CN104926649B - Hydrogenation Pyromellitic Acid orthocarbonate and the preparation method of 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride - Google Patents
Hydrogenation Pyromellitic Acid orthocarbonate and the preparation method of 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride Download PDFInfo
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- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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Abstract
The invention discloses hydrogenation Pyromellitic Acid orthocarbonate and 1,2,4, the preparation method of 5 cyclohexanetetracarboxylic acid dianhydrides, the preparation method of hydrogenation Pyromellitic Acid orthocarbonate is, Pyromellitic Acid orthocarbonate is hydrogenation synthesis hydrogenation of benzene tetracarboxylic acid orthocarbonate under hydrogenation catalyst effect, and the carrier of described hydrogenation catalyst is cocoanut active charcoal, and active component is the metal Ru of mass fraction 1 5%, the composition metal of the metal Ce of the metal Pd of mass fraction 0.5 2%, mass fraction 0.3 2% composition；The invention also discloses the preparation method of described hydrogenation catalyst.Activity of hydrocatalyst prepared by the present invention and high life, effectively reduce reaction temperature and reaction pressure；Use fixed bed hydrogenation reactor is hydrogenated with, and low pressure reaction is low for equipment requirements, and emptying hydrogen is easy to recycling by low pressure force (forcing) pump.
Description
Technical field
The present invention relates to hydrogenated pyromellitic acid ester and 1, the preparation method of 2,4,5-cyclohexanetetracarboxylic acid dianhydrides, relate to especially
And the hydrogenation preparation of Pyromellitic Acid orthocarbonate and the method for being prepared 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride by it.
Background technology
1,2,4,5-cyclohexanetetracarboxylic acid dianhydride is a kind of alicyclic anhydride, and polyimides prepared therefrom has excellent
The transparency, low-k and dielectric loss, high breakdown strength, low hydroscopicity and the adhesiveness good with the base material such as metal,
Have wide in fields such as Aero-Space, automobile, microelectronics, large scale integrated circuit, semi-conducting material and flat faced displays
Application prospect.The preparation of 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride is mainly completed by following reaction:
1, Pyromellitic Acid catalytic hydrogenation obtains hydrogenating Pyromellitic Acid
2, hydrogenation Pyromellitic Acid cyclodehydration prepares 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride
Comprehensive prior art, in the preparation of 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, key problem in technology is to hydrogenate equal benzene tetramethyl
The preparation of acid, material choice can be Pyromellitic Acid or its esters, can reach for hydrogenating materials with Pyromellitic Acid esters
To high conversion, high selectivity.For obtaining the efficient production of hydrogenation pyromellitic acid ester, technology focuses on pyromellitic acid ester
Catalytic hydrogenation preparation hydrogenation pyromellitic acid ester.
Summary of the invention
One of present invention solves the technical problem that and to be to provide a kind of preparation method hydrogenating Pyromellitic Acid orthocarbonate, described
Preparation method is, Pyromellitic Acid orthocarbonate is hydrogenation synthesis hydrogenation of benzene tetracarboxylic acid orthocarbonate under hydrogenation catalyst effect, described
The carrier of hydrogenation catalyst is cocoanut active charcoal, and active component is the metal Ru of mass fraction 1-5%, mass fraction 0.5-2%
Metal Pd, mass fraction 0.3-2% metal Ce composition composition metal.
The preparation method of described hydrogenation catalyst comprises the steps:
1. taking 94 weight portion cocoanut active charcoals, adding equal-volume mass fraction is soaked overnight in 3-5%HCl, filters, mistake
Activated carbon after filter adds 400 parts by weight of deionized water and 100 weight portion concentrated hydrochloric acid, drips 2-10 weight portion RuCl3、0.9-
3.5 weight portion PdCl2, 1-6.3 weight portion six water cerous nitrate, 50 parts by weight of deionized water, 50 weight portion concentrated hydrochloric acid be made into mixed
Close solution；
2. adding NaOH solution and be adjusted to pH=14, be heated to 60 DEG C, dropping 80-90 weight portion mass fraction is the first of 36%
Aldehyde aqueous solution, finishes and drips NaOH solution again, it is ensured that pH=14, is heated to 90 DEG C of insulated and stirred, lowers the temperature, filters, and filter cake adds
Deionized water stirs, and filters, with deionized water drip washing repeatedly until filtrate pH=7, addition mass fraction are 1%AgNO3Solution
Till not becoming cloudy.
The another kind of technical scheme of hydrogenation catalyst, the step of the preparation method of described hydrogenation catalyst is prepared as the present invention
Suddenly 2. it is to stir after dropping, filters, the deionized water drip washing of filter cake i.e. catalyst, until filtrate pH=6-7；By above-mentioned
Catalyst is added in fixed bed, is warmed up to 220-230 DEG C, is passed through the mixed gas reducing catalyst of hydrogen or hydrogen and nitrogen,
It is 2.5L/min that gas is passed through speed, and reduction reaction pressure 0.1-0.2MPa, without HCl gas to tail gas.
In the present invention, the carrier of hydrogenation catalyst is 80 mesh cocoanut active charcoals, activated carbon inner ratio surface area 1000-
1500m2/g；Active component is the metal Ru of mass fraction 1-5%, the metal Pd of mass fraction 0.5-2%, mass fraction 0.3-
The composition metal of the metal Ce composition of 2%.The addition of metal Ce can allow metal Ru, Pd are dispersed, be adsorbed onto on activated carbon,
Using metallurgical microscopes analysis to find, average 3-5 Pd, Ru metallic atom flocks together and forms solid solution nucleus, dispersion
The highest.The highest dispersion not only allows catalyst have outstanding catalysis activity, and prevents metal crystal nuclei in hydrogenation reaction
Sinter because of heat release, improve catalyst service life.
The composition metal nucleus dispersion degree of depth is 100-150 micron under activated carbon surface, at this degree of depth, noble metal solid solution
Being easily absorbing hydrogen and hydrogenating materials, utilization rate is the highest.The nitrogen BET surface area of hydrogenation catalyst reach 1500～
2000m2/g.Compared with the catalyst conventional with this reaction, catalyst activity and service life prepared by the present invention are higher, effectively drop
Low reaction temperature and reaction pressure, hydrogenation reaction temperature is at 100-110 DEG C, and reaction pressure only has 0.2～0.5Mpa；Use solid
Fixed bed hydrogenation reactor is hydrogenated with, and low pressure reaction is low for equipment requirements, and emptying hydrogen is easy to reclaim profit again by low pressure force (forcing) pump
With.
Described Pyromellitic Acid orthocarbonate be with Pyromellitic Acid and propanol as raw material, H-type modenite as catalyst,
Prepare through esterification.
Compared with the sulphuric acid used by usual esterification and tetrabutyl titanate catalyst, used by the esterification in the present invention
Catalyst is acidic solid catalyst H-type modenite, does not has corrosivity, catalyst can by simple filter method and
Product separates, simple to operate, does not produce any waste water.
Invent two solved the technical problem that and be to provide the preparation method of a kind of 1,2,4,5-cyclohexanetetracarboxylic acid dianhydrides, profit
The hydrogenation Pyromellitic Acid orthocarbonate prepared in aforementioned manners, through hydrolysis system 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,
4,5-cyclohexanetetracarboxylic acid prepares 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride through dehydration；Wherein, hydrolysis catalysis used
Agent is H-type modenite.
Present invention propanol, as the raw material of esterification, has compared a lot of advantage with by methanol, esterified by butyl alcohol, and this is not only
It is only that a simple alcohols is replaced.The hydrogenated reaction of product generated with propanol esterification generates hydrogenation Pyromellitic Acid orthocarbonate,
Hydrogenate Pyromellitic Acid orthocarbonate compared with hydrogenating Pyromellitic Acid four methyl ester, hydrogenation Pyromellitic Acid four butyl ester etc., the more Yishui River
Solution, hydrolysis required time are shorter, and production efficiency is high；The more important thing is that cyclohexanetetracarboxylic acid ester type compound has ship, chair form
Spatial configuration, has four hand-type atoms, the hydrogenation hydrogenation of Pyromellitic Acid methyl ester, Pyromellitic Acid ethyl ester, Pyromellitic Acid butyl ester
After become corresponding cyclohexanetetracarboxylic acid ester type compound, stereoisomer is a lot, the only hexamethylene tetramethyl after hydrogenation
Propyl propionate stereoisomerism is little, wherein, content most for cis, cis, cis-1,2,4,5-cyclohexanetetracarboxylic acid propyl ester, remaining
Less four the little isomerized products of content are cis, tran, tran ,-1,2,4,5-cyclohexanetetracarboxylic acid propyl ester, cis, cis,
Tran ,-1,2,4,5-cyclohexanetetracarboxylic acid propyl ester, tran, tran, tran ,-1,2,4,5-cyclohexanetetracarboxylic acid propyl ester, tran,
Cis, tran ,-1,2,4,5-cyclohexanetetracarboxylic acid propyl ester.
Due to hydrogenation Pyromellitic Acid orthocarbonate facile hydrolysis, the present invention uses H-type modenite to do hydrolyst, mistake
Filter just can be completely separated catalyst, it is not necessary to adds high boiling solvent.The disadvantage using sulphuric acid to make hydrolyst is, produces
The sulphuric acid of meeting residual minim in product.
The preparation method of described H-type modenite is as follows, takes 100 parts by weight of powder shape modenites, adds 10 weight portions
Powder γ-aluminium sesquioxide, 10-15 weight portion dust technology, stir into dried noodle shape, be extruded into strip, in 100-110 DEG C of baking oven
Dry, be ground into graininess；Then by 10% aqueous ammonium chloride solution soaked overnight, filter, dry moisture, then at 500-600
DEG C Muffle kiln roasting 3-4 hour, cooling.
Beneficial effects of the present invention is as follows:
(1) catalyst activity and the service life of the Pyromellitic Acid orthocarbonate hydrogenation reaction that prepared by the present invention are higher, urge
Agent can reach 2000 hours service life, reaction conversion ratio 99.2%, and hydrogenation reaction selects 98.2%, effectively reduces anti-
Answering temperature and reaction pressure, hydrogenation reaction temperature is at 100-110 DEG C, and reaction pressure only has 0.2～0.5Mpa；Use fixed bed adds
Hydrogen reactor is hydrogenated with, and low pressure reaction is low for equipment requirements, and emptying hydrogen is easy to recycling by low pressure force (forcing) pump.
(2) the esterification used catalyst in the present invention is H-type modenite, does not has corrosivity, and catalyst can lead to
Cross simple filter method to separate with product, simple to operate, do not produce any waste water；
(3) present invention propanol generates as the raw material of esterification, the hydrogenated reaction of product generated with propanol esterification
Hydrogenation Pyromellitic Acid orthocarbonate more facile hydrolysis, hydrolysis required time shorter, production efficiency is high；
(4) due to hydrogenation Pyromellitic Acid orthocarbonate facile hydrolysis, the present invention uses H-type modenite to make hydrolyst,
Filter and just can be completely separated catalyst, it is not necessary to add high boiling solvent.
Detailed description of the invention
Following nonlimiting examples can make those of ordinary skill in the art that the present invention be more fully understood, but not with
Any mode limits the present invention.
Embodiment 1
1, Pyromellitic Acid lactate synthesis Pyromellitic Acid orthocarbonate
In tetra-mouthfuls of reactors of 2L, add 218g Pyromellitic Acid, 380g propanol, 10gH-type modenite, be warmed up to
110 DEG C, reaction refluxes at such a temperature, and with gas chromatogram (GC) monitoring reaction, within about 5 hours, reaction conversion ratio reaches 90%,
Distill out aqueous propanol.Adding the new propanol of 300g and continue reaction, gas chromatogram monitoring reaction conversion ratio reaches 95%.
Cooling to 30-40 DEG C, filter out catalyst, with a small amount of propanol drip washing catalyst, filtrate is lowered the temperature, is entered at 10-15 DEG C
Row recrystallization, filters out filter cake, filtrate recycle, and filter cake dries to obtain 388g Pyromellitic Acid orthocarbonate, GC purity 99.3%, yield
93%.
2, Pyromellitic Acid orthocarbonate hydrogenation synthesis hydrogenation Pyromellitic Acid orthocarbonate
(1) preparation of catalyst for hydrogenation
1. the preparation of catalyst A
Take 94g cocoanut active charcoal (60-80 mesh), add in the HCl solution that equal-volume mass fraction is 3-5% and soaked
At night, within second day, filter, add and drip 8.5gRuCl under 400g deionized water and 100g concentrated hydrochloric acid, stirring2、1.6g PdCl2、3.2g
The mixed solution that six water cerous nitrates, 50g deionized water, 50g concentrated hydrochloric acid are made into, drips off for 2-3 hour, finishes stirring 1 hour.Add
Mass fraction is that 20%NaOH solution is adjusted to pH=14, is heated to 60 DEG C, and dropping 80-90g mass fraction is that 36% formaldehyde is water-soluble
Liquid reduces, and finishing and dripping mass fraction again is 20%NaOH solution, it is ensured that pH=14, is heated to 90 DEG C of insulated and stirred 1 little
Time, to lower the temperature, filter, filter cake adds 400g deionized water and stirs 1 hour, filters, with deionized water drip washing repeatedly until filtrate pH
=7, adding mass fraction is 1%AgNO3Till solution does not becomes cloudy.
Now adsorb metal chloride on the activated carbon and be reduced into metallic state by alkali and formaldehyde, after reduction
Catalyst is added in 400g ethanol stirring 1 hour, filters, is saved in dehydrated alcohol stand-by.
2. the preparation of catalyst B
Identical with the preparation process of catalyst A, the difference is that only in the preparation of catalyst B and be added without nitric acid
Cerium, rest materials proportioning, reducing process condition etc. are constant.
3. the preparation of catalyst C
Take 94g cocoanut active charcoal (60-80 mesh), add in the HCl solution that equal-volume mass fraction is 3-5% and soaked
At night, within second day, filter, add and drip 8.5gRuCl under 400g deionized water and 100g concentrated hydrochloric acid, stirring2、1.6g PdCl2、3.2g
The mixed solution that six water cerous nitrates, 50g deionized water, 50g concentrated hydrochloric acid are made into, drips off for 2-3 hour, finishes stirring 1 hour, mistake
Filter, catalyst deionized water drip washing, until filtrate pH=6-7.
Being added to by above-mentioned for 40g catalyst in 30cm length, diameter 2cm fixed bed, catalyst hair plates support, hair plates is fixing
At bed lower end 5cm, add 5cm magnet ring above catalyst and do preheating section.By heating by electric cooker fixed bed to 100-110 DEG C, use nitrogen
Air in metathesis reactor, does not has oxygen until analyzing in tail gas.Being warmed up to 220-230 DEG C, being passed through volume ratio is 1；9
Hydrogen and nitrogen mixed gas reducing catalyst, it is 2.5L/min that mixed gas is passed through speed, reduction reaction pressure 0.1-
0.2MPa, tail gas mass fraction is to be vented after 3%NaOH aqueous solution absorbs.After reducing 5-6 hour, improve hydrogen intake,
In mixed gas, hydrogen, nitrogen volume ratio are 3；7, mixed gas is passed through speed 2.5L/min, reduction reaction temperature, reduction pressure
Constant.After 5 hours, keeping reduction temperature, reduction pressure constant, improve hydrogen intake, hydrogen, nitrogen volume ratio are 1；1.5
Making pure hydrogen reduction after hour into, reduction temperature, pressure are constant.After reducing 10 hours, tail gas terminates without HCl gas, reduction.
(2) hydrogenation reaction
1. the hydrogenation reaction of catalyst A is utilized
Being added to by above-mentioned for 40g catalyst A in 30cm length, diameter 2cm fixed bed, catalyst hair plates support, hair plates is solid
At the 5cm of fixed bed lower end, add 5cm magnet ring above catalyst and do preheating section.By heating by electric cooker fixed bed to 100-110 DEG C, first use
Then nitrogen use hydrogen exchange reactor, does not has oxygen, ethanol until analyzing in tail gas.
By Pyromellitic Acid orthocarbonate that weight ratio is 3:7 and propanol, add 200-220g per hour.Hydrogen is passed through speed
Being maintained at 2.5L/min, reaction pressure 0.2-0.5MPa, reaction temperature is maintained at 200-220 DEG C.Product solution is through condenser
Cooling, collects in reception tank, and the pressurization of hydrogen diaphragm pressure pump is recovered in steel cylinder standby.The solution collected distills out third
Alcohol, propanol can be with reuse, and in distillating still, material is exactly product hydrogenated cyclohexyl alkane tetracarboxylic acid propyl ester.
In GC monitoring hydrogenation reaction, the activity rating of catalyst A is as follows；
2. the hydrogenation reaction of catalyst B is utilized
Using above-mentioned catalyst B, other process conditions are constant, and reaction runs 500 hours, and gas chromatogram GC monitors, reaction
Conversion ratio 98%, main product purity 97%, four little isomers add up to 1%；It is warmed up to 230-240 DEG C of reaction, 1000 hours GC prisons
Control, reaction conversion ratio 99%, main product purity 94%, four little isomers add up to 3%.
3. the hydrogenation reaction of catalyst C is utilized
Using catalyst C, be added to by above-mentioned for 40g catalyst C in 30cm length, diameter 2cm fixed bed, catalyst hair plates props up
Holding, hair plates, at the 5cm of fixed bed lower end, adds 5cm magnet ring and does preheating section above catalyst.By heating by electric cooker fixed bed to 100-
110 DEG C, with air in nitrogen metathesis reactor, there is no oxygen until analyzing in tail gas.
By Pyromellitic Acid orthocarbonate that weight ratio is 3:7 and propanol, add 200-220g per hour.Hydrogen is passed through speed
Being maintained at 2.5L/min, reaction pressure 0.2-0.5MPa, reaction temperature is maintained at 200-220 DEG C.Product solution is through condenser
Cooling, collects in reception tank, and the pressurization of hydrogen diaphragm pressure pump is recovered in steel cylinder standby.The solution collected distills out third
Alcohol, propanol can be with reuse, and in distillating still, material is exactly product hydrogenated cyclohexyl alkane tetracarboxylic acid propyl ester.
In GC monitoring hydrogenation reaction, the activity rating of catalyst C is as follows；
3, hydrogenation Pyromellitic Acid orthocarbonate is through hydrolysis 1,2,4,5-cyclohexanetetracarboxylic acid
Pyromellitic Acid 4 third is hydrogenated at 1000ml reactor addition 10gH-type mordenite catalyst, 500g water, 100g
Ester, is warmed up to 102-103 DEG C, and reaction starts backflow, after reacting 5 hours, makes distillation into.Distillation speed 1g/min, controls temperature
100-150 DEG C, when distilling out 300g fraction, add 300g water, continue distillation, go out fraction alcohol content by analytical distillation and supervise
Control reaction.When distilling out fraction without propanol when, take organic layer in reactor, anti-with high performance liquid chromatography (HPLC) monitoring
Should, until product spectrogram content reaches more than 99% stopping distillation.
Cool to room temperature, filter out catalyst, then liquid pressure-reducing is distilled pulpous state, filter, filtrate reuse Han product,
Filter cake vacuum drying, oven temperature 100-120 DEG C, vacuum-0.09MPa, until product moisture ＜ 0.2%.
Single batch obtains product 50g, yield 80%, and filtrate cycle uses, and yield can reach 90%..
4,1,2,4,5-cyclohexanetetracarboxylic acid is through dehydration 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride
Add 200g acetic acid, 240g acetic anhydride, 140g1,2,4,5-cyclohexanetetracarboxylic acid in 1L reactor, be warmed up to 110-
120 DEG C, reaction starts backflow, insulation reaction 5 minutes, cooling, filters, and filter cake is dried and obtained 69g product that is 1,2,4,5-hexamethylenes
Alkane tetracarboxylic acid dianhydride, yield 80%, filtrate can be with reuse.
Wherein, the H-type modenite in step 1 and step 3 prepare as follows；
Take 100g ZSM-8 powder modenite, add 10g powder γ-aluminium sesquioxide, 10-15g mass fraction
It is 5% dust technology, stirs into dried noodle shape, be extruded into diameter 2mm strip with banded extruder, dry in 100-110 DEG C of baking oven, be ground into
Diameter 2mm, the graininess of long 2mm.Then with mass fraction be 10% aqueous ammonium chloride solution soak 10-12 hour, carry out Na from
Son and NH4Ion exchanges.Ion exchange terminates to filter.In the baking oven of 100-110 DEG C, first dry moisture, then at 500-600
DEG C Muffle kiln roasting 3-4 hour, by-NH4Ion roasting becomes-H ion, stores stand-by after cooling to room temperature.
Claims (4)
1. hydrogenating the preparation method of Pyromellitic Acid orthocarbonate, described preparation method is, Pyromellitic Acid orthocarbonate is urged at hydrogenation
Hydrogenation synthesis hydrogenation of benzene tetracarboxylic acid orthocarbonate under agent effect, it is characterised in that the carrier of described hydrogenation catalyst is that coconut husk is lived
Property charcoal, active component is the metal Ru of mass fraction 1-5%, the metal Pd of mass fraction 0.5-2%, mass fraction 0.3-2%
Metal Ce composition composition metal.
Hydrogenate the preparation method of Pyromellitic Acid orthocarbonate the most according to claim 1, it is characterised in that described hydrogenation catalyst
The preparation method of agent comprises the steps:
1. taking 94 weight portion cocoanut active charcoals, adding equal-volume mass fraction is soaked overnight in 3-5%HCl, filters, after filtration
Activated carbon in add 400 parts by weight of deionized water and 100 weight portion concentrated hydrochloric acid, drip 2-10 weight portion RuCl3、0.9-3.5
Weight portion PdCl2, the mixing that is made into of 1-6.3 weight portion six water cerous nitrate, 50 parts by weight of deionized water, 50 weight portion concentrated hydrochloric acid molten
Liquid；
2. adding NaOH solution and be adjusted to pH=14, be heated to 60 DEG C, dropping 80-90 weight portion mass fraction is the formalin of 36%
Solution, finishes and drips NaOH solution again, it is ensured that pH=14, is heated to 90 DEG C of insulated and stirred, lowers the temperature, filters, filter cake add go from
Sub-water stirs, and filters, with deionized water drip washing repeatedly until filtrate pH=7, addition mass fraction are 1%AgNO3Solution is constant
Till muddiness.
Hydrogenate the preparation method of Pyromellitic Acid orthocarbonate the most according to claim 1, it is characterised in that described equal benzene tetramethyl
Acid orthocarbonate be with Pyromellitic Acid and propanol as raw material, H-type modenite as catalyst, prepare through esterification.
Hydrogenate the preparation method of Pyromellitic Acid orthocarbonate the most according to claim 3, it is characterised in that described H-type mercerising
The preparation method of zeolite is as follows: take 100 parts by weight of powder shape modenites, add 10 parts by weight of powder shape γ-aluminium sesquioxide,
10-15 weight portion dust technology, stirs into dried noodle shape, is extruded into strip, dries, be ground into graininess in 100-110 DEG C of baking oven；So
Afterwards by 10% aqueous ammonium chloride solution soaked overnight, filter, dry moisture, then little at 500-600 DEG C of Muffle kiln roasting 3-4
Time, cooling.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510260112.5A CN104926649B (en) | 2015-05-20 | 2015-05-20 | Hydrogenation Pyromellitic Acid orthocarbonate and the preparation method of 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride |
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Inventor after: Yuanfeng Inventor after: Jiang Dianbao Inventor after: Li Chengbin Inventor after: Pei Xiong Inventor before: Yuanfeng Inventor before: Jiang Dianping Inventor before: Li Chengbin Inventor before: Pei Xiong |