CN101445418A - Gas phase SO3 film-scrapping sulfonating technology - Google Patents
Gas phase SO3 film-scrapping sulfonating technology Download PDFInfo
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- CN101445418A CN101445418A CNA2008101642429A CN200810164242A CN101445418A CN 101445418 A CN101445418 A CN 101445418A CN A2008101642429 A CNA2008101642429 A CN A2008101642429A CN 200810164242 A CN200810164242 A CN 200810164242A CN 101445418 A CN101445418 A CN 101445418A
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Abstract
The invention relates to a gas phase SO3 film-scraping sulfonating technology which belongs to the technical field of production technology which prepares anionic surfactant by using gas phase SO3 film-scraping sulfonating liquid organic materials. The invention is carried out according to the following steps: A: liquid SO3 is vaporized to gas phase SO3, the gas phase SO3 is sucked in a mixer shaft through a turbo-blower, the gas phase SO3 is mixed with inert gases recycled in a sulfonating reactor to reaction gas with the volume concentration being 0.1 to 10 percent, and then the reaction gas goes into a reaction cylinder body through reaction gas distribution holes on the upper part of the scraping plate shaft; B: the organic materials go into the sulfonating reactor and downwards flow along the inner wall of the reaction cylinder body, a scraping plate is rotated along with the mixer shaft under the action of a transmission system, the organic materials are continuously suffered with film scaping-spread coating-film scaping in the inner wall of the reaction cylinder body, the organic material are alternately updated and uniformly coated on the inner wall of the reaction cylinder body, and the organic materials are completely contacted and reacted with the reaction gas which goes from the reaction gas distribution holes to form reaction products. The design of the technology is reasonable, and the invention can be suitable for sulfonating or sulphating materials with various viscosities.
Description
Technical field
The present invention relates to a kind of gas phase SO
3Film-scrapping sulfonating technology belongs to gas phase SO
3Film-scrapping sulfonating liquid state organics material prepares the technical field of producing of anion surfactant.
Background technology
At present in the tensio-active agent industry, anion surfactant be develop the earliest, output maximum, a most widely used series products.With gas phase SO
3For sulphonating agent carries out sulfonation/Sulfated technology to organic materials, be the present suitability for industrialized production anion surfactant Technology of widespread use the most.With gas phase SO
3For the sulfonation/sulfation technology of sulphonating agent comprises: SO
3/ air generation systems, sulfonation reaction system, tail gas absorption system.SO
3Comprise air dry-set and SO in/the air generation systems
3Generating unit, SO
3The preparation of more employing combustion sulphur method takes place.According to the difference of sulphonator in the sulfonation reaction system, can be divided into falling film type process for sulfonation, jet-type process for sulfonation and continuously stirring pot group type process for sulfonation.Italy Ballestra has many relevant patents of invention with companies such as Mazzoni, U.S. Chemithom, Japanese Lion.
Sulphonator in the falling film type process for sulfonation is divided into multitube falling film type or two film falling film type, and pattern and tube and shell heat exchanger are similar, and (or other modes) form film, SO from top to bottom in reaction tube to the liquid state organics material through the slit
3Gas also passes through in reaction tubes from top to bottom, and reaction is finished in the two contact, and reaction heat is removed by the water coolant of chuck.During the membrane-type sulfonation reaction process has and alkali consumption few, inorganic salt content is low, the advantage of good product quality, but sulphonator complex structure, apparatus processing, manufacturing and setting accuracy are had relatively high expectations; The SO of air dry-set and combustion sulphur method
3The generating unit investment is high, energy consumption is bigger, and the processing requirement strictness is not suitable for frequent start-stop car, and turndown ratio is little; Be not suitable for high viscosity, be difficult for the sulfonation of organic materialss such as film forming or thermo-sensitivity; And because SO
3Gas flow rate is very fast, has more organic materials to be atomized and brings exhaust system into, needs to handle by electrostatic precipitator, produces more static spent acid, has increased material loss.
The injection-type reactor patent relevant with the jet-type process for sulfonation mainly contains: United States Patent (USP) U.S4113438 is with organic materials and SO
3Gas is sent into Venturi tube simultaneously and is carried out Forced Mixing, takes away reaction heat through the material refrigeration cycle, improves the transformation efficiency of reaction; CN 96107060 is with the liquid gas class injection circulation reactor of high speed liquid phase as working medium.The circulation that above-mentioned patent is by sulfonated products realizes cooling and improves conversion rate of products that for the high product of reaction back viscosity, side reaction easily takes place cyclic spray difficulty height, influences quality product.CN 1973989 is to be the gas blowing type process for sulfonation of working medium with the high speed gas phase, promptly reach required transformation efficiency without the circulation primary injection, but be that sulfonation is once sprayed in employing, conversion rate of products can not get guaranteeing, the transient liquid temperature of atomizing reaction is very high, the oversulfonate reaction easily takes place, and the color and luster of product is dark, is not suitable for the sulfonation of heat-sensitive material.
Summary of the invention
It is reasonable to the purpose of this invention is to provide a kind of technological design, can be suitable for sulfonation of various viscosity material or Sulfated gas phase SO
3Film-scrapping sulfonating technology.
The present invention is a kind of gas phase SO
3Film-scrapping sulfonating technology is characterized in that carrying out according to the following steps:
A, liquid SO
3After the under meter metering, enter vaporizer and be vaporized into gas phase SO
3The back enters from the sulfonation reactor bottom by the vapour pressure that vaporization produces, suck in the stir shaft via fan impeller, being mixed into volumetric concentration with the rare gas element that recycles in the sulfonation reactor is 0.1～10% reactant gases, enters reacting cylinder body through the reactant gases distribution hole on scraper shaft top again;
B, organic materials enter behind the sulfonation reactor dirty along the reacting cylinder body inwall, scraper plate rotates under the effect of transmission system with stir shaft, make organic materials at the reacting cylinder body inwall constantly by knifing-coating-knifing, alternately upgrade, be uniformly coated on the reacting cylinder body inwall, the abundant contact reacts of reactant gases of coming out with reactant gases distribution hole forms reaction product;
C, reaction product be through bottom discharge, need not gas-liquid separation directly by existing technology wear out, hydrolysis, neutralization obtain finished product.
Described gas phase SO
3The temperature in that enters sulfonation reactor can be 35～80 ℃.
Described organic materials and liquid SO
3Mol ratio can be 1:0.5～1.5, described organic materials and reactant gases are-10～100 ℃ in the intravital temperature of reaction of reaction tube.Be preferably 10～90 ℃.
The flow velocity of described reactant gases in stir shaft can be 1～20m/s.
The tail gas that described step B reaction back produces can be handled by device for absorbing tail gas 19.
Described rare gas element can be nitrogen or air or carbonic acid gas etc.
Described sulfonation reactor can be by reacting cylinder body, place the stir shaft in interior belt scraping plate of reacting cylinder body and reactant gases distribution hole, place the blower fan axle of band fan blade in the stir shaft, place reacting cylinder body top to have the organic materials distributing disc of machine material inlet, place the gas phase SO of reacting cylinder body bottom
3Import and reacting product outlet, the scraper plate transmission system that places reacting cylinder body top to be connected, the formations such as blower fan transmission system that place the reacting cylinder body bottom to be connected with the blower fan axle with stir shaft.
The periphery of described reacting cylinder body also can be provided with the cooling jacket of 1～3 section band cooling water intakeoutfall, and reaction heat is removed fast by the chuck water coolant.
Described organic materials can be any of following compound: C
8～C
20Fatty Alcohol(C12-C14 and C12-C18), C
8～C
20Fatty alcohol-polyoxyethylene ether, C
8～C
20Fatty acid methyl ester, alkene, C
8～C
18Linear alkylbenzene, sulfonated petro-leum, alkyl diphenyl ether, natural fats and oils, soybean phospholipid, naphthalene.
The present invention compared with prior art has following outstanding advantage and positively effect:
1, by outer power knifing, can force organic materials to keep good filming, make the organic materials on the liquid-vapo(u)r interface obtain bringing in constant renewal in by knifing, effectively avoid the side reactions such as oversulfonate, coking of product.
2, the sulphonating agent gas phase SO of process using
3By liquid SO
3Vaporization obtains (liquid SO being arranged
3The factory of supply all can implement), diluent gas adopts rare gas elementes such as nitrogen, air, carbonic acid gas (even rare gas element adopts combustion sulphur method, the dry air amount also can reduce).Rare gas element recycles in sulphonator, does not need complicated dry air system and exhaust treatment system, therefore invest little, energy consumption is low, the start-stop car convenient, tailing almost without a head (can prolong sulfonation time and circulation sulfonation), turndown ratio is big.
3, the reactant gases speed control in the technology is at lower flow velocity, overcome the defective that organic materials easily atomizes under the flow velocity about prior art 30m/s, make material loss low, need not Separate System of Water-jet, the organic materials of carrying secretly in a small amount of reactant gases that displaces is few, does not produce the static nigrotic acid in traditional membrane-type sulfonation; Simultaneously reaction temperature and, effectively, transform fully SO
3In reactor, recycle, the utilization ratio height, SO in the tail gas that displacement produces
3Content is low, handles by absorbing, and does not produce the soda-wash tower waste water in traditional membrane-type sulfonation; Therefore need not complicated exhaust treatment system, belong to the technology of cleaning, energy-saving and environmental protection type.
4, the processing condition setting range is wide, and reaction temperature and controlled is avoided traditional membrane type sulfonation reaction fierceness, temperature of reaction peak value height.The processing of sulphonator, use and clean all simple and convenient.
The present invention makes gas phase SO
3Film-scrapping sulfonating technology more becomes rationally, and turndown ratio is big, and the reaction of process using scraped film type sulfonation reactor by the mode of outer power knifing, makes organic materials coat sulfonation reactor surface and gaseous state SO uniformly
3Reaction; The gaseous state SO of process using
3By liquid SO
3Vaporization obtains, thereby has save the combustion sulphur conversion system of complexity in the traditional technology; Unreacted SO
3/ diluent gas (nitrogen or air) mixed gas uses at the sulfonation reactor internal recycle, only need the clean substitution gas of small amount of supplemental to get final product, so the vent gas treatment amount is few, has saved the exhaust treatment system in the traditional technology, cleaning, energy-saving and environmental protection.Be applicable to the sulfonation of all kinds of liquid state organics material, comprise: Fatty Alcohol(C12-C14 and C12-C18), fatty alcohol-polyoxyethylene ether, alkene, fatty acid methyl ester, alkylbenzene etc., be specially adapted to the sulfonation of high-viscosity material, as: sulfonated petro-leum, alkyl diphenyl ether disulfonate, naphthene sulfonic acid etc. also are specially adapted to easy coking, the difficult SO of absorption
3The sulfonation of organic materials, as natural fats and oils, soybean phospholipid and heat-sensitive material etc.
Description of drawings
Accompanying drawing is the one-piece construction synoptic diagram of sulfonation reactor of the present invention.
Among the figure, 1 is the scraper plate transmission system, and 2 is thermometer, 3 is tensimeter, and 4 is flange, and 5 is the reactant gases thief hole, 6 is the organic materials import, and 7 is the organic materials distributing disc, and 8 is reacting cylinder body, 9 is reactant gases distribution hole, and 10 is scraper plate, and 11 is cooling water intakeoutfall, 12 is cooling jacket, and 13 is stir shaft, and 14 is the blower fan axle, 15 is fan blade, and 16 is reacting product outlet, and 17 is gas phase SO
3Import, 18 is the blower fan transmission system, 19 is device for absorbing tail gas.
Embodiment
Sulfonation reactor of the present invention is mainly by reacting cylinder body 8, place the stir shaft 13 in reacting cylinder body 8 interior belt scraping plates 10 and reactant gases distribution hole 9, place the blower fan axle 14 of band fan blade 15 in the stir shaft 13, place reacting cylinder body 8 tops to have the organic materials distributing disc 7 of machine material inlet 6, thermometer 2, tensimeter 3, flange 4, reactant gases thief hole 5, place the gas phase SO of reacting cylinder body 8 bottoms
3Import 17 and reacting product outlet 16, the scraper plate transmission system 1 that places reacting cylinder body 8 tops to be connected with stir shaft 13, the blower fan transmission system 18 that places reacting cylinder body 8 bottoms to be connected with blower fan axle 14 places 1～3 section cooling jacket, 12 formations such as grade of reacting cylinder body 8 outer shroud cooling water intakeoutfall 11.
Technical process of the present invention is: liquid SO
3Be metered into vaporizer by under meter, after vaporization, by the water cooler cooling, enter sulfonation reactor, carry out sulfonation reaction with organic materials, the a small amount of tail gas of metathetical is handled by device for absorbing tail gas 19, material after the sulfonation is discharged from the sulfonation reactor bottom, and it is aging to enter digestor by prior art, then by the hydrolyzer hydrolysis, in neutralized system, neutralize, obtain surfactant product.
Working process by the visible sulfonation reactor of the present invention of accompanying drawing is: organic materials enters from organic materials import 6, by organic material distributing disc 7, flow downward along the even film forming of reacting cylinder body 8 inwalls, scraper plate 10 rotates under the transmission system effect with stir shaft 13, make organic materials at the reacting cylinder body inwall by the coating-knifing of knifing-again, liquid film constantly alternately upgrades, with SO
3Mixed gas fully contacts, and is able to evenly, effectively reacts; Gas phase SO
3From following gas phase SO
3Import 17 enters in the stir shaft 13, under the drive of fan impeller, mixes in stir shaft 13 with diluent gas in the reacting cylinder body 8, and mixed reactant gases is from bottom to top through the SO on scraper shaft 13 tops
3 Gas distribution hole 9 enters reactor from inside to outside, and from top to bottom, with the following current contact reacts of organic materials, the sulfonated products of finishing reaction enters next workshop section through reacting product outlet 16 to reactant gases in reacting cylinder body 8.By SO in the monitoring reactor
3Gas concentration, after reaction process or reaction end, a small amount of gas that displaces is handled by device for absorbing tail gas 19.Scraper plate makes organic materials good in reacting cylinder body inwall film forming, SO
3Gas fully contacts with organic liquid film, helps the carrying out of sulfonation or sulfating reaction, the generation of side reactions such as the oversulfonate that effectively prevents, and the reaction heat that reaction produces is in time removed by the water coolant in the cooling jacket 12.
The sulfonation of embodiment 1, dodecylbenzene: liquid SO
3By being metered into vaporizer, after the vaporization, cool off through supercooler, 52～55 ℃ of temperature, enter from the sulfonation reactor bottom, in stir shaft with sulfonation reactor in diluent gas be mixed into reactant gases (pilot-gas volumetric concentration: 6%), reactant gases enters reacting cylinder body through the reactant gases distribution hole on stir shaft top from bottom to top with the speed of 15m/s, the dodecylbenzene (average molar mass 246) downward with following current carries out abundant contact reacts, the control sulfonation temperature: 52～55 ℃, liquid SO
3/ dodecylbenzene mol ratio: 1.03:1; Sulfonated products through aging, hydrolysis, obtains sodium alkyl benzene sulfonate with the aqueous sodium hydroxide solution neutralization after reacting product outlet is discharged.
The sulfonation of embodiment 2, fatty alcohol-ether: liquid SO
3By being metered into vaporizer, after the vaporization, cool off through supercooler, 42～45 ℃ of temperature, enter from the sulfonation reactor bottom, in stir shaft with sulfonation reactor in diluent gas be mixed into reactant gases (pilot-gas volumetric concentration: 3%), reactant gases enters reacting cylinder body through the reactant gases distribution hole on stir shaft top from bottom to top with the speed of 20m/s, carry out abundant contact reacts with the fatty alcohol-polyoxyethylene ether (3) (average molar mass 340) that following current is downward, the control sulfonation temperature: 33～35 ℃, liquid SO
3/ fatty alcohol-polyoxyethylene ether (3) mol ratio: 1.01:1; Sulfonated products with the trolamine neutralization, obtains fatty alcohol-ether sulfuric acid triethanolamine salt after being discharged by reacting product outlet.
Embodiment 3, toluene sulfonation: liquid SO
3By being metered into vaporizer, after vaporization, cool off through supercooler, 35～38 ℃ of temperature enter from sulfonation reactor bottom, in stir shaft with sulfonation reactor in diluent gas hybrid reaction gas (pilot-gas volumetric concentration: 5.0%), reactant gases enters reacting cylinder body through the reactant gases distribution hole on stir shaft top from bottom to top with the speed of 10m/s, the toluene downward with following current carries out contact reacts, the control sulfonation temperature: 13～15 ℃, and liquid SO
3/ toluene mole ratio: 1:1; Sulfonated products through aging, obtains the toluenesulphonic acids product after reacting product outlet is discharged.
Embodiment 4, the sulfonation of oil bavin wax prepare sulfonated petro-leum: liquid SO
3By being metered into vaporizer, after the vaporization, cool off through supercooler, 60～62 ℃ of temperature, enter from the sulfonation reactor bottom, in stir shaft with sulfonation reactor in diluent gas be mixed into reactant gases (pilot-gas volumetric concentration: 3.5%), reactant gases enters reacting cylinder body through the reactant gases distribution hole on stir shaft axle top from bottom to top with the speed of 6m/s, the oil bavin wax downward with following current carries out abundant contact reacts, sulfonation temperature: 65～68 ℃, control sulfonated products neutralization value: 80～100KOHmg/kg; Sulfonated products obtains the mahogany acid ammonium with the neutralization of 25% concentration ammoniacal liquor after reacting product outlet is discharged.
Claims (10)
1, a kind of gas phase SO
3Film-scrapping sulfonating technology is characterized in that carrying out according to the following steps:
A, liquid SO
3After the under meter metering, enter vaporizer and be vaporized into gas phase SO
3The back enters from the sulfonation reactor bottom by the vapour pressure that vaporization produces, suck in the stir shaft via fan impeller, being mixed into volumetric concentration with the rare gas element that recycles in the sulfonation reactor is 0.1～10% reactant gases, enters reacting cylinder body through the reactant gases distribution hole on scraper shaft top again;
B, organic materials enter behind the sulfonation reactor dirty along the reacting cylinder body inwall, scraper plate rotates under the effect of transmission system with stir shaft, make organic materials at the reacting cylinder body inwall constantly by knifing-coating-knifing, alternately upgrade, be uniformly coated on the reacting cylinder body inwall, the abundant contact reacts of reactant gases of coming out with reactant gases distribution hole forms reaction product;
C, reaction product be through bottom discharge, need not gas-liquid separation directly by existing technology wear out, hydrolysis, neutralization obtain finished product.
2, by the described a kind of gas phase SO of claim 1
3Film-scrapping sulfonating technology is characterized in that described gas phase SO
3The temperature in that enters sulfonation reactor is 35～80 ℃.
3, by the described a kind of gas phase SO of claim 1
3Film-scrapping sulfonating technology is characterized in that described organic materials and liquid SO
3Mol ratio be 1:0.5～1.5, described organic materials and reactant gases are-10～100 ℃ in the intravital temperature of reaction of reaction tube.
4, by the described a kind of gas phase SO of claim 1
3Film-scrapping sulfonating technology is characterized in that described organic materials and reactant gases are 10～90 ℃ in the intravital temperature of reaction of reaction tube.
5, by the described a kind of gas phase SO of claim 1
3Film-scrapping sulfonating technology is characterized in that the flow velocity of described reactant gases in stir shaft is 1～20m/s.
6, by the described a kind of gas phase SO of claim 1
3Film-scrapping sulfonating technology is characterized in that the tail gas that described step B reaction back produces passes through device for absorbing tail gas (19) processing.
7, by the described a kind of gas phase SO of claim 1
3Film-scrapping sulfonating technology is characterized in that described rare gas element is nitrogen or air or carbonic acid gas etc.
8, by the described a kind of gas phase SO of claim 1
3Film-scrapping sulfonating technology, it is characterized in that described sulfonation reactor is by reacting cylinder body (8), place the stir shaft (13) in interior belt scraping plate of reacting cylinder body (8) (10) and reactant gases distribution hole (9), place the blower fan axle (14) of band fan blade (15) in the stir shaft (13), place reacting cylinder body (8) top to have the organic materials distributing disc (7) of machine material inlet (6), place the gas phase SO of reacting cylinder body (8) bottom
3Import (17) and reacting product outlet (16), the scraper plate transmission system (1) that places reacting cylinder body (8) top to be connected with stir shaft (13), the blower fan transmission system (18) that places reacting cylinder body (8) bottom to be connected with blower fan axle (14) constitutes.
9, by the described a kind of gas phase SO of claim 8
3Film-scrapping sulfonating technology is characterized in that the periphery of described reacting cylinder body (8) also is provided with the cooling jacket (12) of 1～3 section band cooling water intakeoutfall (11).
10, by claim 1 or 3 described a kind of gas phase SO
3Film-scrapping sulfonating technology is characterized in that described organic materials is any of following compound: C
8～C
20Fatty Alcohol(C12-C14 and C12-C18), C
8～C
20Fatty alcohol-polyoxyethylene ether, C
8～C
20Fatty acid methyl ester, alkene, C
8～C
18Linear alkylbenzene, sulfonated petro-leum, alkyl diphenyl ether, natural fats and oils, soybean phospholipid, naphthalene.
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|---|---|---|---|
| CN 200810164242 CN101445418B (en) | 2008-12-28 | 2008-12-28 | Gas phase SO3 film-scrapping sulfonating technology |
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|---|---|---|---|
| CN 200810164242 CN101445418B (en) | 2008-12-28 | 2008-12-28 | Gas phase SO3 film-scrapping sulfonating technology |
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| CN101445418A true CN101445418A (en) | 2009-06-03 |
| CN101445418B CN101445418B (en) | 2011-07-06 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103566839A (en) * | 2012-07-26 | 2014-02-12 | 中国石油天然气股份有限公司 | Adjustable downward-spray film sulfonation reactor and application thereof |
| CN105251414A (en) * | 2015-10-30 | 2016-01-20 | 嘉兴赞宇科技有限公司 | Method and device for producing anionic surfactant through sulfonation of liquid SO3 |
| CN105439910A (en) * | 2015-11-24 | 2016-03-30 | 浙江赞宇科技股份有限公司 | Production method for improving color of alkyl benzene sulfonic acid |
| CN107827788A (en) * | 2017-11-21 | 2018-03-23 | 赞宇科技集团股份有限公司 | A kind of production technology of high-quality alkyl benzene sulphonate |
| CN107903195A (en) * | 2017-11-21 | 2018-04-13 | 赞宇科技集团股份有限公司 | A kind of production technology of high-quality alhpa olefin sulfonate |
| CN108380156A (en) * | 2018-02-12 | 2018-08-10 | 北京国能中林科技开发有限公司 | A kind of scraper-type falling film reactor of hydrogenation reaction suitable for liquid hydrogen storage carrier |
| CN109926008A (en) * | 2019-04-08 | 2019-06-25 | 江苏丰益化工科技有限公司 | A kind of surfactant production neutralization drying device |
| CN110606795A (en) * | 2018-06-15 | 2019-12-24 | 孔繁昇 | Method for preparing organic sulfonic acid by using combustion flue gas of sulfur-containing fuel |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1086602C (en) * | 1998-11-11 | 2002-06-26 | 浙江省轻工业研究所 | Process for preparing surfactant from soybean phosphatide by SO3 membrane-type sulfonation device |
| CN100475977C (en) * | 2005-07-08 | 2009-04-08 | 浙江赞宇科技股份有限公司 | Method of preparing new type sulfonation leather fattening agent by gaseous phase method |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103566839A (en) * | 2012-07-26 | 2014-02-12 | 中国石油天然气股份有限公司 | Adjustable downward-spray film sulfonation reactor and application thereof |
| CN103566839B (en) * | 2012-07-26 | 2015-10-28 | 中国石油天然气股份有限公司 | Adjustable lower spraying film sulphonation reactor and application thereof |
| CN105251414A (en) * | 2015-10-30 | 2016-01-20 | 嘉兴赞宇科技有限公司 | Method and device for producing anionic surfactant through sulfonation of liquid SO3 |
| CN105251414B (en) * | 2015-10-30 | 2017-11-28 | 嘉兴赞宇科技有限公司 | Using liquid SO3The method and device of sulfonation production anion surfactant |
| CN105439910A (en) * | 2015-11-24 | 2016-03-30 | 浙江赞宇科技股份有限公司 | Production method for improving color of alkyl benzene sulfonic acid |
| CN107827788A (en) * | 2017-11-21 | 2018-03-23 | 赞宇科技集团股份有限公司 | A kind of production technology of high-quality alkyl benzene sulphonate |
| CN107903195A (en) * | 2017-11-21 | 2018-04-13 | 赞宇科技集团股份有限公司 | A kind of production technology of high-quality alhpa olefin sulfonate |
| CN108380156A (en) * | 2018-02-12 | 2018-08-10 | 北京国能中林科技开发有限公司 | A kind of scraper-type falling film reactor of hydrogenation reaction suitable for liquid hydrogen storage carrier |
| CN110606795A (en) * | 2018-06-15 | 2019-12-24 | 孔繁昇 | Method for preparing organic sulfonic acid by using combustion flue gas of sulfur-containing fuel |
| CN109926008A (en) * | 2019-04-08 | 2019-06-25 | 江苏丰益化工科技有限公司 | A kind of surfactant production neutralization drying device |
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| CN101445418B (en) | 2011-07-06 |
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