CN102766078B - Method for synchronizing low-level mercaptan - Google Patents
Method for synchronizing low-level mercaptan Download PDFInfo
- Publication number
- CN102766078B CN102766078B CN201210272979.9A CN201210272979A CN102766078B CN 102766078 B CN102766078 B CN 102766078B CN 201210272979 A CN201210272979 A CN 201210272979A CN 102766078 B CN102766078 B CN 102766078B
- Authority
- CN
- China
- Prior art keywords
- plasma
- low
- mercaptan
- hydrogen sulfide
- reaction
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for directly producing low-level mercaptan by byproducts of the petrochemical industry, including gaseous olefin and hydrothion gas. The method includes the following steps of sufficiently mixing gaseous olefin and hydrothion gas in a static pipeline mixer, subjecting the mixed gas to react in a plasma reaction bin at normal temperature and normal pressure, separating and purifying to obtain target products. Conditions of reaction at the normal temperature and normal pressure are mild, and the method is high in safety, low in cost and high in yield.
Description
Technical field
The present invention relates to a kind of synthetic method of mercaptan, be specifically related to a kind of synthetic method of low-grade thioalcohol.
Background technology
Low-grade thioalcohol is important chemical intermediate, is widely used in the industries such as agricultural chemicals, medicine, rubber, plastics, spices and essence.
In prior art, the preparation of low-grade thioalcohol is mainly with the addition reaction and obtaining under High Temperature High Pressure of hydrogen sulfide and corresponding alkene, with chemical equation, is expressed as follows:
Wherein R, R
'h, CH
3-, CH
3cH
2-in a kind of.The shortcoming of the method is that this reaction is carried out under High Temperature High Pressure, and energy consumption is large; Catalyzer is easily poisoning, and selectivity, reactivity are poor, and utilize the method product yield only can reach 20 ~ 80%, and production cost is relative also higher.
Summary of the invention
For prior art, preparing mercaptan is all to carry out under High Temperature High Pressure, cause energy consumption large, catalyst selectivity and reactivity are poor, and product yield is low, the deficiency that production cost is high, the invention provides a kind of synthetic method of low-grade thioalcohol, under normal temperature and pressure, gaseous olefin and hydrogen sulfide react under the synergy of plasma body and catalyzer, make that catalyst selectivity is high, long service life, products obtained therefrom yield is high, production cost is low, and production process is safe.
The synthetic method that the invention provides the low-grade thioalcohol that a kind of product yield is high, production cost is low, safe, concrete steps comprise:
(1) gaseous olefin and hydrogen sulfide are passed through to static line mixer, two kinds of gases are fully mixed, adjust the temperature to 10 ~ 30 ℃ simultaneously, mixed gas is with 0.1 ~ 100min
-1air speed enter plasma reaction storehouse, under the effect of plasma power supply and catalyzer, generate low-grade thioalcohol;
(2) low-grade thioalcohol and the unreacted gas that in step (1), generate are entered to condensate recycling device, after condensation separation, the thick mercaptan that contains impurity flows into thick product storage tank, and unreacted gas is through reclaiming, compress, recycling;
(3) thick mercaptan step (2) being obtained distills, and collects the fraction under differing temps, obtains target product mercaptan.
Gaseous olefin in described step (1) is a kind of in gaseous ethylene under normal temperature and pressure, propylene, 1-butylene, 2-butylene or iso-butylene.
Because moisture is conducting material, in plasma environment, can not there is the existence of conducting material, so the hydrogen sulfide in described step (1) is hydrogen sulfide massfraction, be the mixed gas of 60%-100%, wherein also contain a small amount of CO, CO
2and CH
4, be the dry hydrogen sulfide of byproduct process purification of petrochemical industry, can form the comprehensive cyclic utilization of resource, production cost is reduced, there is economy.
In described step (1), the mol ratio of gaseous olefin and hydrogen sulfide is 1 ~ 2:1 ~ 2, in static line mixer, fully mix like this, the static mixer that wherein used is without the tubular reactor stirring, for existing installation, not only make alkene and hydrogen sulfide fully mix, and be convenient to install and realize serialization and produce.
Described plasma reaction storehouse is pipe reaction storehouse, can be so that hydrogen sulfide and gaseous olefin fully react, and can guarantee that two kinds of materials react according to the requirement to target product in reaction warehouse.
Plasma electrical source is a kind of in medium barrier plasma, glow plasma, low-temperature plasma, microwave plasma, radio-frequency plasma or jet plasma, by prior art, can obtain.The high-energy state electronics producing under plasma body electric field action directly acts on hydrogen sulfide, produces high reactivity hydrogen and sulphur hydrogen species, and active specy acts on the alkene of excited state, generates target product with alkene effect.Participation due to high-energy state electronics, make temperature of reaction and the reaction pressure of system be converted into low-temp low-pressure state, temperature of reaction is 10 ~ 30 ℃, and reaction pressure is-0.08 ~ 0.1MPa, reaction system adopts such condition, makes the selectivity of target product and transformation efficiency the highest.
Described catalyzer is a kind of in transition metal oxide, salt, solid acid, many heteroacid or ionic liquid at room temperature;
Described catalyzer is with one or more in the transition metal oxide of molecular sieve, aluminium sesquioxide load, salt, solid acid, many heteroacid;
Described catalyzer is with one or more in the ionic liquid of gac, molecular sieve, aluminium sesquioxide load.
Described catalyzer is to prepare according to prior art, be filled in plasma reaction storehouse, both as filled media, be full of whole reaction warehouse, it is again the catalyzer of alkene and hydrogen sulfide reaction, for the present invention, these selected catalyzer costs are low, and selectivity is good, can reduce reaction energy barrier, improve the transformation efficiency of target product.
Catalyzer is under action of plasma, and activation energy reduces, and reduces the required energy of reaction, excites different carbon atoms and the effect of sulphur hydrogen activity species simultaneously, thereby improves reaction preference.
Described low-grade thioalcohol is a kind of in sulfur alcohol, propane thiol, isopropyl mercaptan, n-butyl mercaptan, sec-butyl thioalcohol or isobutyl mercaptan.
The present invention utilizes the synergy of plasma body and catalyzer, the high-energy state electronics producing under plasma body electric field action makes the temperature of reaction of system and reaction pressure be converted into low-temp low-pressure state, high-energy state electronics directly acts on hydrogen sulfide, produce high reactivity hydrogen and sulphur hydrogen species, active specy acts on the alkene of excited state, generates target product with alkene effect; Catalyzer is under action of plasma, and activation energy reduces, and reduces the required energy of reaction, excites different carbon atoms and the effect of sulphur hydrogen activity species simultaneously, thereby improves reaction preference.
Compared with prior art, its beneficial effect has in the present invention:
(1) plasma body has clean-up performance to catalyzer, has avoided catalyst carbon deposit or sulfur poisoning to lose activity, and extending catalyst reaches 2000h left and right work-ing life, reduces Catalyst Production or regeneration cost;
(2) compared with prior art, the present invention utilizes the synergy of plasma body and catalyzer to complete addition reaction to generate target product mercaptan, and its product yield is high compared to existing technology;
(3) the high-energy state electronics that the present invention produces under plasma body electric field action makes the temperature of reaction of system and reaction pressure be converted into low-temp low-pressure state, and than the high-temperature high-voltage reaction of prior art, operational condition is gentle, not only safe, and has reduced energy consumption;
(4) for unreacted gas in the present invention through reclaiming, compress, recycling, be conducive to cleaner production control and resource circulation utilization in commercial run, production cost is reduced;
(5) technological operation of the present invention is simple, has alleviated labour intensity, has reduced equipment requirements, and production cost is further reduced;
(6) catalyzer of the present invention is with low cost, and catalysis time is long.
Embodiment
Embodiment 1
The petrochemical industry byproduct propylene of drying, purification, hydrogen sulfide, the mol ratio that adjust flux is controlled material is propylene: hydrogen sulfide=1.0:1.0, enter static line mixer and fully mix and regulate mixed gas temperature to 20 ℃ simultaneously, with 0.1min
-1air speed enter continuously the plasma reaction storehouse of the filling catalyst of transition metal oxide of evacuation of air, system temperature of reaction is 20 ℃, reaction pressure is-0.08MPa to take medium barrier plasma as plasma electrical source.In plasma reaction storehouse, there is following chemical reaction:
Reactant is through condensate recycling device, and after condensation separation, liquid phase enters thick product storage tank, and gas phase is compressed, recycling use.Thick product distills mutually, collects 67～68 ℃ of fractions.
This cut is propane thiol through mass spectrum, infrared analysis products obtained therefrom, and in gas chromatographic analysis fraction, propane thiol purity is 99.87%, with propylene, calculates, and yield is 99.10%.
Embodiment 2
The petrochemical industry byproduct propylene of drying, purification, hydrogen sulfide, it is propylene: hydrogen sulfide=1.0:2.0 that adjust flux is controlled molar ratio of material, enters static line mixer and fully mixes, and regulate mixed gas temperature to 30 ℃ simultaneously, with 1min
-1air speed enter continuously the plasma reaction storehouse that is filled with activated carbon supported ionic liquid of evacuation of air, take glow plasma as plasma electrical source.In plasma reaction storehouse, there is following chemical reaction:
Reactant is through condensate recycling device, and after condensation separation, liquid phase enters thick product storage tank, and gas phase is used through recovery, compression cycle.Thick product distills mutually, collects 57～60 ℃ of fractions.
This cut is isopropyl mercaptan through mass spectrum, infrared analysis products obtained therefrom, and in gas chromatographic analysis fraction, isopropyl mercaptan purity is 99.04%, with propylene, calculates, and yield is 98.09%.
Embodiment 3
The petrochemical industry byproduct 2-butylene of drying, purification, hydrogen sulfide, it is that 2-butylene: hydrogen sulfide=1.0:1.0 enters static mixer and fully mixes and regulate mixed gas temperature to 10 ℃ simultaneously that adjust flux is controlled material mole proportioning, with 50min
-1air speed enter continuously the plasma reaction storehouse that is filled with molecular sieve carried phosphorus heteropoly tungstic acid of evacuation of air, take low-temperature plasma as plasma electrical source.In plasma reaction storehouse, there is following chemical reaction:
Reactant is through condensate recycling device, and after condensation separation, liquid phase enters thick product storage tank, and gas phase is compressed, recycling use.Thick product distills mutually, collects 80～95 ℃ of fractions.
This cut is sec-butyl thioalcohol through mass spectrum, infrared analysis products obtained therefrom, and in gas chromatographic analysis fraction, sec-butyl thioalcohol purity is 99.80%, calculates yield 98.08% with 2-butylene.
Embodiment 4
The petrochemical industry byproduct 1-butylene of drying, purification, hydrogen sulfide, adjust flux control material mole proportioning 1-butylene: a hydrogen sulfide=2.0:2.0 enters static mixer and fully mixes and regulate mixed gas temperature to 30 ℃ simultaneously, with 100min
-1air speed enter continuously the plasma reaction storehouse that is filled with molybdenum phospha polyacid of evacuation of air, take microwave plasma as plasma electrical source.In plasma reaction storehouse, there is following chemical reaction:
Reactant is through condensate recycling device, and after condensation separation, liquid phase enters thick product storage tank, and gas phase is compressed, recycling use.Thick product distills mutually, collects 97.8～99.2 ℃ of fractions.
This cut is n-butyl mercaptan through mass spectrum, infrared analysis products obtained therefrom, and in gas chromatographic analysis fraction, n-butyl mercaptan purity is 99.40%, calculates yield 98.01% with 1-butylene.
Embodiment 5
The petrochemical industry byproduct iso-butylene of drying, purification, hydrogen sulfide, adjust flux is controlled material mole proportioning iso-butylene: hydrogen sulfide=1.0:1.5, enters static mixer and fully mixes, and regulate mixed gas temperature to 15 ℃ simultaneously, with 75min
-1air speed enter continuously the plasma reaction storehouse that is filled with alumina load titanium dioxide of evacuation of air, take radio-frequency plasma as plasma electrical source.In plasma reaction storehouse, there is following chemical reaction:
Reactant is through condensate recycling device, and after condensation separation, liquid phase enters thick product storage tank, and gas phase is compressed, recycling use.Thick product distills mutually, collects 97.8～99.2 ℃ of fractions.
This cut is iso-butyl sulfhydryl through mass spectrum, infrared analysis products obtained therefrom, and in gas chromatographic analysis fraction, iso-butyl sulfhydryl purity is 99.65%, calculates yield 99.11% with iso-butylene.
Embodiment 6
The petrochemical industry byproduct ethene of drying, purification, hydrogen sulfide, it is that ethene: hydrogen sulfide=1.5:1.0 enters static mixer and fully mixes and regulate mixed gas temperature to 25 ℃ simultaneously that adjust flux is controlled material mole proportioning, with 25min
-1air speed enter continuously the plasma reaction storehouse that is filled with molecular sieve carried ionic liquid of evacuation of air, take jet plasma as plasma electrical source.In plasma reaction storehouse, there is following chemical reaction:
Reactant is through condensate recycling device, and after condensation separation, liquid phase enters thick product storage tank, and gas phase is compressed, recycling use.Thick product distills mutually, collects 35.9～36.5 ℃ of fractions.
This cut is sulfur alcohol through mass spectrum, infrared analysis products obtained therefrom, and in gas chromatographic analysis fraction, sulfur alcohol purity is 99.30%, with ethene, calculates, and yield is 98.01%.
By embodiment 1-6, can find out, raw materials used is the petrochemical industry byproduct of drying, purification, and unreacted gas is compressed, recycling use, is conducive to cleaner production control and resource circulation utilization in commercial run, and production cost is reduced; Technological operation is simple, and the yield of resulting target product is all more than 98%, and products obtained therefrom yield is high, production cost is low, and reaction conditions is gentle, and production process is safe.
Claims (2)
1. a synthetic method for low-grade thioalcohol, take gaseous olefin and hydrogen sulfide as raw material, it is characterized in that: concrete steps comprise:
(1) gaseous olefin and hydrogen sulfide are passed through to static line mixer, two kinds of gases are fully mixed, adjust the temperature to 10 ~ 30 ℃ simultaneously, mixed gas is with 0.1 ~ 100min
-1air speed enter plasma reaction storehouse, under the effect of plasma power supply and catalyzer, generate low-grade thioalcohol;
(2) low-grade thioalcohol and the unreacted gas that in step (1), generate are entered to condensate recycling device, after condensation separation, the thick mercaptan that contains impurity flows into thick product storage tank, and unreacted gas is through reclaiming, compress, recycling;
(3) thick mercaptan step (2) being obtained distills, and collects the fraction under differing temps, obtains target product mercaptan;
Catalyzer in described step (1) is the transition metal oxide of alchlor load;
Described plasma electrical source is a kind of in medium barrier plasma, glow plasma, low-temperature plasma, microwave plasma, radio-frequency plasma or jet plasma;
Described low-grade thioalcohol is a kind of in sulfur alcohol, propane thiol, isopropyl mercaptan, n-butyl mercaptan, sec-butyl thioalcohol or isobutyl mercaptan.
2. the synthetic method of low-grade thioalcohol according to claim 1, is characterized in that: the gaseous olefin in described step (1) is a kind of in gaseous ethylene under normal temperature and pressure, propylene, 1-butylene, 2-butylene or iso-butylene.
3, the synthetic method of low-grade thioalcohol according to claim 1, is characterized in that: described hydrogen sulfide is that hydrogen sulfide massfraction is the mixed gas of 60-100%.
4, the synthetic method of low-grade thioalcohol according to claim 1, is characterized in that: the mol ratio of described gaseous olefin and hydrogen sulfide is 1-2:1-2.
5, the synthetic method of low-grade thioalcohol according to claim 1, is characterized in that: in described step (2), the reaction conditions of system is: temperature of reaction is 10-30 ℃, and reaction pressure is-0.08-0.1MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210272979.9A CN102766078B (en) | 2012-08-02 | 2012-08-02 | Method for synchronizing low-level mercaptan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210272979.9A CN102766078B (en) | 2012-08-02 | 2012-08-02 | Method for synchronizing low-level mercaptan |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102766078A CN102766078A (en) | 2012-11-07 |
| CN102766078B true CN102766078B (en) | 2014-03-05 |
Family
ID=47093689
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210272979.9A Active CN102766078B (en) | 2012-08-02 | 2012-08-02 | Method for synchronizing low-level mercaptan |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102766078B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496869B (en) * | 2014-12-18 | 2016-07-20 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of isopropyl mercaptan |
| CN104492477B (en) * | 2014-12-18 | 2016-06-29 | 黄河三角洲京博化工研究院有限公司 | A kind of propylene synthesizes the catalyst of isopropyl mercaptan with hydrogen sulfide |
| CN107501147B (en) * | 2017-09-19 | 2019-08-27 | 黄河三角洲京博化工研究院有限公司 | A kind of synthetic method of 3- mercaptopropionic acid |
| CN109593663B (en) * | 2018-12-27 | 2021-12-07 | 山东海景天环保科技股份公司 | Efficient biological desulfurization microbial inoculum and application method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3036133A (en) * | 1960-07-25 | 1962-05-22 | Pennsalt Chemicals Corp | Process for the preparation of sulfur compounds |
| CN1701053A (en) * | 2002-09-25 | 2005-11-23 | 阿肯马公司 | Catalytic method of producing alkyl mercaptans by adding hydrogen sulphide to an olefin |
| JP2008055020A (en) * | 2006-09-01 | 2008-03-13 | Gunma Prefecture | Deodorizing apparatus for odor containing oil droplets and fine particles, and deodorizing method |
-
2012
- 2012-08-02 CN CN201210272979.9A patent/CN102766078B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3036133A (en) * | 1960-07-25 | 1962-05-22 | Pennsalt Chemicals Corp | Process for the preparation of sulfur compounds |
| CN1701053A (en) * | 2002-09-25 | 2005-11-23 | 阿肯马公司 | Catalytic method of producing alkyl mercaptans by adding hydrogen sulphide to an olefin |
| JP2008055020A (en) * | 2006-09-01 | 2008-03-13 | Gunma Prefecture | Deodorizing apparatus for odor containing oil droplets and fine particles, and deodorizing method |
Non-Patent Citations (6)
| Title |
|---|
| 低温等离子体;李学丹;《现代物理知识》;19901231(第3期);第22-23页 * |
| 低温等离子体和催化剂协同作用处理有害气体;杨小平 等;《化工学报》;20051231;第25卷(第3期);第204-209页 * |
| 基于杂多酸或有机配体的配位化合物的合成及其催化性质研究;施连旭;《浙江大学博士学位论文》;20110731;正文第1-199页 * |
| 施连旭.基于杂多酸或有机配体的配位化合物的合成及其催化性质研究.《浙江大学博士学位论文》.2011,正文第1-199页. |
| 李学丹.低温等离子体.《现代物理知识》.1990,(第3期),第22-23页. |
| 杨小平 等.低温等离子体和催化剂协同作用处理有害气体.《化工学报》.2005,第25卷(第3期),第204-209页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102766078A (en) | 2012-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102766078B (en) | Method for synchronizing low-level mercaptan | |
| Tang et al. | Catalytic dehydration of lactic acid to acrylic acid over dibarium pyrophosphate | |
| CN103772125B (en) | Take oil refinery dry gas as the method for waste ethylbenzene | |
| CN104418754B (en) | A kind of method by iso-butylene direct Study on Catalytic Amination of Alcohols production TERTIARY BUTYL AMINE | |
| CN103772126B (en) | Take oil refinery dry gas as the combined method of waste ethylbenzene | |
| CN104672054B (en) | A kind of acetylene and methylene dichloride coupling reaction prepare the method for vinylchlorid coproduction Ethylene Dichloride and vinyl trichloride | |
| CN103724315A (en) | Method used for synthesizing cyclic carbonate in enhanced microreactor system | |
| CN102489225A (en) | Slurry bubble column technology for preparing ethylene through acetylene hydrogenation and device thereof | |
| CN104478644A (en) | Method for preparing isobutylene from tert-butanol | |
| CN103664485A (en) | Method for producing ethylbenzene and styrene through side chain alkylation of toluene and methanol | |
| CN102757371B (en) | Synthetic method of higher mercaptan | |
| CN104829411A (en) | Method for continuously preparing paraxylene in microchannel reactor | |
| CN103664831A (en) | System and method for producing derivatives of olefin | |
| CN103420768A (en) | Method for preparing isobutene from isobutane | |
| CN104774162B (en) | Method used for preparing diethyl sulfate | |
| CN103772117A (en) | Method for preparing butadiene through multistage adiabatic oxidative dehydrogenation of butylene | |
| CN102416348A (en) | Polymer supported imidazole ion catalyst as well as preparation method and application thereof | |
| CN105272810A (en) | Method for separating ethylene/propylene mixed gas | |
| CN203668268U (en) | System for preparing propylene with methanol | |
| CN102336630B (en) | Catalytic synthesis method of 2, 3-dichloro-1, 1, 1-trifluoropropane | |
| CN203346306U (en) | Experimental system for producing methanol by converting coal-mine gas under synergistic effect of plasmas and catalyst | |
| CN102030666B (en) | New process for synthesizing diethanol amine | |
| CN113754510B (en) | Method for preparing 1,3-butadiene | |
| CN111500313B (en) | Method for preparing alkylated gasoline by catalysis | |
| CN106365939A (en) | Method for preparing isobutene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200716 Address after: 256500 Boxing Economic Development Zone, Binzhou, Shandong Patentee after: SHANDONG EFIRM BIOCHEMISTRY AND ENVIRONMENTAL PROTECTION Co.,Ltd. Address before: 256500 Boxing Economic Development Zone, Binzhou, Shandong Patentee before: YELLOW RIVER DELTA JINGBO RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 256500 Boxing Economic Development Zone, Shandong, Binzhou Patentee after: Yifeng New Material Co.,Ltd. Address before: 256500 Boxing Economic Development Zone, Shandong, Binzhou Patentee before: SHANDONG EFIRM BIOCHEMISTRY AND ENVIRONMENTAL PROTECTION Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |