CN103360287B - MethyIsuIfino benzaldehyde preparation method - Google Patents
MethyIsuIfino benzaldehyde preparation method Download PDFInfo
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- CN103360287B CN103360287B CN201310302438.0A CN201310302438A CN103360287B CN 103360287 B CN103360287 B CN 103360287B CN 201310302438 A CN201310302438 A CN 201310302438A CN 103360287 B CN103360287 B CN 103360287B
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- phenyl aldehyde
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 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 40
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 40
- 239000003513 alkali Substances 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 33
- 238000005406 washing Methods 0.000 claims abstract description 33
- 239000000126 substance Substances 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 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 108
- -1 methylsulfonyl phenyl aldehyde Chemical class 0.000 claims description 95
- 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
- 239000002994 raw material Substances 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 38
- 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 34
- 239000005711 Benzoic acid Substances 0.000 claims description 33
- 235000010233 benzoic acid Nutrition 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 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
- 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
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000012528 membrane Substances 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
- 150000002500 ions Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 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
- 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
- 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
- 238000006460 hydrolysis reaction Methods 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
- 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
- 239000002253 acid Substances 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
- 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
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 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 methylsulfonyl phenyl aldehyde, particularly a kind of so that methylsulfonyltoluene is prepared to the method to methylsulfonyl phenyl aldehyde as raw material chemical oxidation, belong to fine chemical technology field.
Background technology
Being a kind of aromatics to methylsulfonyltoluene, is the powder of white crystals shape under normal temperature, and molecular formula is C
8h
10o
2s, 88 DEG C～89 DEG C of melting ranges, 312 DEG C of boiling points, density is 1.154g/cm
3, be dissolved in the organic solvent 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 methylsulfonyl phenyl aldehyde.English name 4-Methylsulfonyl benzaldehyde, English another name p-methylsufonyl benzaldehyde, molecular formula is C
8h
8o
3s, molecular weight is 184.21.Be yellow crystal powder to methylsulfonyl phenyl aldehyde, density is 1.289g/cm
3, fusing point is 155 DEG C～161 DEG C, boiling point is 378.3 DEG C, is slightly soluble in water.
A kind of important medicine intermediate to methylsulfonyl phenyl aldehyde, mainly for the production of Broad spectrum antibiotics thiamphenicol, be also the intermediate of producing beta-lactam antiseptic-germicide, white dyes, dihydrogen pyridine derivative class antianginal drug and anti-inflammatory antirheumatic medicine simultaneously.
Chinese patent (201210350777.1) discloses a kind of so that methylsulfonyltoluene is prepared to the method to methylsulfonyl phenyl aldehyde as raw material.This processing method taking to methylsulfonyltoluene as raw material, obtain methylsulfonyl dibromomethylbenzene through high temperature bromination, directly join in the hydrobromic water making containing bromination reactive absorption and be hydrolyzed, obtain methylsulfonyl phenyl aldehyde crude product.
Chinese patent (201210560425.9) discloses a kind of to methylsulfonyl phenyl aldehyde synthetic method, this processing method taking to methylsulfonyltoluene and bromine as raw material, at 100 DEG C～200 DEG C, add catalyst reaction to obtain liquid crude product to methylsulfonyl dibromomethylbenzene; Remove the hydrogen bromide and the unreacted bromine that in reaction, produce; Obtain product to methylsulfonyl dibromomethylbenzene through neutralization, washing; Obtain to methylsulfonyl dibromomethylbenzene in add the water reaction that is hydrolyzed; Cooling, filtration, dry obtaining 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 taking to methylsulfonyltoluene as raw material, heating is lower react generation 4-methylsulfonyl dibromomethylbenzene with bromine, then obtains methylsulfonyl phenyl aldehyde through being hydrolyzed, its chemical equation is:
It is existing so that methylsulfonyltoluene is had to 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 to need a large amount of chlorine or bromines of using to methylsulfonyl phenyl aldehyde, conventionally there is the by products such as a replacement, three replacements in operation, follow light and heat simultaneously, reaction is difficult control but also easily to environment not only, and chlorine or bromine also quite serious to the corrosion of equipment;
(2) technical process is long, and yield is low, and the reaction product complexity obtaining 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, seriously polluted.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, provide that a kind of technique is reasonable, preparation method is simple, production cost is low, product purity is high, the process for cleanly preparing to methylsulfonyl phenyl aldehyde of process safety.
The technical scheme that realizes above-mentioned purpose is: a kind of preparation method to methylsulfonyl phenyl aldehyde is that described method steps is as follows so that methylsulfonyltoluene is prepared to the processing method to methylsulfonyl phenyl aldehyde as raw material through selective oxidation:
(1) melting: in fusion apparatus, will be warmed up to 90 DEG C～150 DEG C to methylsulfonyltoluene, make under room temperature in solid-state be liquid material to methylsulfonyltoluene melting;
(2) preheating: in preliminary heating device, add aqueous sulfuric acid and oxygenant potassium bichromate, and heat to 90 DEG C～120 DEG C;
(3) chemical oxidation: in liquid-liquid-liquid heterogeneous reaction device, by previous step through the aqueous sulfuric acid of the potassium bichromate of preheating join through melting in methylsulfonyltoluene, potassium bichromate will be to methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid to methylsulfonyltoluene selective oxidation, Cr (VI) in potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in solid-liquid separating device, material obtained in the previous step is carried out to solid-liquid separation, solid-phase material enters next step, and liquid phase material enters the tenth step and carries out electrochemical oxidation regeneration;
(5) alkali cleaning: in washing plant, alkali cleaning agent and solid-phase material obtained in the previous step are carried out to mixing, washing, by product in solid-phase material reacts with alkali cleaning agent thiamphenicol benzoic acid and generates thiamphenicol benzoic acid salt, the water-soluble solution of thiamphenicol benzoic acid salt is entered in liquid phase, and unreacted raw material is still solid-phase material to methylsulfonyltoluene and reaction product to the mixture of methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in solid-liquid separating device, material obtained in the previous step is carried out to solid-liquid separation, 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 at 60 DEG C～80 DEG C, methylsulfonyltoluene is entered to liquid phase, solid-phase material is to methylsulfonyl phenyl aldehyde;
(8) solid-liquid separates: in solid-liquid separating device, material obtained in the previous step is carried out to solid-liquid separation, liquid phase material obtains aqueous ethanolic solution and to methylsulfonyltoluene through further separating, wherein methylsulfonyltoluene is recycled as the raw material of the 3rd step chemical oxidation, aqueous ethanolic solution recycles as the alcohol washing lotion of the 7th step, and solid-phase material enters next step;
(9) dry: in drying plant, solid-phase material obtained in the previous step to be carried out to drying treatment at 80 DEG C～100 DEG C, obtain methylsulfonyl phenyl aldehyde product;
(10) electrochemical oxidation: in electrochemical reactor, liquid phase material in the 4th step is carried out to electrochemical oxidation, make Cr (III) be converted into Cr (VI), the Cr (VI) that regeneration obtains enters second step and uses as the Recycling of oxidize of oxidizing reaction.
Further, in 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, the 3rd described step chemical oxidation step is that the aqueous sulfuric acid of potassium bichromate is joined in methylsulfonyltoluene, is 1:0.20～0.60 to the mol ratio of methylsulfonyltoluene and oxygenant potassium bichromate, and service temperature is 90 DEG C～150 DEG C.
Further, the reactor of the 3rd described step chemical oxidation is any one in stirred-tank reactor or 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 sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus, sodium hydroxide, 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 DEG C～60 DEG C.
Further, in described the 7th step alcohol wash step, the massfraction of aqueous ethanolic solution is 70%～95%.
Further, the solid-liquid separating device described in the 4th step, the 6th step and the 8th step is any one in decanter type or filtering type or centrifugal or 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 electrochemical oxidation system, the concentration of sulfuric acid is 0.5mol/L～4.0mol/L, and service temperature is 20 DEG C～60 DEG C, and actuating current density is 500A/m
2～2000A/m
2.
The major equipment that realizing 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) methylsulfonyltoluene selective oxidation is generated 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 the reaction (taking sodium carbonate as example) of by product to thiamphenicol benzoic acid:
Adopt principle and the advantage of technique scheme to be:
(1) utilize methylsulfonyltoluene oxidizable feature under acidic conditions, by the acidity of regulation and control reactive system and the oxidisability of temperature of reaction adjusting potassium bichromate, realize the selective oxidation to methylsulfonyltoluene, thereby obtain methylsulfonyl phenyl aldehyde product.In order to make that the selective oxidation of methylsulfonyltoluene is rested on methylsulfonyl phenyl aldehyde is not continued to be oxidized to thiamphenicol benzoic acid, in reaction process, be that the sulphuric acid soln of potassium bichromate is joined in methylsulfonyltoluene, and in reaction process oxygenant potassium bichromate as control component, to regulate and control the degree of depth of oxidizing reaction.
(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 selective oxidation process as raw material, generate to methylsulfonyl phenyl aldehyde can be further to thiamphenicol benzoic acid by deep oxidation, therefore, in reaction product except containing methylsulfonyl phenyl aldehyde, also contain unreacted raw material to methylsulfonyltoluene and by product to thiamphenicol benzoic acid, therefore 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 thiamphenicol benzoic acid physical property, raw material is recycled in to 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.Utilize to less to thiamphenicol benzoic acid solubleness in water, with easily salify and the salt that 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 be still solid phase to methylsulfonyl phenyl aldehyde, thereby will be to thiamphenicol benzoic acid be separated and is removed from mixture.
2. to methylsulfonyltoluene and separating methylsulfonyl phenyl aldehyde.At the same temperature, the solubleness to methylsulfonyltoluene in aqueous ethanolic solution is greater than methylsulfonyl phenyl aldehyde, and along with the rising of temperature, solubleness obviously increases.Therefore, utilize to methylsulfonyltoluene with to the methylsulfonyl phenyl aldehyde difference that solubleness and solubility with temperature change in aqueous ethanolic solution, adopt aqueous ethanolic solution washing to methylsulfonyltoluene and to methylsulfonyl phenyl aldehyde mixed solution, wash away methylsulfonyltoluene, thereby realize methylsulfonyltoluene and separating methylsulfonyl phenyl aldehyde.Can continue to use as raw material through further separating treatment to methylsulfonyltoluene.
Technique of the present invention is reasonable, and 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 green chemical industry demand for development.
Brief description of the drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further detailed explanation.
Embodiment mono-
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 methylsulfonyl phenyl aldehyde is that described method steps is as follows so that methylsulfonyltoluene is prepared to the processing method to methylsulfonyl phenyl aldehyde as raw material through selective oxidation:
(1) melting: in stirring tank, will be warmed up to 90 DEG C to methylsulfonyltoluene, make under room temperature in solid-state be liquid material to methylsulfonyltoluene melting;
(2) preheating: in stirring tank, add aqueous sulfuric acid and oxygenant potassium bichromate, heat to 90 DEG C, in system, the concentration of potassium bichromate is 0.5mol/L, the concentration of sulfuric acid is 0.1mol/L, and this material is mixed by heat temperature raising to methylsulfonyltoluene during with raw material, system is in liquid state;
(3) chemical oxidation: in stirred-tank reactor, by previous step through the aqueous sulfuric acid of the potassium bichromate of preheating join through melting in methylsulfonyltoluene, be 1:0.20 to the mol ratio of methylsulfonyltoluene and oxygenant potassium bichromate, service temperature is 90 DEG C, potassium bichromate will be to methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid to methylsulfonyltoluene selective oxidation, Cr (VI) in potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in decanter type solid-liquid separator, material obtained in the previous step is carried out to solid-liquid separation, solid-phase material enters next step, and liquid phase material enters the tenth step and carries out electrochemical oxidation regeneration;
(5) alkali cleaning: in stirring tank, taking 0.1mol/L aqueous sodium carbonate as alkaline wash, service temperature is 20 DEG C, alkali cleaning is 8 to the pH value of system, by product in solid-phase material reacts with alkali cleaning agent thiamphenicol benzoic acid and generates thiamphenicol benzoic acid salt, the water-soluble solution of thiamphenicol benzoic acid salt is entered in liquid phase, and unreacted raw material is still solid-phase material to methylsulfonyltoluene and reaction product to the mixture of methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in decanter type solid-liquid separator, material obtained in the previous step is carried out to solid-liquid separation, 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 70% aqueous ethanolic solution washing by solid-phase material obtained in the previous step at 60 DEG C with massfraction, methylsulfonyltoluene is entered to liquid phase, solid-phase material is to methylsulfonyl phenyl aldehyde;
(8) solid-liquid separates: in decanter type solid-liquid separator, material obtained in the previous step is carried out to solid-liquid separation, liquid phase material obtains aqueous ethanolic solution and to methylsulfonyltoluene through further separating, wherein methylsulfonyltoluene is recycled as the raw material of the 3rd step chemical oxidation, aqueous ethanolic solution recycles as the alcohol washing lotion of the 7th step, and solid-phase material enters next step;
(9) dry: in drying plant, solid-phase material obtained in the previous step to be carried out to drying treatment at 80 DEG C, 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 to electrochemical oxidation, make Cr (III) be converted into Cr (VI), in reaction system, the concentration of sulfuric acid is 0.5mol/L, service temperature is 20 DEG C, and actuating current density is 500A/m
2, the Cr (VI) that regeneration obtains enters second step and uses as the Recycling of oxidize of oxidizing reaction.
Embodiment bis-
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 falling film type fusion apparatus, will be warmed up to 150 DEG C to methylsulfonyltoluene, make under room temperature in solid-state be liquid material to methylsulfonyltoluene melting;
(2) preheating: in stirring tank, add aqueous sulfuric acid and oxygenant potassium bichromate, heat to 120 DEG C, in system, the concentration of potassium bichromate is 3.0mol/L, the concentration of sulfuric acid is 8.0mol/L, and this material is mixed by heat temperature raising to methylsulfonyltoluene during with raw material, system is in liquid state;
(3) chemical oxidation: in static mixing reactor, by previous step through the aqueous sulfuric acid of the potassium bichromate of preheating join reaction raw materials through melting to methylsulfonyltoluene in, be 1:0.60 to the mol ratio of methylsulfonyltoluene and oxygenant potassium bichromate, service temperature is 150 DEG C, potassium bichromate will be to methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid to methylsulfonyltoluene selective oxidation, Cr (VI) in potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in filtering type solid-liquid separator, material obtained in the previous step is carried out to solid-liquid separation, solid-phase material enters next step, and liquid phase material enters the tenth step and carries out electrochemical oxidation regeneration;
(5) alkali cleaning: in stirring tank, wet chemical taking concentration as 6.0mol/L is alkaline wash, service temperature is 60 DEG C, alkali cleaning is 10 to the pH value of system, by product in solid-phase material generates thiamphenicol benzoic acid salt sour the reaction with alkali cleaning agent of methylsulfonyltoluene, the water-soluble solution of thiamphenicol benzoic acid salt is entered in liquid phase, and unreacted raw material is still solid-phase material to methylsulfonyltoluene and reaction product to the mixture of methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in filtering type solid-liquid separator, material obtained in the previous step is carried out to solid-liquid separation, 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, by solid-phase material obtained in the previous step aqueous ethanolic solution washing with massfraction 95% at 80 DEG C, methylsulfonyltoluene is entered to liquid phase, solid-phase material is to methylsulfonyl phenyl aldehyde;
(8) solid-liquid separates: in filtering type solid-liquid separator, material obtained in the previous step is carried out to solid-liquid separation, liquid phase material obtains aqueous ethanolic solution and to methylsulfonyltoluene through further separating, wherein methylsulfonyltoluene is recycled as the raw material of the 3rd step chemical oxidation, aqueous ethanolic solution recycles as the alcohol washing lotion of the 7th step, and solid-phase material enters next step;
(9) dry: in drying plant, solid-phase material obtained in the previous step to be carried out at 100 DEG C to drying treatment, 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 to electrochemical oxidation, make Cr (III) be converted into Cr (VI), in reaction system, the concentration of sulfuric acid is 4.0mol/L, service temperature is 60 DEG C, and actuating current density is 2000A/m
2, the Cr (VI) that regeneration obtains enters second step and uses as the Recycling of oxidize of oxidizing reaction.
Embodiment tri-
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 DEG C to methylsulfonyltoluene, make under room temperature in solid-state be liquid material to methylsulfonyltoluene melting;
(2) preheating: in stirring tank, add aqueous sulfuric acid and oxygenant potassium bichromate, heat to 100 DEG C, in system, the concentration of potassium bichromate is 2.0mol/L, the concentration of sulfuric acid is 4.0mol/L, and this material is mixed by heat temperature raising to methylsulfonyltoluene during with raw material, system is in liquid state;
(3) chemical oxidation: in static mixing reactor, by previous step through the aqueous sulfuric acid of the potassium bichromate of preheating join reaction raw materials through melting to methylsulfonyltoluene in, be 1:0.50 to the mol ratio of methylsulfonyltoluene and oxygenant potassium bichromate, service temperature is 120 DEG C, potassium bichromate will be to methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid to methylsulfonyltoluene selective oxidation, Cr (VI) in 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 to solid-liquid separation, solid-phase material enters next step, and liquid phase material enters the tenth step and carries out electrochemical oxidation regeneration;
(5) alkali cleaning: in stirring tank, aqueous sodium hydroxide solution taking concentration as 3.0mol/L is alkaline wash, 60 DEG C of wash temperatures, alkali cleaning is 10 to the pH value of system, by product in solid-phase material reacts with alkali cleaning agent thiamphenicol benzoic acid and generates thiamphenicol benzoic acid salt, the water-soluble solution of thiamphenicol benzoic acid salt is entered in liquid phase, and unreacted raw material is still 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 to solid-liquid separation, 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, the aqueous ethanolic solution that is 90% with massfraction at 70 DEG C by solid-phase material obtained in the previous step washing, enters liquid phase to methylsulfonyltoluene, and solid-phase material is to methylsulfonyl phenyl aldehyde;
(8) solid-liquid separates: in centrifugal solid-liquid separator, material obtained in the previous step is carried out to solid-liquid separation, liquid phase material obtains aqueous ethanolic solution and to methylsulfonyltoluene through further separating, wherein methylsulfonyltoluene is recycled as the raw material of the 3rd step chemical oxidation, aqueous ethanolic solution recycles as the alcohol washing lotion of the 7th step, and solid-phase material enters next step;
(9) dry: in drying plant, solid-phase material obtained in the previous step to be carried out at 90 DEG C to drying treatment, 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 to electrochemical oxidation, make Cr (III) be converted into Cr (VI), in electrochemical oxidation system, the concentration of sulfuric acid is 2.0mol/L, service temperature is 50 DEG C, actuating current density 1000A/m
2, the Cr (VI) that regeneration obtains enters second step and uses as the Recycling of oxidize of oxidizing reaction.
Embodiment tetra-
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 falling film type fusion apparatus, will be warmed up to 120 DEG C to methylsulfonyltoluene, make under room temperature in solid-state be liquid material to methylsulfonyltoluene melting;
(2) preheating: in stirring tank, add aqueous sulfuric acid and oxygenant potassium bichromate, heat to 120 DEG C, in system, the concentration of potassium bichromate is 2.0mol/L, the concentration of sulfuric acid is 4.0mol/L, and this material is mixed by heat temperature raising to methylsulfonyltoluene during with raw material, system is in liquid state;
(3) chemical oxidation: in stirred-tank reactor, by previous step through the aqueous sulfuric acid of the potassium bichromate of preheating join reaction raw materials through melting to methylsulfonyltoluene in, be 1:0.5 to the mol ratio of methylsulfonyltoluene and oxygenant potassium bichromate, service temperature is 120 DEG C, potassium bichromate will be to methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid to methylsulfonyltoluene selective oxidation, Cr (VI) in potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in vane-type solid-liquid separator, material obtained in the previous step is carried out to solid-liquid separation, solid-phase material enters next step, and liquid phase material enters the tenth step and carries out electrochemical oxidation regeneration;
(5) alkali cleaning: in stirring tank, taking concentration as 1.0mol/L saleratus and 1.0mol/L potassium hydroxide aqueous solution as alkaline wash, alkali cleaning service temperature is 50 DEG C, alkali cleaning is to 10 of system, by product in solid-phase material reacts with alkali cleaning agent thiamphenicol benzoic acid and generates thiamphenicol benzoic acid salt, the water-soluble solution of thiamphenicol benzoic acid salt is entered in liquid phase, and unreacted raw material is still solid-phase material to methylsulfonyltoluene and reaction product to the mixture of methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in vane-type solid-liquid separator, material obtained in the previous step is carried out to solid-liquid separation, 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, the aqueous ethanolic solution that is 95% with massfraction at 60 DEG C by solid-phase material obtained in the previous step washing, enters liquid phase to methylsulfonyltoluene, and solid-phase material is to methylsulfonyl phenyl aldehyde;
(8) solid-liquid separates: in vane-type solid-liquid separator, material obtained in the previous step is carried out to solid-liquid separation, liquid phase material obtains aqueous ethanolic solution and to methylsulfonyltoluene through further separating, wherein methylsulfonyltoluene is recycled as the raw material of the 3rd step chemical oxidation, aqueous ethanolic solution recycles as the alcohol washing lotion of the 7th step, and solid-phase material enters next step;
(9) dry: in drying plant, solid-phase material obtained in the previous step to be carried out at 100 DEG C to drying treatment, 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 to electrochemical oxidation, make Cr (III) be converted into Cr (VI), in electrochemical oxidation system, the concentration of sulfuric acid is 4.0mol/L, service temperature is 60 DEG C, and actuating current density is 150A/m
2, the Cr (VI) that regeneration obtains enters second step and uses as the Recycling of oxidize 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 DEG C to methylsulfonyltoluene, make under room temperature in solid-state be liquid material to methylsulfonyltoluene melting;
(2) preheating: in stirring tank, add aqueous sulfuric acid and oxygenant potassium bichromate, heat to 120 DEG C, in system, the concentration of potassium bichromate is 3.0mol/L, the concentration of sulfuric acid is 8.0mol/L, and this material is mixed by heat temperature raising to methylsulfonyltoluene during with raw material, system is in liquid state;
(3) chemical oxidation: in stirred-tank reactor, by previous step through the aqueous sulfuric acid of the potassium bichromate of preheating join reaction raw materials through melting to methylsulfonyltoluene in, be 1:0.60 to the mol ratio of methylsulfonyltoluene and oxygenant potassium bichromate, service temperature is 150 DEG C, potassium bichromate will be to methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid to methylsulfonyltoluene selective oxidation, Cr (VI) in potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in decanter type solid-liquid separator, material obtained in the previous step is carried out to solid-liquid separation, solid-phase material enters next step, and liquid phase material enters the tenth step and carries out electrochemical oxidation regeneration;
(5) alkali cleaning: in stirring tank, sodium bicarbonate taking total concn as 6.0mol/L and the aqueous solution of salt of wormwood are alkaline wash, alkali cleaning service temperature is 40 DEG C, alkali cleaning is 8 to the pH value of system, by product in solid-phase material reacts with alkali cleaning agent thiamphenicol benzoic acid and generates thiamphenicol benzoic acid salt, the water-soluble solution of thiamphenicol benzoic acid salt is entered in liquid phase, and unreacted raw material is still solid-phase material to methylsulfonyltoluene and reaction product to the mixture of methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in decanter type solid-liquid separator, in solid-liquid separating device, material obtained in the previous step is carried out to solid-liquid separation, 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 70% aqueous ethanolic solution washing by solid-phase material obtained in the previous step at 80 DEG C with massfraction, methylsulfonyltoluene is entered to liquid phase, solid-phase material is to methylsulfonyl phenyl aldehyde;
(8) solid-liquid separates: in decanter type solid-liquid separator, material obtained in the previous step is carried out to solid-liquid separation, liquid phase material obtains aqueous ethanolic solution and to methylsulfonyltoluene through further separating, wherein methylsulfonyltoluene is recycled as the raw material of the 3rd step chemical oxidation, aqueous ethanolic solution recycles as the alcohol washing lotion of the 7th step, and solid-phase material enters next step;
(9) dry: in drying plant, to carry out drying treatment by 100 DEG C of 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 to electrochemical oxidation, make Cr (III) be converted into Cr (VI), in electrochemical oxidation system, the concentration of sulfuric acid is 2.0mol/L, service temperature is 60 DEG C, and actuating current density is 1000A/m
2, the Cr (VI) that regeneration obtains enters second step and uses as the Recycling of oxidize 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 DEG C to methylsulfonyltoluene, make under room temperature in solid-state be liquid material to methylsulfonyltoluene melting;
(2) preheating: in stirring tank, add aqueous sulfuric acid and oxygenant potassium bichromate, heat to 20 DEG C, in system, the concentration of potassium bichromate is 1.0mol/L, the concentration of sulfuric acid is 2.0mol/L, and this material is mixed by heat temperature raising to methylsulfonyltoluene during with raw material, system is in liquid state;
(3) chemical oxidation: in static mixing reactor, by previous step through the aqueous sulfuric acid of the potassium bichromate of preheating join reaction raw materials through melting to methylsulfonyltoluene in, be 1:0.5 to the mol ratio of methylsulfonyltoluene and oxygenant potassium bichromate, service temperature is 100 DEG C, potassium bichromate will be to methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid to methylsulfonyltoluene selective oxidation, Cr (VI) in 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 to solid-liquid separation, solid-phase material enters next step, and liquid phase material enters the tenth step and carries out electrochemical oxidation regeneration;
(5) alkali cleaning: in stirring tank, the sodium carbonate that is 6.0mol/L by total concn, sodium bicarbonate, salt of wormwood, saleratus, sodium hydroxide, potassium hydroxide aqueous solution are as alkaline wash, alkali cleaning service temperature is 50 DEG C, alkali cleaning is 10 to the pH value of system, by product in solid-phase material reacts with alkali cleaning agent thiamphenicol benzoic acid and generates thiamphenicol benzoic acid salt, the water-soluble solution of thiamphenicol benzoic acid salt is entered in liquid phase, and unreacted raw material is still 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 solid-liquid separating device, material obtained in the previous step is carried out to solid-liquid separation, 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, the aqueous ethanolic solution that is 85% with massfraction at 80 DEG C by solid-phase material obtained in the previous step washing, enters liquid phase to methylsulfonyltoluene, and solid-phase material is to methylsulfonyl phenyl aldehyde;
(8) solid-liquid separates: in centrifugal solid-liquid separator, material obtained in the previous step is carried out to solid-liquid separation, liquid phase material obtains aqueous ethanolic solution and to methylsulfonyltoluene through further separating, wherein methylsulfonyltoluene is recycled as the raw material of the 3rd step chemical oxidation, aqueous ethanolic solution recycles as the alcohol washing lotion of the 7th step, and solid-phase material enters next step;
(9) dry: in drying plant, solid-phase material obtained in the previous step to be carried out at 100 DEG C to drying treatment, 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 to electrochemical oxidation, make Cr (III) be converted into Cr (VI), in electrochemical oxidation system, the concentration of sulfuric acid is 3.0mol/L, service temperature is 60 DEG C, and actuating current density is 1800A/m
2, the Cr (VI) that regeneration obtains enters second step and uses as the Recycling of oxidize 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, all within protection scope of the present invention.
Claims (9)
1. the preparation method to methylsulfonyl phenyl aldehyde, is so that methylsulfonyltoluene is prepared to the processing method to methylsulfonyl phenyl aldehyde as raw material through selective oxidation, it is characterized in that described method steps is as follows:
(1) melting: in fusion apparatus, will be warmed up to 90 DEG C～150 DEG C to methylsulfonyltoluene, make under room temperature in solid-state be liquid material to methylsulfonyltoluene melting;
(2) preheating: in preliminary heating device, add aqueous sulfuric acid and oxygenant potassium bichromate, and heat to 90 DEG C～120 DEG C;
(3) chemical oxidation: in liquid-liquid-liquid heterogeneous reaction device, by previous step through the aqueous sulfuric acid of the potassium bichromate of preheating join through melting in methylsulfonyltoluene, potassium bichromate will be to methylsulfonyl phenyl aldehyde with to thiamphenicol benzoic acid to methylsulfonyltoluene selective oxidation, Cr (VI) in potassium bichromate is reduced to Cr (III) simultaneously, and reacted material enters next step;
(4) solid-liquid separates: in solid-liquid separating device, material obtained in the previous step is carried out to solid-liquid separation, solid-phase material enters next step, and liquid phase material enters the tenth step and carries out electrochemical oxidation regeneration;
(5) alkali cleaning: in washing plant, alkali cleaning agent and solid-phase material obtained in the previous step are carried out to mixing, washing, by product in solid-phase material reacts with alkali cleaning agent thiamphenicol benzoic acid and generates thiamphenicol benzoic acid salt, the water-soluble solution of thiamphenicol benzoic acid salt is entered in liquid phase, and unreacted raw material is still solid-phase material to methylsulfonyltoluene and reaction product to the mixture of methylsulfonyl phenyl aldehyde;
(6) solid-liquid separates: in solid-liquid separating device, material obtained in the previous step is carried out to solid-liquid separation, 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 at 60 DEG C～80 DEG C, methylsulfonyltoluene is entered to liquid phase, solid-phase material is to methylsulfonyl phenyl aldehyde;
(8) solid-liquid separates: in solid-liquid separating device, material obtained in the previous step is carried out to solid-liquid separation, liquid phase material obtains aqueous ethanolic solution and to methylsulfonyltoluene through further separating, wherein methylsulfonyltoluene is recycled as the raw material of the 3rd step chemical oxidation, aqueous ethanolic solution recycles as the alcohol washing lotion of the 7th step, and solid-phase material enters next step;
(9) dry: in drying plant, solid-phase material obtained in the previous step to be carried out to drying treatment at 80 DEG C～100 DEG C, obtain methylsulfonyl phenyl aldehyde product;
(10) electrochemical oxidation: in electrochemical reactor, liquid phase material in the 4th step is carried out to electrochemical oxidation, make Cr (III) be converted into Cr (VI), the Cr (VI) that regeneration obtains enters second step and uses as the Recycling of oxidize of oxidizing reaction.
2. the preparation method to methylsulfonyl phenyl aldehyde according to claim 1, it is characterized in that: in (2) described 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. the preparation method to methylsulfonyl phenyl aldehyde according to claim 1, it is characterized in that: (3) described step chemical oxidation step is that the aqueous sulfuric acid of potassium bichromate is joined in methylsulfonyltoluene, be 1:0.20～0.60 to the mol ratio of methylsulfonyltoluene and oxygenant potassium bichromate, service temperature is 90 DEG C～150 DEG C.
4. the preparation method to methylsulfonyl phenyl aldehyde according to claim 1, is characterized in that: the reactor of (3) described step chemical oxidation is any one in stirred-tank reactor or static mixing reactor.
5. the preparation method to methylsulfonyl phenyl aldehyde according to claim 1, it is characterized in that: in (5) step alkali cleaning step, described alkali cleaning agent is the aqueous solution of any one or arbitrary combination in sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus, sodium hydroxide, potassium hydroxide, the concentration of alkali cleaning agent is 0.1mol/L～6.0mol/L, alkali cleaning service temperature is 20 DEG C～60 DEG C, and alkali cleaning is 8～10 to the pH value of system.
6. the preparation method to methylsulfonyl phenyl aldehyde according to claim 1, is characterized in that: in described (7) step alcohol wash step, the massfraction of aqueous ethanolic solution is 70%～95%.
7. the preparation method to methylsulfonyl phenyl aldehyde according to claim 1, is characterized in that: the solid-liquid separating device described in (4) step, (6) step and (8) step is any one in decanter type or filtering type or centrifugal or vane-type solid-liquid separating device.
8. the preparation method to 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; In electrochemical oxidation system, the concentration of sulfuric acid is 0.5mol/L～4.0mol/L, and service temperature is 20 DEG C～60 DEG C, and actuating current density is 500A/m
2～2000A/m
2.
9. the preparation method to methylsulfonyl phenyl aldehyde according to claim 1, is characterized in that: described barrier film is cationic membrane.
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| CN103058899A (en) * | 2012-12-21 | 2013-04-24 | 山东润科化工股份有限公司 | Synthetic method for methyl-sulfuryl benzaldehyde |
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