CN104174402A - Catalyst for medium and low temperature catalytic coal gasification for producing natural gas and preparation method thereof - Google Patents
Catalyst for medium and low temperature catalytic coal gasification for producing natural gas and preparation method thereof Download PDFInfo
- Publication number
- CN104174402A CN104174402A CN201310196018.9A CN201310196018A CN104174402A CN 104174402 A CN104174402 A CN 104174402A CN 201310196018 A CN201310196018 A CN 201310196018A CN 104174402 A CN104174402 A CN 104174402A
- Authority
- CN
- China
- Prior art keywords
- potassium
- catalyst
- mass fraction
- calcium
- preparation
- 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
Abstract
The invention relates to a catalyst for medium and low temperature catalytic coal gasification for producing natural gas and a preparation method thereof, and in particular, the catalyst consists mainly of alkali metals, alkaline earth metals, and transition metals; the alkali metals are mainly potassium salts, such as potassium carbonate, potassium sulfate or potassium nitrate and the like, the potassium/ carbon mass fraction is 1-20%; the alkaline earth metals are calcium salts, the calcium/potassium mass fraction is 10-50%; the transition metals are mainly one or two of iron, nickel, molybdenum, cobalt and cadmium, can be salts or oxides thereof, and the transition metal / potassium mass fraction is 5-30%. The catalyst is helpful to solve the problem of poisoning deactivation and unstable catalyst activity and other problems caused for the reason that the catalyst for the medium and low temperature catalytic coal gasification for producing the natural gas is easy to react with minerals in coal, and the problems are solved, so that future realization of industrialization can be facilitated.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method for low temperature catalytic coal gasifaction preparing natural gas, particularly, relate to a kind of Catalysts and its preparation method that mainly contains one or both elements in alkali metal, alkaline-earth metal and transition metal.
Background technology
From the seventies in last century, the Exxon Mobil Corporation of the U.S. (Exxon) has just developed with K
2cO
3for the technique of the coal steam gasification production substitute natural gas of catalyst, traditional coal high-temperature gasification is obtained crude synthesis gas by this technique, then be incorporated in a gasification reactor through operations such as sulphur-resistant conversion, low-temperature rectisol, fine desulfurization process by dry and multistage methanation reactions, there is the plurality of advantages such as flow process is short, simple to operate, energy consumption is low, cost is low.But this catalyst is narrower to the scope of application of coal, activity is stable not, and the recycling of catalyst all has problems.Huge the energy (GPE) company of the U.S. on the basis of the above afterwards, through technological improvement and upgrading for many years, release the technology of " one-step method low-temperature catalysis gasification coal preparing natural gas ", i.e. " blue gas technology ", at present actively carry out business promotion, but still the one way rate of gasification that has coal is low, catalyst Suitability of Coals is narrower, catalyst easily reacts the silicate and the sulfuration molysite that generate indissoluble with coal mineral, partially catalyzed agent is difficult to the problems such as recovery, thereby cause partially catalyzed agent inactivation, increased production cost.
Summary of the invention
In order to address the above problem, the present invention proposes a kind of combined type multicomponent catalyst, by the method for dipping, alkali metal, alkaline-earth metal and transition metal is added on coal dust uniformly, thereby can effectively improve catalyst activity, stability and methane yield.Therefore the object of this invention is to provide a kind of combined type multicomponent catalyst that is applicable to middle low temperature catalytic coal gasifaction preparing natural gas and preparation method thereof.
In the present invention, the coal dust of mentioning is a kind of 20～40 object coal particles that untreated coal is made through operating procedures such as oven dry, pulverizing, screenings.
In the present invention, the catalysis coal dust of mentioning is to be a kind ofly dispersed in the mixture on coal dust surfaces externally and internally by catalyst.
In the present invention, the pretreatment sample of mentioning refers to the mixture of processing through alkaline-earth metal.
In the present invention, the middle low temperature of mentioning refers to 600～800 DEG C.
In the present invention, the efficiency of carbon con version of mentioning refers to from reaction while starting to each collection sample, the ratio of the total mole number of carbon in the total mole number of carbonaceous material and the coal dust that feeds intake in the gas product of collecting.
In addition in the present invention, the methane yield of mentioning refers to while starting to each collection sample from reaction, the ratio of the gross mass of carbon in total methane molal quantity of collecting and the coal dust that feeds intake.
Solving the technical scheme that this goal of the invention takes is:
For a catalyst for low temperature catalytic coal gasifaction preparing natural gas, it is characterized in that described catalyst mainly comprises alkali metal, alkaline-earth metal and transition metal, wherein alkali metal is sylvite, potassium/carbon mass fraction is 1～20%; Alkaline-earth metal is calcium salt, and calcium/potassium mass fraction is 10～50%; Transition metal is one or both in iron, nickel, molybdenum, cobalt, cadmium, and transition metal/potassium mass fraction is 5～30%.
Usually, described alkaline-earth metal is mainly sylvite, as potash, potassium sulfate or potassium nitrate etc., and preferably potash.
Described potassium/carbon mass fraction is 1～20%, preferred 5～15%, optimum 8～12%.
Described alkaline-earth metal is mainly calcium salt, and it can be: calcium nitrate, calcium acetate, calcium phosphate or calcium chloride etc., preferred calcium nitrate, calcium acetate, most preferred calcium nitrate.
Described calcium/potassium mass fraction is 10～50%, preferred 20～40%, most preferred 25～35%.
Described transition metal is mainly one or both in iron, nickel, molybdenum, cobalt, cadmium, can be its esters or oxide, and its esters can be sulfate, nitrate or chloride.
Described transition metal/potassium mass fraction is 5～30%, preferred 10～25%, most preferred 15～20%.
For a preparation method for low temperature catalytic coal gasifaction preparing natural gas catalyst, it is characterized in that this preparation method comprises the following steps:
1) take coal dust, be impregnated in calcium salt soln, at normal temperature～90 DEG C, stir 1～4h, then in suction filtration, 100～200 DEG C of nitrogen atmospheres, dry 1～5h, then obtain pretreatment sample through cooling grinding; And
2) get part pretreatment sample, be impregnated in and contain in alkali metal salt and transition metal salt solution, at normal temperature～90 DEG C, stir 1～4h, then through suction filtration, in 100～200 DEG C of nitrogen atmospheres, dry 1～5h, then obtain final catalysis coal dust through cooling sieving, sealing saves backup.
3) granularity > 20 orders of pretreatment sample in described step 1).
Described step 2) in the granularity of catalysis coal dust be 10～60 orders, preferred 20～40 orders.
Beneficial effect of the present invention is as follows:
(1) the present invention be conducive to solve in low temperature catalytic coal gasifaction preparing natural gas catalyst easily react and the problem of poisoning and deactivation with coal mineral.
(2), by preparation method of the present invention, can improve the gasification rate of coal dust.
(3) due to the present invention adopt be composite multi-component catalyst, not only can solve catalyst poisoning inactivation and the slow problem of coal dust gasification speed, can also effectively improve methane production in gas product.
Brief description of the drawings
Fig. 1 is the interior temporal evolution methane production curve map of 5h in the embodiment of the present invention.
Detailed description of the invention
In order to describe content of the present invention in detail, exemplified some specific embodiments below, but protection scope of the present invention is not only limited in the embodiment enumerating.
The coal that this invention is used is Shengli Brown (this laboratory data measured: carbon element content 52.03%, total sulfur content 0.97%), before use, obtain 20～40 object coal dusts through operating procedures such as oven dry, pulverizing, screening, as the former coal dust of each embodiment below.
Embodiment 1
Preparation one pack system sylvite catalysis coal dust, take 20g coal dust, be impregnated in the solution of potassium carbonate of 40ml, at normal temperature～90 DEG C, stir 1～4h, then through suction filtration, in 100～200 DEG C of nitrogen atmospheres, dry 1～5h, then obtain " K " catalysis coal dust through cooling sieving, sealing saves backup, and wherein potassium/carbon mass fraction is about 10%.
Embodiment 2
Preparation bi-component catalysis coal dust, takes the coal dust of 20g, is impregnated in 40ml calcium nitrate solution, at normal temperature～90 DEG C, stirs 1～4h, then in suction filtration, 100～200 DEG C of nitrogen atmospheres, dries 1～5h, then obtains pretreatment sample through cooling grinding.
Then get 10g pretreatment sample, be impregnated in the potash of 40ml, at normal temperature～90 DEG C, stir 1～4h, then through suction filtration, in 100～200 DEG C of nitrogen atmospheres, dry 1～5h, then obtain " K-Ca " catalysis coal dust through cooling sieving, sealing saves backup.Wherein potassium/carbon mass fraction is about 10%, and calcium/potassium mass fraction is about 30%.
Embodiment 3
Preparation combined type multiple catalyzing coal dust, takes the coal dust of 20g, is impregnated in 40ml calcium nitrate solution, at normal temperature～90 DEG C, stirs 1～4h, then in suction filtration, 100～200 DEG C of nitrogen atmospheres, dries 1～5h, then obtains pretreatment sample through cooling grinding.
Then get 10g pretreatment sample, be impregnated in the potash and nickel nitrate solution of 40ml, at normal temperature～90 DEG C, stir 1～4h, then through suction filtration, in 100～200 DEG C of nitrogen atmospheres, dry 1～5h, then obtain " K-Ca-Ni " catalysis coal dust through cooling sieving, sealing saves backup.Wherein potassium/carbon mass fraction is about 10%, and calcium/potassium mass fraction is about 30%, and nickel/potassium mass fraction is approximately 20%.
Mainly investigate for example the impact of different transition metal salts on catalyst activity and selectivity below.
Embodiment 4
Take the coal dust of 20g, be impregnated in 40ml calcium nitrate solution, at normal temperature～90 DEG C, stir 1～4h, then in suction filtration, 100～200 DEG C of nitrogen atmospheres, dry 1～5h, then obtain pretreatment sample through cooling grinding.
Then get 10g pretreatment sample, be impregnated in the potash and copperas solution of 40ml, at normal temperature～90 DEG C, stir 1～4h, then through suction filtration, in 100～200 DEG C of nitrogen atmospheres, dry 1～5h, then obtain " K-Ca-Fe " catalysis coal dust through cooling sieving, sealing saves backup, wherein potassium/carbon mass fraction is about 10%, and calcium/potassium mass fraction is about 30%, and iron/potassium mass fraction is approximately 20%.
Embodiment 5
Take the coal dust of 20g, be impregnated in 40ml calcium nitrate solution, at normal temperature～90 DEG C, stir 1～4h, then in suction filtration, 100～200 DEG C of nitrogen atmospheres, dry 1～5h, then obtain pretreatment sample through cooling grinding.
Then get 10g pretreatment sample, be impregnated in the potash and two molybdic acid hydrate sodium solutions of 40ml, at normal temperature～90 DEG C, stir 1～4h, then through suction filtration, in 100～200 DEG C of nitrogen atmospheres, dry 1～5h, then obtain " K-Ca-Mo " catalysis coal dust through cooling sieving, sealing saves backup.Wherein potassium/carbon mass fraction is about 10%, and calcium/potassium mass fraction is about 30%, and molybdenum/potassium mass fraction is approximately 20%.
Embodiment 6
Take the coal dust of 20g, be impregnated in 40ml calcium nitrate solution, at normal temperature～90 DEG C, stir 1～4h, then in suction filtration, 100～200 DEG C of nitrogen atmospheres, dry 1～5h, then obtain pretreatment sample through cooling grinding.
Then get 10g pretreatment sample, be impregnated in the potash and Chromium nitrate (Cr(NO3)3),nonahydrate solution of 40ml, at normal temperature～90 DEG C, stir 1～4h, then through suction filtration, in 100～200 DEG C of nitrogen atmospheres, dry 1～5h, then obtain " K-Ca-Cr " catalysis coal dust through cooling sieving, sealing saves backup.Wherein potassium/carbon mass fraction is about 10%, and calcium/potassium mass fraction is about 30%, and cadmium/potassium mass fraction is approximately 20%.
Embodiment 7
Directly select above-mentioned coal dust to carry out gasification experiment, be relatively labeled as raw coal for convenient, and experimental result is listed in table 1 together with embodiment 1～6.
Above-mentioned sample is carried out to activity rating in self-control fixed bed device.Appreciation condition: catalysis coal dust 0.5g, 20～40 orders, temperature: 700～750 DEG C, pressure: 3～4MPa, carrier gas (Ar) flow: 100～150ml/min, discharge: 0.5～1.0ml/h.In the time that pressure and temperature is stabilized in setting value, by carrier gas, catalysis coal dust is compressed into reactor.Then carry out chromatography every 15min with sampling bag sampling, the reaction time is 5h, and evaluation result is in table 1 and Fig. 1.
Table 1 evaluation result
| Embodiment | Catalyst | Efficiency of carbon con version/% | Methane production/(mmol/g C) |
| 1 | K | 46.9 | 7.7 |
| 2 | K-Ca | 54.3 | 11.6 |
| 3 | K-Ca-Ni | 62.3 | 14.5 |
| 4 | K-Ca-Fe | 65.1 | 13.3 |
| 5 | K-Ca-Mo | 68.7 | 16.06 |
| 6 | K-Ca-Cr | 59.2 | 10.7 |
| 7 | Raw coal | 13.5 | 4.3 |
The catalysis coal dust that embodiment 3～6 makes as can be seen from Table 1, its efficiency of carbon con version and methane production are all higher than the catalysis coal dust of raw coal and other one pack system and bi-component, and therefore this catalyst has the performance that improves efficiency of carbon con version and methane production.As can be seen from Figure 1 in 5h, in uphill process, there is the trend that comparatively significantly slows down in " K " catalysis coal dust methane production curve that embodiment 1 makes, illustrate that intoxicating phenomenon may appear in catalyst in course of reaction, and significantly slowing down or downward trend does not appear in the methane production curve of the catalysis coal dust that embodiment 3～6 makes, therefore this catalyst performance stabilised, has good anti-poisoning performance.
Claims (10)
1. for a catalyst for low temperature catalytic coal gasifaction preparing natural gas, it is characterized in that comprising alkali metal, alkaline-earth metal and transition metal, wherein alkali metal is sylvite, and potassium/carbon mass fraction is 1～20%; Alkaline-earth metal is calcium salt, and calcium/potassium mass fraction is 10～50%; Transition metal is one or both in iron, nickel, molybdenum, cobalt, cadmium, or its esters or oxide, transition metal/potassium mass fraction is 5～30%.
2. catalyst according to claim 1, is characterized in that alkali metal is potash, potassium sulfate or potassium nitrate.
3. catalyst according to claim 1, is characterized in that potassium/carbon mass fraction is 5～15%.
4. catalyst according to claim 1, is characterized in that alkaline-earth metal is calcium nitrate, calcium acetate, calcium phosphate or calcium chloride.
5. catalyst according to claim 4, is characterized in that calcium/potassium mass fraction is 20～40%.
6. catalyst according to claim 1, is characterized in that transition metal is salt or the oxide of iron, nickel, molybdenum, cobalt, cadmium.
7. catalyst according to claim 1, is characterized in that transition metal/potassium mass fraction is 10～25%.
8. the preparation method of catalyst as claimed in claim 1, it is characterized in that this preparation method comprises the following steps: take coal dust, be impregnated in calcium salt soln, at normal temperature～90 DEG C, stir 1～4h, then in suction filtration, 100～200 DEG C of nitrogen atmospheres, dry 1～5h, then obtain pretreatment sample through cooling grinding; And get part pretreatment sample, and be impregnated in and contain in alkali metal salt and transition metal salt solution, at normal temperature～90 DEG C, stir 1～4h, then through suction filtration, in 100～200 DEG C of nitrogen atmospheres, dry 1～5h, then obtain final catalysis coal dust through cooling sieving, sealing saves backup.
9. preparation method according to claim 8, is characterised in that granularity > 20 orders of pretreatment sample in step 1).
10. preparation method according to claim 8, is characterised in that step 2) in the granularity of catalysis coal dust sample be 10～60 orders.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310196018.9A CN104174402A (en) | 2013-05-24 | 2013-05-24 | Catalyst for medium and low temperature catalytic coal gasification for producing natural gas and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310196018.9A CN104174402A (en) | 2013-05-24 | 2013-05-24 | Catalyst for medium and low temperature catalytic coal gasification for producing natural gas and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104174402A true CN104174402A (en) | 2014-12-03 |
Family
ID=51955912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310196018.9A Pending CN104174402A (en) | 2013-05-24 | 2013-05-24 | Catalyst for medium and low temperature catalytic coal gasification for producing natural gas and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104174402A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923234A (en) * | 2015-04-30 | 2015-09-23 | 菏泽学院 | Supported red mud composite catalyst for catalytic coal gasification and preparation method therefor |
| CN106311339A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Catalyst used for coal hydrogenation catalytic gasification, and preparation method and use thereof |
| CN106590762A (en) * | 2015-10-15 | 2017-04-26 | 中国石油化工股份有限公司 | Method for improving performance of catalyst in catalytic coal gasification by using composite additive |
| CN106590752A (en) * | 2015-10-15 | 2017-04-26 | 中国石油化工股份有限公司 | Method for increasing activity and recovery rate of catalyst in catalytic gasification of coal |
| CN106947559A (en) * | 2017-04-06 | 2017-07-14 | 中国科学院山西煤炭化学研究所 | A kind of method of coal catalytic hydrogenation gasification production methane and tar light oil |
| CN109225234A (en) * | 2018-09-19 | 2019-01-18 | 石河子大学 | A kind of composition for carbon catalytic hydrogenation methane |
| WO2020088398A1 (en) * | 2018-10-29 | 2020-05-07 | 中国石油化工股份有限公司 | Pulverized coal preprocessing method and pulverized coal gasiifying method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500387A (en) * | 2011-11-17 | 2012-06-20 | 中国石油化工股份有限公司 | Catalyst for preparing substitute natural gas by using coal based synthesis gas, and preparation method thereof |
| CN102527392A (en) * | 2010-12-24 | 2012-07-04 | 新奥科技发展有限公司 | Ternary catalyst for catalytic coal gasification and preparation method thereof |
-
2013
- 2013-05-24 CN CN201310196018.9A patent/CN104174402A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527392A (en) * | 2010-12-24 | 2012-07-04 | 新奥科技发展有限公司 | Ternary catalyst for catalytic coal gasification and preparation method thereof |
| CN102500387A (en) * | 2011-11-17 | 2012-06-20 | 中国石油化工股份有限公司 | Catalyst for preparing substitute natural gas by using coal based synthesis gas, and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 马涛等: ""煤的催化气化技术研究进展"", 《中国科技信息》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923234A (en) * | 2015-04-30 | 2015-09-23 | 菏泽学院 | Supported red mud composite catalyst for catalytic coal gasification and preparation method therefor |
| CN104923234B (en) * | 2015-04-30 | 2017-12-19 | 菏泽学院 | Support type red mud composite catalyst for catalytic coal gasifaction and preparation method thereof |
| CN106311339A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Catalyst used for coal hydrogenation catalytic gasification, and preparation method and use thereof |
| CN106590762A (en) * | 2015-10-15 | 2017-04-26 | 中国石油化工股份有限公司 | Method for improving performance of catalyst in catalytic coal gasification by using composite additive |
| CN106590752A (en) * | 2015-10-15 | 2017-04-26 | 中国石油化工股份有限公司 | Method for increasing activity and recovery rate of catalyst in catalytic gasification of coal |
| CN106947559A (en) * | 2017-04-06 | 2017-07-14 | 中国科学院山西煤炭化学研究所 | A kind of method of coal catalytic hydrogenation gasification production methane and tar light oil |
| CN106947559B (en) * | 2017-04-06 | 2020-06-30 | 中国科学院山西煤炭化学研究所 | Method for producing methane and light tar by catalytic hydro-gasification of coal |
| CN109225234A (en) * | 2018-09-19 | 2019-01-18 | 石河子大学 | A kind of composition for carbon catalytic hydrogenation methane |
| CN109225234B (en) * | 2018-09-19 | 2021-07-20 | 石河子大学 | Composition for preparing methane by carbon catalytic hydrogenation |
| WO2020088398A1 (en) * | 2018-10-29 | 2020-05-07 | 中国石油化工股份有限公司 | Pulverized coal preprocessing method and pulverized coal gasiifying method |
| US11560524B2 (en) | 2018-10-29 | 2023-01-24 | China Petroleum & Chemical Corporation | Coal powder pretreatment method and coal powder gasification method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104174402A (en) | Catalyst for medium and low temperature catalytic coal gasification for producing natural gas and preparation method thereof | |
| CN101054538B (en) | Iron-base desulfurizer for catalyzing, translating and absorbing carbonyl sulfur at middle-low temperature and preparation thereof | |
| CN101100622B (en) | Method and device for synthesizing natural gas by using coke oven gas | |
| CN103275777B (en) | Method for preparing hydrogen and liquefied natural gas through using gas retort raw gas | |
| CN103204470B (en) | Gas transformation deep purifying technique for separating and purifying CO and H2 of calcium carbide furnace | |
| CN102259003B (en) | Coke-oven gas methanation catalyst and preparation method thereof | |
| CN108325548B (en) | Molybdenum sulfide-based catalyst for preparing low-carbon alcohol from synthesis gas and preparation method thereof | |
| CN103272610B (en) | A kind of titanium base fine desulfurization catalyst and preparation method thereof and using method | |
| CN101797477B (en) | Method for reducing concentration of carbonyl sulfide on outlet of hydrogen sulfide (H2S) desulfurizer | |
| CN103380199A (en) | Process | |
| CN105312056B (en) | Catalyst based on natural minerals and the gasification process using the catalyst | |
| CN101864324B (en) | Method for synthesizing liquid hydrocarbon | |
| CN102041019B (en) | Method for coproducing substitute natural gas through coal liquefaction | |
| CN109880654A (en) | A method of utilizing volatile matter Fischer Tropsch waxes in low-order coal | |
| CN101219392A (en) | Catalyst for producing gas rich in hydrogen with coke oven gas and method for producing the same | |
| CN104511281A (en) | Water gas wide temperature shift catalyst, preparation and application thereof | |
| CN101733121B (en) | Catalyst for preparing hydrocarbon from carbon dioxide-containing synthesis gas, preparation method and application | |
| CN103602357B (en) | Production process of liquefied natural gas | |
| CN101239317B (en) | Catalyst for dry gasification for moisture component of coke oven gas and preparation thereof | |
| CN104984769A (en) | Synthesis-gas carbon-based catalyst preparation method by reforming methane and carbon dioxide | |
| Xu et al. | Recent advances and prospects in high purity H2 production from sorption enhanced reforming of bio-ethanol and bio-glycerol as carbon negative processes: A review | |
| CN204848257U (en) | Device of methane catalytic cracking production hydrogen | |
| CN109762603A (en) | A method of ammonia is synthesized using low-order coal multipath | |
| CN107312572B (en) | Catalytic coal gasification method | |
| CN104119972A (en) | Multifunctional sulfur-resistant methanation transformation process adapting to coal gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141203 |