CN113045370A - Sulfonation method - Google Patents
Sulfonation method Download PDFInfo
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- CN113045370A CN113045370A CN201911373490.9A CN201911373490A CN113045370A CN 113045370 A CN113045370 A CN 113045370A CN 201911373490 A CN201911373490 A CN 201911373490A CN 113045370 A CN113045370 A CN 113045370A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B45/00—Formation or introduction of functional groups containing sulfur
- C07B45/02—Formation or introduction of functional groups containing sulfur of sulfo or sulfonyldioxy groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
Abstract
The present application provides a sulfonation process. The sulfonation process is carried out in a shell and tube reactor, comprising3Is fed from the gas feed unit into the shell and tube reactor, and an organic liquid phase feedstock to be sulphonated is fed from the liquid feed unit into the shell and tube reactorIn the tubular reactor. The method can remove reaction heat in time and is safe for sulfonation production; the gas-liquid cavity-separated feeding of the invention can improve SO3The volume fraction and the flow rate thereof improve the production efficiency; the method can realize the reaction of organic liquid phase and gaseous SO3The materials are fed from the bottom to the top, and the gas phase rises to drive the liquid phase to rise and react at the same time, so that the reaction area is increased, and the over sulfonation caused by over-high temperature is avoided; the method can feed at a temperature slightly higher than the melting point of the organic liquid phase, so that the organic phase structure is maintained to the maximum extent, and the performance of the sulfonated product is improved.
Description
Technical Field
The invention relates to a sulfonation method, in particular to a method for sulfonating by using a tubular reactor.
Background
In recent years, SO of our country3The development of the sulfonation technology and the sulfonation device gradually becomes a hot problem in the scientific field, and the improvement of the technology and the device level not only can save energy and reduce consumption and cost, but also can ensure the improvement of the quality of the sulfonated products. Currently, sulfonation reactors widely used in various regions around the world are multi-tube falling-film sulfonation reactors and falling-film sulfonation reactors with quenching circulation reactors, and in addition, continuous stirring tank group reactors, double-film reactors, impact jet reactors, falling-film reactors and the like. The general multi-tube falling film type sulfonation reactor has a wider application range, can be used for producing various products such as linear alkyl benzene sulfonate (LAS), fatty alcohol polyoxyethylene ether sulfate (AES), alpha-olefin sodium sulfonate (AOS) and the like, and is mainly dedicated to the popularization of fatty acid Methyl Ester Sulfonate (MES) products at present.
CN1566083A discloses a method for preparing naphthalene sulfonic acid, which is characterized in that molten naphthalene is continuously and quantitatively pumped into a membrane type or tubular reactor and simultaneously proportionally fed into a reactor containing SO3Gaseous sulfonating agent, molten naphthalene, flowing down in the form of film along the reactor wall, and SO3Gas is contacted withAnd (3) carrying out instantaneous reaction at the temperature of 80-170 ℃ to obtain a reaction product. SO used3The gas is used as a sulfonating agent, the moisture of reactants is generated, the reaction is full, no waste sulfuric acid is generated, the unreacted naphthalene amount is low, the reaction is continuously carried out in a membrane type or tubular reactor, the by-products are few, the product quality is good, and the production efficiency is high.
CN109232327A discloses a method for preparing p-toluenesulfonic acid by toluene sulfonation, which takes toluene as raw material, adopts a multi-tube membrane type sulfonation reactor, and introduces SO into the reactor3And carrying out sulfonation reaction on the mixed gas of the/nitrogen to prepare the p-toluenesulfonic acid.
The film sulfonation is widely applied in the industrial field of surfactants and has the advantages of high sulfonation reaction rate, high reaction rate, good cooling effect and the like. The disadvantages are that the viscosity of the organic matter is required and moderate, and the difference between the viscosity of the sulfonation product and the viscosity of the raw material is not great. If the viscosity is too low, the flow is fast and the film is easy to break; the retention time is short, and the reaction is insufficient; the viscosity is too high, and the falling film flow rate is slow and the pipe is easy to block; meanwhile, membrane sulfonation is not suitable for sulfonation of more volatile raw materials because of greater loss of raw materials. In addition, the volume of the organic matter distribution cavity needs to be increased in the conventional multi-tube membrane type sulfonation reactor to reduce the influence of the pressure fluctuation of the feeding material on the pressure stability in the cavity and facilitate the uniform distribution of the organic matter, namely the conventional multi-tube membrane type reactor realizes the SO3There is a certain conflict between the inflow rate and the low temperature reaction.
CN103936636A relates to a method for preparing p-toluenesulfonic acid by sulfonating toluene in a microreactor, which is characterized in that the method uses low-concentration liquid SO3Toluene as sulfonating agent in excess of SO3The method adopts a sulfonation process of feeding high-concentration toluene and circulating product mother liquor (filtrate), and simultaneously adopts a microchannel in-situ heat exchange technology to accurately regulate and control the sulfonation reaction temperature. Has the advantages that the liquid SO is used3The sulfonating agent is basically free from waste acid generation in the product, is easy to separate, and has safe and continuous micro-reaction sulfonation technical process and high efficiency. Although the invention can realize continuous high efficiency, the excessive toluene is used as the solvent in the process, which is relatively not environment-friendly.
CN209348635U relates to a kettle reactor for producing surfactant, and the reaction temperature range that is applicable is-20 to 40 ℃, and can control the sulfonation reaction depth of complex raw materials under the low temperature condition and can also sulfonate difficultly reacted materials under the high temperature condition. The patent can realize sulfonation reaction at lower temperature, but cannot realize continuous operation, and the cost is relatively high.
Both the membrane reactor and the kettle reactor adopt a feeding mode from top to bottom, and the feeding mode from bottom to top cannot be realized. Organic substances (e.g. alkylbenzenes) with SO3The sulfonation reaction of (a) is a highly exothermic, very rapid reaction process. This highly exothermic process, which is accomplished instantaneously, necessarily results in a sudden temperature rise of the reactants. Therefore, design of the sulfonator must be considered to take measures to moderate the reaction and to effectively remove the heat of reaction. Generally, the organic feed is in the usual range, SO3The volume fraction is not more than 3%. At the same time due to SO3The volume fraction is low and to achieve complete sulphation the gas velocity must be increased to ensure sufficient SO3The influent reacts with the organic phase. For the raw material with higher viscosity, the method of adding an inert solvent cannot be adopted to reduce the viscosity of the raw material, the raw material can be naturally cast on the inner wall of the reactor to form a film only by increasing the reaction temperature, and the excessive sulfonation of the raw material is easily caused due to the excessively high reaction temperature, so that the raw material loss and the product quality are reduced.
Therefore, how to solve SO simultaneously3Timely heat removal and safe SO increase in sulfonation reaction3Three technical difficulties of volume fraction and achieving sulfonation at lower temperatures are issues to be solved by those skilled in the art.
Disclosure of Invention
The present application provides a sulfonation process, wherein the sulfonation process is carried out in a shell and tube reactor comprising:
the box body of the reactor is provided with a plurality of reaction chambers,
a plurality of tubes arranged in the reactor box at intervals;
a heat exchange medium inlet and a heat exchange medium outlet provided on the reactor tank, and one or more baffles located between the heat exchange medium inlet and the heat exchange medium outlet, forming a shell side between the heat exchange medium inlet and the heat exchange medium outlet,
a reactor outlet disposed at an upper portion of the reactor box, the reactor outlet in fluid communication with the interior of the plurality of tubes;
a gas feed unit and a liquid feed unit disposed at a lower portion of the reactor box, the liquid feed unit being in fluid communication with the interior of the plurality of tubes, the liquid feed unit being located at an upper portion of the gas feed unit;
a gas distributor spacing the liquid feed unit from the gas feed unit, the gas distributor having a plurality of axial through holes disposed therein to place the liquid feed unit in fluid communication with the gas feed unit;
the sulfonation process comprises adding a sulfur-containing compound containing SO3Is fed into the shell and tube reactor from the gas feed unit, and the organic liquid phase feedstock to be sulphonated is fed into the shell and tube reactor from the liquid feed unit.
In one embodiment, the gas feed unit comprises a gas inlet located below the gas distributor, and a gas cavity drain located at the bottom of the reactor; wherein said SO comprises3Is fed into the gas feed unit from the gas inlet.
In one embodiment, the liquid feed unit comprises a liquid feed chamber, a liquid tangential feed inlet located in the reactor wall, and a baffle; wherein the organic matter liquid phase raw material to be sulfonated is fed into the liquid feeding unit through the liquid tangent feeding port.
In one embodiment, the baffle is mounted at the top of the liquid feeding cavity and is 5-50 mm away from the bottom of the liquid feeding cavity.
In one embodiment, the plurality of tubes are arranged on a mounting plate with through holes, through which the liquid feed chamber of the liquid feed unit is in fluid communication with the interior of the plurality of tubes.
In one embodiment, the organic to be sulfonated is with SO3Is used in a molar ratio of 1:0.07-1.30, preferably 1: 0.1-1.10.
In one embodiment, the temperature of the shell and tube reactor is from 20 to 60 ℃.
In one embodiment, the plurality of tubes are in a vertical tube array structure, the inner diameter of each tube array is 10-50 mm, and the length of each tube array is 2-30 m.
In one embodiment, the SO comprises3The feed gas of (a) further comprises a shielding gas, the SO3The volume ratio of the protective gas to the protective gas is 2: 26-48.
In one embodiment, the shielding gas is nitrogen.
The method of the invention can solve the following problems in the prior art: (1) the method can avoid local temperature runaway or incomplete reaction caused by uneven heat distribution due to uneven gas-liquid flow field/temperature distribution, can timely remove reaction heat, and is safe for sulfonation production; (2) the traditional gas-liquid cavity-separated feeding local channeling easily causes the liquid phase in the liquid cavity to form a dead zone and a detention layer, and the gas-liquid cavity-separated feeding can improve SO3The volume fraction and the flow rate thereof improve the production efficiency; (3) the method can realize the reaction of organic liquid phase and gaseous SO3The materials are fed from the bottom to the top, and the gas phase rises to drive the liquid phase to rise and react at the same time, so that the reaction area is increased, and the over sulfonation caused by over-high temperature is avoided; (4) the method can feed at a temperature slightly higher than the melting point of the organic liquid phase, so that the organic phase structure is maintained to the maximum extent, and the performance of the sulfonated product is improved.
Drawings
Fig. 1 shows a schematic structural diagram of a shell-and-tube reactor used in the present application.
Detailed Description
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.
The present application provides a sulfonation process that is carried out in a shell and tube reactor.
As shown in FIG. 1, the shell and tube reactor used in the process of the present application comprises:
the reactor housing (20) is provided with a plurality of,
a plurality of tubes 8 arranged at intervals in the reactor box 20,
a heat exchange medium inlet 10 and a heat exchange medium outlet 7 provided on the reactor tank 20, and one or more baffles 9 located between the heat exchange medium inlet 10 and the heat exchange medium outlet 7, forming a shell side between the heat exchange medium inlet 10 and the heat exchange medium outlet 7,
a reactor outlet 6 disposed at an upper portion of the reactor tank 20, the reactor outlet 6 being in fluid communication with the interior of the plurality of tubes 8;
a gas feed unit and a liquid feed unit disposed at a lower portion of the reactor box, the liquid feed unit being in fluid communication with the interior of the plurality of tubes, the liquid feed unit being located at an upper portion of the gas feed unit;
a gas distributor 3, said gas distributor 3 spacing said liquid feed unit from said gas feed unit, said gas distributor having a plurality of axial through holes therein to place said liquid feed unit in fluid communication with said gas feed unit.
In the shell and tube reactor of the present application, the reactor tank 20 may be in the shape of a cylinder for accommodating the tubes of the shell and serving as a container for the shell-side fluid.
In the shell and tube reactor of the present application, a plurality of shell and tube units 8 are provided at intervals in the reactor casing 20. Preferably, a plurality of tubes 8 in the tube-type reactor are in a vertical tube-type structure. The inner diameter, length, spacing, number and the like of the tubes can be selected as required. In one embodiment, the inner diameter of the tubes is 10-50 mm, the length is 2-50 m, the distance is 12-60 mm, and the number is 100-5000, preferably 200-. Such a tube arrangement is particularly advantageous for the sulfonation reaction of the present application. In one embodiment, the plurality of tubes are arranged on a perforated mounting plate 21, and the liquid feed chamber of the liquid feed unit is in fluid communication with the interior of the plurality of tubes 8 through the perforated mounting plate 21.
In the shell and tube reactor of the present application, a heat exchange medium inlet 10 and a heat exchange medium outlet 7 are provided on the reactor tank 20, and one or more baffles 9 are provided between the heat exchange medium inlet 10 and the heat exchange medium outlet 7, forming a shell side between the heat exchange medium inlet 10 and the heat exchange medium outlet 7. The heat exchange medium can be introduced from the heat exchange medium inlet 10 and can be led out of the reactor from the heat exchange medium outlet 7, so that the heat generated in the reaction process can be led out quickly. In one embodiment, the number of baffles 9 may be 1 to 50, preferably 5 to 30, more preferably 10 to 20. Each baffle plate can be arranged in the reactor box body at equal intervals or unequal intervals and forms an angle of 90 degrees with the axial direction of the reactor box body.
In this application, a gas feed unit and a liquid feed unit are provided in the lower portion of the reactor box, the liquid feed unit being in fluid communication with the interior of the tubes of the plurality of tubes. Also, in order to facilitate the transport of the liquid feed into the tubes, the liquid feed unit is located at the upper portion of the gas feed unit so that the liquid feed is introduced into each tube together by the gas flow rising.
In the present application, a gas distributor 3 is also included, the gas distributor 3 spacing the liquid feed unit from the gas feed unit. A plurality of axial through holes are provided in the gas distributor 3 to place the liquid feed unit in fluid communication with the gas feed unit. In one embodiment, the through holes extend through the gas distributor 3 in the axial direction, so that a gas feed introduced from the lower part of the gas distributor 3 can enter the liquid feed chamber through the through holes and thereby bring the liquid feed together into the reaction tubes. In one embodiment, the through holes in the gas distributor 3 are evenly distributed to ensure that the gas feed is fed evenly into the liquid feed chamber, thereby ensuring an even distribution of gas volume in each tube. The gas distributor 3 has a thickness (i.e. height in axial direction) of 0.02-0.5m, such as 0.05-0.5m, or 0.02-0.1m, such as 20-26 mm. The through holes in the gas distributor 3 are uniformly distributed and may have an inner diameter of 10-1000 μm, or 50-1500 μm.
In the present invention, the gas feed unit comprises a gas inlet 2 located below the gas distributor 3, and a gas cavity drain 1 located at the bottom of the reactor. In the method of the present application, the SO is contained3Is fed into the gas feed unit by the gas inlet 2. In the present invention, the gas feed unit and the gas distributor may together form a gas feed chamber for feeding the gas feed to the shell and tube reactor.
In one embodiment of the invention, the liquid feed unit comprises a liquid feed chamber 30, a liquid tangential feed inlet 5 at the reactor wall, and baffles 11. In the process of the present application, the organic liquid phase feedstock to be sulphonated is fed into the liquid feed unit through this liquid tangential feed inlet 5. In order to ensure the uniform distribution of gas and liquid in each pipe, the liquid feeding adopts a tangent feeding and baffle plate adjusting feeding mode. The design that tangent line feeding mode and baffle constitute inside water conservancy diversion component has guaranteed that the liquid feeding is stable even, eliminates the disturbance that the feeding brought, has realized that liquid evenly distributed is to every in the pipe. In one embodiment, the baffle 11 is mounted at the top of the liquid feed chamber 30 and is 5-50 mm from the bottom of the liquid feed chamber 30. In one embodiment, the liquid feed unit further comprises a liquid chamber drain 4 communicating with the liquid feed chamber. The material in the liquid feeding cavity can be discharged out of the reactor through the liquid cavity liquid outlet 4 during production maintenance or failure. In one embodiment, the liquid chamber drain 4 may be disposed in the reactor housing near the upper end face of the gas distributor 3.
In the present application, the tubes 8 may be free of any material, SO that SO3The organic matter to be sulfonated may be contacted and reacted inside the tubes 8. Thus, SO3With the organic substance to be sulphonatedThe product is sulfonated in the tube array 8 to generate the required sulfonated product, and the heat released by the reaction can be taken away by the heat exchange medium in the shell side.
In one embodiment, the organic to be sulfonated is with SO3Is used in a molar ratio of 1:0.07-1.30, preferably 1: 0.1-1.10.
In the invention, the organic matter to be sulfonated and the SO-containing organic matter can be obtained by the type and flow rate of the heat exchange medium3The temperature of the tubular reactor is controlled by the factors of the feed flow rate of the raw material gas, the feed ratio and the like. In one embodiment, the temperature of the shell and tube reactor is from 20 to 60 ℃. In the present application, the heat exchange medium that can be used may be various heat exchange media known in the art, such as water, brine, and the like.
In the present application, the organic substance to be sulfonated may be any substance requiring sulfonation, for example, alkylbenzenes such as toluene, fatty acid esters such as fatty acid methyl esters, derivatives of polyethers, and the like. In the present application, SO is included3May comprise SO3Gas, which may be SO3A mixture of gas and shielding gas. The shielding gas may be any gas that does not interfere with the sulfonation reaction, such as various inert gases, nitrogen, and the like. In one embodiment, the SO comprises3The feed gas of (a) further comprises a shielding gas, the SO3The volume ratio of the protective gas to the protective gas is 2: 26-48.
Preferably, the specific operation process of the sulfonation method comprises the following steps:
(1) in N2Under protection, heating the organic liquid phase to a temperature above the melting point, and after the organic liquid phase flows sufficiently, feeding the organic liquid phase tangentially through a liquid feed port at the bottom of the tubular reactor;
(2) while the organic liquid phase is fed tangentially through the liquid feed inlet, SO3/N2Feeding the mixed gas through a gas-phase feed inlet at the bottom of the tubular reactor to perform continuous sulfonation reaction;
(3) and discharging the product from a discharge port at the top of the tubular reactor after sulfonation is finished.
Compared with the prior art, the invention has the following beneficial effects:
the method for preparing the sulfonated product by using the tubular reactor can realize gas-liquid cavity-separated feeding, thereby not only avoiding uneven liquid distribution caused by gas-liquid cavity feeding, but also preventing over sulfonation.
The method for preparing the sulfonated product by the tubular reactor adopts the method of feeding the gas and the liquid in separate cavities and adopts the tangential feeding baffle plate to adjust the feeding mode, so that the gas and the liquid are uniformly distributed in each tube, the dead zone and the retention layer in the liquid cavity are eliminated, and the sulfonation yield is improved.
The method for preparing the sulfonated product by using the tube reactor solves the engineering design problems of slow heat transfer and low reaction efficiency of the sulfonation reaction by using the design of the heat exchange tube for heat removal of the reactor.
The method for preparing the sulfonated product by using the tubular reactor can realize sulfonation at a lower temperature of 20-60 ℃, and products with a melting point lower than 60 ℃ can be sulfonated by using the tubular reactor.
The invention adopts a method for preparing sulfonated products by a tubular reactor, an organic liquid phase and SO3The reaction is sufficient, and an aging process is not needed.
The present invention is not limited to the following examples, and variations and modifications are included within the technical scope of the present invention without departing from the spirit of the invention described above and below.
Example 1
The sulfonated product is prepared in a tubular reactor. The tubular reactor is vertically installed, 2200 tubes are uniformly distributed in the reactor, the inner diameter of each tube is 25mm, the length of each tube is 6m, and the distance between the tubes is 40 mm. The number of the baffle plates is 5, and the baffle plates and the shell form an angle of 90 degrees.
In N2Under protection, heating organic liquid phase fatty acid methyl ester (sold in the market) to 40 ℃, and after the organic liquid phase fatty acid methyl ester flows sufficiently, feeding the organic liquid phase fatty acid methyl ester tangentially through a liquid feeding port at the bottom of a tubular reactor; SO (SO)3/N2The mixed gas enters from the gas inlet, is uniformly distributed into the tubular reactor through the gas inlet distributor, and is subjected to sulfonation reaction with organic liquid-phase fatty acid methyl ester at 40 ℃ to produceThe substances are discharged from a discharge port at the top of the tubular reactor, and the active substance content of the obtained fatty acid methyl ester sulfonate is 60 percent. SO (SO)3/N2SO in the mixed gas3And N2In a volume ratio of 2:29, organic liquid phase fatty acid methyl ester and SO3The molar ratio of the amount of (A) to (B) used is 1: 1.04.
Example 2
The sulfonated product is prepared in a tubular reactor. The shell and tube reactor is vertically installed, 1600 shell and tube reactors are evenly distributed in the reactor, the inner diameter of the shell and tube is 20mm, the length of the shell and tube is 10m, and the interval between the shell and tube is 32 mm. The number of baffles is 9, and the baffles form an angle of 90 degrees with the shell.
In N2Under protection, heating an organic liquid-phase isomeric alcohol alkoxylate (isooctanol polyoxypropylene ether, the polyoxypropylene addition number is 5, and the product is sold in the market) to 40 ℃, and after the organic liquid-phase isomeric alcohol alkoxylate flows sufficiently, feeding the alcohol alkoxylate tangentially through a liquid feed inlet at the bottom of a tubular reactor; SO (SO)3/N2The mixed gas enters from a gas inlet, is uniformly distributed into the tubular reactor through a gas inlet distributor, and is subjected to sulfonation reaction with the organic liquid-phase isomeric alcohol alkoxylate at 40 ℃, and the product is discharged from a discharge port at the top of the tubular reactor, so that the sulfonation rate of the prepared isomeric alcohol alkoxylate sulfonate is 95%. SO (SO)3/N2SO in the mixed gas3And N2In a volume ratio of 2:35, organic liquid phase isomeric alcohol alkoxylate and SO3The molar ratio of the used amount of (A) to (B) is 1: 1.02.
Example 3
The sulfonated product is prepared in a tubular reactor. The tubular reactor is vertically installed, 2600 tubes are uniformly distributed in the reactor, the inner diameter of each tube is 30mm, the length of each tube is 9m, and the distance between the tubes is 40 mm. The number of the baffle plates is 8, and the angle between the baffle plates and the shell is 90 degrees.
In N2Under protection, heating an organic liquid phase castor oil methyl ester alkoxylate (the addition amount of ethylene oxide is 4, which is sold in the market) to 20 ℃, and after the organic liquid phase castor oil methyl ester alkoxylate flows sufficiently, feeding the organic liquid phase castor oil methyl ester alkoxylate tangentially through a liquid feed inlet at the bottom of a tubular reactor; SO (SO)3/N2The mixed gas enters from a gas inlet, is uniformly distributed into the tubular reactor through a gas inlet distributor, and is mixed with the organic liquid-phase fatty acid methyl ester at the temperature of 20 DEG CAfter sulfonation reaction, discharging a product from a discharge hole at the top of the tubular reactor, wherein the sulfonation degree of the prepared castor oil methyl ester alkoxylate sulfonate is 0.57.
SO3/N2SO in the mixed gas3And N2In a volume ratio of 2:48, organic liquid phase castor oil methyl ester alkoxylate and SO3The molar ratio of the amount of (A) to (B) used is 1: 1.05.
Example 4
The sulfonated product is prepared in a tubular reactor. The tubular reactor is vertically installed, 2600 tubes are uniformly distributed in the reactor, the inner diameter of each tube is 30mm, the length of each tube is 9m, and the distance between the tubes is 40 mm. The number of the baffle plates is 8, and the angle between the baffle plates and the shell is 90 degrees.
In N2Under protection, heating an organic liquid-phase fatty acid methyl ester ethoxylate (the addition quantity of ethylene oxide is 7, sold in the market) to 30 ℃, and after the organic liquid-phase fatty acid methyl ester ethoxylate fully flows, feeding the organic liquid-phase fatty acid methyl ester ethoxylate tangentially through a liquid feed inlet at the bottom of a tubular reactor; SO (SO)3/N2The mixed gas enters from the gas inlet, is uniformly distributed into the tubular reactor through the gas inlet distributor, and is subjected to sulfonation reaction with the organic liquid-phase fatty acid methyl ester at 30 ℃, and the product is discharged from a discharge port at the top of the tubular reactor, so that the active substance component of the prepared fatty acid methyl ester ethoxylate sulfonate is 70%.
SO3/N2SO in the mixed gas3And N2In a volume ratio of 2:42, organic liquid phase fatty acid methyl ester ethoxylate to SO3The molar ratio of the amount of (A) to (B) used is 1: 1.05.
Example 5
The sulfonated product is prepared in a tubular reactor. The tubular reactor is vertically installed, 1500 tubular reactors are uniformly distributed in the reactor, the inner diameter of each tubular reactor is 20mm, the length of each tubular reactor is 9m, and the distance between the tubular reactors is 20 mm. The number of the baffle plates is 8, and the angle between the baffle plates and the shell is 90 degrees.
In N2Under protection, heating organic liquid-phase toluene (sold in the market) to 50 ℃, and after the organic liquid-phase toluene flows sufficiently, feeding the organic liquid-phase toluene tangentially through a liquid feed port at the bottom of a tubular reactor; SO (SO)3/N2The mixed gas enters from the gas inlet and is uniformly distributed to the gas inlet distributorIn the tubular reactor, after the sulfonation reaction with organic liquid phase toluene at 50 ℃, the product is discharged from a discharge hole at the top of the tubular reactor, and the purity of the prepared p-toluenesulfonic acid is 97.9%.
SO3/N2SO in the mixed gas3And N2In a volume ratio of 2:33, organic liquid phase of toluene and SO3The molar ratio of the amount of (A) to (B) used is 1: 0.08.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (10)
1. A sulfonation process, wherein the sulfonation process is carried out in a shell and tube reactor comprising:
the box body of the reactor is provided with a plurality of reaction chambers,
a plurality of tubes arranged in the reactor box at intervals;
a heat exchange medium inlet and a heat exchange medium outlet provided on the reactor tank, and one or more baffles located between the heat exchange medium inlet and the heat exchange medium outlet, forming a shell side between the heat exchange medium inlet and the heat exchange medium outlet,
a reactor outlet disposed at an upper portion of the reactor box, the reactor outlet in fluid communication with the interior of the plurality of tubes;
a gas feed unit and a liquid feed unit disposed at a lower portion of the reactor box, the liquid feed unit being in fluid communication with the interior of the plurality of tubes, the liquid feed unit being located at an upper portion of the gas feed unit;
a gas distributor spacing the liquid feed unit from the gas feed unit, the gas distributor having a plurality of axial through holes disposed therein to place the liquid feed unit in fluid communication with the gas feed unit;
the sulfonation process comprises adding a sulfur-containing compound containing SO3Is fed into the shell and tube reactor from the gas feed unit, and the organic liquid phase feedstock to be sulphonated is fed into the shell and tube reactor from the liquid feed unit.
2. The sulfonation process of claim 1, wherein the gas feed unit comprises a gas inlet located below the gas distributor, and a gas cavity drain located at the bottom of the reactor; wherein said SO comprises3Is fed into the gas feed unit from the gas inlet.
3. The sulfonation process of claim 1, wherein the liquid feed unit comprises a liquid feed chamber, a liquid tangential feed inlet located at the reactor wall, and a baffle; wherein the organic matter liquid phase raw material to be sulfonated is fed into the liquid feeding unit through the liquid tangent feeding port.
4. The sulfonation process of claim 3, wherein the baffle is mounted at the top of the liquid feed chamber and is 5 to 50mm from the bottom of the liquid feed chamber.
5. The sulfonation process of claim 3, wherein the plurality of tubes are disposed on a perforated mounting tray through which the liquid feed cavity of the liquid feed unit is in fluid communication with the interior of the plurality of tubes.
6. Sulfonation process according to any one of claims 1 to 5, characterized in that the organic substance to be sulfonated is reacted with SO3Is used in a molar ratio of 1:0.07-1.30, preferably 1: 0.1-1.10.
7. Sulfonation process according to any one of claims 1 to 5, wherein the temperature of the shell and tube reactor is from 20 to 60 ℃.
8. The sulfonation method of any one of claims 1 to 5, wherein the plurality of tubes are of a vertical tube array structure, wherein the inner diameter of the tubes is 10 to 50mm, and the length of the tubes is 2 to 30 m.
9. Sulfonation process according to any one of claims 1 to 5, characterized in that the SO-containing phase comprises3The feed gas of (a) further comprises a shielding gas, the SO3The volume ratio of the protective gas to the protective gas is 2: 26-48.
10. Sulfonation process according to claim 9, wherein the protective gas is nitrogen.
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| CN115594616A (en) * | 2022-10-09 | 2023-01-13 | 浙江迪邦化工有限公司（Cn） | Multistage continuous sulfonation method of 1-aminoanthraquinone |
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| CN201406388Y (en) * | 2009-05-11 | 2010-02-17 | 中北大学 | Equipment for preparing aromatic sulfonic acid by utilizing gas-phase sulfonation of aromatic organic matters |
| CN106824019A (en) * | 2017-01-19 | 2017-06-13 | 北京神雾环境能源科技集团股份有限公司 | Shell and tube paste state bed reactor and reaction system |
| CN206519141U (en) * | 2017-01-19 | 2017-09-26 | 神雾科技集团股份有限公司 | Shell and tube paste state bed reactor and reaction system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN201406388Y (en) * | 2009-05-11 | 2010-02-17 | 中北大学 | Equipment for preparing aromatic sulfonic acid by utilizing gas-phase sulfonation of aromatic organic matters |
| CN106824019A (en) * | 2017-01-19 | 2017-06-13 | 北京神雾环境能源科技集团股份有限公司 | Shell and tube paste state bed reactor and reaction system |
| CN206519141U (en) * | 2017-01-19 | 2017-09-26 | 神雾科技集团股份有限公司 | Shell and tube paste state bed reactor and reaction system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115594616A (en) * | 2022-10-09 | 2023-01-13 | 浙江迪邦化工有限公司（Cn） | Multistage continuous sulfonation method of 1-aminoanthraquinone |
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