• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to an alkane sulfonation process using alkane and sulfur trioxide, especially pure (100%) sulfur trioxide under solvent-free conditions in the presence of an initiator. It further relates to the use of a precursor which forms an in situ initiator for the manufacture of alkanesulfonic acids, especially methanesulfonic acids.
    公开号:BR112019010643A2
    申请号:R112019010643
    申请日:2017-11-27
    公开日:2019-10-01
    发明作者:Biertümpel Ingo；Ott Timo
    申请人:Grillo Werke Ag；
    IPC主号:
    专利说明:

    SOLVENT-FREE ALKAN SULPHONATION [01] The present invention relates to a process for alkane sulfonation using alkane and sulfur trioxide, especially pure sulfur trioxide (100%) under solvent-free conditions in the presence of an initiator. It also refers to the use of a precursor that forms an initiator in situ for the manufacture of alkanesulfonic acids, especially methanesulfonic acids.
    [02] Alkosuifonic acids are organic acids that can reach an acidic force like that of inorganic mineral acids, for example, sulfuric acid. However, in contrast to the usual mineral acids such as sulfuric and nitric acids, sulfonic acids are non-oxidizing and do not emit harmful vapors, as can be seen with hydrochloric and nitric acids. In addition, many sulfonic acids, for example methanesulfonic acid, are biologically degradable. The applications of sulfonic acids are many, for example, in cleaning agents, surfactants, galvanic and electronic industry, as catalysts, and in organic synthesis, pharmaceutical chemistry, for example, as protecting groups. Sulfonic acid salts are used, for example, as surfactants, for example, sodium dodecyl sulfonate, or in the electroplating industry, especially as tin, zinc, silver, lead and indium alkyl sulfonates, but also of other metals. In addition, organic salts are used in pharmaceutical chemistry. The very high solubility of alkyl sulfonates plays an important role, in particular. In addition, no harmful gases are formed in electrolysis, and the use of toxic compounds, for example, cyanide, which is common
    Petition 870190048644, of 05/24/2019, p. 5/24
    2/12 in many cases is waived.
    [03] The structurally simplest representative of alkanesulfonic acids is methanesulfonic acid. US 2493038 describes the preparation of methanesulfonic acid from SO 3 and methane. US 2005/0070614 describes additional methods for preparing methanesulfonic acid and its application. Methods known in the art are partly complicated, expensive and lead to undesirable products due to severe reaction conditions.
    [04] The reaction conditions in conventional processes for the production of alkanesulfonic acids can result in undesirable by-products, which manifest themselves even as disruptive inhibitors in the production of alkanesulfonic acids. This can lead to the termination of the reaction itself for the preparation of alkanesulfonic acid, but also to impurities, formation of by-products and low yields, based on sulfur trioxide and methane.
    [05] WO 2007/136425 A2 describes the use of the compound di (methanesulfonyl) peroxide (DMSP), which has to be prepared by complex electrolysis and, in addition, it is a highly explosive crystallisable solid, as an initiator in a reaction wherein methanesulfonic acid is formed from sulfur trioxide and methane.
    [06] WO 2015/071365 A1 and WO 2015/071455 A1 both describe processes for the sulfonation of alkanes. The main steps are:
    1) Synthesis of an initiator / initiator solution.
    Petition 870190048644, of 05/24/2019, p. 6/24
    12/3
    2) Preparation of a sulfur trioxide (oleum) solution by dissolving sulfur trioxide in an inert solvent (eg sulfuric acid)
    3) Reaction of the oleum with the corresponding alkane after or during the addition of the initiator / initiator solution in a high pressure reactor.
    4) Deactivation of unreacted starting material
    5) Purification (eg distillation, crystallization, etc.)
    6) Recycling of the inert solvent (eg sulfuric acid).
    [07] It is the object of the present invention to provide an improved process for the manufacture of alkanesulfonic acid, especially methanesulfonic acid, allowing better control of the reaction. In addition, the requirements for sulfur trioxide and alkanes should not be relevant, meaning that not only pure raw materials can be used, but that impurities do not adversely affect the reaction.
    [08] The object of the present invention is accomplished by using a compound of the formula (I) alk-so 2 -oox, (I) [09] where ALK is a branched or unbranched alkyl group, especially a methyl group, ethyl, propyl, butyl, isopropyl, isobutyl or a higher alkyl group, and X = hydrogen, zinc, aluminum, an alkali or alkaline earth metal, as a precursor to the initiator for the preparation of alkanesulphonic acids, especially methanesulphonic acids from alkane ,
    Petition 870190048644, of 05/24/2019, p. 7/24
    4/12 especially methane, and sulfur trioxide, especially pure sulfur trioxide.
    [010] In another embodiment, the object of the invention is accomplished by a process for the manufacture of the compound as defined above with X = H, comprising the reaction of an alkanesulfonic acid, especially methanesulfonic acid, with hydrogen peroxide. It can be followed by isolation of the compound.
    [011] In another embodiment, the object of the invention is realized by a process for the manufacture of aminosulfonic acids, especially methanesulfonic acid, comprising the following steps:
    providing sulfur trioxide;
    reacting the sulfur trioxide with an alkane, especially methane, in a high pressure autoclave or laboratory reactor;
    adjust the pressure to 1 to 200 bar;
    preparing the initiator precursor according to formula (I), by reacting an alkanesulfonic acid or a solution containing the alkanesulfonic acid with a solution of 30% to 100% hydrogen peroxide (w / w);
    adding the initiator precursor according to formula (I) or a solution thereof to the reactor;
    controlling the temperature of the reaction mixture at 0 ° C to 100 ° C;
    if necessary, purify the reaction product, for example, by distillation or extraction.
    [012] After the reaction has taken place, the reaction mixture essentially contains the respective alkanesulfonic acid, especially methanesulfonic acid, as well as sulfuric acid. This mixture of
    Petition 870190048644, of 05/24/2019, p. 8/24
    5/12 alkanesulfonic acid, especially methanesuifonic acid (MSA) and H2SO4, can later be used as the respective mixture. The combination of ananicosulfonic acid, especially methanesulfonic acid, and sulfuric acid provides a strong acid in which even gold can be dissolved, allowing for different fields of technical applicability.
    [013] Alternatively, the alkanesulfonic acid, especially MSA, can be separated, that is, the method of the invention comprises the optional step of purifying the reaction product, which can be done by distillation or extraction.
    [014] But also alkanesulfonic acids, and especially methanesulfonic acids, can be used in different technical fields, that is, as a cleaning agent (cleaning comprising the area of cleaning and care, home care and industrial and institutional cleaning of surfaces hard, soft, ie dishwashing, commercial laundry, cleaning and sanitation, vehicle care and transportation, cement cleaning, membrane cleaning, and others), for regeneration of ion exchange resins, in galvanic processes, in oil, gas, mining, metal treatment and / or their surfaces, in different areas of the pharmaceutical, chemical and agro-chemical industry or in the production of biodiesel. MSA can also be used in the process of galvanizing plastics, in the wide area of batteries, as recycling lead batteries and recycling in general, such as metal recycling, as well as the generation of borane are other possible areas of application.
    [015] This invention allows for important modifications that lead to
    Petition 870190048644, of 05/24/2019, p. 9/24
    6/12 to an improved process compared to the state of the art by:
    Prepare the preferred initiator in situ using less or even no solvent.
    Purification of the product is easier, due to higher concentrations of the product.
    There is no recycling of the inert solvent.
    If applicable:
    Avoid the preparation of sulfur trioxide solutions.
    Reaction conditions without addition of solvent.
    Evaporation of unreacted sulfur trioxide instead of deactivation.
    [016] In particular, the compound as defined above in formula (I) is present in a mixture of the invention that additionally contains at least one compound selected from the group consisting of formula II to XI, i.e. II, III, IV, V, VI, VII, VIII, IX, X or XI:
    Petition 870190048644, of 05/24/2019, p. 10/24
    7/12 οο
    Me. | ί] C3
    S '> 5' · ΟΗ
    QO ο
    ν '’ΌΗ
    Ü
    Ο ο η ο II ο s Όη ό
    νπ
    VIII IX [017] and their combinations.
    [018] In another embodiment, the compound as defined above or the mixture of the invention is present in sulfuric acid or alkanesulfonic acid, especially methanesulfonic acid.
    [019] For example, the compound of formula (I) with X = H can be manufactured by a process comprising reacting alkanesulfonic acids, especially methanesulfonic acid, with hydrogen peroxide. The compound thus obtained can be isolated, but it will preferably be used as a precursor to the initiator without any further isolation and / or cleaning step.
    [020] In particular, isolation can be carried out by extraction, chromatography, precipitation, recrystallization, lyophilization or similar methods under mild conditions. In a specific embodiment of the process according to the invention, the isolation can be carried out by means of precipitation or chromatography. Inert support materials and inert solvents, such as sulfuric or sulfonic acids, are used there. The use of organic solvents is also possible.
    [021] The inert support materials used for insulation are in particular those that do not interfere negatively with the components that are the true partners of the reaction, for example by reducing the yield of the compound of the invention. In addition, inert support materials can either chemisorver or
    Petition 870190048644, of 05/24/2019, p. 11/24
    8/12 fisissorver - ου both · a chemical compound, without irreversibly destroying its functionality or structure. Examples are materials based on, for example, silicon dioxide, aluminum oxide, zirconium oxide and the like.
    [022] Surprisingly, it has been found that, instead of using oleum, as described in the prior art, pure sulfur trioxide can also be used according to the present invention. This avoids the preparation of sulfur trioxide solutions. The reaction conditions are here without added solvents. In addition, unreacted sulfur trioxide can evaporate, avoiding the need to deactivate it.
    [023] In another embodiment, sulfur trioxide is used in a form of oleum with a trioxide content of 50% (w / w) or less, or 65% (w / w) or more. Surprisingly, it was found that, contrary to the state of the art for the processes of the present invention, oleum with a sulfur trioxide content of 65% (w / w) or more, especially 70% w / w or moreover, without negative effects affecting the process of the invention. Even pure sulfur trioxide (100% (w / w) sulfur trioxide) can be used.
    [024] Due to the advantages that are associated with the use of pure sulfur trioxide mentioned above, the use of pure sulfur trioxide is preferred in the process of making alkanesulfonic acids according to the present invention. Contrary to the state of the art, no solvent circulation is necessary, alkanes comprising larger amounts of impurities can be used compared to the state of the art.
    Petition 870190048644, of 05/24/2019, p. 12/24
    9/12 technique. Impurities are usually enriched in the solvent, leading to reduced MSA yield. By avoiding solvents and, therefore, their circulation, impurities from alkanes are not having a negative influence on the production of MSA when pure sulfur trioxide is used.
    [025] The invention also relates to a process for the manufacture of alkanesulfonic acids, especially methanesulfonic acids, comprising the steps indicated below:
    [026] Sulfur trioxide, especially pure sulfur trioxide, reacts with an alkane in a reactor. For alkanes with a low boiling point, the use of a high pressure reactor is required. For pentane and higher alkanes, a common laboratory reactor is sufficient. In the case of gaseous alkanes, for example, methane, a pressure of 1 to 200 bar of gas pressure is adjusted. The primer precursor (e.g., alkanesulfonic hydroperoxide) which reacts in situ to give a suitable initiator is added to this solution. The initiator precursor is prepared by reacting an alkanesulfonic acid or a solution of that alkanesulfonic acid with hydrogen peroxide to the alkanesulfonic hydroperoxide according to reaction scheme 1 and can optionally be isolated:
    [027] Reaction scheme 1: ALK-SCMDH + H 2 O 2 ~> ALK-SO 2 OOH + H 2 O.
    [028] The alkanesulfonic hydroperoxide (initiator precursor) reacts in situ during addition to the reactor to a sulfuric alkanesulfonic peroxoanhydride according to reaction scheme 2: [029] Reaction scheme 2: ALK ~ SO2 ~ O ~ OH + SO 3 ALK -SO 2 -O-OSO 2 ~ OH. (Reaction in situ)
    Petition 870190048644, of 05/24/2019, p. 13/24
    10/12 [030] The respective sulfuric alkanesulfonic peroxoanhydrides as initiators in the production of methanesulfonic acids are described in WO 2015/071455 A1. In said prior art document, the initiator is first produced in an additional reactor and then added to the main reactor in which the process for producing methanesulfonic acid or any other alkanesulfonic acid takes place. Contrary to this, in the present application a primer precursor is formed which can be isolated but can be added without further purification. Said initiator precursor, being an alkanesulfonic hydroperoxide, reacts in situ during the addition to the main reactor with the alkane and the sulfur trioxide to form methanesulfonic acid.
    [031] The hydrogen peroxide concentration can be from 20 to 100% (w / w). Subsequently, the reaction is completed at 0 to 100 ° C. The crude product can be processed by extraction, crystallization, distillation or chromatography.
    [032] This process can be applied to reactor systems both in batch and continuous.
    [033] The invention further relates to the use of a primer precursor as defined above or a mixture as defined above in a device to carry out the process for the manufacture of an alkanesulfonic acid, especially methanesulfonic acid, wherein the device comprises a reactor (1) in which sulfur trioxide reacts with the compound of formula (I) as a precursor to the initiator to form an initiator; and reacting said initiator formed in situ with an alkane, especially methane; a distillation means (2) for distilling the product formed in the reactor (1); and a means of
    Petition 870190048644, of 05/24/2019, p. 14/24
    11/12 filling (3); as well as connection means for connecting the reactor (1) to the distillation means (2), and the filling means (3) to the distillation means (2). Fig. 1 is a schematic of a process for sulfonation, using pure sulfur trioxide, an alkane (for example, methane) including purification (for example, distillation) as well as a device for the production of methanesulfonic acid. [034] The process according to the invention allows alkanesulfonation, especially methanesulfonation, in a reactor system using sulfur trioxide, especially pure sulfur trioxide, with alkane, especially methane, with the addition of an initiator precursor. The crude product can be purified by distillation, allowing the production of high purity alkanesulfonic acid, especially methanesulfonic acid, as a distillate.
    [035] In the following, the invention is further illustrated by way of example, taking the methanesulfonic acid preparation as an example.
    Example 1:
    [036] Preparation of the initiator precursor solution [037] To 100 ml of methanesulfonic acid, 78 ml of 60% (w / w) hydrogen peroxide were added dropwise with external cooling and intense stirring.
    Synthesis protocol:
    [038] In a 3.75 L autoclave, 2000 g of pure sulfur trioxide was loaded and the temperature was controlled at 50 ° C. After a pressure of 100 bar of methane has been set, intense stirring is carried out. Then, the primer precursor is added to the solution dropwise in a measured amount. The pressure dropped to
    Petition 870190048644, of 05/24/2019, p. 15/24
    12/12 bar in 30 minutes. Then the pressure was adjusted to 100 bar again. The pressure dropped again to 50 bar. The pressure was adjusted again to 100 bar. Finally, the pressure dropped to 30 bar. The yield is over 90%, based on sulfur trioxide. The reaction product contains 91% (w / w) methanesuifonic acid.
    权利要求:
    Claims (9)
    [1]
    CLAIMS:
    1. Use of a compound, characterized by a formula (I) ALK “SO 2 “ O “O“ X (I), where ALK is a branched or unbranched alkyl group, especially a methyl, ethyl, propyl, butyl group , isopropyl, isobutyl or a higher alkyl group, and X = hydrogen, zinc, aluminum, an alkali or alkaline earth metal, as an initiator precursor for the preparation of alkanesulfonic acids, especially methanesulfonic acids from alkane, especially methane, and sulfur trioxide, especially pure sulfur trioxide.
    [2]
    Mixture containing a compound according to claim 1, characterized by at least one compound selected from the group consisting of the following formulas (II) to (X)

    and their combinations.
    Petition 870190048644, of 05/24/2019, p. 17/24
    2/4
    [3]
    Compound according to claim 1 or the mixture according to claim 2, characterized in that in suifuric acid or alkyl sulfonic acid, especially methanesuifonic acid or combinations thereof.
    [4]
    Use of the mixture according to claim 2 or 3, characterized in that as a precursor to the initiator for the preparation of alkanesulfonic acids, especially methanesuifonic acid, from alkane, especially methane, and sulfur trioxide, especially pure sulfur trioxide .
    [5]
    Process for the manufacture of the compound according to claim 1, characterized in that with X - H, comprising the following steps:
    reaction of an alkanesulfonic acid, especially methanesuifonic acid, with hydrogen peroxide;
    if necessary, followed by isolation of the compound.
    [6]
    6. Process for the manufacture of alkanesulphonic acids, characterized by in particular methanesuifonic acid, comprising the following steps:
    - provide sulfur trioxide;
    - react the sulfur trioxide with an alkane, especially methane, in a high pressure autoclave or laboratory reactor;
    - adjust the pressure from 1 to 200 bar;
    - preparing the compound according to claim 1 or the mixture according to claim 2 or 3 as a precursor to the initiator by reacting an alkanesulfonic acid or a solution containing the alkanesulfonic acid with a solution
    Petition 870190048644, of 05/24/2019, p. 18/24
    3/4 of hydrogen peroxide at 30% to 100% (w / w);
    - adding the initiator precursor or a solution thereof to the reactor;
    - controlling the temperature of the reaction mixture at 0 ° C to 100 ° C;
    - if necessary, purify the reaction product, for example, by distillation or extraction.
    [7]
    Process according to claim 5 or 6, characterized in that the sulfur trioxide is oleum, preferably with a sulfur trioxide content of 50% (w / w) or less or 65% (w / w) or more.
    [8]
    Process according to claim 5 or 6, characterized in that the sulfur trioxide is pure sulfur trioxide.
    [9]
    Use of an initiator precursor according to claim 1 or the mixture according to claim 2 or 3, characterized in that in a device for carrying out the process according to claim 6, wherein the device comprises:
    a reactor (1) in which sulfur trioxide reacts with the compound according to claim 1 as a primer precursor to form an initiator; and reacting said initiator formed in situ with an alkane, especially methane;
    a distillation means (2) for distilling the product formed in the reactor (1); and a filling means (3); as well as connection means for connecting the reactor (1) to the distillation means (2), and the filling means (3) to the
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112019010643A2|2019-10-01|solvent free alkane sulfonation
    US11180448B2|2021-11-23|Initiator for preparing alkanesulfonic acids from alkane and oleum
    US10927063B2|2021-02-23|Process for the preparation of halogenated carboxylic anhydrides
    JP2010159242A|2010-07-22|Fluorine-containing n-alkylsulfonylimide compound and method for producing the same, and method for producing ionic compound
    TWI714964B|2021-01-01|Catalysts for the synthesis of alkanesulfonic acids
    DK2625163T3|2018-10-15|PROCEDURE FOR THE PREPARATION OF | 4,4'-DISULPHANDYLBIS |
    BRPI0814887B1|2016-11-22|process for toluidine compound production
    US2821549A|1958-01-28|Production of nuclear sulfonated vinyl aromatic compounds
    JP2011246385A|2011-12-08|Method for production of fluorine-containing sulfonyl imide compound
    US3948922A|1976-04-06|Oxidation of thiols and disulfides to sulfonic acids
    US20220033354A1|2022-02-03|Cations as catalyst in the production of alkane sulfonic acids
    WO2020064466A1|2020-04-02|Catalyst for the synthesis of alkanesulfonic acids
    BRPI1004019A2|2013-02-26|a process for creating 5-amino-1- | -3-cyano-4-trifluoromethyl sulfinyl pyrazole
    WO2011104724A2|2011-09-01|A process for the manufacture of triflic acid
    同族专利:
    公开号 | 公开日
    RU2019120030A|2020-12-28|
    KR102300703B1|2021-09-09|
    CN110023281A|2019-07-16|
    KR20190072598A|2019-06-25|
    US20190270701A1|2019-09-05|
    AU2017365556A1|2019-05-02|
    TW201829378A|2018-08-16|
    TWI653219B|2019-03-11|
    EP3544954A1|2019-10-02|
    MX2019004519A|2019-10-14|
    WO2018096138A1|2018-05-31|
    US10961182B2|2021-03-30|
    RU2019120030A3|2021-03-24|
    CA3041752A1|2018-05-31|
    JP2019535774A|2019-12-12|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2493038A|1946-05-31|1950-01-03|Houdry Process Corp|Reaction of methane with sulfur trioxide|
    US2619507A|1951-01-05|1952-11-25|Dow Chemical Co|Di peroxide and its preparation|
    US4680095A|1986-11-03|1987-07-14|Pennwalt Corporation|Continuous preparation of dialkanesulfonyl peroxide|
    FR2610320A1|1987-02-03|1988-08-05|Atochem|PEROXIDE COMPOUNDS INCLUDING ISOTOPE 17O|
    US4910335A|1989-08-01|1990-03-20|Pennwalt Corporation|Decolorization of alkanesulfonic and arenesulfonic acids|
    GB9023433D0|1990-10-27|1990-12-12|Interox Chemicals Ltd|Peroxoacid manufacture|
    EA200500779A1|2002-11-05|2006-02-24|Алан К. Ричардс|NON-WATER CONVERSION OF METHANE AND OTHER LIGHT ALKANES TO METHANOL AND OTHER DERIVATIVES|
    CN1318361C|2002-11-05|2007-05-30|艾伦·K·理查兹|Anhydrous conversion of methane and other light alkanes into methanol and other derivatives, using radical pathways and chain reactions with minimal waste products|
    US20080161591A1|2003-06-21|2008-07-03|Richards Alan K|Anhydrous processing of methane into methane-sulfonic acid, methanol, and other compounds|
    OA13183A|2003-06-21|2006-12-13|Alan K Richards|Anhydrous processing of methane into methane-sulfonic acid, methanol, and other compounds.|
    US7119226B2|2004-04-20|2006-10-10|The Penn State Research Foundation|Process for the conversion of methane|
    US20070282151A1|2006-05-19|2007-12-06|Richards Alan K|Manufacture of higher hydrocarbons from methane, via methanesulfonic acid, sulfene, and other pathways|
    WO2015071365A1|2013-11-13|2015-05-21|Grillo Chemie Gmbh|Process for preparing alkanesulfonic acids from sulfur trioxide and an alkane|
    WO2015071351A1|2013-11-13|2015-05-21|Grillo Chemie Gmbh|Process for preparing bis|
    WO2015071371A1|2013-11-13|2015-05-21|Grillo Chemie Gmbh|Process for preparing bis peroxide by oxidation|
    JP6412570B2|2013-11-18|2018-10-24|グリロ‐ヴェルケ アーゲー|A novel initiator for the production of alkanesulfonic acids from alkanes and fuming sulfuric acid|SG11201905997SA|2017-02-07|2019-08-27|Grillo Werke Ag|Method for the production of alkane sulfonic acids|
    US10894766B2|2017-05-30|2021-01-19|Basf Se|Process for the production of alkanesulfonic acids|
    WO2020048965A1|2018-09-04|2020-03-12|Basf Se|Method for the production of alkane sulfonic acids|
    WO2020064573A1|2018-09-25|2020-04-02|Basf Se|Catalysts for the synthesis of alkanesulfonic acids|
    EP3890869A1|2018-12-06|2021-10-13|Grillo-Werke AG|Method for the recycling or disposal of halocarbons|
    WO2020126855A1|2018-12-21|2020-06-25|Basf Se|Mixture comprising methanesulfonic acid and sulfuric acid|
    EP3712123A1|2019-03-21|2020-09-23|Grillo-Werke AG|Process for the preparation of isotope labelled alkane sulfonic acid|
    WO2020187901A1|2019-03-21|2020-09-24|Grillo-Werke Ag|Process for the preparation of haloalkanesulfonic acids from sulfur trioxide and a haloalkane at superacidic conditions|
    CA3134649A1|2019-03-21|2020-09-24|Basf Se|Method for the purification of alkanes|
    WO2020187897A1|2019-03-21|2020-09-24|Basf Se|Method for the production of alkane sulfonic acid at non-superacidic conditions|
    WO2020187893A1|2019-03-21|2020-09-24|Basf Se|Method for the production of alkane sulfonic acid at superacidic conditions|
    WO2020187902A1|2019-03-21|2020-09-24|Grillo-Werke Ag|Method for the production of haloalkane sulfonic acid at non-super acidic conditions|
    EP3956302A1|2019-04-18|2022-02-23|Basf Se|Process for the production of anhydrous methanesulfonic acid from methane and so3|
    WO2021005086A1|2019-07-10|2021-01-14|Grillo-Werke Ag|Method for reducing the concentration of so3 in a reaction mixture comprising a sulfonic acid and so3|
    WO2021023583A1|2019-08-07|2021-02-11|Basf Se|Process for the production of alkanesulfonic acids|
    WO2021063730A1|2019-10-01|2021-04-08|Basf Se|Process for manufacturing alkanesulfonic acids|
    WO2021063768A1|2019-10-02|2021-04-08|Basf Se|Process for manufacturing alkanesulfonic acids|
    法律状态:
    2020-03-10| B25A| Requested transfer of rights approved|Owner name: BASF SE (DE) |
    2021-10-05| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    2022-02-15| B06W| Patent application suspended after preliminary examination (for patents with searches from other patent authorities) chapter 6.23 patent gazette]|
    优先权:
    申请号 | 申请日 | 专利标题
    EP16200928|2016-11-28|
    PCT/EP2017/080495|WO2018096138A1|2016-11-28|2017-11-27|Solvent-free alkane sulfonation|
    [返回顶部]