CN103819346B - A kind of production unit of precursor of 4-ADPA and production technique - Google Patents
A kind of production unit of precursor of 4-ADPA and production technique Download PDFInfo
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- CN103819346B CN103819346B CN201410098622.2A CN201410098622A CN103819346B CN 103819346 B CN103819346 B CN 103819346B CN 201410098622 A CN201410098622 A CN 201410098622A CN 103819346 B CN103819346 B CN 103819346B
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Abstract
The present invention relates to a kind of production technique of precursor of 4-ADPA, by oil of mirbane, aniline respectively by alkalimetal oxide or hydroxide treatment and degassed; Quaternary Ammonium Alkali Catalyst is after reduced under vacuum, aniline after process and the Quaternary Ammonium Alkali Catalyst after concentrating enter tubular type condensation reactor continuously by flow metering according to a certain ratio, aniline reaction is first made to form aniline negatively charged ion, nitro benzo subsequently after tubular type condensation reactor different positions multiple spot adds process continuously controls the water yield, makes negatively charged ion generate 4-nitrosodiphenylamine and 4-nitrodiphenylamine condensated liquid by the H-H reaction on nucleophilic addition substituted-nitrobenzene.Present invention process step composition rationally, under equipment advanced fully-closed state by raw materials used carry out pre-treatment after enter high efficiency reactor pipeline continuous production device manufacture 4-nitrosodiphenylamine and 4-nitrodiphenylamine technique.
Description
Technical field
The present invention relates to a kind of precursor of 4-ADPA, be specially direct and oil of mirbane Reactive Synthesis by aniline, reaction is caused by alkali, it forms aniline negatively charged ion by reaction, and negatively charged ion prepares production technique and the equipment of 4-nitrosodiphenylamine and 4 nitrodiphenyl amine by the hydrogen on nucleophilic addition substituted-nitrobenzene subsequently.
Background technology
4-nitrosodiphenylamine and 4-nitrodiphenylamine be a kind of be widely used in produce there is the precursor of the 4-ADPA of antiozonidate, oxidation inhibitor and stablizer.
In prior art preparation of industrialization 4-nitrosodiphenylamine and 4-nitrodiphenylamine majority be using quaternary ammonium hydroxide as alkali by aniline directly and oil of mirbane react.Patent CN1193010A discloses a kind of under the alkali containing oxyhydroxide and/or oxide groups and heterogeneous catalyst exist and under inertia aprotonic solvent exists, the method for use hydrogen hydrogenation oil of mirbane under the pressure of 0 ~ 200 DEG C and 0.1 ~ 150 bar.Although existing method achieves highly selective and high yield, exist due to resolution problem under quaternary ammonium hydroxide poor heat stability high temperature; In prior art, also useful compound alkali as a catalyst realizes industrialization, but there is solid matter to separate out the blocking causing pipeline and pump at the end of there is reaction, and have certain difficulty when compound alkaline catalysts reclaims and is separated, because having mineral alkali and salt to ensure finite concentration, catalyzer is not easily thoroughly separated causes consumption high, want fully to reclaim and must water consumption strengthen, when catalyst concn will too lowly cause concentrated, energy consumption is very large, when catalyst recirculation after recovery uses, the analysis of each component content is comparatively difficult, and the accuracy of proportioning is poor.
Summary of the invention
The present invention for solve existing using quaternary ammonium hydroxide as alkali by aniline directly and oil of mirbane reacts preparation 4-nitrosodiphenylamine and 4-nitrodiphenylamine catalyzer easily decomposes and reclaims difficulty, the problem of further reduction energy consumption and raw material consumption, there is provided a kind of make use of known advantage and eliminate their shortcoming, processing step composition rationally, under equipment advanced fully-closed state by raw materials used carry out pre-treatment after enter high efficiency reactor pipeline continuous production device manufacture 4-nitrosodiphenylamine and 4-nitrodiphenylamine technique.
The present invention is achieved through the following technical solutions:
The present invention is respectively by alkalimetal oxide or hydroxide treatment and degassed by oil of mirbane, aniline; Quaternary Ammonium Alkali Catalyst is after reduced under vacuum, aniline after process and the Quaternary Ammonium Alkali Catalyst after concentrating enter tubular type condensation reactor continuously by flow metering according to a certain ratio, first make aniline reaction form aniline negatively charged ion, the oil of mirbane subsequently after tubular type condensation reactor different positions multiple spot adds process continuously makes negatively charged ion generate by the H-H reaction on nucleophilic addition substituted-nitrobenzene the complex compound and condensated liquid (precursor for the preparation of 4-ADPA) that 4-nitrosodiphenylamine and 4-nitrodiphenylamine and Quaternary Ammonium Alkali Catalyst formed.
Season, ammonia alkali catalyzer was quaternary ammonium hydroxide Tetramethylammonium hydroxide.
Oil of mirbane before entering condensation reaction, aniline, respectively by alkalimetal oxide or hydroxide treatment and degassed, to dissolve in object removing raw material and the acidic substance of absorption and part are unfavorable for that the reaction of oil of mirbane, aniline condensation generates the gas of object product.
Through alkalimetal oxide or hydroxide treatment and degassed after aniline by control flow by a certain percentage with Quaternary Ammonium Alkali Catalyst by after controlling flow and entering vacuum state concentrating unit continuously by a certain percentage, converge and enter static mixer continuously and fully mix and finally enter tubular type condensation reactor (inner with heat transfer tube) and form aniline negatively charged ion through row dehydration and reaction, oil of mirbane adds at tubular type condensation reactor different positions multiple spot, along with three kinds of raw materials enter the increase of mixture through tubular type condensation reactor distance of reactor continuously, water content can reduce gradually, condensation reaction can progressively be accelerated.
For effectively controlling the amount generating the side reaction such as nitrogen benzide, azophenlyene, remaining nitrobenzene is to the last generated in the mixture and condensated liquid that 4-nitrosodiphenylamine and 4-nitrodiphenylamine and quaternary ammonium hydroxide Tetramethylammonium hydroxide catalyzer formed 1-2% by controlling dehydrating amount, the amount that this mode not only controls side reaction also effectively inhibits the decomposition of quaternary ammonium hydroxide Tetramethylammonium hydroxide catalyzer, and remaining oil of mirbane all generates aniline through being separated Posterior circle use with a small amount of nitrogen benzide by subsequent catalyst hydrogenation.
The tubular type condensation reactor that the present invention adopts, Lower Half composes in parallel by organizing heat-exchanging tube bundle more, ensure the water of enough heat interchanging areas at a lower temperature in vaporization reaction system, top multiple spot is provided with Despumation device, making the aniline that reactor distills out--water azeotrope shifts out reaction system in time in steam state mode, ensures that reaction is moved to expectation object product direction.
There is two-step reaction in condensation reaction, the first step is caused by quaternary ammonium hydroxide Tetramethylammonium hydroxide, first makes aniline reaction form aniline negatively charged ion; Second step oil of mirbane makes negatively charged ion generate 4-nitrosodiphenylamine and 4-nitrodiphenylamine by the H-H reaction on nucleophilic addition substituted-nitrobenzene, because second step reaction has water to generate, and quaternary ammonium hydroxide Tetramethylammonium hydroxide catalyzer enters reaction system with aqueous solution state, want to make second step react smooth, must ensure that oil of mirbane addition point water-content is less than certain value, take, at tubular type condensation reactor different positions multiple spot feed postition, to control nitro by difference heat-exchanging tube bundle
The water-content of benzene addition point, makes oil of mirbane enter reaction system and is fully reacted with shortest time highly selective.
The processing parameter that condensation reaction controls is: quaternary ammonium hydroxide Tetramethylammonium hydroxide catalyzer vacuum state thickening temperature is: 72-78(DEG C), pressure (vacuum tightness)-0.085 ~-0.095(Mpa), content 35%-36%(weight after concentrated); The proportioning of oil of mirbane, quaternary ammonium hydroxide Tetramethylammonium hydroxide and aniline is 1:1-10:20-100(mole), optimum ratio is 1:1-4:20-60(mole), this proportioning take oil of mirbane as the dynamic proportioning of benchmark at tubular type condensation reactor different positions; Oil of mirbane drips water rate control in some reaction system: oil of mirbane and water are than being 1:4-6(mole), water herein refers to the water beyond water of hydration (i.e. crystal water); Reaction pressure (vacuum tightness)-0.096--0.1(Mpa); Temperature of reaction is 40-85(DEG C), the best is 60-78(DEG C); In tubular type condensation reactor, residence time of material is 1-3(hour); Oil of mirbane residual volume 1-2%(quality in condensated liquid).
The present invention removes in raw material the acidic substance that dissolve and adsorb and part is unfavorable for oil of mirbane with oil of mirbane and aniline for raw material carries out pre-treatment, the gas of aniline condensation reaction, multipoint mode adds oil of mirbane, and the oil of mirbane residual volume controlled when oil of mirbane dropping point reaction system water-content and condensation reaction termination, what effectively inhibit side reaction improves yield, decrease going bad and consuming of expensive season ammonia alkali Tetramethylammonium hydroxide catalyzer, remaining oil of mirbane all generates aniline with a small amount of nitrogen benzide by subsequent catalyst hydrogenation and uses through being separated Posterior circle, reaction preference is greater than 99%, run under fully-closed state, continuity is strong, level of automation is high, labour intensity is low, environmental pollution is little, equipment corrosion is little, energy consumption is low is be conducive to ecological and economic better industrial-scale process and device.
A production unit for the precursor of 4-ADPA, comprises vacuum outgas washing tank device, vacuum concentrating apparatus, flow rate control device, static mixer, pressure control device, tubular type condensation reactor;
Wherein, vacuum outgas washing tank device comprises aniline vacuum outgas washing tank, oil of mirbane vacuum outgas washing tank; Quaternary Ammonium Alkali Catalyst enters vacuum concentrating apparatus through flow rate control device, and aniline enters aniline vacuum outgas washing tank through flow rate control device; Quaternary Ammonium Alkali Catalyst after vacuum concentration, aniline after the degassed pre-treatment of vacuum outgas washing tank, after ducts converge, connect static mixer, static mixer is through connecting pipe of pipeline formula condensation reactor;
Oil of mirbane enters oil of mirbane vacuum outgas washing tank through flow rate control device, and oil of mirbane vacuum outgas washing tank is through connecting pipe of pipeline formula reactor; Pressure control device one end connects tubular type condensation reactor, and the other end connects aniline---water storage tank;
Tubular type condensation reactor, Lower Half composes in parallel by organizing heat-exchanging tube bundle more, and top multiple spot is provided with Despumation device; Tubular type condensation reactor is provided with condensated liquid discharge port.
Accompanying drawing explanation
Accompanying drawing is the process flow sheet of the production technology and equipments of a kind of 4-nitrosodiphenylamine and 4-nitrodiphenylamine;
Wherein: 1, vacuum concentrating apparatus, 2, aniline vacuum outgas washing tank, 3 oil of mirbane vacuum outgas washing tanks, 4, static mixer, 5 heat transfer tubes, 6 tubular type condensation reactors, 7 Despumation devices, 8, pressure control device, 9, aniline---water storage tank, 10, condensated liquid discharge port.
Embodiment
Embodiment (industrialized unit embodiment)
First oil of mirbane is opened, aniline, it is 13.2 cubic meters/hour that quaternary ammonium hydroxide Tetramethylammonium hydroxide catalyst transport pump controls aniline flow by Flow-rate adjustment, oil of mirbane flow is 2 cubic meters/hour, continue through the vacuum outgas washing tank process that alkali metal hydroxide (30%NaOH) is housed respectively, object is the acidic substance of dissolving and absorption in removing raw material and is partly unfavorable for oil of mirbane, the gas of aniline condensation reaction, through alkali metal hydroxide process and degassed after oil of mirbane (adding tubular type condensation reactor different positions 4) respectively be 0.6 cubic meter/hour from starting point, 0.6 cubic meter/hour, 0.5 cubic meter/hour, 0.3 cubic meter/hour, through alkali metal hydroxide process and degassed after aniline and quaternary ammonium hydroxide Tetramethylammonium hydroxide catalyzer by entering after controlling flow 6 cubic meters/hour to enter vacuum state concentrating unit continuously through static mixer to tubular type condensation reactor (inside is with heat transfer tube), control reaction pressure (vacuum tightness)-0.096(Mpa), temperature of reaction is 76(DEG C), material is 3(hour through the tubular type condensation reactor time), along with oil of mirbane can reduce with the increase water content of streams through tubular type condensation reactor distance gradually in adding of tubular type condensation reactor difference, condensation reaction can progressively be accelerated, by controlling the water yield until oil of mirbane residual qualities content is 1-2% in condensated liquid, now by-product nitrogen benzide, azophenlyene equivalent are minimum, finally generate mixture and condensated liquid that 4-nitrosodiphenylamine and 4-nitrodiphenylamine and quaternary ammonium hydroxide Tetramethylammonium hydroxide catalyzer formed.Be 99.06% relative to transform portion oil of mirbane selectivity.
The processing parameter that condensation reaction controls is: quaternary ammonium hydroxide Tetramethylammonium hydroxide catalyzer vacuum state thickening temperature is: 72-78(DEG C), pressure (vacuum tightness)-0.085 ~-0.095(Mpa), content 35%-36%(weight after concentrated); The proportioning of oil of mirbane, quaternary ammonium hydroxide Tetramethylammonium hydroxide and aniline is 1:1-10:20-100(mole), optimum ratio is 1:1-4:20-60(mole), this proportioning take oil of mirbane as the dynamic proportioning of benchmark at tubular type condensation reactor different positions; Oil of mirbane drips water rate control in some reaction system: the water beyond oil of mirbane and water of hydration (i.e. crystal water) compares for 1:4-6(mole); Reaction pressure (vacuum tightness)-0.096--0.1(Mpa); Temperature of reaction is 40-85(DEG C), the best is 60-78(DEG C); In tubular type condensation reactor, residence time of material is 1-3(hour); Oil of mirbane residual volume 1-2%(quality in condensated liquid).
Claims (6)
1. a production unit for the precursor of 4-ADPA, is characterized in that: comprise vacuum outgas washing tank device, vacuum concentrating apparatus, flow rate control device, static mixer, pressure control device, tubular type condensation reactor;
Wherein, vacuum outgas washing tank device comprises aniline vacuum outgas washing tank, oil of mirbane vacuum outgas washing tank; Quaternary Ammonium Alkali Catalyst enters vacuum concentrating apparatus through flow rate control device, and aniline enters aniline vacuum outgas washing tank through flow rate control device; Quaternary Ammonium Alkali Catalyst after vacuum concentration, aniline after the degassed pre-treatment of vacuum outgas washing tank, after ducts converge, connect static mixer, static mixer is through connecting pipe of pipeline formula condensation reactor;
Oil of mirbane enters oil of mirbane vacuum outgas washing tank through flow rate control device, and oil of mirbane vacuum outgas washing tank is through connecting pipe of pipeline formula reactor; Pressure control device one end connects tubular type condensation reactor, and the other end connects aniline---water storage tank;
Tubular type condensation reactor, Lower Half composes in parallel by organizing heat-exchanging tube bundle more, and top multiple spot is provided with Despumation device; Tubular type condensation reactor is provided with condensated liquid discharge port.
2. a production technique for the precursor of 4-ADPA, is characterized in that: the production unit using the precursor of 4-ADPA described in claim 1, by oil of mirbane, aniline respectively by alkalimetal oxide or hydroxide treatment and degassed; Quaternary ammonium hydroxide Tetramethylammonium hydroxide catalyzer is after reduced under vacuum, aniline after process and the quaternary ammonium hydroxide Tetramethylammonium hydroxide catalyzer after concentrating enter tubular type condensation reactor continuously by flow metering according to a certain ratio, aniline reaction is first made to form aniline negatively charged ion, nitro benzo subsequently after tubular type condensation reactor different positions multiple spot adds process continuously controls the water yield, makes negatively charged ion generate 4-nitrosodiphenylamine and 4 nitrodiphenyl amine condensated liquid by the H-H reaction on nucleophilic addition substituted-nitrobenzene;
Wherein, the mol ratio of oil of mirbane, quaternary ammonium hydroxide Tetramethylammonium hydroxide catalyzer and aniline is 1:1-10:20-100.
3. production technique according to claim 2, is characterized in that: it is 1:4-6 that oil of mirbane drips water rate control oil of mirbane and water mol ratio in some reaction system.
4. production technique according to claim 2, is characterized in that: reaction pressure is-0.096 ~-0.1Mpa; Temperature of reaction is 40 ~ 85 DEG C; In tubular type condensation reactor, residence time of material is 1-3 hour.
5. production technique according to claim 2, is characterized in that: oil of mirbane residual qualities content 1-2% in condensated liquid.
6. production technique according to claim 2, is characterized in that: quaternary ammonium hydroxide Tetramethylammonium hydroxide catalyzer vacuum state thickening temperature is: 72 ~ 78 DEG C, pressure is-0.085 ~-0.095Mpa, weight content 35% ~ 36% after concentrated.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107686449B (en) * | 2016-08-05 | 2020-02-21 | 中国石油化工股份有限公司 | Reducing tubular reactor device and method for preparing 4-nitrodiphenylamine and 4-nitrosodiphenylamine by using same |
| CN109232275B (en) * | 2018-10-26 | 2021-06-11 | 科迈化工股份有限公司 | Preparation method of 4-nitrodiphenylamine and 4-nitrosodiphenylamine |
| CN114478202A (en) * | 2022-02-16 | 2022-05-13 | 江苏飞宇医药科技股份有限公司 | Method for continuously preparing 2- (2,2, 2-trifluoroethoxy) phenol |
| CN116554038B (en) * | 2022-11-10 | 2024-04-12 | 圣奥化学科技有限公司 | Polyalkyl p-phenylenediamine anti-aging agent, intermediate thereof and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1470500A (en) * | 2003-07-04 | 2004-01-28 | 余瑞标 | Method for synthesizing 4-nitro diphenylamine and 4-nitroso diphenylamine or/and their salts |
| CN1865224A (en) * | 2005-05-20 | 2006-11-22 | 中国石油天然气集团公司 | Method for improving 4-amino diphenylamine yield |
| RU2369595C1 (en) * | 2008-04-07 | 2009-10-10 | Государственное образовательное учреждение высшего профессионального образования Томский политехнический университет | Method of obtaining 4-aminodiphenylamine and intermediate products of its synthesis |
| CN102010339A (en) * | 2009-09-04 | 2011-04-13 | 南化集团研究院 | Synthetic method of 4-aminodiphenylamine |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5117063A (en) * | 1991-06-21 | 1992-05-26 | Monsanto Company | Method of preparing 4-aminodiphenylamine |
| EP1414782A1 (en) * | 2001-07-23 | 2004-05-06 | Flexsys America L.P. | Process for preparing 4-aminodiphenylamines |
| EP2543654B1 (en) * | 2011-01-26 | 2018-09-12 | Sumitomo Rubber Industries, Ltd. | Synthesis system, rubber chemical substance for tires, synthetic rubber for tires, and pneumatic tire |
-
2014
- 2014-03-17 CN CN201410098622.2A patent/CN103819346B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1470500A (en) * | 2003-07-04 | 2004-01-28 | 余瑞标 | Method for synthesizing 4-nitro diphenylamine and 4-nitroso diphenylamine or/and their salts |
| CN1865224A (en) * | 2005-05-20 | 2006-11-22 | 中国石油天然气集团公司 | Method for improving 4-amino diphenylamine yield |
| RU2369595C1 (en) * | 2008-04-07 | 2009-10-10 | Государственное образовательное учреждение высшего профессионального образования Томский политехнический университет | Method of obtaining 4-aminodiphenylamine and intermediate products of its synthesis |
| CN102010339A (en) * | 2009-09-04 | 2011-04-13 | 南化集团研究院 | Synthetic method of 4-aminodiphenylamine |
Non-Patent Citations (5)
| Title |
|---|
| 4-硝基二苯胺合成工艺的研究;危青 等;《精细化工中间体》;20010228;第31卷(第1期);第26-28页 * |
| 4-硝基二苯胺合成工艺研究进展;孙伟 等;《天津化工》;20030930;第17卷(第5期);第8-9页 * |
| 硝基苯法制备4-氨基二苯胺;刘辉 等;《石化技术与应用》;20061130;第24卷(第6期);第464-467页 * |
| 硝基苯法制对氨基二苯胺的研究进展;张超林;《化工进展》;20080205;第27卷(第2期);第180-183页 * |
| 芳香亲核取代氢反应及4-氨基二苯胺的合成;刘腾飞 等;《化学工业与工程》;20031030;第20卷(第5期);第297-302页 * |
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