CN101260025B - Separation purification method for producing isobutyl alcohol by methylacrolein hydrogenation - Google Patents
Separation purification method for producing isobutyl alcohol by methylacrolein hydrogenation Download PDFInfo
- Publication number
- CN101260025B CN101260025B CN2008100360872A CN200810036087A CN101260025B CN 101260025 B CN101260025 B CN 101260025B CN 2008100360872 A CN2008100360872 A CN 2008100360872A CN 200810036087 A CN200810036087 A CN 200810036087A CN 101260025 B CN101260025 B CN 101260025B
- Authority
- CN
- China
- Prior art keywords
- isopropylcarbinol
- methylacrylaldehyde
- solvent
- boiling point
- rectifying
- 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.)
- Active
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method of separating and purifying isobutanol from methacrolein hydrotreating reaction liquid. Hydrogenated reaction liquid comprises methacrolein, solvent, isobutyraldehyde and isobutanol which are hydrotreating products, heavy constituents which are by-products, and other unconverted raw materials. In separation process, methacrolein, isobutyraldehyde, low boiling point solvent and other light constituents are removed first through rectification; then high purity isobutanol products are obtained through atmospheric or vacuum rectification; finally a small amount of heavy constituents are separated from high boiling point solvent, and high boiling point solvent is recycled. The method has the advantages of simple process, low energy consumption, high product yield and purity, etc.
Description
Technical field
The invention belongs to organic chemical industry's product separation technical field, specially refer to a kind of technology and method of from the Methylacrylaldehyde hydrogenation reaction solution, separating the purification isopropylcarbinol.
Background technology
Isopropylcarbinol is a kind of important Organic Chemicals, extensive application in a lot of fields, as be used to make petroleum additive, isobutyl acetate, diisobutyl phthalate softening agent and synthetic musk etc.At present, the isopropylcarbinol main production methods is to be come of age/by product isobutyric aldehyde hydrogenation during octanol and getting by the propylene carbonyl compound.In recent years, in order to improve the yield of fourth/octanol product, the propylene carbonylation is gradually to low-pressure process (rhodium catalyst method) development, and product is just different from increasing, and makes that the isopropylcarbinol source is restricted on the market.For this reason, the new isopropylcarbinol production technique of numerous and confused both at home and abroad exploration.Utilize synthetic gas production mixture of lower alcohols to have industrial application, owing to contain a certain amount of isopropylcarbinol in this alcohol mixture, so people consider to obtain isobutanol product by further separation.But because alcohol mixture is formed complexity, separating difficulty is very big, also is difficult to reach industrial requirement at present at aspects such as quality product and economy.
With cheap and easy to get and lower refining of petroleum or the cracking by-product C of chemical utilization rate
4Iso-butylene in the cut is a starting raw material, by the synthetic isopropylcarbinol of Methylacrylaldehyde hydrogenation that selective oxidation generates, is a kind of brand-new technology of producing isopropylcarbinol that proposes recently.Present industrial Methylacrylaldehyde is mainly got through catalytic gas phase oxidation by the iso-butylene or the trimethyl carbinol, and relevant patent has CN200410084589.4, CN02124256.9 etc.The heat effect of methacrylic aldehyde hydrogenation reaction is remarkable, thereby with solvent Methylacrylaldehyde is diluted, and temperature of reaction is controlled in the OK range.Except that isopropylcarbinol, also comprise water, Methylacrylaldehyde, isobutyric aldehyde, solvent and a small amount of heavy constituent in the Methylacrylaldehyde hydrogenation reaction solution, as the Methylacrylaldehyde dimer etc.Obtain isobutanol product by this hydrogenation reaction solution being separated purify.
Existing isopropylcarbinol prepares patent and is primarily aimed at isobutyric aldehyde gas phase hydrogenation technology, as patent CN 94103353 and EP-A-0322049 etc., compare with Methylacrylaldehyde hydrogenation technique of the present invention, there were significant differences for the two reaction product composition, and the process for separating and purifying of product isopropylcarbinol is also inequality.
Summary of the invention
The object of the present invention is to provide a kind of isopropylcarbinol to separate the method for purifying.This method is primarily aimed at the Methylacrylaldehyde hydrogenation reaction solution and separates purification, can obtain highly purified isobutanol product under high yield.
The present invention is achieved by the following technical solutions:
A kind of method of separating isopropylcarbinol in the purification Methylacrylaldehyde hydrogenation reaction solution, may further comprise the steps: (a) hydrogenation reaction takes place in Methylacrylaldehyde and hydrogen under catalyst action, except that isopropylcarbinol, also comprise Methylacrylaldehyde, isobutyric aldehyde, solvent and heavy constituent in the reaction solution; (b) by rectifying the solvent that Methylacrylaldehyde, isobutyric aldehyde and boiling point in the reaction solution are lower than isopropylcarbinol is deviate from, and returned hydrogenator and recycle; (c) by rectifying the reaction solution mid-boiling point is higher than the solvent and the heavies removal of isopropylcarbinol, obtains purity greater than 99.5% isobutanol product; (d) reclaim boiling point by rectifying and be higher than the solvent of isopropylcarbinol, and return hydrogenator and recycle.
Hydrogenation reaction raw material Methylacrylaldehyde quality percentage composition is 10～100% in the aforesaid method, it can be pure Methylacrylaldehyde, also can be the Methylacrylaldehyde solution of solvent cut, wherein solvent can be selected water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, 2-Ethylhexyl Alcohol (being commonly called as octanol), hexalin, phenylcarbinol, ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1, one or more in 4-butyleneglycol, benzene, toluene, normal hexane, hexanaphthene, dme, diethyl ether or the dipropyl ether.The Methylacrylaldehyde solution of hydrogenation reaction raw material preferred solvent dilution, wherein solvent preferably water, methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, 2-Ethylhexyl Alcohol, ethylene glycol, 1, one or more in the 2-propylene glycol.
The quality group of hydrogenation reaction solution becomes: Methylacrylaldehyde 0～80%, isopropylcarbinol 60～98%, isobutyric aldehyde 0～40%, solvent 0～90%, heavy constituent 0.1～10%.When rectifying removed Methylacrylaldehyde, isobutyric aldehyde and boiling point and is lower than the solvent of isopropylcarbinol, the rectifying tower number of theoretical plate was 8～20, and working pressure is 0.05～1.0MPa, and reflux ratio is 0.5～10; When rectifying removed boiling point and is higher than the solvent of isopropylcarbinol and heavy constituent, the rectifying tower number of theoretical plate was 10～30, and working pressure is 0.02～0.1MPa, and reflux ratio is 0.5～20.
Technical scheme of the present invention has following characteristics: provide a kind of isopropylcarbinol to separate novel process for purifying, particularly at the separation of Methylacrylaldehyde hydrogenation reaction solution, had that flow process is simple, energy consumption is low, product yield and a purity advantages of higher.
Fig. 1 is a process flow diagram of the present invention.Wherein, 1-raw material Methylacrylaldehyde, 2-raw hydrogen, 3-hydrogenator, 4-gas-liquid separator, 5-cut light tower, 6-product purification tower, 7-isobutanol product, 8-solvent recovery tower, 9-heavy constituent.
Flow process below in conjunction with accompanying drawing 1 is elaborated to implementation process of the present invention.
Raw material Methylacrylaldehyde [1] and hydrogen [2] enter hydrogenator [3] by top after mixing, hydrogenation reaction solution enters gas-liquid separator [4], excessive hydrogen returns hydrogenator [3] and recycles after gas-liquid separation, liquid product enters cut light tower [5], cat head steams a small amount of isobutyric aldehyde, Methylacrylaldehyde and low boiling point solvent etc., and it is circulated to hydrogenator [3].Cut light tower [5] tower bottoms enters product purification tower [6], and cat head obtains isobutanol product [7], and tower bottoms enters solvent recovery tower [8], and the cat head high boiling solvent returns hydrogenator [3], a small amount of heavy constituent of tower still extraction [9].
In the specific implementation process, if only in the hydrogenating materials Methylacrylaldehyde, add low boiling point solvent such as methyl alcohol or/and the ethanol etc. that boiling point is lower than the product isopropylcarbinol, perhaps only add the diluting solvent of product isopropylcarbinol itself as the hydrogenating materials Methylacrylaldehyde, the separation of hydrogenation products isopropylcarbinol is purified under the both of these case only needs three towers, and promptly gas-liquid separator [4], cut light tower [5] and product purification tower [6] just can obtain isobutanol product.Be higher than the high boiling solvent of product isopropylcarbinol such as 2-Ethylhexyl Alcohol etc. if only add boiling point in the hydrogenating materials Methylacrylaldehyde, perhaps add the mixture of two or more mixed solvents such as ethanol and 2-Ethylhexyl Alcohol etc., the separation of hydrogenation products isopropylcarbinol is purified in both cases then needs four towers, and promptly gas-liquid separator [4], cut light tower [5], product purification tower [6] and solvent recovery tower [8] just can obtain isobutanol product.
Below in conjunction with specific embodiment content of the present invention is described further.
Technical process as shown in Figure 1.Hydrogenation reaction raw material liquid phase feeding quality group becomes Methylacrylaldehyde 80% and methyl alcohol 20%, behind the hydrogenation, enters gas-liquid separator [4] and carries out gas-liquid separation in hydrogenator [3], and hydrogen recycle is used; The liquid product that quality group becomes Methylacrylaldehyde 25.4%, isobutyric aldehyde 1.8%, methyl alcohol 19.3%, isopropylcarbinol 52.7% and heavy constituent 0.8% enters cut light tower [5], carries out rectifying under normal pressure, and number of theoretical plate is 10, and reflux ratio is 3.Cut light tower [5] liquid of top of the tower quality group becomes Methylacrylaldehyde 54.6%, isobutyric aldehyde 3.9%, methyl alcohol 41.5% and micro-isopropylcarbinol, and it is circulated to hydrogenator [3]; The tower bottoms quality group becomes isopropylcarbinol 98.5% and heavy constituent 1.5%.Cut light tower [5] tower bottoms is sent into product purification tower [6] rectification under vacuum under 0.05MPa, and number of theoretical plate is 11, and reflux ratio is 1.5, and cat head obtains the isobutanol product that purity is 99.9 quality %, a small amount of heavy constituent of tower still extraction.Whole sepn process isopropylcarbinol yield is 99.5%.
Technical process as shown in Figure 1.Hydrogenation reaction raw material liquid phase feeding quality group becomes Methylacrylaldehyde 40% and ethanol 60%, behind the hydrogenation, enters gas-liquid separator [4] and carries out gas-liquid separation in hydrogenator [3], and hydrogen recycle is used; The liquid product that quality group becomes Methylacrylaldehyde 2.1%, isobutyric aldehyde 5.9%, ethanol 59.6%, isopropylcarbinol 31.3% and heavy constituent 1.1% enters cut light tower [5], carries out rectifying under normal pressure, and number of theoretical plate is 11, and reflux ratio is 3.Cut light tower [5] liquid of top of the tower quality group becomes Methylacrylaldehyde 3.1%, isobutyric aldehyde 8.7%, ethanol 88.1% and micro-isopropylcarbinol, and it is circulated to hydrogenator [3]; The tower bottoms quality group becomes isopropylcarbinol 96.3%, heavy constituent 3.6% and micro ethanol.Cut light tower [5] tower bottoms is sent into product purification tower [6] rectification under vacuum under 0.05MPa, and number of theoretical plate is 11, and reflux ratio is 3, and cat head obtains the isobutanol product that purity is 99.8 quality %, a small amount of heavy constituent of tower still extraction.Whole sepn process isopropylcarbinol yield is 99.7%.
Technical process as shown in Figure 1.Hydrogenation reaction raw material liquid phase feeding quality group becomes Methylacrylaldehyde 40% and isopropylcarbinol 60%, behind the hydrogenation, enters gas-liquid separator [4] and carries out gas-liquid separation in hydrogenator [3], and hydrogen recycle is used; The liquid product that quality group becomes Methylacrylaldehyde 0.5%, isobutyric aldehyde 1.3%, isopropylcarbinol 97.1% and heavy constituent 1.1% enters cut light tower [5], carries out rectifying under normal pressure, and number of theoretical plate is 11, and reflux ratio is 1.Cut light tower [5] liquid of top of the tower quality group becomes Methylacrylaldehyde 27.7%, isobutyric aldehyde 72.3% and micro-isopropylcarbinol, and it is circulated to hydrogenator [3]; The tower bottoms quality group becomes isopropylcarbinol 98.8% and heavy constituent 1.2%.Cut light tower [5] tower bottoms is sent into product purification tower [6] rectification under vacuum under 0.05MPa, and number of theoretical plate is 11, and reflux ratio is 3, and cat head obtains the isobutanol product that purity is 99.8 quality %, a small amount of heavy constituent of tower still extraction.Whole sepn process isopropylcarbinol yield is 99.5%.
Technical process as shown in Figure 1.Hydrogenation reaction raw material liquid phase feeding quality group becomes Methylacrylaldehyde 10% and 2-Ethylhexyl Alcohol (being commonly called as octanol) 90%, behind the hydrogenation, enters gas-liquid separator [4] and carries out gas-liquid separation in hydrogenator [3], and hydrogen recycle is used; The liquid product that quality group becomes Methylacrylaldehyde 0.2%, isobutyric aldehyde 0.8%, 2-Ethylhexyl Alcohol 89.5%, isopropylcarbinol 8.9% and heavy constituent 0.6% enters cut light tower [5], carries out rectifying under normal pressure, and number of theoretical plate is 10, and reflux ratio is 2.Cut light tower [5] liquid of top of the tower quality group becomes Methylacrylaldehyde 20.0%, isobutyric aldehyde 80.0% and micro-isopropylcarbinol, and it is circulated to hydrogenator [3]; The tower bottoms quality group becomes isopropylcarbinol 9.0%, 2-Ethylhexyl Alcohol 90.3% and heavy constituent 0.7%.Cut light tower [5] tower bottoms is sent into product purification tower [6], under normal pressure, carry out rectifying, number of theoretical plate is 11, reflux ratio is 2, cat head obtains the isobutanol product that purity is 99.7 quality %, and tower bottoms is 2-Ethylhexyl Alcohol and a small amount of heavy constituent, and it is added solvent recovery tower [8], the 2-Ethylhexyl Alcohol that cat head obtains returns hydrogenator [3], and heavy constituent are by the extraction of tower still.Whole sepn process isopropylcarbinol yield is 99.4%.
Technical process as shown in Figure 1.Hydrogenation reaction raw material liquid phase feeding quality group becomes Methylacrylaldehyde 50%, ethanol 30% and 2-Ethylhexyl Alcohol (being commonly called as octanol) 20%, behind the hydrogenation, enters gas-liquid separator [4] and carries out gas-liquid separation in hydrogenator [3], and hydrogen recycle is used; The liquid product that quality group becomes Methylacrylaldehyde 2.8%, isobutyric aldehyde 7.8%, ethanol 29.7%, 2-Ethylhexyl Alcohol 19.7%, isopropylcarbinol 38.2% and heavy constituent 0.8% enters cut light tower [5], under normal pressure, carry out rectifying, number of theoretical plate is 10, and reflux ratio is 2.Cut light tower [5] liquid of top of the tower quality group becomes Methylacrylaldehyde 6.9%, isobutyric aldehyde 19.4%, ethanol 73.7% and micro-isopropylcarbinol, and it is circulated to hydrogenator [3]; The tower bottoms quality group becomes isopropylcarbinol 65.1%, 2-Ethylhexyl Alcohol 33.6%, heavy constituent 1.3% and micro ethanol.Cut light tower [5] tower bottoms is sent into product purification tower [6], carry out rectifying under normal pressure, number of theoretical plate is 11, and reflux ratio is 2, and it is 99.7% isobutanol product that cat head obtains purity; Product purification tower [6] tower bottoms quality group becomes 2-Ethylhexyl Alcohol 96.1%, heavy constituent 3.9%, and it is added solvent recovery tower [8], and cat head obtains the 2-Ethylhexyl Alcohol that purity is 99.7 quality %, and it is returned hydrogenator [3], and heavy constituent are by the extraction of tower still.Whole sepn process isopropylcarbinol yield is 99.5%.
Claims (2)
1. method of separating isopropylcarbinol in the purification Methylacrylaldehyde hydrogenation reaction solution is characterized in that this method may further comprise the steps:
(a) hydrogenation reaction takes place in Methylacrylaldehyde and hydrogen under catalyst action, except that isopropylcarbinol, also comprises Methylacrylaldehyde, isobutyric aldehyde, solvent and heavy constituent in the reaction solution;
(b) by rectifying the solvent that the Methylacrylaldehyde in the reaction solution, isobutyric aldehyde and boiling point are lower than isopropylcarbinol is deviate from, and returned hydrogenator and recycle;
(c) by rectifying the reaction solution mid-boiling point is higher than the solvent and the heavies removal of isopropylcarbinol, obtains purity greater than 99.5% isobutanol product;
(d) reclaim boiling point by rectifying and be higher than the solvent of isopropylcarbinol, and return hydrogenator and recycle;
The hydrogenation reaction raw material is the pure Methylacrylaldehyde or the Methylacrylaldehyde solution of solvent cut, Methylacrylaldehyde quality percentage composition is 10～100%, wherein solvent is selected water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, 2-Ethylhexyl Alcohol, hexalin, phenylcarbinol, ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1, one or more in 4-butyleneglycol, benzene, toluene, normal hexane, hexanaphthene, dme, diethyl ether or the dipropyl ether;
When rectifying removed Methylacrylaldehyde, isobutyric aldehyde and boiling point and is lower than the solvent of isopropylcarbinol, the rectifying tower number of theoretical plate was 8～20, and working pressure is 0.05～1.0MPa, and reflux ratio is 0.5～10;
When rectifying removed boiling point and is higher than the solvent of isopropylcarbinol and heavy constituent, the rectifying tower number of theoretical plate was 10～30, and working pressure is 0.02～0.1MPa, and reflux ratio is 0.5～20.
2. according to the described method of claim 1, it is characterized in that the hydrogenation reaction raw material is the Methylacrylaldehyde solution of solvent cut, wherein solvent is selected water, methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, 2-Ethylhexyl Alcohol, ethylene glycol, 1, one or more in the 2-propylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100360872A CN101260025B (en) | 2008-04-16 | 2008-04-16 | Separation purification method for producing isobutyl alcohol by methylacrolein hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100360872A CN101260025B (en) | 2008-04-16 | 2008-04-16 | Separation purification method for producing isobutyl alcohol by methylacrolein hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101260025A CN101260025A (en) | 2008-09-10 |
| CN101260025B true CN101260025B (en) | 2011-04-20 |
Family
ID=39960762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100360872A Active CN101260025B (en) | 2008-04-16 | 2008-04-16 | Separation purification method for producing isobutyl alcohol by methylacrolein hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101260025B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101570469B (en) * | 2009-06-15 | 2012-09-26 | 上海华谊丙烯酸有限公司 | Method for continuously producing isobutyl alcohol through hydrogenation of methylacrolein |
| CN114262257B (en) * | 2020-09-16 | 2023-07-14 | 万华化学集团股份有限公司 | Method for recycling isoamyl alcohol through citral process waste liquid hydrogenation |
| CN113209985B (en) * | 2021-04-08 | 2022-04-26 | 西南化工研究设计院有限公司 | Catalyst for removing trace olefin in dimethyl ether through hydrogenation, preparation method and application |
| CN114100640B (en) * | 2021-12-01 | 2023-08-11 | 万华化学集团股份有限公司 | Inorganic solid super acidic supported palladium catalyst, preparation method thereof and method for producing 1, 4-butanediol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1720210A (en) * | 2002-12-04 | 2006-01-11 | 三菱化学株式会社 | Process for producing alcohol |
-
2008
- 2008-04-16 CN CN2008100360872A patent/CN101260025B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1720210A (en) * | 2002-12-04 | 2006-01-11 | 三菱化学株式会社 | Process for producing alcohol |
Non-Patent Citations (1)
| Title |
|---|
| JP特开平6-122638A 1994.05.06 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101260025A (en) | 2008-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105622337B (en) | Novel reactive distillation coupling process and device for separating liquid-phase product of ethylene glycol prepared from coal | |
| RU2594159C2 (en) | Method of separating ethylene glycol and 1,2-butanediol | |
| CN102372596B (en) | Method for producing glycol product by separating synthetic gas | |
| CN110878007B (en) | Refining method of non-petroleum ethylene glycol | |
| CN104355975B (en) | A kind of method of acetone two step synthesis methyl iso-butyl ketone (MIBK) | |
| CN104447243B (en) | The reactive distillation method of low pressure oxo process butyraldehyde and device | |
| CN103193595B (en) | Ethylene glycol rectification device system and rectification technique in industry of producing ethylene glycol by synthesis gas | |
| CN101239886B (en) | Method for separating and reclaiming organic matter from high-temperature Fischer-Tropsch synthesis reaction water | |
| CN101260025B (en) | Separation purification method for producing isobutyl alcohol by methylacrolein hydrogenation | |
| CN102372600A (en) | Separation method for glycol, propylene glycol and butylene glycol | |
| CN107915612B (en) | Method for preparing purified MIBK from industrial byproduct waste liquid acetone | |
| CN109851586A (en) | The purification process of propylene oxide | |
| CN102372597B (en) | Method for separating glycol product produced from syngas | |
| CN101830788A (en) | Method for separating azeotropic mixture of ethyl methyl ketone and water through variable-pressure rectification | |
| CN112920144B (en) | Preparation method of propylene oxide | |
| CN102452934A (en) | Preparation method of sec-butyl acetate | |
| CN101570469A (en) | Method for continuously producing isobutyl alcohol through hydrogenation of methylacrolein | |
| CN105384593A (en) | Method for producing olefin by using fusel oil | |
| CN103864587B (en) | Method for synthesizing 2-ethyl-2-hexenal | |
| CN104230855B (en) | Cumyl hydroperoxide and the method for epoxidation of propylene | |
| CN107286004B (en) | Method for refining polyformaldehyde dimethyl ether | |
| CN107286002B (en) | Method for refining polymethoxy dimethyl ether 2 | |
| CN204342703U (en) | The reaction and rectification device of low pressure oxo process butyraldehyde | |
| CN109704911B (en) | Method for producing hexane from aromatic raffinate oil | |
| CN100363327C (en) | Production of pivalic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170208 Address after: 201424 Fengxian District Cang Road, lane, Lane 357, room 100, room 295 Patentee after: Shanghai Hua Yi new material Co., Ltd Address before: 200137 Pudong North Road, Shanghai, No. 2031, No. Patentee before: Shanghai Huayi Acrylic Acid Co., Ltd. |
|
| TR01 | Transfer of patent right |