CN103360287A - MethyIsuIfino benzaldehyde preparation method - Google Patents
MethyIsuIfino benzaldehyde preparation method Download PDFInfo
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- CN103360287A CN103360287A CN2013103024380A CN201310302438A CN103360287A CN 103360287 A CN103360287 A CN 103360287A CN 2013103024380 A CN2013103024380 A CN 2013103024380A CN 201310302438 A CN201310302438 A CN 201310302438A CN 103360287 A CN103360287 A CN 103360287A
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- methylsulfonyltoluene
- phenyl aldehyde
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 title abstract description 8
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 title abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 99
- 230000003647 oxidation Effects 0.000 claims abstract description 41
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 41
- 239000003513 alkali Substances 0.000 claims abstract description 38
- 238000001035 drying Methods 0.000 claims abstract description 33
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000005406 washing Methods 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims description 136
- BEARMXYKACECDH-UHFFFAOYSA-N methylsulfonylmethylbenzene Chemical compound CS(=O)(=O)CC1=CC=CC=C1 BEARMXYKACECDH-UHFFFAOYSA-N 0.000 claims description 107
- -1 methylsulfonyl phenyl aldehyde Chemical class 0.000 claims description 86
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 69
- 239000007790 solid phase Substances 0.000 claims description 67
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 66
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 54
- 229960003053 thiamphenicol Drugs 0.000 claims description 51
- 239000007791 liquid phase Substances 0.000 claims description 49
- OTVAEFIXJLOWRX-NXEZZACHSA-N thiamphenicol Chemical compound CS(=O)(=O)C1=CC=C([C@@H](O)[C@@H](CO)NC(=O)C(Cl)Cl)C=C1 OTVAEFIXJLOWRX-NXEZZACHSA-N 0.000 claims description 42
- 239000002994 raw material Substances 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 38
- 239000005711 Benzoic acid Substances 0.000 claims description 33
- 235000010233 benzoic acid Nutrition 0.000 claims description 33
- 241000196324 Embryophyta Species 0.000 claims description 26
- 238000002844 melting Methods 0.000 claims description 25
- 230000008018 melting Effects 0.000 claims description 25
- 238000004140 cleaning Methods 0.000 claims description 22
- 239000006227 byproduct Substances 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 17
- 230000008929 regeneration Effects 0.000 claims description 16
- 238000011069 regeneration method Methods 0.000 claims description 16
- 239000012459 cleaning agent Substances 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 230000004927 fusion Effects 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 230000004888 barrier function Effects 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 10
- 238000004064 recycling Methods 0.000 claims description 9
- 239000011344 liquid material Substances 0.000 claims description 8
- 239000006210 lotion Substances 0.000 claims description 8
- 230000003068 static effect Effects 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000003672 processing method Methods 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000015320 potassium carbonate Nutrition 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 230000005518 electrochemistry Effects 0.000 claims description 2
- 150000001559 benzoic acids Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000003723 Smelting Methods 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 22
- 239000010408 film Substances 0.000 description 9
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- AZAJHHFJZFFMLA-UHFFFAOYSA-N CS(=O)(=O)C1=C(C=CC=C1)C(Br)Br Chemical compound CS(=O)(=O)C1=C(C=CC=C1)C(Br)Br AZAJHHFJZFFMLA-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 125000001246 bromo group Chemical class Br* 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000011552 falling film Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- JRRKYOFPKIKWOL-UHFFFAOYSA-N 1-(dibromomethyl)-4-methylsulfonylbenzene Chemical compound CS(=O)(=O)C1=CC=C(C=C1)C(Br)Br JRRKYOFPKIKWOL-UHFFFAOYSA-N 0.000 description 1
- PSVPUHBSBYJSMQ-UHFFFAOYSA-N 4-methylsulfonylbenzaldehyde Chemical compound CS(=O)(=O)C1=CC=C(C=O)C=C1 PSVPUHBSBYJSMQ-UHFFFAOYSA-N 0.000 description 1
- XDKSFUPZGIWLQE-UHFFFAOYSA-N CS(=O)(=O)CC1=CC=CC=C1.C(C1=CC=CC=C1)(=O)O Chemical compound CS(=O)(=O)CC1=CC=CC=C1.C(C1=CC=CC=C1)(=O)O XDKSFUPZGIWLQE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000004004 anti-anginal agent Substances 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000003356 anti-rheumatic effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000003435 antirheumatic agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 150000003952 β-lactams Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a methyIsuIfino benzaldehyde preparation method mainly comprising the steps of: (1) smelting; (2) preheating; (3) chemical oxidation; (4) solid-liquid separation; (5) alkali washing; (6) solid-liquid separation; (7) alcohol washing; (8) solid-liquid separation; (9) drying; and (10) electrochemical oxidation. The process provided by the invention is reasonable, the preparation method is simple, production cost is low, product purity is high, and the process is safe. The method is suitable for realizing large-scale industrialization. The process is a clean production process of methyIsuIfino benzaldehyde preparation. The process satisfies the requirement of green chemical engineering development.
Description
Technical field
The present invention relates to a kind of preparation method to the methylsulfonyl phenyl aldehyde, particularly a kind of take to methylsulfonyltoluene as the raw material chemical oxidation preparation method to the methylsulfonyl phenyl aldehyde, belong to the fine chemical technology field.
Background technology
Being a kind of aromatics to methylsulfonyltoluene, is the powder of white crystals shape under the normal temperature, and molecular formula is C
8H
10O
2S, 88 ℃～89 ℃ of melting ranges, 312 ℃ of boiling points, density is 1.154g/cm
3, be dissolved in the organic solvents such as alcohol, ether, be slightly soluble in water.
Product of the present invention has another name called 4-methylsulfonyl phenyl aldehyde, 4-sulfonyloxy methyl phenyl aldehyde, 4-sulfonyloxy methyl benzaldehyde to the methylsulfonyl phenyl aldehyde.English name 4-Methylsulfonyl benzaldehyde, English another name p-methylsufonyl benzaldehyde, molecular formula is C
8H
8O
3S, molecular weight are 184.21.Be the yellow crystal powder to the methylsulfonyl phenyl aldehyde, density is 1.289g/cm
3, fusing point is 155 ℃～161 ℃, boiling point is 378.3 ℃, is slightly soluble in water.
A kind of important medicine intermediate to the methylsulfonyl phenyl aldehyde, mainly for the production of the Broad spectrum antibiotics thiamphenicol, it also is simultaneously the intermediate of producing beta-lactam antiseptic-germicide, white dyes, dihydrogen pyridine derivative class antianginal drug and anti-inflammatory antirheumatic medicine.
Chinese patent (201210350777.1) disclose a kind of take to methylsulfonyltoluene as the raw material preparation method to the methylsulfonyl phenyl aldehyde.This processing method take to methylsulfonyltoluene as raw material, obtain the methylsulfonyl dibromomethylbenzene through the high temperature bromination, directly join to contain in the hydrobromic water that the bromination reactive absorption makes and be hydrolyzed, get methylsulfonyl phenyl aldehyde crude product.
Chinese patent (201210560425.9) discloses a kind of to methylsulfonyl phenyl aldehyde synthetic method, this processing method take to methylsulfonyltoluene and bromine as raw material, under 100 ℃～200 ℃, add catalyst reaction and obtain liquid crude product to the methylsulfonyl dibromomethylbenzene; Remove the hydrogen bromide and the unreacted bromine that produce in the reaction; Obtain product to the methylsulfonyl dibromomethylbenzene through neutralization, washing; Obtain to the methylsulfonyl dibromomethylbenzene in add the entry reaction that is hydrolyzed; Cooling, filtration, drying obtain the methylsulfonyl phenyl aldehyde.
The main drawback of above-mentioned two patented methods is to have used a large amount of bromines, not only has the problem of the waste of resource, but also has produced a large amount of acid waste water.
Existing preparation to the Technology of methylsulfonyl phenyl aldehyde mainly take to methylsulfonyltoluene as raw material, heating lower with bromine reaction generation 4-methylsulfonyl dibromomethylbenzene, obtain the methylsulfonyl phenyl aldehyde through hydrolysis again, its chemical equation is:
It is existing so that methylsulfonyltoluene is had technical maturity, yield advantages of higher through bromo and hydrolysis reaction system to the technique of methylsulfonyl phenyl aldehyde as raw material.But mainly there is following problem in this technique:
(1) adopt the production technique preparation of halo and hydrolysis reaction that the methylsulfonyl phenyl aldehyde is needed a large amount of chlorine or bromines used, usually there are the by products such as a replacement, three replacements in operation, follow simultaneously light and heat, not only difficult control but also easily to environment of reaction, and chlorine or bromine are also quite serious to the corrosion of equipment;
(2) technical process is long, and yield is low, and the reaction product that obtains is complicated, makes the separation and purification difficulty of product, and quality product is low;
(3) reaction process is difficult to control, and safe reliability is poor, and is seriously polluted.
Summary of the invention
The objective of the invention is for the deficiencies in the prior art, provide that a kind of technique is reasonable, the preparation method is simple, production cost is low, product purity is high, the process for cleanly preparing to the methylsulfonyl phenyl aldehyde of process safety.
The technical scheme that realizes above-mentioned purpose is: a kind of preparation method to the methylsulfonyl phenyl aldehyde, be take to methylsulfonyltoluene as raw material through the processing method of selective oxidation preparation to the methylsulfonyl phenyl aldehyde, described method steps is as follows:
(1) melting: in fusion apparatus, will be warmed up to 90 ℃～150 ℃ to methylsulfonyltoluene, and make that to be in solid-state under the room temperature be liquid material to the methylsulfonyltoluene melting;
(2) preheating: in preliminary heating device, add aqueous sulfuric acid and oxygenant potassium bichromate, and heat to 90 ℃～120 ℃;
(3) chemical oxidation: in liquid-liquid-liquid heterogeneous reaction device, with previous step through the aqueous sulfuric acid of the potassium bichromate of preheating join through melting in the methylsulfonyltoluene, potassium bichromate will be to the methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid to the methylsulfonyltoluene selective oxidation, Cr (VI) in the potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in the solid-liquid separating device, material obtained in the previous step is carried out solid-liquid separate, solid-phase material enters next step, and liquid phase material entered for the tenth step and carries out electrochemical oxidation regeneration;
(5) alkali cleaning: in washing plant, mixing, washing is carried out in alkali cleaning agent and solid-phase material obtained in the previous step, by product in the solid-phase material generates thiamphenicol benzoic acid salt thiamphenicol benzoic acid and alkali cleaning agent reaction, the water-soluble solution of thiamphenicol benzoic acid salt is entered in the liquid phase, and unreacted raw material still is solid-phase material to methylsulfonyltoluene and reaction product to the mixture of methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in the solid-liquid separating device, material obtained in the previous step is carried out solid-liquid separate, liquid phase material obtains by product to thiamphenicol benzoic acid through further separation and purification, and solid-phase material enters next step;
(7) alcohol wash: in washing plant, solid-phase material obtained in the previous step is washed with aqueous ethanolic solution under 60 ℃～80 ℃, methylsulfonyltoluene is entered liquid phase, solid-phase material is to the methylsulfonyl phenyl aldehyde;
(8) solid-liquid separates: in the solid-liquid separating device, material obtained in the previous step is carried out solid-liquid to be separated, liquid phase material obtains aqueous ethanolic solution through further separation and reaches methylsulfonyltoluene, wherein the raw material of methylsulfonyltoluene as the 3rd step chemical oxidation recycled, aqueous ethanolic solution then recycles as the pure washing lotion in the 7th step, and solid-phase material enters next step;
(9) drying: in drying plant, solid-phase material obtained in the previous step is carried out drying treatment under 80 ℃～100 ℃, obtain methylsulfonyl phenyl aldehyde product;
(10) electrochemical oxidation: in electrochemical reactor, liquid phase material in the 4th step is carried out electrochemical oxidation, make Cr (III) be converted into Cr (VI), the Cr (VI) that regeneration obtains enters second step as the Recycling of oxidize use of oxidizing reaction.
Further, in the described second step pre-heating step, the concentration of oxygenant potassium bichromate is 0.5mol/L～3.0mol/L, and the concentration of sulfuric acid is 0.1mol/L～8.0mol/L.
Further, described the 3rd step chemical oxidation step is that the aqueous sulfuric acid with potassium bichromate joins in the methylsulfonyltoluene, is 1:0.20～0.60 to the mol ratio of methylsulfonyltoluene and oxygenant potassium bichromate, and service temperature is 90 ℃～150 ℃.
Further, the reactor of described the 3rd step chemical oxidation is any one in stirred-tank reactor or the static mixing reactor.
Further, in the 5th step alkali cleaning step, described alkali cleaning agent is the aqueous solution of any one or arbitrary combination in yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, sodium hydroxide, the potassium hydroxide, the concentration of alkali cleaning agent is 0.1mol/L～6.0mol/L, the pH value of system is 8～10, and service temperature is 20 ℃～60 ℃.
Further, in described the 7th step alcohol wash step, the massfraction of aqueous ethanolic solution is 70%～95%.
Further, the 4th step, the 6th step and described solid-liquid separating device of the 8th step are any one in decanter type or filtering type or centrifugal or the vane-type solid-liquid separating device.
Further, described the tenth one-step electrochemistry oxidation reactor is plate electrochemical reactor or three-dimensional electrochemical reactor, and anolyte compartment and the cathode compartment of reactor are isolated by barrier film, barrier film preferred cationic film.In the electrochemical oxidation system, the concentration of sulfuric acid is 0.5mol/L～4.0mol/L, and service temperature is 20 ℃～60 ℃, and actuating current density is 500A/m
2～2000A/m
2
Realize that the major equipment that the present invention needs is: liquid-liquid-liquid heterogeneous reaction device, electrochemical reactor, fusion apparatus, preliminary heating device, solid-liquid separating device, washing plant, drying plant etc.
The equation of chemical reaction involved in the present invention is:
(1) the methylsulfonyltoluene selective oxidation is generated the methylsulfonyl phenyl aldehyde:
(2) Cr (III) electrochemical oxidation is converted into Cr (VI):
Cr
3++H
2O→Cr
2O
7 2-+H
+
(3) alkali cleaning removes by product to the reaction (take yellow soda ash as example) of thiamphenicol benzoic acid:
Adopt principle and the advantage of technique scheme to be:
(1) utilization is to the characteristics of methylsulfonyltoluene easy oxidation under acidic conditions, and the oxidisability by acidity and the temperature of reaction of regulation and control reactive system are regulated potassium bichromate realizes the selective oxidation to methylsulfonyltoluene, thereby obtains methylsulfonyl phenyl aldehyde product.For selective oxidation to methylsulfonyltoluene is rested on the methylsulfonyl phenyl aldehyde is not continued to be oxidized to thiamphenicol benzoic acid, that sulphuric acid soln with potassium bichromate joins in the methylsulfonyltoluene in the reaction process, and in reaction process the oxygenant potassium bichromate as control component, with regulation and control oxidizing reaction the degree of depth.
(2) having selected potassium bichromate is oxygenant, and the Cr (III) that oxidizing reaction generates can be converted into Cr (VI) by electrochemical oxidation, has realized recycling of oxygenant, has reduced pollution, has reduced cost.
(3) so that methylsulfonyltoluene is carried out in the selective oxidation process as raw material, generate to the methylsulfonyl phenyl aldehyde can be further be to thiamphenicol benzoic acid by deep oxidation, therefore, in the reaction product except containing the methylsulfonyl phenyl aldehyde, also contain unreacted raw material to methylsulfonyltoluene and by product to thiamphenicol benzoic acid, so need carry out separation and purification to this mixture.The art of this patent utilize raw material to methylsulfonyltoluene, product to methylsulfonyl phenyl aldehyde and by product to the difference to the thiamphenicol benzoic acid physical property, raw material is recycled in to the methylsulfonyl phenyl aldehyde to methylsulfonyltoluene isolating product, and can be obtained by product to thiamphenicol benzoic acid.
1. to the separation to thiamphenicol benzoic acid.Utilization to less to thiamphenicol benzoic acid solubleness in water, with easy salify and the salt that the generates characteristic soluble in water of alkali metal compound (alkali, alkalimetal oxide or alkaline carbonate), will be to thiamphenicol benzoic acid being converted into to thiamphenicol benzoic acid salt, be dissolved in liquid phase, and to methylsulfonyltoluene and still be solid phase to the methylsulfonyl phenyl aldehyde, thereby will remove thiamphenicol benzoic acid is separated from mixture.
2. to methylsulfonyltoluene and separating the methylsulfonyl phenyl aldehyde.Under uniform temp, greater than to the methylsulfonyl phenyl aldehyde, and along with the rising of temperature, solubleness obviously increases to the solubleness of methylsulfonyltoluene in aqueous ethanolic solution.Therefore, utilization to methylsulfonyltoluene with to the methylsulfonyl phenyl aldehyde difference that solubleness and solubility with temperature change in aqueous ethanolic solution, adopt the aqueous ethanolic solution washing to methylsulfonyltoluene and to methylsulfonyl phenyl aldehyde mixed solution, flush away is to methylsulfonyltoluene, thereby realization is to methylsulfonyltoluene and separating the methylsulfonyl phenyl aldehyde.Can continue to use as raw material through further separating treatment to methylsulfonyltoluene.
Technique of the present invention is reasonable, and the preparation method is simple, and production cost is low, and product purity is high, and process safety is convenient to realize heavy industrialization, is a kind of process for cleanly preparing that meets the green chemical industry demand for development.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
The present invention is further detailed explanation below in conjunction with drawings and Examples.
Embodiment one
Main technique equipment: stirred-tank reactor, plate electrochemical reactor, decanter type solid-liquid separator, fusion apparatus, preliminary heating device, washing plant, drying plant etc.
As shown in Figure 1, a kind of preparation method to the methylsulfonyl phenyl aldehyde, be take to methylsulfonyltoluene as raw material through the selective oxidation preparation processing method to the methylsulfonyl phenyl aldehyde, described method steps is as follows:
(1) melting: in stirring tank, will be warmed up to 90 ℃ to methylsulfonyltoluene, and make that to be in solid-state under the room temperature be liquid material to the methylsulfonyltoluene melting;
(2) preheating: in stirring tank, add aqueous sulfuric acid and oxygenant potassium bichromate, heat to 90 ℃, the concentration of potassium bichromate is 0.5mol/L in the system, the concentration of sulfuric acid is 0.1mol/L, and system is in liquid state when by heat temperature raising this material being mixed to methylsulfonyltoluene with raw material;
(3) chemical oxidation: in stirred-tank reactor, with previous step through the aqueous sulfuric acid of the potassium bichromate of preheating join through melting in the methylsulfonyltoluene, mol ratio to methylsulfonyltoluene and oxygenant potassium bichromate is 1:0.20, service temperature is 90 ℃, potassium bichromate will be to the methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid to the methylsulfonyltoluene selective oxidation, Cr (VI) in the potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in the decanter type solid-liquid separator, material obtained in the previous step is carried out solid-liquid separate, solid-phase material enters next step, and liquid phase material entered for the tenth step and carries out electrochemical oxidation regeneration;
(5) alkali cleaning: in stirring tank, take the 0.1mol/L aqueous sodium carbonate as alkaline wash, service temperature is 20 ℃, alkali cleaning is 8 to the pH value of system, by product in the solid-phase material generates thiamphenicol benzoic acid salt thiamphenicol benzoic acid and alkali cleaning agent reaction, the water-soluble solution of thiamphenicol benzoic acid salt is entered in the liquid phase, and unreacted raw material still is solid-phase material to methylsulfonyltoluene and reaction product to the mixture of methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in the decanter type solid-liquid separator, material obtained in the previous step is carried out solid-liquid separate, liquid phase material obtains by product to thiamphenicol benzoic acid through further separation and purification, and solid-phase material enters next step;
(7) alcohol wash: in stirring tank, be the washing of 70% aqueous ethanolic solution with massfraction with solid-phase material obtained in the previous step down at 60 ℃, methylsulfonyltoluene is entered liquid phase, solid-phase material is to the methylsulfonyl phenyl aldehyde;
(8) solid-liquid separates: in the decanter type solid-liquid separator, material obtained in the previous step is carried out solid-liquid to be separated, liquid phase material obtains aqueous ethanolic solution through further separation and reaches methylsulfonyltoluene, wherein the raw material of methylsulfonyltoluene as the 3rd step chemical oxidation recycled, aqueous ethanolic solution then recycles as the pure washing lotion in the 7th step, and solid-phase material enters next step;
(9) drying: in drying plant, solid-phase material obtained in the previous step is carried out drying treatment at 80 ℃, obtain methylsulfonyl phenyl aldehyde product;
(10) electrochemical oxidation: in the plate electrochemical reactor of positively charged ion barrier film, liquid phase material in the 4th step is carried out electrochemical oxidation, make Cr (III) be converted into Cr (VI), in the reaction system, the concentration of sulfuric acid is 0.5mol/L, service temperature is 20 ℃, and actuating current density is 500A/m
2, the Cr (VI) that regeneration obtains enters second step as the Recycling of oxidize use of oxidizing reaction.
Embodiment two
Main technique equipment: static mixing reactor, three-dimensional electrochemical reactor, filtering type solid-liquid separator, fusion apparatus, preliminary heating device, washing plant, drying plant etc.
Method steps is as follows:
(1) melting: in the falling film type fusion apparatus, will be warmed up to 150 ℃ to methylsulfonyltoluene, and make that to be in solid-state under the room temperature be liquid material to the methylsulfonyltoluene melting;
(2) preheating: in stirring tank, add aqueous sulfuric acid and oxygenant potassium bichromate, heat to 120 ℃, the concentration of potassium bichromate is 3.0mol/L in the system, the concentration of sulfuric acid is 8.0mol/L, and system is in liquid state when by heat temperature raising this material being mixed to methylsulfonyltoluene with raw material;
(3) chemical oxidation: in static mixing reactor, with previous step through the aqueous sulfuric acid of the potassium bichromate of preheating join reaction raw materials through melting to methylsulfonyltoluene in, mol ratio to methylsulfonyltoluene and oxygenant potassium bichromate is 1:0.60, service temperature is 150 ℃, potassium bichromate will be to the methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid to the methylsulfonyltoluene selective oxidation, Cr (VI) in the potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in the filtering type solid-liquid separator, material obtained in the previous step is carried out solid-liquid separate, solid-phase material enters next step, and liquid phase material entered for the tenth step and carries out electrochemical oxidation regeneration;
(5) alkali cleaning: in stirring tank, wet chemical take concentration as 6.0mol/L is alkaline wash, service temperature is 60 ℃, alkali cleaning is 10 to the pH value of system, by product in the solid-phase material generates thiamphenicol benzoic acid salt methylsulfonyltoluene acid and alkali cleaning agent reaction, the water-soluble solution of thiamphenicol benzoic acid salt is entered in the liquid phase, and unreacted raw material still is solid-phase material to methylsulfonyltoluene and reaction product to the mixture of methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in the filtering type solid-liquid separator, material obtained in the previous step is carried out solid-liquid separate, liquid phase material obtains by product to thiamphenicol benzoic acid through further separation and purification, and solid-phase material enters next step;
(7) alcohol wash: in stirring tank, solid-phase material obtained in the previous step 80 ℃ of lower aqueous ethanolic solution washings with massfraction 95%, is entered liquid phase to methylsulfonyltoluene, solid-phase material is to the methylsulfonyl phenyl aldehyde;
(8) solid-liquid separates: in the filtering type solid-liquid separator, material obtained in the previous step is carried out solid-liquid to be separated, liquid phase material obtains aqueous ethanolic solution through further separation and reaches methylsulfonyltoluene, wherein the raw material of methylsulfonyltoluene as the 3rd step chemical oxidation recycled, aqueous ethanolic solution then recycles as the pure washing lotion in the 7th step, and solid-phase material enters next step;
(9) drying: in drying plant, solid-phase material obtained in the previous step is carried out drying treatment under 100 ℃, obtain methylsulfonyl phenyl aldehyde product;
(10) electrochemical oxidation: in positively charged ion barrier film three-dimensional electrochemical reactor, liquid phase material in the 4th step is carried out electrochemical oxidation, make Cr (III) be converted into Cr (VI), in the reaction system, the concentration of sulfuric acid is 4.0mol/L, service temperature is 60 ℃, and actuating current density is 2000A/m
2, the Cr (VI) that regeneration obtains enters second step as the Recycling of oxidize use of oxidizing reaction.
Embodiment three
Main technique equipment: static mixing reactor, plate electrochemical reactor, centrifugal solid-liquid separator, fusion apparatus, preliminary heating device, washing plant, drying plant etc.
Method steps is as follows:
(1) melting: in stirring tank, will be warmed up to 120 ℃ to methylsulfonyltoluene, and make that to be in solid-state under the room temperature be liquid material to the methylsulfonyltoluene melting;
(2) preheating: in stirring tank, add aqueous sulfuric acid and oxygenant potassium bichromate, heat to 100 ℃, the concentration of potassium bichromate is 2.0mol/L in the system, the concentration of sulfuric acid is 4.0mol/L, and system is in liquid state when by heat temperature raising this material being mixed to methylsulfonyltoluene with raw material;
(3) chemical oxidation: in static mixing reactor, with previous step through the aqueous sulfuric acid of the potassium bichromate of preheating join reaction raw materials through melting to methylsulfonyltoluene in, mol ratio to methylsulfonyltoluene and oxygenant potassium bichromate is 1:0.50, service temperature is 120 ℃, potassium bichromate will be to the methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid to the methylsulfonyltoluene selective oxidation, Cr (VI) in the potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in centrifugal solid-liquid separator, material obtained in the previous step is carried out solid-liquid separate, solid-phase material enters next step, and liquid phase material entered for the tenth step and carries out electrochemical oxidation regeneration;
(5) alkali cleaning: in stirring tank, aqueous sodium hydroxide solution take concentration as 3.0mol/L is alkaline wash, 60 ℃ of wash temperatures, alkali cleaning is 10 to the pH value of system, by product in the solid-phase material generates thiamphenicol benzoic acid salt thiamphenicol benzoic acid and alkali cleaning agent reaction, the water-soluble solution of thiamphenicol benzoic acid salt is entered in the liquid phase, and unreacted raw material still is solid-phase material to methylsulfonyltoluene and reaction product to the mixture of methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in centrifugal solid-liquid separator, material obtained in the previous step is carried out solid-liquid separate, liquid phase material obtains by product to thiamphenicol benzoic acid through further separation and purification, and solid-phase material enters next step;
(7) alcohol wash: in stirring tank, with solid-phase material obtained in the previous step 70 ℃ lower be that 90% aqueous ethanolic solution washs with massfraction, methylsulfonyltoluene is entered liquid phase, solid-phase material is to the methylsulfonyl phenyl aldehyde;
(8) solid-liquid separates: in centrifugal solid-liquid separator, material obtained in the previous step is carried out solid-liquid to be separated, liquid phase material obtains aqueous ethanolic solution through further separation and reaches methylsulfonyltoluene, wherein the raw material of methylsulfonyltoluene as the 3rd step chemical oxidation recycled, aqueous ethanolic solution then recycles as the pure washing lotion in the 7th step, and solid-phase material enters next step;
(9) drying: in drying plant, solid-phase material obtained in the previous step is carried out drying treatment under 90 ℃, obtain methylsulfonyl phenyl aldehyde product;
(10) electrochemical oxidation: in the plate electrochemical reactor of positively charged ion barrier film, liquid phase material in the 4th step is carried out electrochemical oxidation, make Cr (III) be converted into Cr (VI), in the electrochemical oxidation system, the concentration of sulfuric acid is 2.0mol/L, service temperature is 50 ℃, actuating current density 1000A/m
2, the Cr (VI) that regeneration obtains enters second step as the Recycling of oxidize use of oxidizing reaction.
Embodiment four
Main technique equipment: stirred-tank reactor, three-dimensional electrochemical reactor, vane-type solid-liquid separator, fusion apparatus, preliminary heating device, washing plant, drying plant etc.
Method steps is as follows:
(1) melting: in the falling film type fusion apparatus, will be warmed up to 120 ℃ to methylsulfonyltoluene, and make that to be in solid-state under the room temperature be liquid material to the methylsulfonyltoluene melting;
(2) preheating: in stirring tank, add aqueous sulfuric acid and oxygenant potassium bichromate, heat to 120 ℃, the concentration of potassium bichromate is 2.0mol/L in the system, the concentration of sulfuric acid is 4.0mol/L, and system is in liquid state when by heat temperature raising this material being mixed to methylsulfonyltoluene with raw material;
(3) chemical oxidation: in stirred-tank reactor, with previous step through the aqueous sulfuric acid of the potassium bichromate of preheating join reaction raw materials through melting to methylsulfonyltoluene in, mol ratio to methylsulfonyltoluene and oxygenant potassium bichromate is 1:0.5, service temperature is 120 ℃, potassium bichromate will be to the methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid to the methylsulfonyltoluene selective oxidation, Cr (VI) in the potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in the vane-type solid-liquid separator, material obtained in the previous step is carried out solid-liquid separate, solid-phase material enters next step, and liquid phase material entered for the tenth step and carries out electrochemical oxidation regeneration;
(5) alkali cleaning: in stirring tank, take concentration as the 1.0mol/L saleratus and the 1.0mol/L potassium hydroxide aqueous solution as alkaline wash, the alkali cleaning service temperature is 50 ℃, alkali cleaning is to 10 of system, by product in the solid-phase material generates thiamphenicol benzoic acid salt thiamphenicol benzoic acid and alkali cleaning agent reaction, the water-soluble solution of thiamphenicol benzoic acid salt is entered in the liquid phase, and unreacted raw material still is solid-phase material to methylsulfonyltoluene and reaction product to the mixture of methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in the vane-type solid-liquid separator, material obtained in the previous step is carried out solid-liquid separate, liquid phase material obtains by product to thiamphenicol benzoic acid through further separation and purification, and solid-phase material enters next step;
(7) alcohol wash: in stirring tank, with solid-phase material obtained in the previous step 60 ℃ lower be that 95% aqueous ethanolic solution washs with massfraction, methylsulfonyltoluene is entered liquid phase, solid-phase material is to the methylsulfonyl phenyl aldehyde;
(8) solid-liquid separates: in the vane-type solid-liquid separator, material obtained in the previous step is carried out solid-liquid to be separated, liquid phase material obtains aqueous ethanolic solution through further separation and reaches methylsulfonyltoluene, wherein the raw material of methylsulfonyltoluene as the 3rd step chemical oxidation recycled, aqueous ethanolic solution then recycles as the pure washing lotion in the 7th step, and solid-phase material enters next step;
(9) drying: in drying plant, solid-phase material obtained in the previous step is carried out drying treatment under 100 ℃, obtain methylsulfonyl phenyl aldehyde product;
(10) electrochemical oxidation: in positively charged ion barrier film three-dimensional electrochemical reactor, liquid phase material in the 4th step is carried out electrochemical oxidation, make Cr (III) be converted into Cr (VI), in the electrochemical oxidation system, the concentration of sulfuric acid is 4.0mol/L, service temperature is 60 ℃, and actuating current density is 150A/m
2, the Cr (VI) that regeneration obtains enters second step as the Recycling of oxidize use of oxidizing reaction.
Embodiment five
Main technique equipment: stirred-tank reactor, three-dimensional electrochemical reactor, decanter type solid-liquid separator, fusion apparatus, preliminary heating device, washing plant, drying plant etc.
Method steps is as follows:
(1) melting: in stirring tank, will be warmed up to 150 ℃ to methylsulfonyltoluene, and make that to be in solid-state under the room temperature be liquid material to the methylsulfonyltoluene melting;
(2) preheating: in stirring tank, add aqueous sulfuric acid and oxygenant potassium bichromate, heat to 120 ℃, the concentration of potassium bichromate is 3.0mol/L in the system, the concentration of sulfuric acid is 8.0mol/L, and system is in liquid state when by heat temperature raising this material being mixed to methylsulfonyltoluene with raw material;
(3) chemical oxidation: in stirred-tank reactor, with previous step through the aqueous sulfuric acid of the potassium bichromate of preheating join reaction raw materials through melting to methylsulfonyltoluene in, mol ratio to methylsulfonyltoluene and oxygenant potassium bichromate is 1:0.60, service temperature is 150 ℃, potassium bichromate will be to the methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid to the methylsulfonyltoluene selective oxidation, Cr (VI) in the potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in the decanter type solid-liquid separator, material obtained in the previous step is carried out solid-liquid separate, solid-phase material enters next step, and liquid phase material entered for the tenth step and carries out electrochemical oxidation regeneration;
(5) alkali cleaning: in stirring tank, sodium bicarbonate take total concn as 6.0mol/L and the aqueous solution of salt of wormwood are alkaline wash, the alkali cleaning service temperature is 40 ℃, alkali cleaning is 8 to the pH value of system, by product in the solid-phase material generates thiamphenicol benzoic acid salt thiamphenicol benzoic acid and alkali cleaning agent reaction, the water-soluble solution of thiamphenicol benzoic acid salt is entered in the liquid phase, and unreacted raw material still is solid-phase material to methylsulfonyltoluene and reaction product to the mixture of methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in the decanter type solid-liquid separator, in the solid-liquid separating device, material obtained in the previous step is carried out solid-liquid separate, liquid phase material obtains by product to thiamphenicol benzoic acid through further separation and purification, and solid-phase material enters next step;
(7) alcohol wash: in stirring tank, be the washing of 70% aqueous ethanolic solution with massfraction with solid-phase material obtained in the previous step down at 80 ℃, methylsulfonyltoluene is entered liquid phase, solid-phase material is to the methylsulfonyl phenyl aldehyde;
(8) solid-liquid separates: in the decanter type solid-liquid separator, material obtained in the previous step is carried out solid-liquid to be separated, liquid phase material obtains aqueous ethanolic solution through further separation and reaches methylsulfonyltoluene, wherein the raw material of methylsulfonyltoluene as the 3rd step chemical oxidation recycled, aqueous ethanolic solution then recycles as the pure washing lotion in the 7th step, and solid-phase material enters next step;
(9) drying: in drying plant, carry out drying treatment with under 100 ℃ of the solid-phase materials obtained in the previous step, obtain methylsulfonyl phenyl aldehyde product;
(10) electrochemical oxidation: in positively charged ion barrier film three-dimensional electrochemical reactor, liquid phase material in the 4th step is carried out electrochemical oxidation, make Cr (III) be converted into Cr (VI), in the electrochemical oxidation system, the concentration of sulfuric acid is 2.0mol/L, service temperature is 60 ℃, and actuating current density is 1000A/m
2, the Cr (VI) that regeneration obtains enters second step as the Recycling of oxidize use of oxidizing reaction.
Embodiment six
Main technique equipment: static mixing reactor, three-dimensional electrochemical reactor, centrifugal solid-liquid separator, fusion apparatus, preliminary heating device, washing plant, solid-liquid separating device, drying plant etc.
Method steps is as follows:
(1) melting: in stirring tank, will be warmed up to 120 ℃ to methylsulfonyltoluene, and make that to be in solid-state under the room temperature be liquid material to the methylsulfonyltoluene melting;
(2) preheating: in stirring tank, add aqueous sulfuric acid and oxygenant potassium bichromate, heat to 20 ℃, the concentration of potassium bichromate is 1.0mol/L in the system, the concentration of sulfuric acid is 2.0mol/L, and system is in liquid state when by heat temperature raising this material being mixed to methylsulfonyltoluene with raw material;
(3) chemical oxidation: in static mixing reactor, with previous step through the aqueous sulfuric acid of the potassium bichromate of preheating join reaction raw materials through melting to methylsulfonyltoluene in, mol ratio to methylsulfonyltoluene and oxygenant potassium bichromate is 1:0.5, service temperature is 100 ℃, potassium bichromate will be to the methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid to the methylsulfonyltoluene selective oxidation, Cr (VI) in the potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in centrifugal solid-liquid separator, material obtained in the previous step is carried out solid-liquid separate, solid-phase material enters next step, and liquid phase material entered for the tenth step and carries out electrochemical oxidation regeneration;
(5) alkali cleaning: in stirring tank, be that the yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, sodium hydroxide, potassium hydroxide aqueous solution of 6.0mol/L is as alkaline wash with total concn, the alkali cleaning service temperature is 50 ℃, alkali cleaning is 10 to the pH value of system, by product in the solid-phase material generates thiamphenicol benzoic acid salt thiamphenicol benzoic acid and alkali cleaning agent reaction, the water-soluble solution of thiamphenicol benzoic acid salt is entered in the liquid phase, and unreacted raw material still is solid-phase material to methylsulfonyltoluene and reaction product to the mixture of methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in centrifugal solid-liquid separator, in the solid-liquid separating device, material obtained in the previous step is carried out solid-liquid separate, liquid phase material obtains by product to thiamphenicol benzoic acid through further separation and purification, and solid-phase material enters next step;
(7) alcohol wash: in stirring tank, with solid-phase material obtained in the previous step 80 ℃ lower be that 85% aqueous ethanolic solution washs with massfraction, methylsulfonyltoluene is entered liquid phase, solid-phase material is to the methylsulfonyl phenyl aldehyde;
(8) solid-liquid separates: in centrifugal solid-liquid separator, material obtained in the previous step is carried out solid-liquid to be separated, liquid phase material obtains aqueous ethanolic solution through further separation and reaches methylsulfonyltoluene, wherein the raw material of methylsulfonyltoluene as the 3rd step chemical oxidation recycled, aqueous ethanolic solution then recycles as the pure washing lotion in the 7th step, and solid-phase material enters next step;
(9) drying: in drying plant, solid-phase material obtained in the previous step is carried out drying treatment under 100 ℃, obtain methylsulfonyl phenyl aldehyde product;
(10) electrochemical oxidation: in positively charged ion barrier film three-dimensional electrochemical reactor, liquid phase material in the 4th step is carried out electrochemical oxidation, make Cr (III) be converted into Cr (VI), in the electrochemical oxidation system, the concentration of sulfuric acid is 3.0mol/L, service temperature is 60 ℃, and actuating current density is 1800A/m
2, the Cr (VI) that regeneration obtains enters second step as the Recycling of oxidize use of oxidizing reaction.
Except the various embodiments described above, embodiment of the present invention also have a lot, and the technical scheme that all employings are equal to or equivalence is replaced is all within protection scope of the present invention.
Claims (8)
1. preparation method to the methylsulfonyl phenyl aldehyde, be take to methylsulfonyltoluene as raw material through the processing method of selective oxidation preparation to the methylsulfonyl phenyl aldehyde, it is characterized in that described method steps is as follows:
(1) melting: in fusion apparatus, will be warmed up to 90 ℃～150 ℃ to methylsulfonyltoluene, and make that to be in solid-state under the room temperature be liquid material to the methylsulfonyltoluene melting;
(2) preheating: in preliminary heating device, add aqueous sulfuric acid and oxygenant potassium bichromate, and heat to 90 ℃～120 ℃;
(3) chemical oxidation: in liquid-liquid-liquid heterogeneous reaction device, with previous step through the aqueous sulfuric acid of the potassium bichromate of preheating join through melting in the methylsulfonyltoluene, potassium bichromate will be to the methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid to the methylsulfonyltoluene selective oxidation, Cr (VI) in the potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in the solid-liquid separating device, material obtained in the previous step is carried out solid-liquid separate, solid-phase material enters next step, and liquid phase material entered for the tenth step and carries out electrochemical oxidation regeneration;
(5) alkali cleaning: in washing plant, mixing, washing is carried out in alkali cleaning agent and solid-phase material obtained in the previous step, by product in the solid-phase material generates thiamphenicol benzoic acid salt thiamphenicol benzoic acid and alkali cleaning agent reaction, the water-soluble solution of thiamphenicol benzoic acid salt is entered in the liquid phase, and unreacted raw material still is solid-phase material to methylsulfonyltoluene and reaction product to the mixture of methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in the solid-liquid separating device, material obtained in the previous step is carried out solid-liquid separate, liquid phase material obtains by product to thiamphenicol benzoic acid through further separation and purification, and solid-phase material enters next step;
(7) alcohol wash: in washing plant, solid-phase material obtained in the previous step is washed with aqueous ethanolic solution under 60 ℃～80 ℃, methylsulfonyltoluene is entered liquid phase, solid-phase material is to the methylsulfonyl phenyl aldehyde;
(8) solid-liquid separates: in the solid-liquid separating device, material obtained in the previous step is carried out solid-liquid to be separated, liquid phase material obtains aqueous ethanolic solution through further separation and reaches methylsulfonyltoluene, wherein the raw material of methylsulfonyltoluene as the 3rd step chemical oxidation recycled, aqueous ethanolic solution then recycles as the pure washing lotion in the 7th step, and solid-phase material enters next step;
(9) drying: in drying plant, solid-phase material obtained in the previous step is carried out drying treatment under 80 ℃～100 ℃, obtain methylsulfonyl phenyl aldehyde product;
(10) electrochemical oxidation: in electrochemical reactor, liquid phase material in the 4th step is carried out electrochemical oxidation, make Cr (III) be converted into Cr (VI), the Cr (VI) that regeneration obtains enters second step as the Recycling of oxidize use of oxidizing reaction.
2. described preparation method to the methylsulfonyl phenyl aldehyde according to claim 1, it is characterized in that: in described (2) the step pre-heating step, the concentration of oxygenant potassium bichromate is 0.5mol/L～3.0mol/L, and the concentration of sulfuric acid is 0.1mol/L～8.0mol/L.
3. described preparation method to the methylsulfonyl phenyl aldehyde according to claim 1, it is characterized in that: described (3) step chemical oxidation step is that the aqueous sulfuric acid with potassium bichromate joins in the methylsulfonyltoluene, mol ratio to methylsulfonyltoluene and oxygenant potassium bichromate is 1:0.20～0.60, and service temperature is 90 ℃～150 ℃.
4. described preparation method to the methylsulfonyl phenyl aldehyde according to claim 1, it is characterized in that: the reactor of described (3) step chemical oxidation is any one in stirred-tank reactor or the static mixing reactor.
5. described preparation method to the methylsulfonyl phenyl aldehyde according to claim 1, it is characterized in that: in (5) the step alkali cleaning step, described alkali cleaning agent is the aqueous solution of any one or arbitrary combination in yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, sodium hydroxide, the potassium hydroxide, the concentration of alkali cleaning agent is 0.1mol/L～6.0mol/L, the alkali cleaning service temperature is 20 ℃～60 ℃, and alkali cleaning is 8～10 to the pH value of system.
6. described preparation method to the methylsulfonyl phenyl aldehyde according to claim 1, it is characterized in that: in described (7) the step alcohol wash step, the massfraction of aqueous ethanolic solution is 70%～95%.
7. described preparation method to the methylsulfonyl phenyl aldehyde according to claim 1, it is characterized in that: (4) step, (6) step and described solid-liquid separating device of (8) step are any one in decanter type or filtering type or centrifugal or the vane-type solid-liquid separating device.
8. described preparation method to the methylsulfonyl phenyl aldehyde according to claim 1, it is characterized in that: described (10) one-step electrochemistry oxidation reactor is plate electrochemical reactor or three-dimensional electrochemical reactor, anolyte compartment and the cathode compartment of reactor are isolated by barrier film, barrier film preferred cationic film.In the electrochemical oxidation system, the concentration of sulfuric acid is 0.5mol/L～4.0mol/L, and service temperature is 20 ℃～60 ℃, and actuating current density is 500A/m
2～2000A/m
2
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| CN104805466B (en) * | 2015-04-09 | 2017-12-19 | 嘉兴学院 | A kind of indirect electrooxidation prepares method of the adjacent nitro to thiamphenicol benzoic acid |
| CN113149875A (en) * | 2021-04-27 | 2021-07-23 | 浙江嘉福新材料科技有限公司 | Method for preparing p-methylsulfonylbenzaldehyde by continuous flow |
| WO2024127254A1 (en) * | 2022-12-15 | 2024-06-20 | Nova Chemicals (International) S.A. | Concentration of aqueous acetic acid by clathrate hydrate formation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104805466B (en) * | 2015-04-09 | 2017-12-19 | 嘉兴学院 | A kind of indirect electrooxidation prepares method of the adjacent nitro to thiamphenicol benzoic acid |
| CN106883155A (en) * | 2017-03-31 | 2017-06-23 | 江西天戌药业有限公司 | A kind of synthetic method to MSM benzaldehyde |
| CN113149875A (en) * | 2021-04-27 | 2021-07-23 | 浙江嘉福新材料科技有限公司 | Method for preparing p-methylsulfonylbenzaldehyde by continuous flow |
| WO2024127254A1 (en) * | 2022-12-15 | 2024-06-20 | Nova Chemicals (International) S.A. | Concentration of aqueous acetic acid by clathrate hydrate formation |
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