take off the free fatty acids of bio-oil; Thereby can produce a large amount of soda acid wastes; Contaminate environment and production cost are high, and the limited range of raw material is big, waste is more, and yield is lower.
Production biofuel main method is an ester-interchange method in the industry.Ester-interchange method comprises acid catalysis, base catalysis, biological enzyme and overcritical ester-interchange method etc.Wherein the catalyzer used of acid catalyzed process is an an acidic catalyst, mainly contains sulfuric acid, hydrochloric acid and phosphoric acid etc.Acid base catalysator was not easy to separate with product when classical acid base catalysis legal system was equipped with biofuel, and the acid base catalysator that exists in the product must neutralize and wash, thereby produced a large amount of sewage, and soda acid can not be reused, and brought higher catalyzer cost.Simultaneously, acid base catalysator has stronger corrodibility to equipment.
The people such as Yang Kaihua of " biochemical engineering " report are earlier with the reaction product static layering; Supernatant liquid is the mixing solutions of fatty acid methyl ester and methyl alcohol;, distillation obtains fatty acid methyl ester after telling methyl alcohol; Lower floor's liquid is the byproduct of reaction raw glycerine, and raw glycerine adds methyl alcohol dilution back and uses the underpressure distillation refining glycerine.Its technical matters route is complicated, and separation is imitated lower, and product activity is lower.
Summary of the invention
The working method that the objective of the invention is to be directed against the defective of above-mentioned existence and a kind of biofuel is provided.The method operational path that the present invention adopted is simple, and makes product and catalyzer separate easily, and catalyzer can be reused, and has practiced thrift the cost that uses catalyzer, can not produce large amount of sewage simultaneously and cause environmental pollution.
Technical scheme of the present invention is: a kind of working method of biofuel, and the step of this working method is following:
(1) physics of biomass oils and chemical refining: adopt and filter hydration degum, adsorption bleaching, solvent method dewaxing process
Biomass starting material oils is refined into the mixture of the transparent tri-glyceride of no color or smell;
(2) production of carbon chain lengths different fatty acids ester: will after step (1) is handled, join in the catalytic rectifying tower by molar ratio 1～6:1 with low-carbon alcohol by the refined raw material oil of gained, this catalytic rectifying tower is with load AlCl
3Strongly acidic cationic exchange resin be beds; With zeyssatite is the inert layer of beds; Said refined raw material oil is 50 ℃～120 ℃ with low-carbon alcohol in temperature of reaction, and reaction pressure is under the non-pressurized condition, carries out catalyzed transesterification; Reaction times is 2～3.5h, obtains fatty ester; Separate purification with carrying out underpressure distillation in this fatty ester adding vaporizer.
Low-carbon alcohol in the said step (2) is methyl alcohol or ethanol, and corresponding fatty ester is fatty acid methyl ester or fatty-acid ethyl ester.
Vaporizer in the said step (2) is a thin-film evaporator.
Beneficial effect of the present invention is: compared with prior art; The present invention adopts solid acid catalyst catalysis biomass oils to compare with the homogeneous acid base catalysis method that extensively adopts at present with the reaction of low-carbon alcohol reacted fatty ester; Product is easy to separate with catalyzer; And avoided the discharging of a large amount of spent acid salkali waste, effectively prevented the pollution of environment.
The method operational path that the present invention adopted is simple; Improved raw material availability; Reduce the usage quantity of low-carbon alcohol, the raw materials components mole ratio of present method raw material oils and alcohols is 1～6:1, and the conventional an acidic catalyst method raw material oils of prior art and the raw materials components mole ratio of alcohols are 1:4.And method used in the present invention makes product and catalyzer separate easily, and catalyzer can be reused, and has practiced thrift the cost that uses catalyzer, can not produce large amount of sewage simultaneously and cause environmental pollution.Operate continuously is convenient in the easily-activated regeneration of used solid acid catalyst, has shortened the production cycle, and the required reaction times of working method of the present invention is 2～3.5h, and the required reaction times of conventional an acidic catalyst method of prior art is 4～9h.Present method has improved the flexibility of technology to raw material on the one hand; Improve utilization ratio of raw materials on the other hand, reduced raw materials cost; Moreover reduced the acid number of product, and improved product production, can know that through the on probation of biofuel that this method is produced it is superior to petrifaction diesel aspect the external combustion.
Biofuel through this process method is produced detects: its each item performance index reach or are superior to the requirement of the up-to-date GB CB/T19147-2003 of diesel oil, meet the requirement of world's fuel oil standard II level diesel quality standard, specific targets such as following table:
Embodiment
Carry out detailed explanation in the face of the technical scheme of invention down.
Embodiment one
(1) physics of biomass oils and chemical refining: from animal and plant body oils; Because the source has various impurity with different the containing of the course of processing, wherein mechanical impurity comprises silt, material embryo powder, fiber, careless bits, sclerotin, metal etc.; Water-soluble impurity comprises moisture, protein, carbohydrate, resene; Colloid, oil soluble impurity comprise free lipid acid, VITAMINs, pigment, wax and phosphatide, polycyclic aromatic hydrocarbons etc., therefore at first must make with extra care the oils raw material.Adopt and filter, hydration degum, adsorption bleaching, solvent method dewaxing process are refined into biomass starting material oils in the mixture of the transparent tri-glyceride of no color or smell;
(2) production of fatty acid methyl ester: will after step (1) is handled, join in the catalytic rectifying tower by molar ratio 4:1 with methyl alcohol by the refined raw material oil of gained, this catalytic rectifying tower is with load AlCl
3Strongly acidic cationic exchange resin be beds, be the inert layer of beds with zeyssatite, said refined raw material oil is 90 ℃ with methyl alcohol in temperature of reaction; Reaction pressure is under the non-pressurized condition; Carry out catalyzed transesterification, the reaction times is 3h, obtains fatty acid methyl ester; Separate purification with carrying out underpressure distillation in this fatty acid methyl ester adding thin-film evaporator.
Embodiment two
(1) physics of biomass oils and chemical refining: from animal and plant body oils; Because the source has various impurity with different the containing of the course of processing, wherein mechanical impurity comprises silt, material embryo powder, fiber, careless bits, sclerotin, metal etc.; Water-soluble impurity comprises moisture, protein, carbohydrate, resene; Colloid, oil soluble impurity comprise free lipid acid, VITAMINs, pigment, wax and phosphatide, polycyclic aromatic hydrocarbons etc., therefore at first must make with extra care the oils raw material.Adopt and filter, hydration degum, adsorption bleaching, solvent method dewaxing process are refined into biomass starting material oils in the mixture of the transparent tri-glyceride of no color or smell;
(2) production of fatty-acid ethyl ester: will after step (1) is handled, join in the catalytic rectifying tower by molar ratio 3:1 with ethanol by the refined raw material oil of gained, this catalytic rectifying tower is with load AlCl
3Strongly acidic cationic exchange resin be beds, be the inert layer of beds with zeyssatite, said refined raw material oil is 80 ℃ with ethanol in temperature of reaction; Reaction pressure is under the non-pressurized condition; Carry out catalyzed transesterification, the reaction times is 2.5h, obtains fatty-acid ethyl ester; Separate purification with carrying out underpressure distillation in this fatty-acid ethyl ester adding thin-film evaporator.
Claims (3)
1. the working method of a biofuel is characterized in that, the step of this working method is following:
(1) physics of biomass oils and chemical refining: adopt and filter, hydration degum, adsorption bleaching, solvent method dewaxing process are refined into biomass starting material oils in the mixture of the transparent tri-glyceride of no color or smell;
(2) production of carbon chain lengths different fatty acids ester: will after step (1) is handled, join in the catalytic rectifying tower by molar ratio 1～6:1 with low-carbon alcohol by the refined raw material oil of gained, this catalytic rectifying tower is with load AlCl
3Strongly acidic cationic exchange resin be beds; With zeyssatite is the inert layer of beds; Said refined raw material oil is 50 ℃～120 ℃ with low-carbon alcohol in temperature of reaction, and reaction pressure is under the non-pressurized condition, carries out catalyzed transesterification; Reaction times is 2～3.5h, obtains fatty ester; Separate purification with carrying out underpressure distillation in this fatty ester adding vaporizer.
2. according to the working method of the said biofuel of claim 1, it is characterized in that the low-carbon alcohol in the said step (2) is methyl alcohol or ethanol, corresponding fatty ester is fatty acid methyl ester or fatty-acid ethyl ester.
3. according to the working method of the said biofuel of claim 1, it is characterized in that the vaporizer in the said step (2) is a thin-film evaporator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210035500XA CN102586032B (en) | 2012-02-17 | 2012-02-17 | Production method for biodiesel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210035500XA CN102586032B (en) | 2012-02-17 | 2012-02-17 | Production method for biodiesel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102586032A true CN102586032A (en) | 2012-07-18 |
| CN102586032B CN102586032B (en) | 2013-07-10 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210035500XA Active CN102586032B (en) | 2012-02-17 | 2012-02-17 | Production method for biodiesel |
Country Status (1)
| Country | Link |
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| CN (1) | CN102586032B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106318648A (en) * | 2015-06-30 | 2017-01-11 | 中国科学院大连化学物理研究所 | Transesterification method based on microchannel reactor |
Citations (5)
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|---|---|---|---|---|
| CN1687312A (en) * | 2005-04-21 | 2005-10-26 | 浙江工业大学 | Method for producing biologic diesel oil through waterpower cavitation |
| CN1966614A (en) * | 2005-11-17 | 2007-05-23 | 香港中文大学 | Method for preparing biological diesel fuel |
| CN101070480A (en) * | 2006-05-12 | 2007-11-14 | 中国石油化工股份有限公司 | Process for preparing biological diesel oil |
| CN101486923A (en) * | 2009-02-05 | 2009-07-22 | 迟洪军 | Environment friendly process for biodiesel |
| CN201330241Y (en) * | 2009-01-05 | 2009-10-21 | 山东省花生研究所 | Device for producing refined biodiesel with high acid value oil |
-
2012
- 2012-02-17 CN CN201210035500XA patent/CN102586032B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1687312A (en) * | 2005-04-21 | 2005-10-26 | 浙江工业大学 | Method for producing biologic diesel oil through waterpower cavitation |
| CN1966614A (en) * | 2005-11-17 | 2007-05-23 | 香港中文大学 | Method for preparing biological diesel fuel |
| CN101070480A (en) * | 2006-05-12 | 2007-11-14 | 中国石油化工股份有限公司 | Process for preparing biological diesel oil |
| CN201330241Y (en) * | 2009-01-05 | 2009-10-21 | 山东省花生研究所 | Device for producing refined biodiesel with high acid value oil |
| CN101486923A (en) * | 2009-02-05 | 2009-07-22 | 迟洪军 | Environment friendly process for biodiesel |
Non-Patent Citations (1)
| Title |
|---|
| 闵恩泽等: "《生物柴油产业链的开拓--生物柴油炼油化工厂》", 31 December 2006, 中国石化出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106318648A (en) * | 2015-06-30 | 2017-01-11 | 中国科学院大连化学物理研究所 | Transesterification method based on microchannel reactor |
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| Publication number | Publication date |
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| CN102586032B (en) | 2013-07-10 |
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Effective date of registration: 20191119 Address after: 276600 west section of Junan County, Linyi City, Shandong Province, Huaihailu Road Patentee after: Linyi Shinengde Environmental Protection Fuel Chemical Co.,Ltd. Address before: 250100, building 2, No. 11, Qilihe Road, Licheng District, Shandong, Ji'nan Patentee before: Xinghuo Sci. & Tech. Research Inst., Jinan Dev. Zone |
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Effective date of registration: 20200713 Address after: Room 401, unit 2, building 11, No.2, Qilihe Road, Licheng District, Jinan City, Shandong Province 250100 Patentee after: SHANDONG XINGHUO INTELLECTUAL PROPERTY SERVICE Co.,Ltd. Address before: 276600 west section of Junan County, Linyi City, Shandong Province, Huaihailu Road Patentee before: LINYI SHINENGDE ENVIRONMENTAL PROTECTION FUEL CHEMICAL Co.,Ltd. |
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Effective date of registration: 20211009 Address after: Room 608, 6 / F, Zhongxing business enterprise development center, Pingshang Town, Lingang Economic Development Zone, Linyi City, Shandong Province Patentee after: Linyi Xinghuo Intellectual Property Service Co.,Ltd. Address before: Room 401, unit 2, building 11, No.2, Qilihe Road, Licheng District, Jinan City, Shandong Province 250100 Patentee before: SHANDONG XINGHUO INTELLECTUAL PROPERTY SERVICE Co.,Ltd. |