CN107597132A - A kind of toluene direct oxidation catalyst and preparation method thereof - Google Patents
A kind of toluene direct oxidation catalyst and preparation method thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
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Abstract
The present invention relates to a kind of toluene direct oxidation catalyst and preparation method thereof, including following component：Zinc oxide, 85~90wt% of alumina composite oxide carrier, 0.5~5wt% of cerium, 2~10wt% of vanadium, 1~2wt% of tin, 1~3.5wt% of copper, the mol ratio of the zinc oxide and aluminum oxide is 1~2, the present invention provide it is a kind of using zinc oxide, alumina mixture as the toluene direct oxidation producing benzaldehyde of carrier catalyst, the catalyst has high toluene conversion, benzaldehyde selectivity and reaction stability, excellent performance, reaction condition is gentle, and is in reactant and product in two-phase, is easily isolated and purifies.
Description
Technical field
The application is to be directed to Application No. 201510465739.4, and the applying date is on July 31st, 2015, entitled " a kind of
The divisional application of the application for a patent for invention of toluene direct oxidation catalyst and preparation method thereof ".
The present invention relates to a kind of catalyst, more particularly to a kind of catalyst of toluene direct oxidation producing benzaldehyde and its preparation
Method, belong to industrial catalysis technical field.
Background technology
Benzaldehyde is a kind of important fine chemical product, is widely used in medicine, dyestuff, spices, agricultural chemicals and material etc.
In industrial circle.The presently disclosed production method for preparing benzaldehyde mainly has following three kinds：Chlorination toluene Hydrolyze method, benzoic acid
(ester) reducing process and toluene direct oxidation method.
Inevitably contain chlorine in the benzaldehyde that chlorination toluene Hydrolyze method is produced, and be used in the industries such as medicine and spices
Chlorine can not be contained in benzaldehyde, therefore the application of the benzaldehyde produced by chlorinolysis receives certain limit
System.Benzoic acid reducing process refers to the method for generating benzaldehyde by catalytic hydrogenating reduction by benzoic acid or benzoic ether, although
The conversion ratio and selectivity of this method are all very high, but the reaction temperature of benzoic ether reducing process must reach more than 300 DEG C, energy
Consumption is very big, very uneconomical.
Toluene direct oxidation generation benzaldehyde under gas phase or liquid-phase condition is relatively inexpensive and environmentally friendly method, China
Patent CN1068755 discloses a kind of method that benzaldehyde is prepared by gas phase oxidation of toluene, is prepared by this method
The selectivity of benzaldehyde reaches 60%, and the once through yield of benzaldehyde can reach 16%, the side that toluene passes through vapor phase method direct oxidation
Method is primarily present reaction temperature height, the defects of toluene easy over oxidation, the selectivity decline of benzaldehyde when improving conversion ratio
It is especially apparent.Report on direct oxidation generation benzaldehyde under liquid-phase condition was a lot, early in Patent No. in 2004
CN1528726 Chinese patent discloses a kind of in acid or neutral ion liquid and acetic acid in the mixed solvent, passes through liquid phase
Toluene is aoxidized to prepare the method for benzaldehyde, toluene is aoxidized under the conditions of 115~120 DEG C, when toluene conversion is 42%, benzene
The selectivity of formaldehyde is only 48%, and the method has widely applied the ionic liquid and acetate solvate of costliness, substantially increases and is produced into
This, and product separation is difficult, industrial production is uneconomical, and Dalian Chemistry and Physics Institute patent CN02143361.5 discloses one kind and is used for toluene
Aoxidize the preparation method of the catalyst of producing benzaldehyde, the active component of the catalyst is zirconium and other transition metal, alkali metal or
Alkaline-earth metal etc., using the catalyst, in 180-195 DEG C of temperature, oxygen is passed through, is reacted under the conditions of pressure 0.8-1.2MPa,
When toluene conversion is 13%, the selectivity of benzaldehyde is 86.6%, and the preparation technology of this method catalyst is more complicated, and
Oxidation is difficult to control the stage in aldehyde, is more easy to generate benzoic acid.
In summary, there is presently no one kind reaction is simple, energy-conserving and environment-protective, product and solvent is easily separated and recovery, reaction
In toluene conversion and benzaldehyde selectivity higher production benzaldehyde simultaneously method.
Layered double hydroxide (LDHs) is a kind of anion lamellar compound, also known as hydrotalcite, and LDHs is by layer
Between anion and the accumulation of positively charged laminate form, there is the structure that can be embedded in anion, LDHs structure such as sandwich
Shape, both sides are made up of the metal ion positive charge piece of divalence and trivalent, and centre is anion and hydrone, when LDHs is heated to
At 450~500 DEG C, dehydration is more complete, generation bimetal composite oxide (LDO), in heating process, LDHs orderly layer
Shape is destructurized, surface area increase, pore volume increase, therefore the LDO formed is very suitable for by carrier making as catalyst
With.
The content of the invention
The present invention is directed to the deficiency of toluene conversion and benzaldehyde selectivity in existing toluene direct oxidation method, there is provided one
Catalyst of kind toluene direct oxidation producing benzaldehyde and preparation method thereof.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：
A kind of toluene direct oxidation catalyst, it is characterised in that including following component：
The mol ratio of the zinc oxide and aluminum oxide is 1~2.
The beneficial effects of the invention are as follows：The present invention provide it is a kind of using zinc oxide, alumina composite oxide as carrier first
The catalyst of benzene direct oxidation producing benzaldehyde, the catalyst have high toluene conversion, benzaldehyde selectivity and stable reaction
Property, excellent performance, reaction condition is gentle, and is in reactant and product in two-phase, is easily isolated and purifies.
The present invention also provides a kind of preparation method of toluene direct oxidation catalyst, comprises the following steps：
1) carrier is prepared：The zinc salt of solubility and aluminium salt are placed in deionized water dissolving are configured to total concentration and be
0.5mol/L solution A, aqueous slkali B is added dropwise in solution A under constant agitation, keeps pH value of solution in the process
Value 9~10, aqueous slkali B continue stirring ageing 3~5 hours, filtering, wash to neutrality, dry repeatedly after being added dropwise, 450~
550 DEG C are calcined to obtain zinc oxide aluminium composite oxide catalyst carrier；
2) cerium and vanadium are impregnated：The carrier of gained in step 1) is soaked with the mixed solution of soluble cerium salt and metavanadate
Stain, dry, be calcined after grinding at 500~600 DEG C；
3) immersion tin and copper：Products obtained therefrom in step 2) is impregnated with the mixed solution of soluble pink salt and mantoquita, dried,
It is calcined after grinding at 500~600 DEG C.
Further, zinc salt described in step 1) and aluminium salt are zinc nitrate and aluminum nitrate, and the aqueous slkali is that sodium hydroxide is molten
Liquid.
Further, the soluble cerium salt described in step 2) is cerous nitrate or Cericammoniumsulfate, and metavanadate is metavanadic acid
Ammonium or potassium metavanadate.
Further, the soluble pink salt described in step 3) is stannous sulfate or stannous chloride, and soluble copper salt is nitric acid
Copper or copper sulphate.
The preparation method of the catalyst of the toluene direct oxidation producing benzaldehyde of the present invention produces after using LDHs baking heats
LDO as catalyst carrier, the bigger serface and the coordinated of pore volume and bimetallic oxide that make full use of LDO are made
With afterwards using step impregnation method, first dipping cerium and vanadium, the rear copper and tin, this preparation method of impregnating can improve cerium, vanadium, copper
With tin in the decentralization and valence stability of carrier surface, give full play between each metallic atom and alumina catalyst support, zinc oxide
Coordinated effect, strengthen metal-auxiliary agent-carrier between interaction.
Embodiment
The principle and feature of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the present invention.
Embodiment 1:
A kind of catalyst of toluene direct oxidation producing benzaldehyde, including following component：Zinc oxide aluminium composite oxide
Carrier 85wt%, wherein zinc oxide and aluminum oxide mol ratio are 1, cerium 10wt%, vanadium 2wt%, tin 2wt%, copper 1wt%.
The preparation method of above-mentioned catalyst comprises the following steps：
1) 150gAl (NO are weighed3)3·9H2O and 59.4g Zn (NO3)2·6H2O is dissolved in 1200mL deionized waters, is prepared
It is 0.5molL into total concentration-1Mixing salt solution, weigh 80g NaOH and be dissolved in 400ml deionized waters and be configured to 5mol
L-1NaOH solution, NaOH solution is added dropwise in mixing salt solution under agitation, the keeping body during dropwise addition
It is pH value 9~10, NaOH solution continues stirring ageing 3 hours after being added dropwise, products therefrom is filtered, uses deionized water
Wash repeatedly 3 times, be placed in 100 DEG C of thermostatic drying chambers and dry, ground after the completion of drying to be placed in 450 DEG C of Muffle kiln roastings 5 small
When obtain catalyst carrier；
2) 36.6g Ce (NO are weighed3)3·6H2O and 5.39g NH4VO3It is dissolved in 200mL deionized waters, takes 100g steps
1) catalyst carrier of gained, the Ce (NO that will be prepared in3)3·6H2O and NH4VO3The aqueous solution is being stirred continuously lower impregnation catalyst
Agent carrier, after by catalyst be placed in 100 DEG C of baking ovens dry, it is ground to be calcined 3 hours at 500 DEG C；
3) 4.4g SnCl are weighed2·2H2O and 3.4g Cu (NO3)2It is dissolved in 100ml deionized waters, the water that will be prepared
Solution impregnation steps 2) in be calcined after product, be placed on afterwards in 100 DEG C of baking ovens dry, it is ground to be calcined 2 at 550 DEG C
Hour obtains catalyst A.
Embodiment 2:
A kind of catalyst of toluene direct oxidation producing benzaldehyde, including following component：Zinc oxide aluminium composite oxide
Carrier 90wt%, wherein zinc oxide and aluminum oxide mol ratio are 1, cerium 5wt%, vanadium 2wt%, tin 0.1wt%, copper 2.9wt%.
The preparation method of above-mentioned catalyst comprises the following steps：
1) 150gAl (NO are weighed3)3·9H2O and 59.4g Zn (NO3)2·6H2O is dissolved in 1200mL deionized waters, is prepared
It is 0.5molL into total concentration-1Mixing salt solution, weigh 80g NaOH and be dissolved in 400ml deionized waters and be configured to 5mol
L-1NaOH solution, NaOH solution is added dropwise in mixing salt solution under agitation, the keeping body during dropwise addition
It is pH value 9~10, NaOH solution continues stirring ageing 3 hours after being added dropwise, products therefrom is filtered, uses deionized water
Wash repeatedly 3 times, be placed in 100 DEG C of thermostatic drying chambers and dry, ground after the completion of drying to be placed in 500 DEG C of Muffle kiln roastings 5 small
When obtain catalyst carrier；
2) 17.2g Ce (NO are weighed3)3·6H2O and 6.0g KVO3It is dissolved in 200mL deionized waters, takes 100g steps 1)
The catalyst carrier of middle gained, the Ce (NO that will be prepared3)3·6H2O and KVO3The aqueous solution is being stirred continuously lower impregnated catalyst
Carrier, after by catalyst be placed in 100 DEG C of baking ovens dry, it is ground to be calcined 2 hours at 600 DEG C；
3) 0.2g SnSO are weighed4With 9.4g Cu (NO3)2It is dissolved in 100ml deionized waters, the aqueous solution prepared is soaked
Product after being calcined in stain step 2), it is placed in 100 DEG C of baking ovens and dries afterwards, it is ground to be calcined at 500 DEG C 2 hours
To catalyst B.
Embodiment 3:
A kind of catalyst of toluene direct oxidation producing benzaldehyde, including following component：Zinc oxide aluminium composite oxide
Carrier 85wt%, wherein magnesia and aluminum oxide mol ratio are 2, cerium 0.5wt%, vanadium 6wt%, tin 5wt%, copper 3.5wt%.
The preparation method of above-mentioned catalyst comprises the following steps：
1) 39.9gAlCl is weighed3With 40.8g ZnCl2It is dissolved in 1200mL deionized waters, being configured to total concentration is
0.5mol·L-1Mixing salt solution, weigh 80gNaOH and be dissolved in 400ml deionized waters and be configured to 5molL-1NaOH it is molten
Liquid, NaOH solution is added dropwise in mixing salt solution under agitation, kept during dropwise addition system pH 9~
10, NaOH solution continues stirring ageing 3 hours after being added dropwise, products therefrom is filtered, washed repeatedly using deionized water 3 times,
Be placed in 100 DEG C of thermostatic drying chambers and dry, after the completion of drying it is ground be placed in 550 DEG C of Muffle kiln roastings 3 hours catalyst
Carrier；
2) 2.5g (NH are weighed4)4Ce(SO4)4With 16.2g NH4VO3It is dissolved in 200mL deionized waters, takes 100g steps 1)
The catalyst carrier of middle gained, the Ce that will be prepared2(SO4)3·8H2O and NH4VO3The aqueous solution is being stirred continuously lower impregnation catalyst
Agent carrier, after by catalyst be placed in 100 DEG C of baking ovens dry, it is ground to be calcined 2 hours at 600 DEG C；
3) 11.1g SnCl are weighed2·2H2O and 16.1g CuSO4·5H2O is dissolved in 100ml deionized waters, will be prepared
Aqueous solution impregnation steps 2) in be calcined after product, be placed on afterwards in 100 DEG C of baking ovens dry, it is ground at 550 DEG C
Roasting obtains catalyst C in 2 hours.
Embodiment 4:
A kind of catalyst of toluene direct oxidation producing benzaldehyde, including following component：Magnesia alumina composite oxides
Carrier 85wt%, wherein magnesia and aluminum oxide mol ratio are 2, cerium 3wt%, vanadium 10wt%, tin 1wt%, copper 1wt%.
The preparation method of above-mentioned catalyst comprises the following steps：
1) 39.9gAlCl is weighed3With 40.8g ZnCl2It is dissolved in 1200mL deionized waters, being configured to total concentration is
0.5mol·L-1Mixing salt solution, weigh 80gNaOH and be dissolved in 400ml deionized waters and be configured to 5molL-1NaOH it is molten
Liquid, NaOH solution is added dropwise in mixing salt solution under agitation, kept during dropwise addition system pH 9~
10, NaOH solution continues stirring ageing 3 hours after being added dropwise, products therefrom is filtered, washed repeatedly using deionized water 3 times,
Be placed in 100 DEG C of thermostatic drying chambers and dry, after the completion of drying it is ground be placed in 550 DEG C of Muffle kiln roastings 3 hours catalyst
Carrier；
2) 15.0g (NH are weighed4)4Ce(SO4)4With 31.8g KVO3It is dissolved in 200mL deionized waters, takes in 100g steps 1)
The catalyst carrier of the gained, (NH that will be prepared4)4Ce(SO4)4And KVO3The aqueous solution is being stirred continuously lower impregnated catalyst load
Body, after by catalyst be placed in 100 DEG C of baking ovens dry, it is ground to be calcined 3 hours at 550 DEG C；
3) 2.1g SnSO are weighed4With 4.6g CuSO4·5H2O is dissolved in 100ml deionized waters, the aqueous solution that will be prepared
Impregnation steps 2) in be calcined after product, be placed on afterwards in 100 DEG C of baking ovens dry, it is ground to be calcined 2 hours at 600 DEG C
Obtain catalyst D.
Gained catalyst in embodiment 1-4 is used in the reaction of toluene direct oxidation producing benzaldehyde, reacted in the anti-of 1.0L
Answer in kettle and carry out, add 50g toluene, 5g catalyst and 500ml acetone and close kettle closedtop as solvent, mixing speed 800r/
Min, 110 DEG C are heated to, blowing air is reacted, and reaction temperature rises to 120 DEG C and controlled is reacted in this temperature, reactant
It is Stress control in 5MPa, in 5 hours reaction time, after reaction terminates, reaction system is down to room temperature, opens kettle cover, sampling point
Analysis.Response data is shown in Table 1.
Table 1：The reactivity data of gained catalyst in embodiment 1-4
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included within the protection domain of invention.
Claims (3)
1. a kind of toluene direct oxidation catalyst, it is characterised in that including following component：
The mol ratio of the zinc oxide and aluminum oxide is 1~2.
2. the preparation method of a kind of toluene direct oxidation catalyst according to claim 1, it is characterised in that including as follows
Step：
1) carrier is prepared：It is 0.5mol/L's that the zinc salt of solubility and aluminium salt, which are placed in dissolving in deionized water to be configured to total concentration,
Solution A, aqueous slkali B is added dropwise in solution A under constant agitation, keeps solution ph 9~10, alkali in the process
Solution B continues stirring ageing 3~5 hours after being added dropwise, filtering, wash to neutrality, dry, 450~550 DEG C are calcined repeatedly
Zinc oxide aluminium composite oxide catalyst carrier, the aluminium salt and zinc salt are aluminum nitrate and zinc nitrate, and the aqueous slkali is
Sodium hydroxide solution；
2) cerium and vanadium are impregnated：The carrier of gained in step 1) is impregnated with the mixed solution of soluble cerium salt and metavanadate, done
It is dry, it is calcined after grinding at 500~600 DEG C, described soluble cerium salt is cerous nitrate or Cericammoniumsulfate, and metavanadate is inclined
Ammonium vanadate or potassium metavanadate；
3) immersion tin and copper：Products obtained therefrom in step 2) is impregnated with the mixed solution of soluble pink salt and mantoquita, dried, grinding
It is calcined afterwards at 500~600 DEG C.
3. the preparation method of a kind of toluene direct oxidation catalyst according to claim 2, it is characterised in that in step 3)
Described soluble pink salt is stannous sulfate or stannous chloride, and soluble copper salt is copper nitrate or copper sulphate.
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| CN201710865904.4A CN107597132A (en) | 2015-07-31 | 2015-07-31 | A kind of toluene direct oxidation catalyst and preparation method thereof |
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| CN201710865904.4A CN107597132A (en) | 2015-07-31 | 2015-07-31 | A kind of toluene direct oxidation catalyst and preparation method thereof |
| CN201510465739.4A CN105126860B (en) | 2015-07-31 | 2015-07-31 | A kind of toluene direct oxidation catalyst and preparation method thereof |
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| CN201710867057.5A Pending CN107519886A (en) | 2015-07-31 | 2015-07-31 | A kind of toluene alkylation catalyst and preparation method thereof |
| CN201710867727.3A Pending CN107497445A (en) | 2015-07-31 | 2015-07-31 | A kind of toluene oxidation catalyst and preparation method thereof |
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| CN201710867727.3A Pending CN107497445A (en) | 2015-07-31 | 2015-07-31 | A kind of toluene oxidation catalyst and preparation method thereof |
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| CN111790454A (en) * | 2020-08-05 | 2020-10-20 | 南京大学 | Bionic iron-based catalyst, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103285865A (en) * | 2012-02-23 | 2013-09-11 | 南京工程学院 | Catalyst for synthesizing benzaldehyde by carrying out liquid-phase high-selectivity catalytic oxidation on methylbenzene |
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| CN1113835C (en) * | 2000-05-08 | 2003-07-09 | 湖南大学 | Process for preparing benzoic acid, henzaldehyde and benzyl alcohol |
| CN1485131A (en) * | 2002-09-26 | 2004-03-31 | 中国科学院大连化学物理研究所 | Catalyst for synthesizing benzaldehyde and benzyl alcohol from toluol, the preparation process and application thereof |
| DE10334132A1 (en) * | 2003-07-25 | 2005-04-07 | Basf Ag | Silver, vanadium and a promoter metal-containing multimetal and its use |
| CN101972646B (en) * | 2010-11-17 | 2012-10-31 | 西北大学 | Toluene liquid-phase selective oxidation catalyst and preparation method thereof |
| CN104693002A (en) * | 2015-03-11 | 2015-06-10 | 南京工业大学 | Method for preparing benzaldehyde by toluene oxidation |
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| CN103285865A (en) * | 2012-02-23 | 2013-09-11 | 南京工程学院 | Catalyst for synthesizing benzaldehyde by carrying out liquid-phase high-selectivity catalytic oxidation on methylbenzene |
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| 曹明鸣等: "钴铝类水滑石液相选择性催化甲苯氧化合成苯甲醛", 《应用化学》 * |
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| CN111790454A (en) * | 2020-08-05 | 2020-10-20 | 南京大学 | Bionic iron-based catalyst, preparation method and application |
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| CN107497445A (en) | 2017-12-22 |
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| CN107519886A (en) | 2017-12-29 |
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