CN104513163A - Method for producing methyl methacrylate by methyl acetate and formaldehyde - Google Patents
Method for producing methyl methacrylate by methyl acetate and formaldehyde Download PDFInfo
- Publication number
- CN104513163A CN104513163A CN201410784248.1A CN201410784248A CN104513163A CN 104513163 A CN104513163 A CN 104513163A CN 201410784248 A CN201410784248 A CN 201410784248A CN 104513163 A CN104513163 A CN 104513163A
- Authority
- CN
- China
- Prior art keywords
- bed reactor
- catalyst
- fluidized
- discharge port
- feed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- 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
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for producing methyl methacrylate, in particular to the method for producing the methyl methacrylate by taking methyl acetate and formaldehyde as raw materials. According to the adopted method, a fluidized bed reactor and a fixed bed reactor are used in a combined manner; unreacted methyl acetate serving as a raw material is cyclically utilized after being separated; methyl propionate generated by conducting hydrogenation on acrylic acid generated by the reaction can be sold as a byproduct, and can also be cyclically utilized with methyl acetate as a process raw material. An aldolization catalyst continuously flows between the fluidized bed reactor and a catalyst regenerator to realize a reaction regeneration process; the utilization rate of the catalyst is greatly improved; the continuity of production is realized. The fluidized bed reactor meets industrial production requirements; the high activity of the catalyst can be maintained for a long time; the use efficiency of the catalyst can be improved; the overall conversion rate is improved by the cycling of unreacted raw materials; the economic benefits are increased.
Description
Technical field
The present invention relates to a kind of method of producing methyl methacrylate, be specifically related to a kind of by ritalin and the formaldehyde method as raw material production methyl methacrylate.
Background technology
Methyl methacrylate is widely used in the production such as synthesis, PVC auxiliary agent, coating of synthetic glass, is a kind of important Organic Chemicals.The production of methyl methacrylate mainly adopts Acetone cyanohydrin method (ACH method) both at home and abroad at present, but the method exists, and technical process is long, use prussic acid has the shortcomings such as severe toxicity.Other operational paths have iso-butylene method, ethylene process, improvement Acetone cyanohydrin method (MGC method) etc.Particularly, Lu Caite company improves ethylene process, proposes α Technology, and this technology mainly comprises two reaction process: ethene and carbon monoxide, methyl alcohol react and generates methyl propionate under certain temperature and pressure; Methyl propionate and formaldehyde reaction generate methyl methacrylate.
Flourish along with Chemical Industry, there is production capacity surplus in the Coal Chemical Industry produce markets such as domestic acetic acid, formaldehyde, most manufacturing enterprises working rate is not enough, and the alternative techniques route synthesizing methylmethacrylate therefore developing Coal Chemical Industry raw material has great importance.
China Patent Publication No. CN103752305A discloses a kind of catalyst composition its preparation method and uses the method for this Catalyst Production methyl acrylate co-production methyl methacrylate.The object that to utilize said composition can realize with ritalin and formaldehyde be raw material production methyl acrylate co-production methyl methacrylate.But which employs three-way catalyst and fixed bed reacts, the easy inactivation of catalyzer, be difficult to regeneration, and the productive rate of methyl methacrylate prepared by this method is low.
Summary of the invention
The present invention is devoted to provide a kind of method by ritalin and Formaldehyde Production methyl methacrylate, by aldolization in a fluidized bed reactor and the associating of the hydrogenation reaction in fixed-bed reactor, realize object that is continuous, stably manufactured methyl methacrylate.
An object of the present invention is to provide a kind of method being raw material production methyl methacrylate with ritalin and formaldehyde.
Another object of the present invention is to provide the device realizing described method.
The object of the invention is to be achieved through the following technical solutions.
Produce a method for methyl methacrylate, the method comprises the following steps:
A) the first aldolization is carried out under making ritalin and the catalysis of formaldehyde under methyl alcohol and/or fluidized gas existence condition, in aldolization catalyst in a fluidized bed reactor:
CH
3COOCH
3+HCHO＝CH
2CHCOOCH
3+H
2O，
Wherein, described fluidized gas is the gas mixture of a kind of gas in nitrogen, argon gas and helium or multiple gases,
Described aldolization catalyst comprises using silicon-dioxide as carrier or using silicon-dioxide and aluminium sesquioxide mixture as carrier loaded base metal catalysts, wherein, described base metal catalysts specifically comprises Cs, Na, K or Li, and comprise be selected from weisspiessglanz, zirconium white, magnesium oxide, lanthanum trioxide, cerium oxide, calcium oxide etc. one or more as auxiliary agent;
Preferably, the reaction conditions of described fluidized-bed reactor is: temperature is 200 ~ 400 DEG C, and pressure is 0.05 ~ 1MPa, and the mol ratio of ritalin and formaldehyde is 1:0.1 ~ 1:3, the mol ratio of methyl alcohol and ritalin is 0 ~ 3:1, and the volume space velocity of ritalin is 1 ~ 1000h
-1;
B) in fixed-bed reactor, make the intermediate product containing methyl acrylate carry out hydrogenation reaction under hydrogen existence condition, under the catalysis of hydrogenation catalyst:
CH
2CHCOOCH
3+H
2＝CH
3CH
2COOCH
3，
Described hydrogenation catalyst is the metal catalyst of aluminium sesquioxide load, and its activeconstituents comprises one or more metals be selected from Pt, Pd, Rh, Ir, Ru, Ag, Cu, Ni;
Preferably, the reaction conditions of described fixed-bed reactor is: temperature is 120 ~ 300 DEG C, and pressure is 0.05 ~ 4MPa, and volume space velocity is 1 ~ 1000h
-1;
C) the second aldolization is carried out under making methyl propionate and the catalysis of formaldehyde under methyl alcohol and/or fluidized gas existence condition, in aldolization catalyst in a fluidized bed reactor:
CH
3CH
2COOCH
3+HCHO＝CH
3CH
2CHCOOCH
3+H
2O，
Wherein, described fluidized gas is the gas mixture of a kind of gas in nitrogen, argon gas and helium or multiple gases,
Described aldolization catalyst comprises using silicon-dioxide as carrier or using silicon-dioxide and aluminium sesquioxide mixture as carrier loaded base metal catalysts, wherein, described base metal catalysts specifically comprises Cs, Na, K or Li, and comprise be selected from weisspiessglanz, zirconium white, magnesium oxide, lanthanum trioxide, cerium oxide, calcium oxide etc. one or more as auxiliary agent.
Preferably, the step of described method a) is carried out as follows:
Make ritalin and formaldehyde mix through interchanger and mixing preheater and be preheated to preset temperature under methyl alcohol and/or fluidized gas existence condition, enter in fluidized-bed reactor with gaseous phase, under the catalysis of aldolization catalyst, carry out the first aldolization,
Wherein, described fluidized gas is the gas mixture of a kind of gas in nitrogen, argon gas and helium or multiple gases, and described preset temperature is 100 ~ 500 DEG C.
Preferably, the step b of described method) carry out as follows:
Make intermediate product containing methyl acrylate under hydrogen existence condition through intermediate product preheater preheats, enter in fixed-bed reactor with gaseous phase, under the catalysis of hydrogenation catalyst, carry out hydrogenation reaction,
Wherein, described intermediate product preheater is set to 100 ~ 400 DEG C.
Preferably, described method also additionally comprises the following steps:
D) by the catalyzer in described fluidized-bed reactor and/or described fixed-bed reactor by catalyst regenerator via regeneration gas regenerates, again drop into afterwards in respective reaction device;
Wherein, the regeneration gas of described catalyzer can be selected from oxygen, air, nitrogen, hydrogen, carbonic acid gas and water vapour one or more.
Wherein, the catalyst regeneration conditions in described fluidized-bed reactor and/or described fixed-bed reactor is: temperature is 200 ~ 600 DEG C, and the volume space velocity of regeneration gas is 10 ~ 1000h
-1, pressure is 0.05 ~ 1MPa, and the regenerative response time is 0.01 ~ 10h.
Preferably, carbon distribution content when described catalyzer enters described catalyst regenerator is 2-12%.
Preferably, by described step b) the product of hydrogenation reaction be back to described step a) in fluidized-bed reactor carry out described step c) reaction; And now, the mol ratio of methyl propionate and ritalin is 1:0.5 ~ 1:5.
According to a further aspect in the invention, which provide a kind of device for above-mentioned reaction, this device comprises (with reference to the solid line in figure 1 and dotted line frame 5 '):
Fluidized-bed reactor 3, it comprises the first opening for feed 301, first discharge port 302, described first opening for feed 301 is for receiving ritalin, formaldehyde, methyl alcohol, methyl propionate, the fluidized gas from raw material or recycle feed, and described first discharge port 302 is for discharging the reaction mixture in reactor 3;
Tripping device 5 ', it comprises the second opening for feed 501, second to the 5th discharge port 502 to 505, wherein, described second opening for feed 501 is connected to the first discharge port 302 of described fluidized-bed reactor 3, to receive from the reaction mixture in described fluidized-bed reactor 3, described reaction mixture is separated in tripping device 5 ', thus obtain unreacted raw material respectively, methyl acrylate, methyl propionate, impurity product and methyl methacrylate, described second discharge port 502 is for discharging unreacted raw material, described 3rd discharge port 503 is for discharging methyl acrylate, methyl propionate and methyl alcohol, described 4th discharge port 504 is for discharging impurity product and formaldehyde, and described 5th discharge port 505 is for discharging required end product methyl methacrylate,
Fixed-bed reactor 13, it comprises the 3rd opening for feed 1301 and the 6th discharge port 1302, described 3rd opening for feed 1301 is for receiving the methyl acrylate of described 3rd discharge port 503 from described separator 5, methyl propionate and methyl alcohol, the methyl propionate that described 6th discharge port 1302 obtains for discharging hydrogenation reaction.
Preferably (the long and short dash line part with reference in figure 1), the 6th discharge port 1302 of described fixed-bed reactor 13 is connected to described first opening for feed 301 of described fluidized-bed reactor 3.
Preferably (with reference to figure 2), described reaction unit also comprises raw material mixing preheater 2, and it comprises material inlet 201 and raw material discharge port 202, and described material inlet 201 is connected to the 6th discharge port 1302 of described fixed-bed reactor 13; Described raw material discharge port 202 is connected to described first opening for feed 301 of described fluidized-bed reactor 3, and the 6th discharge port 1302 of the no longer direct and described fixed-bed reactor 13 of described first opening for feed 301 of described fluidized-bed reactor 3 is connected.
Preferably, described reaction unit also comprises intermediate product preheater 12, it comprises intermediate product opening for feed 1201 and intermediate product discharge port 1202, described intermediate product opening for feed 1201 is connected to the 3rd discharge port 503 of described separator 5, described intermediate product discharge port 1202 is connected to described 3rd opening for feed 1301 of described fixed-bed reactor 13, and the 3rd discharge port 503 of the no longer direct and described separator 5 of described 3rd opening for feed 1301 of described fixed-bed reactor 13 is connected.
Preferably, described reaction unit also comprises catalyst regenerator 4, and it comprises resurgent gases entrance 401, pneumatic outlet 402, the first catalyst inlet 403 (not shown), the first catalyst outlet 404 (not shown).In the case, described fluidized-bed reactor also comprises the second catalyst inlet 303 (not shown) in addition, second catalyst outlet 304 (not shown), and described first catalyst inlet 403 is connected to described second catalyst outlet 304, described first catalyst outlet 404 is connected to described second catalyst inlet 403, described resurgent gases entrance 401 is for introducing resurgent gases, and described pneumatic outlet 402 is for discharging the gas after regenerative response.
Preferably, described reaction unit also comprises methyl propionate storage tank 14.
Preferably, described tripping device 5 ' specifically comprises the first separator 5, second separator 6, the 3rd separator 7 and product purification tower 8.
Described first separator 5 comprises the first isolate relief outlet 506, described second opening for feed 501 and described 4th discharge port 504, described second opening for feed 501 is connected to the first discharge port 302 of described fluidized-bed reactor 3, to receive from the reaction mixture in described fluidized-bed reactor 3, described first isolate relief outlet 506 is for discharging ritalin, methyl alcohol, methyl acrylate, methyl propionate, methyl methacrylate and the water etc. that are separated and obtain; Described 4th discharge port 504 is for discharging formaldehyde, impurity product and water etc.
Described second separator 6 comprises the first isolate opening for feed 601, second isolate relief outlet 602 and described 3rd isolate relief outlet 603, described first isolate opening for feed 601 is connected to the described first isolate relief outlet 506 of described first separator 5, and described second isolate relief outlet 602 is for discharging ritalin, methyl alcohol, methyl acrylate and the methyl propionate etc. that are separated and obtain; Described 3rd isolate relief outlet 603 is separated the methyl methacrylate that obtains and water etc. for discharging.
Described 3rd separator 7 comprises the second isolate opening for feed 701, described second discharge port 502 and described 3rd discharge port 503, and described second isolate opening for feed 701 is connected to described second isolate relief outlet 602.
Described product purification tower 8 comprises the 3rd isolate opening for feed 801 and described 5th discharge port 505, and described 3rd isolate opening for feed 801 is connected to the described 3rd isolate relief outlet 603 on described second separator 6.
Preferably, described reaction unit also comprises interchanger (not shown), it is connected to described raw material mixing preheater 2 and described fluidized-bed reactor 3, thus is used for the material in raw material mixing preheater 2 described in the preheating of self-fluidized type bed bioreactor 3 liberated heat.
The following specifically describes method of the present invention.With reference to accompanying drawing 2, make ritalin and formaldehyde under methyl alcohol and/or fluidized gas existence condition after interchanger (not shown) and raw material mixing preheater 2 mix and be preheated to assigned temperature, enter in fluidized-bed reactor 3 with gaseous phase and react, reaction product enters tripping device 5 ' and is separated after entering in interchanger (not shown) and carrying out heat exchange with raw material, by opening the valve (not shown) on the connecting tube between the second catalyst outlet 304 (not shown) in described fluidized-bed reactor 3 and the first catalyst inlet 403 (not shown) in catalyst regenerator 4, make decaying catalyst flow out into catalyst regenerator 4 from described fluidized-bed reactor 3 to regenerate, by opening the valve (not shown) on the connecting tube between the first catalyst outlet 404 (not shown) in described catalyst regenerator 4 and the second catalyst inlet 303 (not shown) in described fluidized-bed reactor 3, the catalyzer in catalyst regenerator 4 is made to flow out from catalyst regenerator outlet and enter fluidized-bed reactor 3, thus realize the reprocessing cycle of catalyzer.
Described product obtains intermediate product containing methyl acrylate and methyl propionate and methyl methacrylate product after being separated, the described intermediate product containing methyl acrylate and methyl propionate is discharged to intermediate product preheater 12 via the 3rd discharge port 503, and make intermediate product containing methyl acrylate and methyl propionate under hydrogen existence condition after described intermediate product preheater 12 is preheated to assigned temperature, enter in fixed-bed reactor 13 with gaseous phase and react, obtain methyl propionate product, and this product is collected in methyl propionate storage tank 14, this product can be sold as byproduct, also can be mixed in raw material mixing preheater 2 as recycle stock and ritalin and formaldehyde, feedstock circulation jointly as fluidized-bed reactor 3 utilizes.
In the present invention, preferably, described fluidized gas can be the gas mixture of a kind of gas in nitrogen, argon gas and helium or multiple gases.
Described fluidized-bed reactor 3 and described catalyst regenerator 4 are provided with catalyst inlet, catalyst outlet.
In fluidized-bed reactor 3 of the present invention and catalyst regenerator 4, second catalyst outlet 304 of fluidized-bed reactor 3 is connected by pipeline with the first catalyst inlet 403 of catalyst regenerator 4, second catalyst inlet 303 of fluidized-bed reactor 3 is connected by pipeline with the first catalyst outlet 404 of catalyst regenerator 4, pipeline is provided with valve (such as, guiding valve, not shown) to control the residence time of catalyzer in each reactor.
In the present invention, preferably, described catalyst regenerator 4 is fluid bed regenerator.
Preferably, according to an embodiment of the invention, the working temperature of described raw material mixing preheater 2 is 100 ~ 500 DEG C, and the working temperature of described intermediate product preheater 12 is 100 ~ 400 DEG C.
In the present invention, preferably, the reaction conditions of described fluidized-bed reactor 3 is: temperature is 200 ~ 400 DEG C, pressure is 0.05 ~ 1MPa, the mol ratio of ritalin and formaldehyde is 1:0.1 ~ 1:3, and the mol ratio of methyl alcohol and ritalin is 0 ~ 3:1, if using hydrogenation reaction product methyl propionate as recycle stock for the production of methyl methacrylate, then the mol ratio of methyl propionate and ritalin is 1:0.5 ~ 1:5, and the volume space velocity of ritalin is 1 ~ 1000h
-1.Prepare in the method for methyl methacrylate in the present invention by ritalin and formaldehyde, methyl alcohol had both played the effect of stabilized oxymethylene, can suppress again the generation of the side reactions such as Ester hydrolysis.
In the present invention, preferably, the reaction conditions of described fixed-bed reactor 13 is: temperature is 120 ~ 300 DEG C, and pressure is 0.05 ~ 4MPa, and volume space velocity is 1 ~ 1000h
-1.
As shown in Figure 3, tripping device 5 ' of the present invention is it further described.
Described tripping device 5 ' specifically comprises the first separator 5, second separator 6, the 3rd separator 7 and product purification tower 8.
Described first separator 5 receives from the reaction mixture in described fluidized-bed reactor 3, after being separated, formaldehyde, impurity product and water are expelled to described 4th discharge port 504, and ritalin, methyl alcohol, methyl acrylate, methyl propionate, methyl methacrylate and water etc. are discharged to described second separator 6.
Ritalin, methyl alcohol, methyl acrylate and methyl propionate, by from the separating substances in described first separator 5, are expelled to described 3rd separator 7, and methyl methacrylate and water are expelled to described product purification tower 8 by described second separator 6.
Described 3rd separator 7 is separated the material from described second separator 6, and ritalin and methyl alcohol are expelled to described second discharge port 502, its further Returning reactor 3 participates in reaction, methyl alcohol, methyl acrylate and methyl propionate are expelled to described 3rd discharge port 503, it enters reactor 13 hydrogenation.
Described product purification tower 8 receives methyl methacrylate from described second separator 6 and water, refining to obtain end product methyl methacrylate further.
Catalyzer used in the present invention is all catalyzer that such building-up reactions is carried out in this area, such as, described aldolization catalyzer can be the basic metal etc. of silicon dioxide carried base metal catalysts or silicon-dioxide and the load of aluminium sesquioxide mixed carrier, auxiliary agent is one or more of zirconium white, magnesium oxide, lanthanum trioxide, cerium oxide, calcium oxide etc., is preferably the open CN103752305A (application number: the catalyzer 201410022889.3) of Chinese patent; Described catalyst for hydrogenation can be the metal catalyst of aluminium sesquioxide load, and representative has precious metals pt, Pd, Rh, Ir, Ru etc., and base metal Ag, Cu, Ni etc.
The method conbined usage fluidized-bed reactor that the present invention adopts and fixed-bed reactor, the recycle after releasing of unreacted ritalin raw material, after the methyl acrylate hydrogenation that reaction generates generates methyl propionate, both can sell as byproduct, again can as process raw material and the common recycle of ritalin.
Aldolization catalyzer is continuous flow realization response regenerative process between fluidized-bed reactor and catalyst regenerator, substantially increases the utilising efficiency of catalyzer, achieves the continuity of production.This fluidized-bed process meets demand of industrial production, can the high reactivity of long term maintenance catalyzer, and improve the service efficiency of catalyzer, the circulation of unreacting material improves transformation in planta rate, adds economic benefit.
Accompanying drawing explanation
For the ease of checking, eliminate some parts well known by persons skilled in the art.
Fig. 1 is the reaction unit of the present invention according to an embodiment of the invention;
Fig. 2 is reaction unit of the present invention according to another implementation of the invention;
Fig. 3 is the device schematic diagram of an illustrative embodiments of tripping device 5 ' in Fig. 2;
Fig. 4 is the schematic diagram of the primary structure of described fluidized-bed reactor A and catalyst regenerator B;
In Fig. 1-3: 1a, ritalin head tank; 1b, formaldehyde raw material tank; 1c, fluidized gas storage tank; 1d, methanol feedstock tank; 2, raw material mixing preheater; 3, fluidized-bed reactor; 4, catalyst regenerator; 5 ', tripping device; 5, separator 1; 6, separator 2; 7, separator 3; 8, product purification tower; 9, impurity storage tank; 10, methyl methacrylate product storage tank; 11, hydrogen-holder; 12, intermediate product preheater; 13, fixed-bed reactor; 14: methyl propionate storage tank.
It is same as above that other respectively import and export label.
In Fig. 4: 3001,4001: gas distributor; 3002,4002: cylindrical shell; 3003,4003: expanding reach; 3004,4004: catalyst inlet; 3005,4005: catalyst outlet; 3006,4006: catalyst transport pipeline; 3007,4007: gas inlet; 3008,4008: pneumatic outlet; 3009,4009: cyclonic separator; 3010: live catalyst entrance; 3011,4011: valve; 4012: interchanger.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be further described, but scope of the present invention is not limited to the following example.
As shown in Figures 2 and 3, of the present invention to prepare the fluidized-bed process of methyl methacrylate by ritalin and formaldehyde as follows: raw material ritalin (being provided by 1a) and formaldehyde (being provided by 1b) enter mixing preheater 2 under methyl alcohol (being provided by 1d) and/or fluidized gas (being provided by 1c) exist to carry out mixing and preheating, then enter fluidized-bed reactor 3 with gaseous phase to react, decaying catalyst is shifted out from fluidized-bed reactor 3 by catalyst transport pipeline, enter catalyst regenerator 4 to regenerate, catalyzer after regeneration enters fluidized-bed reactor 3 again by catalyst transport pipeline, complete the reprocessing cycle of catalyzer, in fluidized-bed reactor 3, reacted Product mix gas enters knockout tower 5 ~ 8 and is separated, unreacted ritalin, formaldehyde and/or methyl alcohol and/or fluidized gas return the recycle of mixing preheater 2, the intermediate product methyl acrylate that reaction generates, methyl propionate and carbinol mixture separate from knockout tower 7, after entering intermediate product preheater 12 preheating, fixed-bed reactor 13 are entered with gaseous phase, react under hydrogen (providing by 11) existence condition, obtain methyl propionate product and enter methyl propionate storage tank, this product can be sold as process by-products, also can be mixed in feed preheater as recycle stock and ritalin and formaldehyde, feedstock circulation jointly as fluidized-bed reactor utilizes, product separates from knockout tower 6, and then enter treating tower 8 and obtain in methyl methacrylate product introduction product storage tank 10, high boiling substance and the methyl alcohol etc. such as heavy ester separate from knockout tower 5 and enters impurity storage tank 9.
Embodiment one
Fluidized-bed used catalyst is silica supported caesium and antimony, and wherein caesium content is 15wt%, and antimony content is 10wt%; Fixed bed used catalyst is the platinum that supports of aluminium sesquioxide and ruthenium.Raw material preheating actuator temperature is 280 DEG C, and fluidized-bed reactor service temperature is 380 DEG C, ritalin: the mol ratio of the third sour first ester ︰ first aldehyde ︰ methyl alcohol is 2:1:1.5:2, and fluidized gas is nitrogen, and air speed is 5h
-1, pressure is 0.1MPa; Catalyst regeneration actuator temperature is 450 DEG C, and be that resurgent gases carries out coke-burning regeneration with air, its air speed is 20h
-1, pressure is 0.1MPa; The catalyzer residence time is in a fluidized bed reactor 4 hours, and carbon deposition quantity when catalyzer enters revivifier is 6%, and the recovery time is 1 hour; Intermediate product preheater temperature is 180 DEG C, and fixed-bed reactor service temperature is 220 DEG C, and charging is methyl acrylate, methyl propionate and carbinol mixture, and air speed is 4h
-1, pressure is 1.5MPa, and hydrogenation products is methyl propionate and carbinol mixture, circulates as the raw material of fluidized-bed reactor.
The molar yield of ritalin is 31.2%, and the molar yield of methyl propionate is 18.3%, and the molar selectivity of methyl methacrylate is 90.2%.
Embodiment two,
Fluidized-bed used catalyst is silica supported caesium and antimony, and wherein caesium content is 15wt%, and antimony content is 10wt%; Fixed bed used catalyst is the platinum that supports of aluminium sesquioxide and ruthenium.Raw material preheating actuator temperature is 280 DEG C, and fluidized-bed reactor service temperature is 380 DEG C, ritalin: formaldehyde: the mol ratio of methyl alcohol is 1:1:2, and fluidized gas is nitrogen, and air speed is 5h
-1, pressure is 0.1MPa; Catalyst regeneration actuator temperature is 450 DEG C, and be that resurgent gases carries out coke-burning regeneration with air, its air speed is 20h
-1, pressure is 0.1MPa; The catalyzer residence time is in a fluidized bed reactor 4 hours, and carbon deposition quantity when catalyzer enters revivifier is 6%, and the recovery time is 1 hour; Intermediate product preheater temperature is 180 DEG C, and fixed-bed reactor service temperature is 220 DEG C, and charging is methyl acrylate and methyl propionate mixture, and air speed is 4h
-1, pressure is 1.5MPa, and hydrogenation products is methyl propionate, as the byproduct of this technological process.
The molar yield of ritalin is 42.5%, and total molar selectivity of methyl propionate is 65.3%, and the molar selectivity of methyl methacrylate is 25.1%.
Claims (10)
1. produce a method for methyl methacrylate, the method comprises the following steps:
A) the first aldolization is carried out under making ritalin and the catalysis of formaldehyde under methyl alcohol and/or fluidized gas existence condition, in aldolization catalyst in a fluidized bed reactor:
CH
3COOCH
3+HCHO＝CH
2CHCOOCH
3+H
2O，
Wherein, described fluidized gas is the gas mixture of a kind of gas in nitrogen, argon gas and helium or multiple gases,
Described aldolization catalyst comprises using silicon-dioxide as carrier or using silicon-dioxide and aluminium sesquioxide mixture as carrier loaded base metal catalysts, wherein, described base metal catalysts specifically comprises Cs, Na, K or Li, and comprise be selected from weisspiessglanz, zirconium white, magnesium oxide, lanthanum trioxide, cerium oxide, calcium oxide etc. one or more as auxiliary agent;
B) in fixed-bed reactor, make the intermediate product containing methyl acrylate carry out hydrogenation reaction under hydrogen existence condition, under the catalysis of hydrogenation catalyst:
CH
2CHCOOCH
3+H
2＝CH
3CH
2COOCH
3，
Described hydrogenation catalyst is the metal catalyst of aluminium sesquioxide load, and its activeconstituents comprises one or more metals be selected from Pt, Pd, Rh, Ir, Ru, Ag, Cu, Ni;
C) the second aldolization is carried out under making methyl propionate and the catalysis of formaldehyde under methyl alcohol and/or fluidized gas existence condition, in aldolization catalyst in a fluidized bed reactor:
CH
3CH
2COOCH
3+HCHO＝CH
3CH
2CHCOOCH
3+H
2O，
Wherein, described fluidized gas is the gas mixture of a kind of gas in nitrogen, argon gas and helium or multiple gases,
Described aldolization catalyst comprises using silicon-dioxide as carrier or using silicon-dioxide and aluminium sesquioxide mixture as carrier loaded base metal catalysts, wherein, described base metal catalysts specifically comprises Cs, Na, K or Li, and comprise be selected from weisspiessglanz, zirconium white, magnesium oxide, lanthanum trioxide, cerium oxide, calcium oxide etc. one or more as auxiliary agent.
2. method according to claim 1, wherein,
The reaction conditions of described fluidized-bed reactor is: temperature is 200 ~ 400 DEG C, and pressure is 0.05 ~ 1MPa, and the mol ratio of ritalin and formaldehyde is 1:0.1 ~ 1:3, and the mol ratio of methyl alcohol and ritalin is 0 ~ 3:1, and the volume space velocity of ritalin is 1 ~ 1000h
-1; And
The reaction conditions of described fixed-bed reactor is: temperature is 120 ~ 300 DEG C, and pressure is 0.05 ~ 4MPa, and volume space velocity is 1 ~ 1000h
-1.
3. method according to claim 1, wherein,
The step of described method a) is carried out as follows:
Make ritalin and formaldehyde mix through interchanger and mixing preheater and be preheated to preset temperature under methyl alcohol and/or fluidized gas existence condition, enter in fluidized-bed reactor with gaseous phase, under the catalysis of aldolization catalyst, carry out the first aldolization,
Wherein, described fluidized gas is the gas mixture of a kind of gas in nitrogen, argon gas and helium or multiple gases, and described preset temperature is 100 ~ 500 DEG C; And
The step b of described method) carry out as follows:
Make intermediate product containing methyl acrylate under hydrogen existence condition through intermediate product preheater preheats, enter in fixed-bed reactor with gaseous phase, under the catalysis of hydrogenation catalyst, carry out hydrogenation reaction,
Wherein, described intermediate product preheater is set to 100 ~ 400 DEG C.
4. method according to claim 1, wherein, described method also additionally comprises the following steps:
D) by the catalyzer in described fluidized-bed reactor and/or described fixed-bed reactor by catalyst regenerator via regeneration gas regenerates, again drop into afterwards in respective reaction device;
Wherein, the regeneration gas of described catalyzer can be selected from oxygen, air, nitrogen, hydrogen, carbonic acid gas and water vapour one or more.
5. method according to claim 4, wherein,
Catalyst regeneration conditions in described fluidized-bed reactor and/or described fixed-bed reactor is: temperature is 200 ~ 600 DEG C, and the volume space velocity of regeneration gas is 10 ~ 1000h
-1, pressure is 0.05 ~ 1MPa, and the regenerative response time is 0.01 ~ 10h; And
Carbon distribution content when described catalyzer enters described catalyst regenerator is 2-12%.
6. method according to claim 1, wherein,
By described step b) the product of hydrogenation reaction be back to described step a) in fluidized-bed reactor carry out described step c) reaction; And now, the mol ratio of methyl propionate and ritalin is 1:0.5 ~ 1:5.
7. produce a device for methyl methacrylate, this device comprises:
Fluidized-bed reactor 3, it comprises the first opening for feed 301, first discharge port 302, described first opening for feed 301 is for receiving ritalin, formaldehyde, methyl alcohol, methyl propionate, the fluidized gas from raw material or recycle feed, and described first discharge port 302 discharges the reaction mixture in reactor 3;
Tripping device 5 ', it comprises the second opening for feed 501, second to the 5th discharge port 502 to 505, wherein, described second opening for feed 501 is connected to the first discharge port 302 of described fluidized-bed reactor 3, to receive from the reaction mixture in described fluidized-bed reactor 3, described reaction mixture is separated in tripping device 5 ', thus obtain unreacted raw material respectively, methyl acrylate, methyl propionate, impurity product and methyl methacrylate, described second discharge port 502 discharges unreacted raw material, described 3rd discharge port 503 discharges methyl acrylate, methyl propionate and methyl alcohol, described 4th discharge port 504 discharges impurity product, formaldehyde, and described 5th discharge port 505 discharges required end product methyl methacrylate,
Fixed-bed reactor 13, it comprises the 3rd opening for feed 1301 and the 6th discharge port 1302, described 3rd opening for feed 1301 is for receiving the methyl acrylate of described 3rd discharge port 503 from described separator 5, methyl propionate and methyl alcohol, and described 6th discharge port 1302 is for the methyl propionate of discharging hydrogenation reaction and obtaining and methyl alcohol.
8. device according to claim 7, wherein,
6th discharge port 1302 of described fixed-bed reactor 13 is connected to described first opening for feed 301 of described fluidized-bed reactor 3.
9. device according to claim 7, wherein,
Described reaction unit also comprises raw material mixing preheater 2, and it comprises material inlet 201 and raw material discharge port 202, and described material inlet 201 is connected to the 6th discharge port 1302 of described fixed-bed reactor 13; Described raw material discharge port 202 is connected to described first opening for feed 301 of described fluidized-bed reactor 3, and the 6th discharge port 1302 of the no longer direct and described fixed-bed reactor 13 of described first opening for feed 301 of described fluidized-bed reactor 3 is connected;
Described reaction unit also comprises intermediate product preheater 12, it comprises intermediate product opening for feed 1201 and intermediate product discharge port 1202, described intermediate product opening for feed 1201 is connected to the 3rd discharge port 503 of described separator 5, described intermediate product discharge port 1202 is connected to described 3rd opening for feed 1301 of described fixed-bed reactor 13, and the 3rd discharge port 503 of the no longer direct and described separator 5 of described 3rd opening for feed 1301 of described fixed-bed reactor 13 is connected;
Described reaction unit also comprises catalyst regenerator 4, and it comprises resurgent gases entrance 401, pneumatic outlet 402, the first catalyst inlet 403, first catalyst outlet 404;
Described fluidized-bed reactor 3 also comprises the second catalyst inlet 303 in addition, second catalyst outlet 304, and described first catalyst inlet 403 is connected to described second catalyst outlet 304, described first catalyst outlet 404 is connected to described second catalyst inlet 403
Described resurgent gases entrance 401 is for introducing resurgent gases, and described pneumatic outlet is for discharging the gas after regenerative response.
10. device according to claim 7, wherein
Described tripping device 5 ' comprises the first separator 5, second separator 6, the 3rd separator 7 and product purification tower 8,
Described first separator 5 comprises the first isolate relief outlet 506, described second opening for feed 501 and described 4th discharge port 504, described second opening for feed 501 is connected to the first discharge port 302 of described fluidized-bed reactor 3, to receive from the reaction mixture in described fluidized-bed reactor 3, described first isolate relief outlet 506 is for discharging ritalin, methyl alcohol, methyl acrylate, methyl propionate, methyl methacrylate and the water etc. that are separated and obtain; Described 4th discharge port 504 is for discharging formaldehyde, impurity product and water etc.;
Described second separator 6 comprises the first isolate opening for feed 601, second isolate relief outlet 602 and described 3rd isolate relief outlet 603, described first isolate opening for feed 601 is connected to the described first isolate relief outlet 506 of described first separator 5, and described second isolate relief outlet 602 is for discharging ritalin, methyl alcohol, methyl acrylate and the methyl propionate etc. that are separated and obtain; Described 3rd isolate relief outlet 603 is separated the methyl methacrylate that obtains and water etc. for discharging;
Described 3rd separator 7 comprises the second isolate opening for feed 701, described second discharge port 502 and described 3rd discharge port 503, and described second isolate opening for feed 701 is connected to described second isolate relief outlet 602;
Described product purification tower 8 comprises the 3rd isolate opening for feed 801 and described 5th discharge port 505, and described 3rd isolate opening for feed 801 is connected to the described 3rd isolate relief outlet 603 on described second separator 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410784248.1A CN104513163A (en) | 2014-12-16 | 2014-12-16 | Method for producing methyl methacrylate by methyl acetate and formaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410784248.1A CN104513163A (en) | 2014-12-16 | 2014-12-16 | Method for producing methyl methacrylate by methyl acetate and formaldehyde |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104513163A true CN104513163A (en) | 2015-04-15 |
Family
ID=52789069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410784248.1A Pending CN104513163A (en) | 2014-12-16 | 2014-12-16 | Method for producing methyl methacrylate by methyl acetate and formaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104513163A (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674010A (en) * | 2015-11-10 | 2017-05-17 | 上海浦景化工技术股份有限公司 | Process for preparing methyl methacrylate according to aldol condensation method |
| CN107337600A (en) * | 2017-07-04 | 2017-11-10 | 湖北三里枫香科技有限公司 | A kind of method and process unit of methanol and methyl acetate production methyl methacrylate |
| CN107721855A (en) * | 2017-10-13 | 2018-02-23 | 北京博迩科技有限公司 | A kind of method for preparing 3 methoxy methyl propionates |
| CN108101768A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of method for preparing unsaturated low-grade fatty acid ester |
| CN109232247A (en) * | 2018-11-12 | 2019-01-18 | 西南化工研究设计院有限公司 | A kind of method of methyl acetate and formaldehyde aldol condensation methyl methacrylate |
| CN110639511A (en) * | 2018-06-27 | 2020-01-03 | 中国石油化工股份有限公司 | Catalyst for carbon-carbon double bond hydrogenation of acrylate and application thereof |
| CN110981727A (en) * | 2019-12-06 | 2020-04-10 | 西南化工研究设计院有限公司 | Methyl methacrylate synthesis process |
| CN111333508A (en) * | 2020-04-17 | 2020-06-26 | 湖北三里枫香科技有限公司 | Production process of acrylic ester |
| CN111517953A (en) * | 2020-05-09 | 2020-08-11 | 江苏湖大化工科技有限公司 | Production process method for synthesizing methyl methacrylate by methyl acetate and formaldehyde |
| CN111574371A (en) * | 2020-06-22 | 2020-08-25 | 北京旭阳科技有限公司 | Method and device for joint production of anhydrous gas-phase formaldehyde and methyl methacrylate |
| CN111905780A (en) * | 2020-08-27 | 2020-11-10 | 中国科学院过程工程研究所 | Catalyst, preparation method thereof and application of catalyst in preparation of methyl methacrylate |
| CN111905745A (en) * | 2020-08-06 | 2020-11-10 | 中国科学院过程工程研究所 | Nickel-based catalyst for methyl acrylate hydrogenation reaction and method thereof |
| CN114292186A (en) * | 2022-01-14 | 2022-04-08 | 万华化学集团股份有限公司 | Preparation method of high-purity MMA |
| CN114478253A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Synthesis method of methyl methacrylate and obtained methyl methacrylate |
| CN114516795A (en) * | 2022-02-25 | 2022-05-20 | 北京石油化工工程有限公司 | Method for producing methyl acrylate by using methanol and methyl acetate as raw materials |
| CN114516795B (en) * | 2022-02-25 | 2024-06-11 | 北京石油化工工程有限公司 | Method for producing methyl acrylate by using methanol and methyl acetate as raw materials |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775302A (en) * | 2012-08-03 | 2012-11-14 | 北京旭阳化工技术研究院有限公司 | Method for preparing methyl methacrylate from methyl propionate and formaldehyde |
| CN103435483A (en) * | 2013-07-05 | 2013-12-11 | 旭阳化学技术研究院有限公司 | Synthesis method for methyl acrylate from methyl acetate and formaldehyde |
-
2014
- 2014-12-16 CN CN201410784248.1A patent/CN104513163A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775302A (en) * | 2012-08-03 | 2012-11-14 | 北京旭阳化工技术研究院有限公司 | Method for preparing methyl methacrylate from methyl propionate and formaldehyde |
| CN103435483A (en) * | 2013-07-05 | 2013-12-11 | 旭阳化学技术研究院有限公司 | Synthesis method for methyl acrylate from methyl acetate and formaldehyde |
Non-Patent Citations (1)
| Title |
|---|
| LI XIAOFEI, ET AL.: "Pd nanoparticles confined in fluoro‐functionalized yolk‐shell‐structured silica for olefin hydrogenation in water", 《CHINESE JOURNAL OF CATALYSIS》 * |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674010B (en) * | 2015-11-10 | 2020-01-07 | 上海浦景化工技术股份有限公司 | Process for preparing methyl methacrylate by aldol condensation method |
| CN106674010A (en) * | 2015-11-10 | 2017-05-17 | 上海浦景化工技术股份有限公司 | Process for preparing methyl methacrylate according to aldol condensation method |
| CN108101768A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of method for preparing unsaturated low-grade fatty acid ester |
| CN108101768B (en) * | 2016-11-25 | 2019-12-13 | 中国科学院大连化学物理研究所 | Method for preparing unsaturated lower fatty acid ester |
| CN107337600A (en) * | 2017-07-04 | 2017-11-10 | 湖北三里枫香科技有限公司 | A kind of method and process unit of methanol and methyl acetate production methyl methacrylate |
| CN107721855A (en) * | 2017-10-13 | 2018-02-23 | 北京博迩科技有限公司 | A kind of method for preparing 3 methoxy methyl propionates |
| CN107721855B (en) * | 2017-10-13 | 2021-01-19 | 北京博迩科技有限公司 | Method for preparing 3-methoxy methyl propionate |
| CN110639511A (en) * | 2018-06-27 | 2020-01-03 | 中国石油化工股份有限公司 | Catalyst for carbon-carbon double bond hydrogenation of acrylate and application thereof |
| CN110639511B (en) * | 2018-06-27 | 2023-03-03 | 中国石油化工股份有限公司 | Catalyst for carbon-carbon double bond hydrogenation of acrylate and application thereof |
| CN109232247B (en) * | 2018-11-12 | 2020-06-30 | 西南化工研究设计院有限公司 | Method for preparing methyl methacrylate by aldol condensation of methyl acetate and formaldehyde |
| CN109232247A (en) * | 2018-11-12 | 2019-01-18 | 西南化工研究设计院有限公司 | A kind of method of methyl acetate and formaldehyde aldol condensation methyl methacrylate |
| CN110981727A (en) * | 2019-12-06 | 2020-04-10 | 西南化工研究设计院有限公司 | Methyl methacrylate synthesis process |
| CN110981727B (en) * | 2019-12-06 | 2020-12-18 | 西南化工研究设计院有限公司 | Methyl methacrylate synthesis process |
| CN111333508A (en) * | 2020-04-17 | 2020-06-26 | 湖北三里枫香科技有限公司 | Production process of acrylic ester |
| CN111517953A (en) * | 2020-05-09 | 2020-08-11 | 江苏湖大化工科技有限公司 | Production process method for synthesizing methyl methacrylate by methyl acetate and formaldehyde |
| CN111574371A (en) * | 2020-06-22 | 2020-08-25 | 北京旭阳科技有限公司 | Method and device for joint production of anhydrous gas-phase formaldehyde and methyl methacrylate |
| CN111574371B (en) * | 2020-06-22 | 2023-02-24 | 北京旭阳科技有限公司 | Method and device for joint production of anhydrous gas-phase formaldehyde and methyl methacrylate |
| CN111905745A (en) * | 2020-08-06 | 2020-11-10 | 中国科学院过程工程研究所 | Nickel-based catalyst for methyl acrylate hydrogenation reaction and method thereof |
| CN111905745B (en) * | 2020-08-06 | 2022-01-04 | 中国科学院过程工程研究所 | Nickel-based catalyst for methyl acrylate hydrogenation reaction and method thereof |
| CN111905780A (en) * | 2020-08-27 | 2020-11-10 | 中国科学院过程工程研究所 | Catalyst, preparation method thereof and application of catalyst in preparation of methyl methacrylate |
| CN114478253A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Synthesis method of methyl methacrylate and obtained methyl methacrylate |
| CN114292186A (en) * | 2022-01-14 | 2022-04-08 | 万华化学集团股份有限公司 | Preparation method of high-purity MMA |
| CN114516795A (en) * | 2022-02-25 | 2022-05-20 | 北京石油化工工程有限公司 | Method for producing methyl acrylate by using methanol and methyl acetate as raw materials |
| CN114516795B (en) * | 2022-02-25 | 2024-06-11 | 北京石油化工工程有限公司 | Method for producing methyl acrylate by using methanol and methyl acetate as raw materials |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104513163A (en) | Method for producing methyl methacrylate by methyl acetate and formaldehyde | |
| CN102775302B (en) | A kind of method being prepared methyl methacrylate by methyl propionate and formaldehyde | |
| CN109232247B (en) | Method for preparing methyl methacrylate by aldol condensation of methyl acetate and formaldehyde | |
| CN111517953A (en) | Production process method for synthesizing methyl methacrylate by methyl acetate and formaldehyde | |
| UA119638C2 (en) | Integrated process for making acetic acid | |
| CN103435483A (en) | Synthesis method for methyl acrylate from methyl acetate and formaldehyde | |
| CN103360215A (en) | Method for synthesizing isopentenol from 3-methyl-3-butene-1-ol through catalytic transposition in water-organic two-phase system | |
| US8962895B2 (en) | Method for the production of ethylene glycol | |
| CN103664529B (en) | The method of coproduction hexalin and ethanol | |
| CN1962588A (en) | Method for synthesis of isopropanol | |
| CN101125802A (en) | Gas phase continuous production method for dimethyl ether from methanol | |
| CN103664530A (en) | Method for coproducing cyclohexanol and ethanol | |
| CN103664587A (en) | Method for preparing cyclohexyl acetate and method for preparing cyclohexanol ethanol | |
| CN102649563B (en) | Method for dehydrogenation through catalytic oxidation of carbon monoxide gas | |
| CN102649562B (en) | Method for dehydrogenation of CO gas raw material in virtue of catalytic oxidation | |
| CN102050710B (en) | Method for preparing 2-methylacraldehyde and 2-methyl-2-pentenal synchronously | |
| CN102649566B (en) | Method for dehydrogenating CO-containing gas mixture by oxidizing reaction | |
| CN212335079U (en) | Production process device for synthesizing methyl methacrylate by methyl acetate and formaldehyde | |
| CN102649734B (en) | Method for producing oxalate through catalytic coupling reaction of carbon monoxide | |
| CN106673958B (en) | Pilot-scale propylene oxide gas phase isomerization fixed bed process prepares the method and system of allyl alcohol | |
| CN112479858A (en) | Methanol carbonylation enhanced reaction system and process with aldehyde recovery function | |
| CN101993369B (en) | Method for producing oxalic ester by gas phase CO coupling | |
| CN212119940U (en) | Methanol carbonylation enhanced reaction system with aldehyde recovery function | |
| CN102649685A (en) | Method for producing ethylene glycol efficiently by oxalic ester | |
| CN102649564A (en) | Method for dehydrogenating CO-containing mixed gas raw material by means of catalytic oxidation reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 100070 Beijing city Fengtai District Haiying Road No. 6 Building No. 6 hospital Applicant after: BEIJING RISUN TECHNOLOGY CO., LTD. Address before: 100070 Beijing city Fengtai District Haiying Road No. 6 Building No. 6 hospital Applicant before: Beijing Xuyang Chemical Technology Research Institute Co., Ltd. |
|
| COR | Change of bibliographic data | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150415 |
|
| RJ01 | Rejection of invention patent application after publication |