Summary of the invention
The object of this invention is to provide a kind of continuous processing and prepare the method for Methanesulfonyl chloride, solved in existing production method that the raw material reaction that complete mixing flow separately or piston flow bring is insufficient, the problems such as in the remaining height of oxidable thing and by-product hydrogen chloride sulfur number loss is serious in product SULPHURYL CHLORIDE; Also solved the heat of reaction of bringing due to reactor exterior cooling and be difficult for removing, temperature of reaction is high, the problem that side reaction is many.
Design of the present invention is such.React advantage separately in conjunction with complete hybrid flowing with plug flow, piston flow and complete mixing flow are combined, realized the axially gradient of " level of response " or " reactant concn ", realized again the abundant mixing of material, reaction can be carried out fully; Introduce refrigerating unit in reaction zone simultaneously, can timely heat of reaction be removed, guaranteed the temperature of reaction that reaction zone is lower, avoided the generation of side reaction and the loss of productive rate.With the by-product hydrogen chloride gas that fully cooling low temperature crude product SULPHURYL CHLORIDE sprays in absorption tower or discharge in falling film absorption washing reaction district, by traces of unreacted mercaptan, the chlorine carried secretly in hydrogen chloride gas, product SULPHURYL CHLORIDE traps, be dissolved in crude product SULPHURYL CHLORIDE, pass back in sedimentation quantizer, in sedimentation quantizer, further " send out chlorine ", fully oxidable thing is reacted away, avoid the loss of sulfur number in the residual and hydrogen chloride gas of oxidable thing in crude product SULPHURYL CHLORIDE, realized the high yield of whole system, high definition clean is produced.
Concrete, a kind of continuous processing of the present invention is prepared the method for Methanesulfonyl chloride, take thiomethyl alcohol as raw material, thiomethyl alcohol and at least stoichiometric chlorine successive reaction in the reactor that contains aqueous hydrochloric acid, the hydrogen chloride gas that reaction produces makes material turbulization, make reactant flowing by rising the mode with piston flow and complete mixing flow combination in the mixing reactor that membrane reactor and perfectly mixed reactor form, fully contact and reaction, reaction mass is through sedimentation layering, spray washing in absorption tower, absorb, separate, take out respectively product Methanesulfonyl chloride and byproduct hydrogen chloride gas.
Method of the present invention, temperature of reaction is in the scope of-30 ~+100 ℃, and more preferably temperature range is at-10~+ 50 ℃, and preferred temperature range is-10 ~+25 ℃.In absorption tower, the temperature of crude product SULPHURYL CHLORIDE circulation fluid is in the scope of-30~+ 100 ℃, even more preferably in the scope of-20~+ 50 ℃, more preferably in the scope of-10~+ 10 ℃.
Method of the present invention, the feeding rate of raw material thiomethyl alcohol, the amount of substance that rises membrane reactor partial material channel cross-sectional area and thiomethyl alcohol with tubulation in described reaction zone calculates, and is 1~150 kmol/ (hr × m
2), more preferably 10~100kmol/ (hr × m
2).The charge proportion of chlorine is RSH or RSSR
11.0~3.0 chemical equivalents, preferred value is 1.0~1.2 equivalents.The charging of water or hydrochloric acid soln keeps settlement separate district to have suitable liquid level.
The beneficial effect that the present invention obtains is as follows:
The present invention is keeping under the prerequisite of larger volumetric efficiency, adopts the mode of complete mixing flow and piston flow combination to make raw material be able to abundant reaction; Low-temp reaction effectively reduces the possibility of side reaction, has improved reaction preference; By low temperature crude product SULPHURYL CHLORIDE, the circulation of by-product hydrogen chloride is absorbed the sulfur number loss effectively reducing in tail gas hydrogenchloride, also reduced oxidable substrate concentration in crude product SULPHURYL CHLORIDE, improved feed stock conversion and reaction yield; Reduce overflowing of " stench " gas mercaptan, reduced pollution and production cost to environment.
Embodiment
Following examples are used for illustrating the present invention.
embodiment 1 thiomethyl alcohol is prepared Methanesulfonyl chloride
Thiomethyl alcohol enters reaction zone with the flow of 60kg/hr, and chlorine enters with the flow of 280kg/hr, and chlorine is 1.05 equivalents, and water, with 1.03 equivalent chargings, is controlled 5~10 ℃ of temperature of reaction.After system operates steadily, the rate of yield 140kg/hr of crude product SULPHURYL CHLORIDE, absorption tower circulation crude product SULPHURYL CHLORIDE temperature is 0 ℃.
By analysis, in extraction crude product SULPHURYL CHLORIDE, oxidable thing content is 10ppm, and the about 200ppm of chloromethyl SULPHURYL CHLORIDE content approximately has 2% sulfur number to be transformed into methylsulphonic acid and has been lost in aqueous hydrochloric acid; Tower top hydrogenchloride, after alkali liquor absorption, is analyzed and is only had 0.07% sulfur number (with the form of Methanesulfonyl chloride) to be lost in hydrogen chloride tail gas, and thiomethyl alcohol does not detect.
embodiment 2 thiomethyl alcohols are prepared Methanesulfonyl chloride
Thiomethyl alcohol enters reaction zone with the flow of 60kg/hr, and chlorine enters with the flow of 280kg/hr, and chlorine is 1.05 equivalents, and water, with 1.03 equivalent chargings, is controlled 35~40 ℃ of temperature of reaction.After system operates steadily, the rate of yield 140kg/hr of crude product SULPHURYL CHLORIDE, absorption tower circulation crude product SULPHURYL CHLORIDE temperature is 30 ℃.
By analysis, in extraction crude product SULPHURYL CHLORIDE, oxidable thing content is 50ppm, and chloromethyl SULPHURYL CHLORIDE content 5000ppm approximately has 15% sulfur number to be transformed into methylsulphonic acid and has been lost in aqueous hydrochloric acid; Tower top hydrogenchloride, after alkali liquor absorption, is analyzed and is had 1.1% sulfur number to be lost in hydrogen chloride tail gas, and thiomethyl alcohol does not detect.
embodiment 3 thiomethyl alcohols are prepared Methanesulfonyl chloride
Thiomethyl alcohol enters reaction zone with the flow of 60kg/hr, and chlorine enters with the flow of 269kg/hr, and chlorine is 1.01 equivalents, and water, with 1.03 equivalent chargings, is controlled 0~5 ℃ of temperature of reaction.After system operates steadily, the rate of yield 140kg/hr of crude product SULPHURYL CHLORIDE, absorption tower circulation crude product SULPHURYL CHLORIDE temperature is 10 ℃.
By analysis, in extraction crude product SULPHURYL CHLORIDE, oxidable thing content is 1000ppm, chloromethyl SULPHURYL CHLORIDE content 50ppm; Approximately having 1% sulfur number to be transformed into methylsulphonic acid has been lost in aqueous hydrochloric acid; Tower top hydrogenchloride, after alkali liquor absorption, is analyzed and is had 0.17% sulfur number to be lost in hydrogen chloride tail gas, the about 20ppm of thiomethyl alcohol concentration in tail gas hydrogenchloride.
embodiment 4 thiomethyl alcohols are prepared Methanesulfonyl chloride
Thiomethyl alcohol enters reaction zone with the flow of 72kg/hr, and chlorine enters with the flow of 330kg/hr, and chlorine is 1.03 equivalents, and water, with 1.03 equivalent chargings, is controlled 5~10 ℃ of temperature of reaction.After system operates steadily, the rate of yield 170kg/hr of crude product SULPHURYL CHLORIDE, absorption tower circulation crude product SULPHURYL CHLORIDE temperature is 0 ℃.
By analysis, in extraction crude product SULPHURYL CHLORIDE, oxidable thing content is 50ppm, chloromethyl SULPHURYL CHLORIDE content 100ppm; Approximately having 2% sulfur number to be transformed into methylsulphonic acid has been lost in aqueous hydrochloric acid; Tower top hydrogenchloride, after alkali liquor absorption, is analyzed and is had 0.08% sulfur number to be lost in hydrogen chloride tail gas, and thiomethyl alcohol does not detect.
embodiment 5 thiomethyl alcohols are prepared Methanesulfonyl chloride
Thiomethyl alcohol enters reaction zone with the flow of 60kg/hr, and chlorine enters with the flow of 293kg/hr, and chlorine is 1.1 equivalents, and water, with 1.03 equivalent chargings, is controlled 5~10 ℃ of temperature of reaction.After system operates steadily, the rate of yield 140kg/hr of crude product SULPHURYL CHLORIDE, absorption tower circulation crude product SULPHURYL CHLORIDE temperature is 20 ℃.
By analysis, in extraction crude product acyl chlorides, oxidable thing content is 1ppm, chloromethyl SULPHURYL CHLORIDE content 300ppm; Approximately having 2% sulfur number to be transformed into methylsulphonic acid has been lost in aqueous hydrochloric acid; Tower top hydrogenchloride, after alkali liquor absorption, is analyzed and is had 0.43% sulfur number to be lost in hydrogen chloride tail gas, and thiomethyl alcohol does not detect.
embodiment 6 thiomethyl alcohols are prepared Methanesulfonyl chloride
Thiomethyl alcohol enters reaction zone with the flow of 48kg/hr, and chlorine enters with the flow of 235kg/hr, and chlorine is 1.1 equivalents, and water, with 1.02 equivalent chargings, is controlled temperature of reaction-5~0 ℃.After system operates steadily, the rate of yield 113kg/hr of crude product SULPHURYL CHLORIDE, absorption tower circulation crude product SULPHURYL CHLORIDE temperature is 10 ℃.
By analysis, in extraction crude product SULPHURYL CHLORIDE, oxidable thing content is 1ppm, chloromethyl SULPHURYL CHLORIDE content 200ppm; Approximately having 0.8% sulfur number to be transformed into methylsulphonic acid has been lost in aqueous hydrochloric acid; Tower top hydrogenchloride, after alkali liquor absorption, is analyzed and is had 0.15% sulfur number to be lost in hydrogen chloride tail gas, and thiomethyl alcohol does not detect.
embodiment 7 thiomethyl alcohols are prepared Methanesulfonyl chloride
Control absorption tower hydrogen chloride tail gas outlet 15 take interior system pressure as 1.75 normal atmosphere, thiomethyl alcohol enters reaction zone with the flow of 48kg/hr, and chlorine enters with the flow of 235kg/hr, and chlorine is 1.1 equivalents, water, with 1.03 equivalent chargings, is controlled 0~5 ℃ of temperature of reaction.After system operates steadily, the rate of yield 113kg/hr of crude product SULPHURYL CHLORIDE, absorption tower circulation crude product SULPHURYL CHLORIDE temperature is 30 ℃.
By analysis, in extraction crude product SULPHURYL CHLORIDE, oxidable thing content is 1ppm, and chloromethyl SULPHURYL CHLORIDE content 230ppm approximately has 1.1% sulfur number to be transformed into methylsulphonic acid and has been lost in aqueous hydrochloric acid; Tower top hydrogenchloride, after alkali liquor absorption, is analyzed and is had 0.6% sulfur number to be lost in hydrogen chloride tail gas, and thiomethyl alcohol does not detect.
It is as follows that thiomethyl alcohol is prepared the process unit flowchart text of Methanesulfonyl chloride:
See Fig. 1, prepare the process unit schema of Methanesulfonyl chloride with thiomethyl alcohol, the top of reactor 8 is connected with upflow tube 10, and air outlet, top is connected with absorption tower 9, and the bottom of reactor 8 is connected with return line 11; The same vertical sedimentation quantizer 12 parallel with reactor 8 is connected with reactor by the upflow tube 10 on top and the return line 11 of bottom respectively, the bottom of sedimentation quantizer 12 is connected to crude product SULPHURYL CHLORIDE recycle pump 13 by pipeline, an outlet material part for recycle pump 13 is as output extraction 14, and a part enters absorption tower 9 through interchanger 16; The bottom liquid outlet on absorption tower 9 connects sedimentation quantizer 12, and the top gas on absorption tower 9, by mouthful 15 discharges, enters next processing unit.
Vertically reactor 8 by lining mould, flanged fittings or the tower of lass lining, glass or graphite material save, and graphite or graphite modified or glass condenser unit connect and combine, the about 0.4m of internal diameter, the about 6m of length of whole reactor.Thiomethyl alcohol is entered by the opening for feed 2 apart from the about 1.2m of reactor bottom, chlorine is entered by the opening for feed 3 apart from the about 1.7m in bottom, the opening for feed of chlorine and thiomethyl alcohol gas is all provided with specially and is beneficial to the feeder that gas uniform distributes, and water or hydrochloric acid are by entering apart from 1 of the about 0.2m in bottom.The packing layer 4 of the 250mm that has an appointment is filled in opening for feed 3 tops of chlorine, is beneficial to abundant contact and the mixing of gas-liquid.The top of packing layer is that shell and tube rises membrane reactor 5, and the shell that rises membrane reactor 5 passes into chilled brine, plays the effect of cooling, rises membrane reactor and is made up of the pipe of 127 internal diameter 16mm, highly about 640mm, the about 5m of heat interchanging area
2, the about 0.02552m of reaction mass channel cross-sectional area
2.The top that rises membrane reactor 5 is that the tower of internal diameter 400mm saves full mixing zone 6, there is the ring baffle of an about 200mm of median pore diameter apart from about 200mm place, tower joint bottom, the top of liquid mixing tower joint 6, again to rise membrane reactor 5, mixing column joint 6, rise membrane reactor 5, be finally the gas-liquid separation unit 7 of about 1m height, liquid enters sedimentation quantizer 12 by upflow tube 10; Gas enters spray absorber 9 from top.
The interface of upflow tube 10 is apart from gas-liquid separator 7 about 200mm places, bottom, diameter 200mm.The interface of return line 11 is at reactor 8 bottoms, diameter 100mm.
Reactor 8 rise membrane flow district rise membrane flow heat-exchanger rig, it can be homemade tubulation heat-exchange equipment, also can select suitable pipe bundle condenser, the gas cooling absorption tower of existing industrial use or similarly install, in pipe, walk reaction mass or air-flow, shell is walked recirculated cooling water or salt solution, and its size can be adjusted as required.Liter membrane flow, heat-exchanger rig unit are alternately connected or otherwise alternately connect in interval one by one with complete mixing flow device unit.Described complete mixing flow reaction zone, can for band shape dividing plate, filler or not the parts with dividing plate, filler form, its internal diameter is with to rise membrane flow device part identical or different, its with rise membrane flow device and be alternately axially connected.Described circulating cooling absorption unit comprises recycle pump, interchanger, spray absorber, heat-exchange equipment and washing absorption equipment can be divided into two independently parts or be those skilled in the art known cooling and absorbing equipment integrating of row, in absorption tower, add or do not add filler, the known various device that reaches same absorption washing effect can be selected in absorption tower.The knowledge design that described device can be known according to industry personnel, and can be equipped with other necessary support equipment.
The reaction formula of thiomethyl alcohol and chlorine is as follows:
In the time that temperature is high, can there is following side reaction:
Produce the hydrolysis of methyl chlorination or Methanesulfonyl chloride.So temperature of reaction-10 of reaction zone~+ 25 ℃ are comparatively suitable, when temperature of reaction is high, not only can there is side reaction, also, likely because the gas phase vigorous reaction of chlorine and thiomethyl alcohol gas causes sudden strain of a muscle quick-fried, there is potential safety hazard.
In reactor 8, control aqueous hydrochloric acid liquid level and reach upflow tube, chlorine, thiomethyl alcohol, water or hydrochloric acid autoreactor 8 bottoms opening for feed separately enter, and the opening for feed of chlorine and thiomethyl alcohol gas is all provided with and is beneficial to specially the feeder that gas uniform distributes.The gas entering, through packing layer 5, fully contacts and mixes in packing layer 5; Then enter reaction zone, the cooling that rises membrane reactor 5 by tubulation keeps lower temperature of reaction, control suitable alkyl sulfhydryl feeding rate, a large amount of hydrogen chloride gas of by-product make material, and in tubulation rises membrane reactor 5, to rise, membrane stage flows and reaction, here, gas-liquid can contact more fully and react; When gas-liquid mixed reaction solution enters perfectly mixed reactor 6, due to stretching of internal diameter, solution-air flow velocity can change rapidly, thereby completes the even mixing of liquid.Gas-liquid mixture rises film reaction unit through three grades and two-stage is mixed after reaction member entirely, enters gas-liquid separation unit 7, and gas enters absorption tower, and liquid flooding enters sedimentation quantizer 12.
In sedimentation quantizer 12, due to the difference of density, Methanesulfonyl chloride is deposited to bottom, got by crude product SULPHURYL CHLORIDE recycle pump 13, a part, as thick product extraction, enters next step crude product refining unit, and a part enters spray absorber 9 after interchanger 16 is fully cooling.
In absorption tower 9, enter through fully cooling crude product SULPHURYL CHLORIDE spray, the by-product hydrogen chloride gas that is entered 9 bottoms, absorption tower by reactor 8 is absorbed, washed; The chlorine, the thiomethyl alcohol that in absorption tower, are absorbed condensation are dissolved in crude product acyl chlorides, enter sedimentation quantizer 12, further " send out chlorine ", fully reaction, reduce the pollution to finished product SULPHURYL CHLORIDE, further improve raw material availability, stopped the odorant pollutant in by-product hydrogen chloride; Tail gas hydrogenchloride enters next step water absorptive unit, by-product hydrochloric acid.
The atmospheric boiling point of chlorine is about-34.5 ℃, approximately 7.6 ℃ of the boiling points of thiomethyl alcohol, and the knowledge of knowing according to industry personnel, under normal condition, if want with condenser, these two kinds of material condensations that are entrained in a large amount of hydrogenchloride to be got off, that is obviously impossible.We know that the atmospheric boiling point of Methanesulfonyl chloride is 164~167 ℃, and its dividing potential drop is very little at low temperatures, and we have following dividing potential drop data:
Temperature (unit ℃) |
0 |
10 |
20 |
30 |
40 |
50 |
55 |
62 |
Saturated vapor pressure (mmHg of unit) |
0.08 |
0.23 |
0.6 |
1.5 |
3.5 |
7.6 |
11 |
18 |
And chlorine and thiomethyl alcohol all have suitable solubleness in Methanesulfonyl chloride, according to our mensuration, under 20 ℃ of normal pressures, the solubleness of thiomethyl alcohol in Methanesulfonyl chloride can reach 40%, thus with low temperature Methanesulfonyl chloride washing, the scheme that absorbs by-product hydrogen chloride gas be feasible.
Take the thiomethyl alcohol charging of 1.5kmol/hr as example, approximately there is the hydrogenchloride of 7.5 kmol/hr to produce, the temperature of setting crude product SULPHURYL CHLORIDE circulating absorption solution is 10 ℃, saturated vapor pressure is 0.23mmHg, calculate thus, the SULPHURYL CHLORIDE of carrying secretly in tail gas hydrogenchloride is 300ppm, only has 0.15% sulfur number (in the amount of substance of sulphur) loss.If the temperature of crude product SULPHURYL CHLORIDE circulating absorption solution is 0 ℃, saturated vapor pressure is 0.08mmHg, calculate thus, the SULPHURYL CHLORIDE of carrying secretly in tail gas hydrogenchloride is 100ppm, only there is 0.05% sulfur number loss, much smaller than 2.4% sulfur number loss under optimal conditions in patent EP675106, even much smaller than the sulfur number loss of (pressurizeing, add rectifying tower) 0.4% under top condition in EP675107.Under the rational operational condition of present method, the mercaptan of carrying secretly in tail gas hydrogenchloride is zero.Method condition of the present invention realizes industrial being easy to, and safety.The temperature of absorption tower 9 interior crude product SULPHURYL CHLORIDE circulation fluid is in the scope of-30~+ 100 ℃, preferably in the temperature range of-20~+ 50 ℃, more excellent in the scope of-10~+ 10 ℃.