CN105617962B - A kind of internal and external circulation type ultrasonic-microwave stirred autoclave - Google Patents
A kind of internal and external circulation type ultrasonic-microwave stirred autoclave Download PDFInfo
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- CN105617962B CN105617962B CN201610111606.1A CN201610111606A CN105617962B CN 105617962 B CN105617962 B CN 105617962B CN 201610111606 A CN201610111606 A CN 201610111606A CN 105617962 B CN105617962 B CN 105617962B
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- 238000003756 stirring Methods 0.000 claims abstract description 27
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000005540 biological transmission Effects 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
- B01J19/0066—Stirrers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/20—Mixing gases with liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/80—Mixing plants; Combinations of mixers
- B01F33/82—Combinations of dissimilar mixers
- B01F33/822—Combinations of dissimilar mixers with moving and non-moving stirring devices in the same receptacle
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
- B01F2101/2204—Mixing chemical components in generals in order to improve chemical treatment or reactions, independently from the specific application
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00101—Reflux columns
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/18—Details relating to the spatial orientation of the reactor
- B01J2219/185—Details relating to the spatial orientation of the reactor vertical
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
A kind of internal and external circulation type ultrasonic-microwave stirred autoclave, it is related to ultrasonic technology application apparatus field, it mainly include autoclave body, autoclave body upper end is equipped with feed inlet, lower end is equipped with discharge port, two parts up and down are broadly divided into inside autoclave body, its middle and upper part is divided, autoclave body upper end center is equipped with axis, axis lower end is equipped with rotor, rotor is located inside autoclave body, inner wall of kettle is equipped with horn-like aggregate bin, the small mouth down of aggregate bin, autoclave body inner lower point mainly includes stirring main shaft, stirring main shaft is attached across autoclave body bottom center, bottom center is equipped with positive tetragonal body ultrasonic transmission device in autoclave body, it connects stirring main shaft and is equipped with stirrer paddle, the inner wall of autoclave body inner lower point is equipped with connecting rod, connecting rod connects cylinder.The configuration of the present invention is simple, design rationally, are divided into kettle using liquid and being mixed three times, and sufficiently, effect is obvious for stirring.
Description
Technical field：
The present invention relates to ultrasonic-microwave-microwave technology application apparatus fields, and in particular to internal and external circulation type ultrasonic wave-
Microwave-microwave stirred autoclave.
Background technique：
Ultrasonic-microwave and microwave play an important role in chemical synthesis, and chemical effect can accelerate chemical anti-
It answers speed and there is selectivity to specific reaction.When ultrasonic-microwave is propagated in the medium, due to ultrasonic-microwave and it is situated between
The interaction of matter, make medium occur physics and chemistry variation, thus generate a series of mechanics, calorifics, electromagnetism
And chemistry ultrasonic effect.The mechanism of ultrasonic-microwave can facilitate point of the emulsification of liquid, the liquefaction of gel and solid
It dissipates；The minute bubbles that ultrasonic cavitation is formed can constantly move, grow up or vanish suddenly with the vibration of surrounding medium.When vanishing
Surrounding liquid pours bubble suddenly and generates high temperature, high pressure, while generating shock wave；The effect of ultrasonic-microwave can promote to occur
Or accelerate certain chemical reactions.Such as the pure sonicated rear generation hydrogen peroxide of distilled water；Dissolved with nitrogen water through ultrasound
Nitrous acid is generated after processing；It can change colour or fade after the aqueous solution of dyestuff is sonicated.Ultrasonic-microwave can also accelerate many
Hydrolysis, decomposition and the polymerization process of chemical substance.Ultrasonic-microwave also has a significant effect to photochemistry and electrochemical process.Respectively
After the aqueous solution of kind amino acid and other organic substances is sonicated, characteristic absorption spectrum band disappears and generally inhales in uniform
It receives, this shows that cavitation changes molecular structure.Under the action of microwave high-frequency electric field, polar molecule is repeatedly quick
Orientation rotates and frictional heat generation；Internal ion vibrates under microwave action can also convert vibrational energy into heat；General molecule
Also increase energy of thermal motion after microwave energy being absorbed；Reactant molecule will be deformed and vibrate, and then influence chemistry
The generation etc. of reaction.
Since the thermo-responsive degree of some reactions is different, and in other reaction process then can endothermic heat of reaction or reaction put
Heat, just unavoidably there is heat transfer process in this.If stirring cannot radiate in time or reaction heat can not be adjusted cause be
Temperature control in uniting, chemical reaction process and equipment can all generate serious danger.The common microwave or ultrasound with stirring
Control of the wave-microwave device for device internal heat, all has no idea to realize, using above there is certain limitation.
Summary of the invention：
The technical problem to be solved by the present invention lies in overcoming the defects of the prior art, provides a kind of internal and external circulation type ultrasound
Wave-microwave-microwave stirred autoclave.
The technical problems to be solved by the invention are realized using following technical scheme.
Internal and external circulation type ultrasonic-microwave stirred autoclave, mainly includes autoclave body, and autoclave body upper end is equipped with feed inlet, lower end
Equipped with discharge port, it is characterised in that：Two parts up and down are broadly divided into inside the autoclave body, middle and upper part, which is divided, mainly includes,
Autoclave body upper end center is equipped with axis, and axis upper end is equipped with belt pulley I, and belt pulley I connects motor I, and motor I is located at autoclave body upper end, under axis
End is equipped with rotor, and rotor is located inside autoclave body, and the inner wall of kettle is equipped with horn-like aggregate bin, aggregate bin osculum court
Under, the autoclave body inner lower point mainly includes stirring main shaft, and stirring main shaft is attached across autoclave body bottom center, stirring main shaft
Lower end is equipped with belt pulley II, and belt pulley II connects motor II, and bottom center is sent out equipped with positive tetragonal body ultrasonic-microwave in the autoclave body
Injection device, connection stirring main shaft are equipped with stirrer paddle, and the inner wall of autoclave body inner lower point is equipped with connecting rod, connecting rod connection
Cylinder.
The horn-like aggregate bin osculum is located at below rotor, and osculum diameter is less than the diameter of rotor, convenient for collection
Hopper collects the liquid that rotor produces.
The upper end nozzle of the cylinder is located at the horizontal top of aggregate bin osculum, and ultrasonic-microwave can be along headwall biography of gathering materials
Enter cylinder interior.
The stirring main shaft is equipped with straight leaf dasher.
The kettle wall lower end of the autoclave body is equipped with hole I, and the kettle wall upper end of autoclave body is equipped with hole II, and hole I and hole II pass through pipeline
Connection, pipeline are equipped with pump, and pipeline is equipped with condenser, re-start mixing convenient for extracting.
The pump is located on the pipeline outside autoclave body.
The pipeline of the connecting hole II extends in rotor.
The feed inlet is equipped with pipeline and is connected on the extensional pipeline in hole II.
The positive tetragonal body ultrasonic-microwave emitter is located in stirring main shaft, and rotatably transmitting range is wide, effect
It is good.
The horn-like aggregate bin lower surface is equipped with support plate, and support plate is perpendicular to horn-like aggregate bin following table
Face, convenient for being refracted into cylinder for super body wave.
The configuration of the present invention is simple, design rationally, four mixings, a bottom flat leaf are divided into using liquid in kettle
Agitating paddle driving liquid recycles the mixing realized on fluid orthogonal direction in guide shell, and intermediate hinged joint stirrer paddle is used for fluid
Mixing in horizontal direction, top filler rotor realize gas-liquid mixed, and the offer of bottom ultrasonic-microwave transmitter can be with liquid in kettle
The whole ultrasonic mixing of body, sufficiently, mixed effect is obvious, high-efficient for stirring.Outer circulation by pump by hydrothermal solution through pipe outside condensation
Device realizes heat exchange cooling, is pumped into top rotor and high-temperature gas carries out heat exchange, realizes that pressure is adjusted in kettle.Bottom microwave dress
It sets and realizes that liquid is evenly heated in kettle, convenient for the control of temperature.
Detailed description of the invention：
Fig. 1 is the structural diagram of the present invention；
1：Autoclave body；2：Feed inlet；3：Discharge port；4：Axis；5：Belt pulley I；6：Motor I；7：Filler rotor；8：Aggregate bin；
9：Stirring main shaft；10：Belt pulley II；11：Motor II；12：Positive tetragonal body ultrasonic-microwave emitter；13：Hinged joint stirring
Paddle；14：Connecting rod；15：Guide shell；16：Straight leaf agitating paddle；17：Hole I；18：Hole II；19：Pump；20：Condenser；21：Support
Plate.
Specific embodiment：
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below
Conjunction is specifically illustrating, and the present invention is further explained.
Internal and external circulation type ultrasonic-microwave microwave stirred autoclave as shown in Figure 1 mainly includes autoclave body 1, autoclave body upper end
Equipped with feed inlet 2, lower end is equipped with discharge port 3, and two parts up and down, the main packet in middle and upper part point are wherein broadly divided into inside autoclave body
It includes, autoclave body upper end center is equipped with axis 4, and axis upper end is equipped with belt pulley I 5, and belt pulley I connects motor I 6, and motor I is located on autoclave body
End, axis lower end are equipped with rotor 7, and rotor is located inside autoclave body, and wherein inner wall of kettle is equipped with horn-like aggregate bin 8, aggregate bin
Small mouth down, wherein autoclave body inner lower point mainly includes stirring main shaft 9, and stirring main shaft is attached across autoclave body bottom center, stirs
Main shaft lower end is mixed equipped with belt pulley II 10, belt pulley II connects motor II 11, and wherein bottom center is super equipped with positive tetragonal body in autoclave body
Sound wave-microwave launcher 12, connection stirring main shaft are equipped with stirrer paddle 13, and the inner wall of autoclave body inner lower point, which is equipped with, to be connected
Extension bar 14, connecting rod connect cylinder 15.
Wherein horn-like aggregate bin osculum is located at below rotor, and osculum diameter is less than the diameter of rotor, convenient for gathering materials
Bucket collects the liquid that rotor produces.
Wherein the upper end nozzle of cylinder is located at the horizontal top of aggregate bin osculum, and ultrasonic-microwave can be incoming along the headwall that gathers materials
Cylinder interior.
Wherein stirring main shaft is equipped with straight leaf dasher 16.
Wherein the kettle wall lower end of autoclave body is equipped with hole I 17, and the kettle wall upper end of autoclave body is equipped with hole II 18, and hole I and hole II pass through pipe
Road connection, pipeline are equipped with pump 19, and pipeline is equipped with condenser 20, re-start mixing convenient for extracting.
Wherein pump is located on the pipeline outside autoclave body.
Wherein the pipeline of connecting hole II extends in rotor.
Its middle charging aperture is equipped with pipeline and is connected on the extensional pipeline in hole II.
Wherein positive tetragonal body ultrasonic-microwave emitter is located in stirring main shaft, and rotatably transmitting range is wide, effect
It is good.
Wherein horn-like aggregate bin lower surface is equipped with support plate 21, and support plate is perpendicular to horn-like aggregate bin following table
Face, convenient for being refracted into cylinder for super body wave.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (1)
1. a kind of internal and external circulation type ultrasonic-microwave stirred autoclave mainly includes autoclave body, autoclave body upper end is equipped with feed inlet, under
End is equipped with discharge port, it is characterised in that：Two parts up and down, the main packet in middle and upper part point are broadly divided into inside the autoclave body
It includes, autoclave body upper end center is equipped with axis, and axis upper end is equipped with belt pulley I, and belt pulley I connects motor I, and motor I is located at autoclave body upper end, axis
Lower end is equipped with rotor, and rotor is located inside autoclave body, and the inner wall of kettle is equipped with horn-like aggregate bin, aggregate bin osculum court
Under, the autoclave body inner lower point mainly includes stirring main shaft, and stirring main shaft is attached across autoclave body bottom center, stirring main shaft
Lower end is equipped with belt pulley II, and belt pulley II connects motor II, and bottom center is equipped with positive tetragonal body ultrasonic wave transmitting dress in the autoclave body
It sets, connection stirring main shaft is equipped with stirrer paddle, and the inner wall of autoclave body inner lower point is equipped with connecting rod, connecting rod connection circle
Cylinder, the stirring main shaft are equipped with straight leaf dasher, and straight leaf dasher leading portion is located under cylinder barrel
End；
The horn-like aggregate bin osculum is located at below rotor, and osculum diameter is less than the diameter of rotor；
The upper end nozzle of the cylinder is located at the horizontal top of aggregate bin osculum；
The kettle wall lower end of the autoclave body is equipped with hole I, and the kettle wall upper end of autoclave body is equipped with hole II, and hole I is connect with hole II by pipeline,
Pipeline is equipped with pump, and pipeline is equipped with condenser；
The pump is located on the pipeline outside autoclave body；
The pipeline of the connecting hole II extends in rotor；
The feed inlet is equipped with pipeline and is connected on the extensional pipeline in hole II；
The positive tetragonal body ultrasonic transmission device is located in stirring main shaft；
The horn-like aggregate bin lower surface is equipped with support plate, and support plate is perpendicular to horn-like aggregate bin lower surface.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610111606.1A CN105617962B (en) | 2016-02-27 | 2016-02-27 | A kind of internal and external circulation type ultrasonic-microwave stirred autoclave |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610111606.1A CN105617962B (en) | 2016-02-27 | 2016-02-27 | A kind of internal and external circulation type ultrasonic-microwave stirred autoclave |
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| CN105617962B true CN105617962B (en) | 2018-11-23 |
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| CN109382053B (en) * | 2018-11-12 | 2020-12-25 | 安徽科技学院 | Multi-transmission process integrated device |
| CN111282906A (en) * | 2020-02-27 | 2020-06-16 | 无锡市张华医药设备有限公司 | A high-efficient boiling and washing all-in-one for inflammable and explosive chemicals |
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| US6015597A (en) * | 1997-11-26 | 2000-01-18 | 3M Innovative Properties Company | Method for coating diamond-like networks onto particles |
| CN103159883B (en) * | 2011-12-09 | 2015-10-21 | 中国石油化工股份有限公司 | For the preparation of the material method for pre mixing of polyisoprene rubber and the preparation method of polyisoprene rubber |
| CN202953834U (en) * | 2012-11-08 | 2013-05-29 | 广西华纳新材料科技有限公司 | Nanometer calcium carbonate carbonation reaction still |
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| CN205495570U (en) * | 2016-02-27 | 2016-08-24 | 安徽海德石油化工有限公司 | Inside and outside circulating ultrasonic wave - microwave stirring reation kettle |
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Address after: 238251 fine chemical base of Wujiang Town, Wujiang, Anhui Province Applicant after: ANHUI HAIDE CHEMICAL TECHNOLOGY Co.,Ltd. Address before: 238251 fine chemical base of Wujiang Town, Wujiang, Anhui Province Applicant before: ANHUI HAIDE PETROCHEMICAL Co.,Ltd. |
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Effective date of registration: 20240130 Address after: 243000 No.1 Chaosan Road, Provincial Fine Chemical Base, Hexian Economic Development Zone, Ma'anshan City, Anhui Province Patentee after: Anhui Jubaoshi Technology Co.,Ltd. Country or region after: China Address before: 238251 fine chemical base of Wujiang Town, Wujiang, Anhui Province Patentee before: ANHUI HAIDE CHEMICAL TECHNOLOGY Co.,Ltd. Country or region before: China |