CN110003002A - A kind of production technology of high yield Trifluoroacetic Acid Ethyl Ester - Google Patents
A kind of production technology of high yield Trifluoroacetic Acid Ethyl Ester Download PDFInfo
- Publication number
- CN110003002A CN110003002A CN201910346362.9A CN201910346362A CN110003002A CN 110003002 A CN110003002 A CN 110003002A CN 201910346362 A CN201910346362 A CN 201910346362A CN 110003002 A CN110003002 A CN 110003002A
- Authority
- CN
- China
- Prior art keywords
- trifluoroacetic acid
- ethyl ester
- titanium dioxide
- hydrochloric acid
- acid ethyl
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3653—Treatment with inorganic compounds
- C09C1/3661—Coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3669—Treatment with low-molecular organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3676—Treatment with macro-molecular organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
- C09C3/063—Coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
-
- 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
- Y02P20/10—Process efficiency
Abstract
The present invention relates to a kind of production technologies of high yield Trifluoroacetic Acid Ethyl Ester, are included under the conditions of reactive distillation, and trifluoro-acetyl chloride and ethyl alcohol carry out continuous non-catalytic method reaction and prepares Trifluoroacetic Acid Ethyl Ester.The present invention may be implemented continuous non-catalytic method and prepare Trifluoroacetic Acid Ethyl Ester, and Trifluoroacetic Acid Ethyl Ester yield is very high, and by-product hydrochloric acid obtains effective recycling, the raw material used is conveniently easy to get, simple process, and reaction condition is mild, energy consumption of reaction is low, and process is remained without waste liquid, is suitble to amplification production.
Description
Technical field
The present invention relates to a kind of production technologies of high yield Trifluoroacetic Acid Ethyl Ester.
Background technique
Trifluoroacetic Acid Ethyl Ester alias ethyltrifluoroacetate is a kind of volatile, colourless transparent liquid, has the smell of ester, easily
It is dissolved in ether, ethyl alcohol, is dissolved in chloroform, is slightly soluble in water, can slowly be hydrolyzed in water.The steam of Trifluoroacetic Acid Ethyl Ester can be with air shape
At explosive mixture, open fire, high fever easily combustion explosion are met, high thermal decomposition is met and releases high poison flue gas, contacted with oxidant instead
It should be violent.
Trifluoroacetic Acid Ethyl Ester (ETFA) as a kind of important Organic Chemicals, synthesis organofluorine compound, medicine,
The industries such as pesticide, liquid crystal and dyestuff have a wide range of applications, wherein the synthesis of organic fluoride have 2- thioyl trifluoroacetone,
Trifluoroacetic ethyl acetoacetate, trifluoroacetylacetone (TFA) etc.；Concrete application is as follows: (1) in terms of the medicine, being mainly used in production bone
Arthritic anti-inflammatory agent, treatment colonitis and antineoplastic, the cardiovascular medicament-Lenno Puli of the carcinoma of the rectum etc.；(2) in pesticide
In aspect, mainly for the manufacture of cell division inhibitor, grass family herbicide and broadleaved herb are removed with being applied to cotton, peanut；(3) exist
In terms of organic synthesis, since Trifluoroacetic Acid Ethyl Ester has lower removal rate under mild environment, it is commonly used for amino group
Protection.
Trifluoroacetic acid esterification reaction is using trifluoroacetic acid and ethyl alcohol as Material synthesis Trifluoroacetic Acid Ethyl Ester, using direct esterification
The advantages of method is: raw material trifluoroacetic acid is mild compared with trifluoro-acetyl chloride, smaller to human injury with hypotoxicity, and is easier to
It obtains.In addition, esterification reaction synthetic method research is mature, mechanism is clear, is the prefered method for synthesizing Trifluoroacetic Acid Ethyl Ester.In recent years
Come, is gradually being developed using esterification process synthesis Trifluoroacetic Acid Ethyl Ester.
Traditional production method is using trifluoroacetic acid and dehydrated alcohol as raw material, using the concentrated sulfuric acid as catalyst, by adding
Heat production obtains Trifluoroacetic Acid Ethyl Ester, but the method yield is not high, and the process of purification process is also more cumbersome, so result
It is less ideal, and this production method to production equipment also can heavy corrosion, therefore this production method is gradually washed in a pan
It eliminates.The main method of production Trifluoroacetic Acid Ethyl Ester is still using trifluoroacetic acid and dehydrated alcohol as main original both at home and abroad at present
Material carries out esterification by using different catalyst and technique and generates Trifluoroacetic Acid Ethyl Ester.
It in the method that storng-acid cation exchange resin is catalysis drug progress esterification is exchanged with highly acidic cation
Resin is new catalyst, and ingredient mass ratio is m (trifluoroacetic acid): m (dehydrated alcohol)=1:0.80~3.2；M (trifluoro second
Acid): m (catalyst)=1:0.3~0.80, reacting liquid temperature are to generate thick trifluoro with this condition between 40~50 degrees Celsius
Obtained thick ester is placed in drying in the thousand dry towers filled with solid particle silica gel, removes remaining moisture content with this by ethyl acetate,
The fraction that air-distillation obtains 58~64 degrees Celsius is Trifluoroacetic Acid Ethyl Ester product, and yield 93.7%, product purity is reachable
98.0%~99.9%.The process program compared with traditional sulphuric acid catalysis reaction method technical aspect have it is very big into
Step, succinctly reliable for the quality analysis of distillation process, the high boiling ethyl alcohol after distillation can also be utilized again, environmental pollution
It is small, it can be improved quality of finished and yield.But because of its technique production procedure not yet mature, being dehydrated into for drying tower is not considered
Originally, efficiency and the reuse rate of catalyst, therefore be not used in industrialized production also.
Using trifluoroacetic acid and dehydrated alcohol as primary raw material, catalyst uses acidic molecular sieve, trifluoro second is prepared
Acetoacetic ester belongs to Fine Organic Chemical field.The method is carries out reaction towards positive reaction direction, so permeable separator is drawn
Enter, timely draws water generated in esterification.Under conditions of 48~50 degrees Celsius of reaction temperature, n (trifluoroacetic acid):
N (dehydrated alcohol)=1:1.2~1:5；M (trifluoroacetic acid): m (molecular sieve)=1:0.2~1:0.5, reaction obtain trifluoroacetic acid
Ethyl ester.It is extracted with saturated aqueous sodium carbonate, is then washed with saturated sodium-chloride water solution, then using solid
Normal pressure steams feedback after body potassium carbonate is dry, after collecting fraction, carries out normal pressure steaming again after reusing phosphorus pentoxide drying at normal temperature
It evaporates, collects shop point and then obtain the Trifluoroacetic Acid Ethyl Ester that purity is up to 99.7% or more.
In view of the density ratio water of Trifluoroacetic Acid Ethyl Ester is big, whens two-phase mixtures, causes organic phase in lower section, and subsequent
Convenience in separation introduces cosolvent in its production technology, and the selection of the cosolvent follows following principle: 1. relative to water
Density less than 1；2. Trifluoroacetic Acid Ethyl Ester and trifluoroacetic acid can be dissolved in；3. not forming azeotropic mixture with Trifluoroacetic Acid Ethyl Ester；4. boiling
Point is higher than the boiling point of Trifluoroacetic Acid Ethyl Ester and trifluoroacetic acid.Select toluene, dimethylbenzene for cosolvent in document, ethyl alcohol is than trifluoro second
Excessive acid 5.5%~9%, to improve trifluoroacetic acid conversion ratio, the concentrated sulfuric acid is catalyst, and cosolvent dosage is 300g/ (l mol
TFA), through reaction of high order split-phase, finally distillation obtains the Trifluoroacetic Acid Ethyl Ester that purity is 99.5% or more.Document above report
Technique mostly process is complicated, and production cost is higher, studies only in the experimental stage, it is difficult to be used for large-batch industrial.
Traditionally the synthesis of carboxylic acid esters is all to use the concentrated sulfuric acid as catalyst, but this method exists to equipment corrosion
It is larger, the disadvantages of being also easy to produce side reaction, cause serious pollution to the environment.Therefore people replace constantly seeking more excellent catalyst
Sulfuric acid.Currently, have the more research report for replacing the concentrated sulfuric acid as catalyst, it can substantially be divided into following a few classes, one
It is general acid type catalyst, second is that heteropolyacid catalyst, third is that solid acid catalyst, fourth is that solid super acid catalyst.Selection
Suitable catalyst playing a crucial role for esterification.
General acid type catalyst carries out that catalysis yield is lower, and the reaction time is long and is worth little.Use sulfuric acid, phosphoric acid etc.
Inorganic acid has serious corrosivity to equipment as catalyst, and the waste liquid formed after simultaneous reactions is not easy to separate with product, rotten
Corrosion is strong, and special " three wastes " facility is needed to handle, and can cause environmental pollution if arbitrarily discharge.But use hydrochloride and sulphur
Hydrochlorate has good prospect as catalyst.Such as use solid sulfate salt as catalyst for esterification reaction, ester yield and catalysis
Speed is suitable with using the concentrated sulfuric acid, but the shortcomings that overcome using the concentrated sulfuric acid, and stability is good, sustainable use.
Self-catalyzed reaction refers in the case where no extra catalyst, is carried out using reactant or reaction product as catalyst
Reaction.According to the literature, most of reaction is reaction product self-catalysis, and in such reaction, reaction rate is both by reactant
The influence of concentration, and influenced by reaction product concentration.It is mainly characterized by: (1) reaction initially enters induction period, reaction rate
Relatively slow, with the accumulation of product, reaction rate improves in turn, and the consumption of following reaction object can be such that reaction rate reduces；(2) certainly
A small amount of product must be added in the starting of catalysis reaction；(3) it will appear a fastest response rate during self-catalyzed reaction.Allusion quotation
The self-catalyzed reaction equation figure of type is tangent bend function, if the reactant or production concentration of experiment abide by tangent bend curve,
This reaction may be self-catalysis.
Chinese granted patent CN103864615B discloses a kind of method that continuous non-catalytic method prepares Trifluoroacetic Acid Ethyl Ester,
This method has the advantage that (1) may be implemented continuous non-catalytic method and prepare Trifluoroacetic Acid Ethyl Ester, and the raw material used facilitates easy
, simple process, reaction condition is mild, and energy consumption of reaction is low, and process is remained without waste liquid, is suitble to amplification production；(2) it is inhaled by HCl
Receiving apparatus is by absorbing hydrogen chloride gas, by-product hydrochloric acid, generates in entire production process without waste liquid, and technique Atom economy is high, green
Colour circle is protected；(3) reaction carries out simultaneously within one device with rectifying, the product that reaction generates is separated in time with reactant, both
The yield of product can be improved, and separated using reaction heat for product, reach energy-efficient purpose.
However, China granted patent CN103864615B does not solve two problems: (1) using trifluoro-acetyl chloride and ethyl alcohol into
The yield that the continuous non-catalytic method reaction of row prepares Trifluoroacetic Acid Ethyl Ester is not still high, and highest yield is only 97.86% (embodiment
4)；(2) application problem for not solving by-product hydrochloric acid, is also not concerned with the effective use of by-product hydrochloric acid, be easy to cause entire work
The waste of skill.Although China granted patent CN105419403B proposes a kind of utilization method of spent acid, this method is prepared into
The titanium dioxide arrived is easy to reunite, cannot achieve and is widely applied.
Summary of the invention
In order to solve the problems, such as following two in the prior art: (1) CN103864615B using trifluoro-acetyl chloride and ethyl alcohol into
The yield that the continuous non-catalytic method reaction of row prepares Trifluoroacetic Acid Ethyl Ester is not still high；(2) CN103864615B does not solve by-product salt
The application problem of acid, is also not concerned with the effective use of by-product hydrochloric acid, be easy to cause the waste of entire technique.
The invention proposes following technical solutions:
A kind of production technology of high yield Trifluoroacetic Acid Ethyl Ester, under the conditions of reactive distillation, trifluoro-acetyl chloride and ethyl alcohol into
The continuous non-catalytic method reaction of row prepares Trifluoroacetic Acid Ethyl Ester, comprising the following steps:
(1) a small amount of ethyl alcohol (2) is added into reactor (A), opens condenser (C)；The additional amount of the ethyl alcohol (2) is anti-
Answer the 0.2~0.4 of device (A) volume；
(2) it is connected with rectifying column (B) on reactor (A), condenser (C) is connected on rectifying column (B), in 35 DEG C of temperature
Under, continue evenly to be passed through trifluoroacetyl chlorine body (1) to reactor (A), and start to stir；
(3) after stirring 30~60min, ethyl alcohol (2) is added dropwise into reactor (A), are warming up to 55~65 when ethyl alcohol is added dropwise
DEG C reactive distillation is carried out, the flow velocity quality proportioning that feeds intake of the trifluoro-acetyl chloride and ethyl alcohol is 1:0.125；
(4) reacting product stream (3) obtains the reacting product stream (4) after rectifying after rectifying column (B) rectifying, then through condenser
(C) Trifluoroacetic Acid Ethyl Ester (5) are obtained after condensing；
(5) logistics containing HCl (6) obtains hydrochloric acid after HCl absorption plant (D) absorption；
(6) hydrochloric acid for obtaining step (5) is as additive in titanium dioxide coating process.
The rectifying pressure of the rectifying column (B) is normal pressure.
Absorbent in the absorption plant (D) is water and/or dilute hydrochloric acid.
Preferably, step (6) specifically comprises the processes of:
The hydrochloric acid that step (5) obtains is configured to the hydrochloric acid solution that mass concentration is 5%~10% by S1, spare；
Titanium dioxide slurry sodium hydroxide is adjusted Titanium dioxide slurry to pH >=9.5 by S2；
S3 is by the mass ratio of sodium metasilicate and titanium dioxide with SiO2: TiO2Silicon is added dropwise to Titanium dioxide slurry in the ratio for being calculated as 1:50
Acid sodium solution, homogeneous, the hydrochloric acid solution that then S1 is prepared are added dropwise, and control pH >=9.0, ageing；
Then S4 presses the mass ratio of sodium metaaluminate and titanium dioxide with Al2O3: TiO2Sodium metaaluminate is added dropwise in the ratio for being calculated as 1:50
Solution；Then hydrochloric acid solution S1 being prepared is added dropwise, and controls pH >=9.0, ageing；
The hydrochloric acid solution that S1 is prepared again by S5 is added dropwise, and controls pH >=7.0, and ageing, washing, drying obtain
The titanium dioxide of inorganic matter coating；
TiO is added to the titanium dioxide of inorganic matter coating obtained by S5 in S62The dispersing agent of the 5wt% of quality, stirring, is dispersed
The titanium dioxide of inorganic matter coating afterwards；
The dispersing agent is made of carboxymethyl cellulose and sodium metnylene bis-naphthalene sulfonate according to mass ratio for 1:1.
Technical solution of the present invention has as follows by beneficial effect:
(1) for one of China's unsolved technical problem of granted patent CN103864615B: the receipts of Trifluoroacetic Acid Ethyl Ester
Rate is not still high.Applicant is carried out on the basis of Chinese granted patent CN103864615B by changing each technological parameter
Many experiments, discovery can be that 1:0.125 can be substantially by adjusting the flow velocity quality proportioning that feeds intake of trifluoro-acetyl chloride and ethyl alcohol
Improve the yield of Trifluoroacetic Acid Ethyl Ester.Although Chinese granted patent CN103864615B discloses biggish ratio range, but not
Open this ratio of 1:0.125, and such ratio is not recorded in the embodiment 1-5 of Chinese granted patent CN103864615B yet
In.
(2) it is directed to the two of China's unsolved technical problem of granted patent CN103864615B: unresolved by-product hydrochloric acid
Application problem.It is found by the applicant that by-product hydrochloric acid can be used in titanium dioxide coating process, and titanium is controlled by many experiments
PH value involved in white powder coating process and dispersing agent composition, have finally been prepared the titanium of dispersed splendid inorganic matter coating
White powder.The present invention also solves that the titanium dioxide that Chinese granted patent CN105419403B is prepared is easy to reunite, Wu Fashi simultaneously
The technical issues of being now widely applied.
(3) present invention may be implemented continuous non-catalytic method and prepare Trifluoroacetic Acid Ethyl Ester, and the raw material used is conveniently easy to get, technique
Simply, reaction condition is mild, and energy consumption of reaction is low, and process is remained without waste liquid, is suitble to amplification production；Reaction and rectifying are in an equipment
In carry out simultaneously, by reaction generate product separated in time with reactant, the yield of product not only can be improved, but also using reaction
Heat is separated for product, reaches energy-efficient purpose.
Detailed description of the invention
Fig. 1 is process flow, in which: A, reactor, B, rectifying column, C, condenser, D, HCl absorption plant；1, trifluoro second
Acyl chlorides gas, 2, ethyl alcohol, 3, reacting product stream, 4, the reacting product stream after rectifying, 5, Trifluoroacetic Acid Ethyl Ester, 6, contain HCl's
Logistics.
Specific embodiment
Embodiment 1
A kind of production technology of high yield Trifluoroacetic Acid Ethyl Ester, under the conditions of reactive distillation, trifluoro-acetyl chloride and ethyl alcohol into
The continuous non-catalytic method reaction of row prepares Trifluoroacetic Acid Ethyl Ester, comprising the following steps:
(1) a small amount of ethyl alcohol (2) is added into reactor (A), opens condenser (C)；The additional amount of the ethyl alcohol (2) is anti-
Answer the 0.3 of device (A) volume；
(2) it is connected with rectifying column (B) on reactor (A), condenser (C) is connected on rectifying column (B), in 35 DEG C of temperature
Under, continue evenly to be passed through trifluoroacetyl chlorine body (1) to reactor (A), and start to stir；
(3) after stirring 60min, ethyl alcohol (2) are added dropwise into reactor (A), 58 DEG C are warming up to when ethyl alcohol is added dropwise and is carried out instead
Answer rectifying, the flow velocity quality proportioning that feeds intake of the trifluoro-acetyl chloride and ethyl alcohol is 1:0.125；
(4) reacting product stream (3) obtains the reacting product stream (4) after rectifying after rectifying column (B) rectifying, then through condenser
(C) Trifluoroacetic Acid Ethyl Ester (5) are obtained after condensing；
(5) logistics containing HCl (6) obtains hydrochloric acid after HCl absorption plant (D) absorption；
(6) hydrochloric acid for obtaining step (5) is as additive in titanium dioxide coating process.
The rectifying pressure of the rectifying column (B) is normal pressure.
Absorbent in the absorption plant (D) is water and/or dilute hydrochloric acid.
Wherein, step (6) specifically comprises the processes of:
The hydrochloric acid that step (5) obtains is configured to the hydrochloric acid solution that mass concentration is 10% by S1, spare；
Titanium dioxide slurry sodium hydroxide is adjusted Titanium dioxide slurry to pH >=9.5 by S2；
S3 is by the mass ratio of sodium metasilicate and titanium dioxide with SiO2: TiO2Silicon is added dropwise to Titanium dioxide slurry in the ratio for being calculated as 1:50
Acid sodium solution, homogeneous, the hydrochloric acid solution that then S1 is prepared are added dropwise, and control pH >=9.0, ageing；
Then S4 presses the mass ratio of sodium metaaluminate and titanium dioxide with Al2O3: TiO2Sodium metaaluminate is added dropwise in the ratio for being calculated as 1:50
Solution；Then hydrochloric acid solution S1 being prepared is added dropwise, and controls pH >=9.0, ageing；
The hydrochloric acid solution that S1 is prepared again by S5 is added dropwise, and controls pH >=7.0, and ageing, washing, drying obtain
The titanium dioxide of inorganic matter coating；
TiO is added to the titanium dioxide of inorganic matter coating obtained by S5 in S62The dispersing agent of the 5wt% of quality, stirring, is dispersed
The titanium dioxide of inorganic matter coating afterwards；
The dispersing agent is made of carboxymethyl cellulose and sodium metnylene bis-naphthalene sulfonate according to mass ratio for 1:1.
Embodiment 2
A kind of production technology of high yield Trifluoroacetic Acid Ethyl Ester, under the conditions of reactive distillation, trifluoro-acetyl chloride and ethyl alcohol into
The continuous non-catalytic method reaction of row prepares Trifluoroacetic Acid Ethyl Ester, comprising the following steps:
(1) a small amount of ethyl alcohol (2) is added into reactor (A), opens condenser (C)；The additional amount of the ethyl alcohol (2) is anti-
Answer the 0.3 of device (A) volume；
(2) it is connected with rectifying column (B) on reactor (A), condenser (C) is connected on rectifying column (B), in 35 DEG C of temperature
Under, continue evenly to be passed through trifluoroacetyl chlorine body (1) to reactor (A), and start to stir；
(3) after stirring 60min, ethyl alcohol (2) are added dropwise into reactor (A), 58 DEG C are warming up to when ethyl alcohol is added dropwise and is carried out instead
Answer rectifying, the flow velocity quality proportioning that feeds intake of the trifluoro-acetyl chloride and ethyl alcohol is 1:0.125；
(4) reacting product stream (3) obtains the reacting product stream (4) after rectifying after rectifying column (B) rectifying, then through condenser
(C) Trifluoroacetic Acid Ethyl Ester (5) are obtained after condensing；
(5) logistics containing HCl (6) obtains hydrochloric acid after HCl absorption plant (D) absorption；
(6) hydrochloric acid for obtaining step (5) is as additive in titanium dioxide coating process.
The rectifying pressure of the rectifying column (B) is normal pressure.
Absorbent in the absorption plant (D) is water and/or dilute hydrochloric acid.
Wherein, step (6) specifically comprises the processes of:
The hydrochloric acid that step (5) obtains is configured to the hydrochloric acid solution that mass concentration is 10% by S1, spare；
Titanium dioxide slurry sodium hydroxide is adjusted Titanium dioxide slurry to pH >=9.5 by S2；
S3 is by the mass ratio of sodium metasilicate and titanium dioxide with SiO2: TiO2Silicon is added dropwise to Titanium dioxide slurry in the ratio for being calculated as 1:50
Acid sodium solution, homogeneous, the hydrochloric acid solution that then S1 is prepared are added dropwise, and control pH >=9.0, ageing；
Then S4 presses the mass ratio of sodium metaaluminate and titanium dioxide with Al2O3: TiO2Sodium metaaluminate is added dropwise in the ratio for being calculated as 1:50
Solution；Then hydrochloric acid solution S1 being prepared is added dropwise, and controls pH >=9.0, ageing；
The hydrochloric acid solution that S1 is prepared again by S5 is added dropwise, and controls pH >=7.0, and ageing, washing, drying obtain
The titanium dioxide of inorganic matter coating；
TiO is added to the titanium dioxide of inorganic matter coating obtained by S5 in S62The dispersing agent of the 5wt% of quality, stirring, is dispersed
The titanium dioxide of inorganic matter coating afterwards；
The dispersing agent is only made of carboxymethyl cellulose.
Embodiment 3
A kind of production technology of high yield Trifluoroacetic Acid Ethyl Ester, under the conditions of reactive distillation, trifluoro-acetyl chloride and ethyl alcohol into
The continuous non-catalytic method reaction of row prepares Trifluoroacetic Acid Ethyl Ester, comprising the following steps:
(1) a small amount of ethyl alcohol (2) is added into reactor (A), opens condenser (C)；The additional amount of the ethyl alcohol (2) is anti-
Answer the 0.3 of device (A) volume；
(2) it is connected with rectifying column (B) on reactor (A), condenser (C) is connected on rectifying column (B), in 35 DEG C of temperature
Under, continue evenly to be passed through trifluoroacetyl chlorine body (1) to reactor (A), and start to stir；
(3) after stirring 60min, ethyl alcohol (2) are added dropwise into reactor (A), 58 DEG C are warming up to when ethyl alcohol is added dropwise and is carried out instead
Answer rectifying, the flow velocity quality proportioning that feeds intake of the trifluoro-acetyl chloride and ethyl alcohol is 1:0.125；
(4) reacting product stream (3) obtains the reacting product stream (4) after rectifying after rectifying column (B) rectifying, then through condenser
(C) Trifluoroacetic Acid Ethyl Ester (5) are obtained after condensing；
(5) logistics containing HCl (6) obtains hydrochloric acid after HCl absorption plant (D) absorption；
(6) hydrochloric acid for obtaining step (5) is as additive in titanium dioxide coating process.
The rectifying pressure of the rectifying column (B) is normal pressure.
Absorbent in the absorption plant (D) is water and/or dilute hydrochloric acid.
Wherein, step (6) specifically comprises the processes of:
The hydrochloric acid that step (5) obtains is configured to the hydrochloric acid solution that mass concentration is 10% by S1, spare；
Titanium dioxide slurry sodium hydroxide is adjusted Titanium dioxide slurry to pH >=9.5 by S2；
S3 is by the mass ratio of sodium metasilicate and titanium dioxide with SiO2: TiO2Silicon is added dropwise to Titanium dioxide slurry in the ratio for being calculated as 1:50
Acid sodium solution, homogeneous, the hydrochloric acid solution that then S1 is prepared are added dropwise, and control pH >=9.0, ageing；
Then S4 presses the mass ratio of sodium metaaluminate and titanium dioxide with Al2O3: TiO2Sodium metaaluminate is added dropwise in the ratio for being calculated as 1:50
Solution；Then hydrochloric acid solution S1 being prepared is added dropwise, and controls pH >=9.0, ageing；
The hydrochloric acid solution that S1 is prepared again by S5 is added dropwise, and controls pH >=7.0, and ageing, washing, drying obtain
The titanium dioxide of inorganic matter coating；
TiO is added to the titanium dioxide of inorganic matter coating obtained by S5 in S62The dispersing agent of the 5wt% of quality, stirring, is dispersed
The titanium dioxide of inorganic matter coating afterwards；
The dispersing agent is only made of sodium metnylene bis-naphthalene sulfonate.
Comparative example 1
A kind of production technology of high yield Trifluoroacetic Acid Ethyl Ester, under the conditions of reactive distillation, trifluoro-acetyl chloride and ethyl alcohol into
The continuous non-catalytic method reaction of row prepares Trifluoroacetic Acid Ethyl Ester, comprising the following steps:
(1) a small amount of ethyl alcohol (2) is added into reactor (A), opens condenser (C)；The additional amount of the ethyl alcohol (2) is anti-
Answer the 0.3 of device (A) volume；
(2) it is connected with rectifying column (B) on reactor (A), condenser (C) is connected on rectifying column (B), in 35 DEG C of temperature
Under, continue evenly to be passed through trifluoroacetyl chlorine body (1) to reactor (A), and start to stir；
(3) after stirring 60min, ethyl alcohol (2) are added dropwise into reactor (A), 58 DEG C are warming up to when ethyl alcohol is added dropwise and is carried out instead
Answer rectifying, the flow velocity quality proportioning that feeds intake of the trifluoro-acetyl chloride and ethyl alcohol is 1:0.1；
(4) reacting product stream (3) obtains the reacting product stream (4) after rectifying after rectifying column (B) rectifying, then through condenser
(C) Trifluoroacetic Acid Ethyl Ester (5) are obtained after condensing；
(5) logistics containing HCl (6) obtains hydrochloric acid after HCl absorption plant (D) absorption；
(6) hydrochloric acid for obtaining step (5) is as additive in titanium dioxide coating process.
Comparative example 2
A kind of production technology of high yield Trifluoroacetic Acid Ethyl Ester, under the conditions of reactive distillation, trifluoro-acetyl chloride and ethyl alcohol into
The continuous non-catalytic method reaction of row prepares Trifluoroacetic Acid Ethyl Ester, comprising the following steps:
(1) a small amount of ethyl alcohol (2) is added into reactor (A), opens condenser (C)；The additional amount of the ethyl alcohol (2) is anti-
Answer the 0.3 of device (A) volume；
(2) it is connected with rectifying column (B) on reactor (A), condenser (C) is connected on rectifying column (B), in 35 DEG C of temperature
Under, continue evenly to be passed through trifluoroacetyl chlorine body (1) to reactor (A), and start to stir；
(3) after stirring 60min, ethyl alcohol (2) are added dropwise into reactor (A), 58 DEG C are warming up to when ethyl alcohol is added dropwise and is carried out instead
Answer rectifying, the flow velocity quality proportioning that feeds intake of the trifluoro-acetyl chloride and ethyl alcohol is 1:0.155；
(4) reacting product stream (3) obtains the reacting product stream (4) after rectifying after rectifying column (B) rectifying, then through condenser
(C) Trifluoroacetic Acid Ethyl Ester (5) are obtained after condensing；
(5) logistics containing HCl (6) obtains hydrochloric acid after HCl absorption plant (D) absorption；
(6) hydrochloric acid for obtaining step (5) is as additive in titanium dioxide coating process.
Experimentation of the invention is carried out referring to China granted patent CN103864615B, to embodiment 1 and comparative example 1-2
The yield of Trifluoroacetic Acid Ethyl Ester detected, and be recorded in following table:
| Number | The flow velocity quality proportioning that feeds intake of trifluoro-acetyl chloride and ethyl alcohol | Yield |
| Embodiment 1 | 1:0.125 | 99.0% |
| Comparative example 1 | 1:0.1 | 98.3% |
| Comparative example 2 | 1:0.155 | 97.9% |
From above-mentioned detection content: the application optimizes reaction temperature and the flow velocity quality proportioning that feeds intake by many experiments,
The flow velocity quality proportioning that most preferably feeds intake should be 1:0.125, at this point, the yield of Trifluoroacetic Acid Ethyl Ester is up to 99.0%.In addition, above-mentioned knot
Fruit show the flow rate mass that feeds intake of ethyl alcohol be not it is more lower better, when the flow velocity quality proportioning that feeds intake of trifluoro-acetyl chloride and ethyl alcohol is
When 1:0.1, yield is only 98.3%.
In order to improve the utilizing status of hydrochloric acid and the dispersion effect of titanium dioxide, the titanium white that embodiment 1-3 is prepared
Powder carries out dispersed detection, and detection method is referring to " study course of Materials Science and Engineering experiment instruction " (Zou Jianxin chief editor, 2010.07)
The experimental method that middle experiment 37 is recorded, i.e. supernatant liquid height value show that more greatly dispersibility is poorer, as a result as follows:
| Number | Supernatant liquid height (after 60min) |
| Embodiment 1 | 43mm |
| Embodiment 2 | 59mm |
| Embodiment 3 | 65mm |
The above results, which show the present invention well, realizes the effective use of Trifluoroacetic Acid Ethyl Ester by-product hydrochloric acid, preparation
Dispersed extraordinary titanium white powder particles out.The present invention also passes through the composition of optimization dispersing agent, finds carboxymethyl cellulose and Asia
Methyl sodium dinaphthalenesulfonate can cooperate with the titanium dioxide of dispersion inorganic matter coating, that is, be conducive to the utilization of by-product hydrochloric acid, also favorably
In the titanium dioxide quality and application range that improve inorganic matter coating.
Claims (4)
1. a kind of production technology of high yield Trifluoroacetic Acid Ethyl Ester, which is characterized in that under the conditions of reactive distillation, trifluoro-acetyl chloride
Continuous non-catalytic method reaction, which is carried out, with ethyl alcohol prepares Trifluoroacetic Acid Ethyl Ester, comprising the following steps:
(1) a small amount of ethyl alcohol (2) is added into reactor (A), opens condenser (C)；The additional amount of the ethyl alcohol (2) is reactor
(A) the 0.2~0.4 of volume；
(2) it is connected with rectifying column (B) on reactor (A), condenser (C) is connected on rectifying column (B), at a temperature of 35 DEG C, to
Reactor (A) continues evenly to be passed through trifluoroacetyl chlorine body (1), and starts to stir；
(3) after stirring 30~60min, toward dropwise addition ethyl alcohol (2) in reactor (A), be warming up to when ethyl alcohol is added dropwise 55~65 DEG C into
The flow velocity quality proportioning that feeds intake of row reactive distillation, the trifluoro-acetyl chloride and ethyl alcohol is 1:0.125；
(4) reacting product stream (3) obtains the reacting product stream (4) after rectifying after rectifying column (B) rectifying, then through condenser (C)
Trifluoroacetic Acid Ethyl Ester (5) are obtained after condensation；
(5) logistics containing HCl (6) obtains hydrochloric acid after HCl absorption plant (D) absorption；
(6) hydrochloric acid for obtaining step (5) is as additive in titanium dioxide coating process.
2. the production technology of high yield Trifluoroacetic Acid Ethyl Ester according to claim 1, which is characterized in that the rectifying column
(B) rectifying pressure is normal pressure.
3. the production technology of high yield Trifluoroacetic Acid Ethyl Ester according to claim 1, which is characterized in that the absorption plant
(D) absorbent in is water and/or dilute hydrochloric acid.
4. the production technology of high yield Trifluoroacetic Acid Ethyl Ester according to claim 1, which is characterized in that the tool of step (6)
Body technology are as follows:
The hydrochloric acid that step (5) obtains is configured to the hydrochloric acid solution that mass concentration is 5%~10% by S1, spare；
Titanium dioxide slurry sodium hydroxide is adjusted Titanium dioxide slurry to pH >=9.5 by S2；
S3 is by the mass ratio of sodium metasilicate and titanium dioxide with SiO2: TiO2Sodium metasilicate is added dropwise to Titanium dioxide slurry in the ratio for being calculated as 1:50
Solution, homogeneous, the hydrochloric acid solution that then S1 is prepared are added dropwise, and control pH >=9.0, ageing；
Then S4 presses the mass ratio of sodium metaaluminate and titanium dioxide with Al2O3: TiO2The ratio dropwise addition sodium metaaluminate for being calculated as 1:50 is molten
Liquid；Then hydrochloric acid solution S1 being prepared is added dropwise, and controls pH >=9.0, ageing；
The hydrochloric acid solution that S1 is prepared again by S5 is added dropwise, and controls pH >=7.0, and ageing, washing, drying obtain inorganic
The titanium dioxide of object coating；
TiO is added to the titanium dioxide of inorganic matter coating obtained by S5 in S62The dispersing agent of the 5wt% of quality, stirring, after being dispersed
The titanium dioxide of inorganic matter coating；
The dispersing agent is made of carboxymethyl cellulose and sodium metnylene bis-naphthalene sulfonate according to mass ratio for 1:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910346362.9A CN110003002B (en) | 2019-04-26 | 2019-04-26 | Production process of high-yield ethyl trifluoroacetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910346362.9A CN110003002B (en) | 2019-04-26 | 2019-04-26 | Production process of high-yield ethyl trifluoroacetate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110003002A true CN110003002A (en) | 2019-07-12 |
| CN110003002B CN110003002B (en) | 2020-03-17 |
Family
ID=67174569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910346362.9A Active CN110003002B (en) | 2019-04-26 | 2019-04-26 | Production process of high-yield ethyl trifluoroacetate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110003002B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115160136A (en) * | 2022-08-30 | 2022-10-11 | 山东华安新材料有限公司 | Preparation method of ethyl trifluoroacetate |
| CN115677497A (en) * | 2022-11-01 | 2023-02-03 | 上海橡实化学有限公司 | Production method of ethyl benzoate |
| CN115677497B (en) * | 2022-11-01 | 2024-05-14 | 山东华泰新材料技术研发有限公司 | Production method of ethyl benzoate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1994541A (en) * | 2006-12-19 | 2007-07-11 | 刘铮 | A continuous industrialized nano material dispersion device and method |
| CN103864615A (en) * | 2012-12-07 | 2014-06-18 | 中化蓝天集团有限公司 | Method for preparing ethyl trifluoroacetate through continuous non-catalytic method |
| CN105419403A (en) * | 2015-11-23 | 2016-03-23 | 攀钢集团攀枝花钢铁研究院有限公司 | Method of applying chloridized waste acid to titanium dioxide film coating |
-
2019
- 2019-04-26 CN CN201910346362.9A patent/CN110003002B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1994541A (en) * | 2006-12-19 | 2007-07-11 | 刘铮 | A continuous industrialized nano material dispersion device and method |
| CN103864615A (en) * | 2012-12-07 | 2014-06-18 | 中化蓝天集团有限公司 | Method for preparing ethyl trifluoroacetate through continuous non-catalytic method |
| CN105419403A (en) * | 2015-11-23 | 2016-03-23 | 攀钢集团攀枝花钢铁研究院有限公司 | Method of applying chloridized waste acid to titanium dioxide film coating |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115160136A (en) * | 2022-08-30 | 2022-10-11 | 山东华安新材料有限公司 | Preparation method of ethyl trifluoroacetate |
| CN115677497A (en) * | 2022-11-01 | 2023-02-03 | 上海橡实化学有限公司 | Production method of ethyl benzoate |
| CN115677497B (en) * | 2022-11-01 | 2024-05-14 | 山东华泰新材料技术研发有限公司 | Production method of ethyl benzoate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110003002B (en) | 2020-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108840358B (en) | Device and method for preparing anhydrous aluminum fluoride | |
| CN103664627A (en) | Method and special production equipment for synthesizing methyl ethyl carbonate | |
| CN106976896B (en) | A kind of method and system using waste sulfuric acid from alkylation production epsom salt | |
| CN103011272A (en) | Method for concentrating and purifying titanium dioxide waste acid by using complex acid | |
| CN105540606A (en) | Method for synthesizing MFI zeolite with clay mineral as raw material in solvent-free mode | |
| CN108862270A (en) | A kind of method of purification of artificial graphite | |
| CN110003002A (en) | A kind of production technology of high yield Trifluoroacetic Acid Ethyl Ester | |
| CN102757027A (en) | System and method for preparing high-purity phosphorus pentafluoride | |
| CN104624140B (en) | The device of hydrogen fluoride in a kind of recovery hydrofluoric acid | |
| CN102992396A (en) | New method for preparing nano titanium dioxide by alcoholysis of titanium tetrachloride | |
| CN109675538A (en) | A kind of mixed crystal titanium dioxide R3-A2TiO2And its application in 5 hydroxymethyl furfural is prepared in catalysis glucose | |
| CN103086865A (en) | Treatment method of perfluoroalkyl acyl fluoride waste | |
| CN106379875B (en) | A kind of production method of nitrosylsulfuric acid and application | |
| CN110845321B (en) | Tower type method and equipment for preparing malonic acid | |
| CN103332751B (en) | Ferrous sulfate method of comprehensive utilization | |
| CN105236369A (en) | Continuously-producing system of h-type P2O5 | |
| CN102153111B (en) | Method for preparing anhydrous sodium hydrogen sulfate by using ethephon production waste liquid | |
| CN105013539A (en) | Solid phase catalyst for preparing methyl formate, preparation method therefor and application thereof | |
| CN106861365B (en) | Treatment method of thionyl chloride tail gas | |
| CN101177243A (en) | Method for producing hydrogen fluoride under the condition of environment protection low temperature liquid condition | |
| CN105399126A (en) | Method used for recovery preparation of aluminum potassium sulfate from activated clay production waste water | |
| CN105523576A (en) | Method for recycling and preparing sodium alum from activated clay production wastewater | |
| CN112366379A (en) | Safe and environment-friendly processing system and method for pole piece after battery disassembly | |
| CN104556208B (en) | A kind of spherical Sm2sn2o7nanocrystalline preparation method | |
| CN110028046A (en) | The method of ferrous sulfate processing titanium dioxide waste acid by sulfuric acid process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |