CN105175367A - Method for converting sugar into 5-HMF (hydroxymethylfurfural) through acid catalysis - Google Patents
Method for converting sugar into 5-HMF (hydroxymethylfurfural) through acid catalysis Download PDFInfo
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- CN105175367A CN105175367A CN201510572296.9A CN201510572296A CN105175367A CN 105175367 A CN105175367 A CN 105175367A CN 201510572296 A CN201510572296 A CN 201510572296A CN 105175367 A CN105175367 A CN 105175367A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
Abstract
The invention provides a method for converting sugar into 5-hydroxymethylfurfural through acid catalysis, and relates to the technical field of 5-HMF (hydroxymethylfurfural) preparation. An ampoule bottle is used as a reaction container; an oil bath kettle oil bath heating mode is adopted; triprotic acid is used as catalysts; the sugar is catalyzed to be converted into 5-HMF. A sugar acid solution is subjected to split charging into the ampoule bottle; then, secondary opening sealing is carried out to form a sealing space; next, oil bath heating is performed; an ampoule bottle oil bath kettle buffers the inner pressure through double-layer combination. The method has the advantages that on one hand, high temperature and inner pressure formed by the solution promote the sugar conversion reaction; on one hand, the sample independence is high; the repeated and mass experiment is convenient; the sampling is convenient; the operability is high. Meanwhile, ingredient consumption of each sample is low; the scientific research cost is reduced; the process is simple; the use of circulation water is not needed; safety and reliability are realized.
Description
Technical field
The present invention relates to 5 hydroxymethyl furfural (HMF) preparing technical field, specifically in ampoule, utilize triprotic acid catalysis glucide to be converted into the method for 5-HMF.
Background technology
Fossil resources is energy substance main in universe's all trades and professions, but due to fossil resources be non-renewable energy material, along with the development of the mankind, in global range, there is energy dilemma.People are badly in need of seeking a kind of renewable green petrochemical industry products substitution thing.Biomass are renewable green resources, and current research direction mainly transforms through efficient biological and chemical, obtain organic chemical industry's intermediate, produce high value added product.5-HMF is wherein a kind of important products, and containing a furan nucleus in its molecular structure, an aldehyde radical and a methylol, which dictates that 5-HMF chemical property is active.In chemical industry, 5-HMF is important fine chemical material, usually as reaction intermediate, by reactions such as oxidation, hydrogenation and condensations, prepares multiple derivative.Such as, selective hydrogenation is carried out to 5-HMF and can obtain 2,5-dimethyl furan (DMF), its calorific value is 31.5MJ/L, suitable with the calorific value (35.0MJ/L) of gasoline, can be used as a kind of clean fuel [Tian Weiliang, Ge Zhenhong, prepare a method for 5 hydroxymethyl furfural, CN201310051442].Given this, utilize biomass-making to be an important new forms of energy research direction for 5-HMF, with renewable biomass resource for raw material, prepare Novel platform compound 5-HMF, there is very wide prospect and profound significance.The present invention is with glucose, fructose for sugar monomer modal in biomass, and as research representative, inquiring into Wood Adhesives from Biomass is the reactive mode of 5-HMF.
The process that glucide dehydration forms 5-HMF can not spontaneously be carried out usually.The mineral acids such as the vitriol oil can as the catalyzer of this reaction, and accelerate the speed of reaction of this reaction, catalytic efficiency is high, and 5-HMF yield is very high.But strong acid should not be used for actual production, the severe corrosive that strong acid has can increase plant and instrument loss, and is unfavorable for environment protection; This patent adopts the acid of organic ternary sour lime, inorganic ternary acid phosphoric acid, and these two kinds of acid are modal ternary weak acid, and compared to hydrochloric acid sulfuric acid etc., these two kinds of acid are very little on the impact of environment.
When saccharic acid solution adopts weak acid as catalyzer, 5-HMF yield is lower, is generally subsidiary conditions with high temperature, improves 5-HMF yield.But under pyroreaction condition, solvent, solute (comprising the side reaction product of 5-HMF, various complexity) can volatilize, and in closed reaction vessel, can produce interior pressure, even blast; In open reactive container, the loss of solvent and volatile solutes can be caused.In current laboratory, be head it off, a part of scholar adopts autoclave as reaction vessel, with the physical properties of material, and pressure in facedown; Part scholar adopts external prolong pump around circuit water of condensation, pressure in alleviating.Autoclave has the danger of blast, and single raw material dosage is large, operation inconvenience, and equipment manufacturing cost is higher; Employing condensate return cushions, and device is simple, although can prevent blast, the consumption of recirculated water is too large, waste water resource.
Summary of the invention
When using weak acid as catalyzer, heat reaction conditions can improve the yield of 5-HMF.The object of the invention is to solve saccharic acid solution solution produce in high-temperature reaction process in press surging force, prevent from meeting accident explosive incident in reaction process, improve 5-HMF yield simultaneously.
The present invention can be achieved through the following technical solutions:
Acid catalysis sugar is converted into a method for 5 hydroxymethyl furfural, carries out according to following step:
(1) according to concentration preparation saccharic acid mixing solutions, stored refrigerated is for subsequent use, and draw solution is placed in the ampoule cleaned up, and is filled with nitrogen, carries out first time sealing with sealed membrane.
(2) will fill the ampoule after nitrogen, adopt the calcination of sitting posture alcohol blast burner immediately, wire drawing, carries out second time flame sealing.
(3) after oil bath pan heats up, put into by ampoule, after reaction for some time, take out, cooling, shakes up, uncork, dilution, high effective liquid chromatography for measuring 5-HMF content.
The sugar acid solution that step (1) is prepared, sugared concentration is 1%-10%, and acid concentration is 0.1%-1%.When being filled with nitrogen, slowly should be filled with, keep 3s-5s, adopt as far as possible few laboratory sealed membrane, when preventing flame sealing, solution is affected.
During step (2) employing second time alcohol blast burner flame sealing, after first should making glass melting, carry out wire drawing, after silk fracture, continue, near flame, to melt and reinvent to port to be mellow and full state, to make sealing tight.
During step (3) uncork, use emery wheel, in bottleneck, pull at and draw, break into two with one's hands gently after there is fine cut.Liquid is poured out, uses distilled water diluting.High performance liquid phase condition determination is: moving phase is 5% methanol aqueous solution, UV-detector, and determined wavelength is 284nm, and flow velocity is 0.65mL/min.
The present invention, compared with existing other technologies, has following advantage: 1) resource is fully used, and in each ampoule, solution is 2mL, and the consumptions such as solvent, catalyzer, raw material are few, economize on resources.Do not need water of condensation, saving water resource simultaneously.2) the independence individual dominance of ampoule, and the type of heating of oil bath pan, determines and adopts the present invention to process in batches.Ampoule picks and places freely, can control the reaction times at any time, and not affect other samples, and collected specimens is convenient.3) before in the present invention, ampoule seals for the first time, be filled with 3s-5s nitrogen, with purity, the higher and nitrogen replacement of stable in properties goes out the mixed gas air of complicated component, decrease the unstable factor of gas in ampoule, thus add the resistance to pressure of ampoule, guarantee that the safety of reacting is carried out.4) when second time ampoule seals in the present invention, alcohol blast burner is adopted, first near flame, make glass material deliquescing, then use the slowly moulding wire drawing of large tweezers, during last silk fracture, by tip portion near flame, due to the surface tension of fluid after fusing, and it is agglomerating to cause most advanced and sophisticated filament to be polymerized, sealing part is mellow and full without corner angle, tight to reach sealing, do not leak pressure, no leakage, thus guarantee that liquor capacity can not reduce, solvent free of losses.5), in the present invention, the interior pressure that the material evaporations such as solvent produce, owing to not being released, be enclosed in ampoule, this pressure may be used for accelerated reaction, and the carrying out of this reaction of catalysis, improves the yield of 5-HMF.6) ampoule is adopted to be reaction vessel in the present invention, oil bath pan is as thermal source, and temperature control is accurate, and ampoule is once bottle explosion occur surprisingly, ampoule buffering bottle explosion surging force, cushioning pocket roomy between oil bath pan and crown cap, form secondary buffer, the reaction solution in ampoule is unlikely to splash out oil bath pan, environment is impacted, damage experimenter, meanwhile, other sample can not be affected.
Accompanying drawing explanation
Fig. 1 is the method process flow sheet that a kind of acid catalysis sugar of the present invention is converted into 5 hydroxymethyl furfural.
Fig. 2 is that ampoule seals schematic diagram twice, a () is first time sealed membrane sealing schematic diagram, b () is second time flame sealing ampoule wire drawing schematic diagram, (c) be flame sealing schematic diagram for the second time, and (d) opens ampoule schematic diagram for emery wheel.
Fig. 3 is two kinds of reactive mode setting drawings, the reactive mode that (a) combines with oil bath pan for ampoule of the present invention, the reactive mode that (b) combines for prolong and oil bath pan.
Specific examples
Below in conjunction with example, the present invention's feature in actual applications and value are described.
Example 1
Take fructose 5.00g, 85% phosphoric acid 0.58g, is settled to 100mL, gets solution 2mL and puts into ampoule, adopts the reactive mode that ampoule of the present invention combines with oil bath pan, as Fig. 3 (a), 393K react 30min, and 3 parallel laboratory tests.Get 20mL and put into round-bottomed flask, connect prolong, put into oil bath pan, the interior pressure that access water of condensation buffering reaction solution at high temperature produces, reaction unit is as Fig. 3 (b).393K reacts 30min, 3 parallel laboratory tests.Result, as table 1, can be found out, the 5-HMF concentration that ampoule reactive mode obtains is higher, and relative deviation is minimum.
5-HMF concentration in solution under table 1 two kinds of reactive modes
Example 2
Take glucose, fructose, 85% phosphoric acid, citric acid, dissolve constant volume, configuration saccharogenesis content is 1%, acid content is the saccharic acid aqueous solution of 0.5%, is distributed in ampoule, after twice sealing, put into oil bath pan, 393K reacts 20min, measures 5-HMF content in solution.Result is as table 2.
5-HMF concentration in table 2 solution-sugared content 1%
Example 3
Take glucose, fructose, 85% phosphoric acid, citric acid, dissolve constant volume, configuration saccharogenesis content is 10%, and acid content is the saccharic acid aqueous solution of 0.5%, coating-dividing sealing, 393K oil bath 20min, measures 5-HMF content in solution.Result is as table 3.In table 3, under phosphoric acid catalyzed effect, fructose content is high, and transform fast, 5-HMF dewaters further and is converted into levulinic acid, and in solution, 5-HMF content is lower.
5-HMF concentration in table 3 solution-sugared content 10%
Example 4
Take glucose, fructose, 85% phosphoric acid, citric acid, dissolve constant volume, being configured to acid content is 0.1%, and sugared content is the saccharic acid aqueous solution of 5%, coating-dividing sealing, 393K oil bath 20min, measures 5-HMF content in solution.Result is as table 4.
5-HMF concentration-acid content 0.1% in table 4 solution
Example 5
Take glucose, fructose, 85% phosphoric acid, citric acid, dissolve constant volume, being configured to acid content is 1%, and sugared content is the saccharic acid aqueous solution of 5%, coating-dividing sealing, 393K oil bath 20min, measures 5-HMF content in solution.Result is as table 5.
5-HMF concentration-acid content 1% in table 5 solution
Example 6
Ampoule is cleaned up, for subsequent use.Take glucose 25.00g, monohydrate potassium 2.55g, deionized water is settled to 500mL, and now glucose in solutions concentration is 5%, and phosphoric acid concentration is 0.5%.Draw 2mL to load in ampoule, then open nitrogen-filling instrument, after 3s-5s, carry out first time sealing.Prepare alcohol blast burner, add appropriate dehydrated alcohol, regulate air flow valve, make the flame of ejection the most vigorous, first by ampoule preheating, bottleneck clamped by large tweezers, and slowly wire drawing is moulding, and second time flame sealing completes, and turns off the light.Finally sample is put into the oil bath pan after intensification; under double-layer bumper protection; reacting by heating; temperature is 373K, 393K, 413K; sample time is 30min, 60min, 90min, 120min, 180min, 240min, 300min, 360min, 420min, 480min; totally ten sampling spots, each sampling spot 3 parallel sample.According to 5-HMF content in the 3rd step HPLC working sample liquid in the present invention.Adopt reactive mode of the present invention, in glucose citric acid systems, 5-HMF concentration can reach 586.56mg/L, and the activation energy of reaction is 121.09kJ/mol.
Example 7
Ampoule is cleaned up, dry for standby.Take glucose 25.00g, 85% phosphoric acid 2.94g, deionized water is settled to 500mL, and now glucose in solutions concentration is 5%, and phosphoric acid concentration is 0.5%.Draw 2mL to load in ampoule, be then filled with nitrogen, carry out first time sealing.Ampoule is rotated preheating, uses large tweezers wire drawing moulding, complete second time flame sealing.Finally sample is put into oil bath pan; under double-layer bumper protection, reacting by heating, temperature is 373K, 393K, 413K; sample time is 30min, 60min, 90min, 120min, 180min, 240min, 300min, 360min, 420min, 480min, and each sampling spot 3 is parallel.5-HMF content in working sample liquid.Adopt reactive mode of the present invention, in glucose phosphate system, 5-HMF concentration can reach 739.95mg/L, and the activation energy of reaction is 109.16kJ/mol.
Claims (7)
1. acid catalysis sugar is converted into a method for 5 hydroxymethyl furfural, it is characterized in that carrying out according to following step:
(1) dissolve: first by sugar, the sour quality weighing according to calculating, deionized water dissolving, dilution, constant volume, be then distributed in ampoule;
(2) substitution gas: open nitrogen-filling instrument, regulates nitrogen flow rate, is filled with by nitrogen in ampoule, keeps 3s-5s, to make purity higher and the nitrogen replacement of stable in properties goes out the mixed gas air of complicated component, guarantees that the safety of reacting is carried out;
(3) first time sealed membrane sealing: after being filled with nitrogen, uses rapidly use for laboratory sealed membrane to seal ampoule;
(4) second time flame sealing: light alcohol blast burner, regulates flame to maximum, and then by the ampoule of first time sealed membrane sealing, slowly rotation limit in limit is near flame, and adopt large tweezers wire drawing, after fusing, melting is moulding again;
(5) double-layer bumper: employing ampoule is reaction vessel, oil bath pan is as thermal source, and ampoule and oil bath pan combine, as reaction unit, double-layer bumper bottle explosion surging force;
(6) uncork: adopt emery wheel according to ampoule body mark, mark vestige gently, fracture and shift out solution.
2. a kind of acid catalysis sugar according to claim 1 is converted into the method for 5 hydroxymethyl furfural, and it is characterized in that the saccharic acid in wherein step (1) takes according to certain consumption, sugared concentration is 1%-10%, and acid concentration is 0.1%-1%, then packing.
3. a kind of acid catalysis sugar according to claim 1 is converted into the method for 5 hydroxymethyl furfural, it is characterized in that wherein nitrogen-filling instrument being opened in step (2), be filled with that composition is single, the nitrogen of stable in properties, displace the air of complicated component, poor stability;
When filling nitrogen, regulate throttling valve, keep 3s-5s, nitrogen flow rate is unsuitable excessive or too small, when slight fluctuations appears in liquid level;
Time excessive, solvent loss, time too small, gas displacement is not thorough, and efficiency is low.
4. a kind of acid catalysis sugar according to claim 1 is converted into the method for 5 hydroxymethyl furfural, it is characterized in that wherein step (3) is middle and adopt use for laboratory sealed membrane, carry out first time sealed membrane sealing, this sealed membrane good-extensibility, consumption less, saves material; Consumption is too much, and sealed membrane will burn when flame sealing, affects sealing effect.
5. a kind of acid catalysis sugar according to claim 1 is converted into the method for 5 hydroxymethyl furfural, it is characterized in that wherein the middle alcohol blast burner that adopts of step (4) carries out second time sealing, first by ampoule slowly near and constantly rotate, carry out preheating, prevent that glass is shock heating to be cracked; Then wire drawing, again moulding after fusing, molten state ensure that ampoule is at moulding rear good airproof performance, and volatile component can not lose, and the interior pressure formed after volatilization has certain positive impact to reaction.
6. a kind of acid catalysis sugar according to claim 1 is converted into the method for 5 hydroxymethyl furfural, it is characterized in that wherein the middle oil bath pan temperature control of step (5) is accurate, if generation bottle explosion, ampoule can cushion the surging force that bottle explosion produces, the wide space simultaneously formed between oil bath pan and crown cap, carry out second time buffering, reaction solution can not splash out oil bath pan, produce potential safety hazard, do not affect other sample simultaneously.
7. a kind of acid catalysis sugar according to claim 1 is converted into the method for 5 hydroxymethyl furfural, it is characterized in that wherein step (5) middle ampoule-oil bath reaction times is 20min-480min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510572296.9A CN105175367A (en) | 2015-09-09 | 2015-09-09 | Method for converting sugar into 5-HMF (hydroxymethylfurfural) through acid catalysis |
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| CN201510572296.9A CN105175367A (en) | 2015-09-09 | 2015-09-09 | Method for converting sugar into 5-HMF (hydroxymethylfurfural) through acid catalysis |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114702522A (en) * | 2022-04-12 | 2022-07-05 | 无锡市江原实业技贸有限公司 | Preparation method and reaction device of diethoxyethylphosphane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB600871A (en) * | 1945-10-17 | 1948-04-21 | Walter Norman Haworth | Improvements relating to the manufacture of 5-hydroxymethyl 2-furfural |
| US2750394A (en) * | 1952-05-22 | 1956-06-12 | Food Chemical And Res Lab Inc | Manufacture of 5-hydroxymethyl 2-furfural |
| CN1555368A (en) * | 2001-09-17 | 2004-12-15 | ��Ļ���Ű˾ | Process for preparing 2,5-diformylfuran from carbohydrates |
| CN101801946B (en) * | 2007-07-18 | 2013-03-13 | 阿彻丹尼尔斯米德兰公司 | Method for production of 5-hydroxymethyl-2-furfural from fructose |
-
2015
- 2015-09-09 CN CN201510572296.9A patent/CN105175367A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB600871A (en) * | 1945-10-17 | 1948-04-21 | Walter Norman Haworth | Improvements relating to the manufacture of 5-hydroxymethyl 2-furfural |
| US2750394A (en) * | 1952-05-22 | 1956-06-12 | Food Chemical And Res Lab Inc | Manufacture of 5-hydroxymethyl 2-furfural |
| CN1555368A (en) * | 2001-09-17 | 2004-12-15 | ��Ļ���Ű˾ | Process for preparing 2,5-diformylfuran from carbohydrates |
| CN101801946B (en) * | 2007-07-18 | 2013-03-13 | 阿彻丹尼尔斯米德兰公司 | Method for production of 5-hydroxymethyl-2-furfural from fructose |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114702522A (en) * | 2022-04-12 | 2022-07-05 | 无锡市江原实业技贸有限公司 | Preparation method and reaction device of diethoxyethylphosphane |
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