CN102276434A - Method for producing vanillin - Google Patents
Method for producing vanillin Download PDFInfo
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- CN102276434A CN102276434A CN2011101815237A CN201110181523A CN102276434A CN 102276434 A CN102276434 A CN 102276434A CN 2011101815237 A CN2011101815237 A CN 2011101815237A CN 201110181523 A CN201110181523 A CN 201110181523A CN 102276434 A CN102276434 A CN 102276434A
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Abstract
The invention provides a method for producing vanillin. The vanillin is prepared from lignan which is taken as a raw material by the steps of condensing raw materials, acidizing condensed solution, extracting the lignan, oxidizing the condensed solution, decarboxylating oxidized solution, extracting the vanillin, distilling the vanillin, crystallizing the vanillin, regenerating a catalyst, and drying a vanillin product and packaging. In the method, the vanillin is prepared from the lignan which is taken as the raw material; and the method has the advantages that: the reaction process is continuous, auxiliary materials are recycled, harmful substances are not discharged, the environment is not polluted, and the prepared vanillin product is high in yield and has few impurities. The method can be applied to the production of vanillin spice.
Description
Technical field
What the present invention proposed is chemical field material synthetic method, specifically a kind of production method of vanillin food grade,1000.000000ine mesh.
Background technology
Vanillin food grade,1000.000000ine mesh:
Chinese synonym: 4-hydroxy 3-methoxybenzene formaldehyde; Vanillin; Vanillin; 4-hydroxyl-3-methoxylbenxaldehyde; 3-methoxyl group-4-hydroxy benzaldehyde; Vanillin food grade,1000.000000ine mesh; Vanillin; Vanillin food grade,1000.000000ine mesh.
Vanillin food grade,1000.000000ine mesh is first kind of essence of human institute synthetic.Usually be divided into methyl vanillin and vanirone.
Methyl vanillin (vanillin), chemical name 3-methoxyl group-4-hydroxy benzaldehyde, appearance white or little yellow crystal have vanilla fragrance and strong milk, being kind maximum in the perfume industry, is the major ingredient of the cream vanilla generally liked of people.Its purposes is very extensive, as in food, daily use chemicals, tobacco industry as perfume material, correctives or fixative, wherein food consumptions such as beverage, candy, cake, biscuit, bread and roasted seeds and nuts are in the majority.Also there is not relevant report to say that vanillin food grade,1000.000000ine mesh is harmful at present.Vanirone is extremely little yellow needle crystal or a crystalline powder of white, similar XIANGJIALANDOU fragrance, and fragrance is denseer than methyl vanillin.Belonging to broad spectrum type spices, is one of most important synthetic perfume in the world today, is indispensable important source material in the foodstuff additive industry, and its fragrance is 3-4 times of vanillin food grade,1000.000000ine mesh, have strong XIANGJIALANDOU fragrance, and lasting is lasting.Be widely used in and play flavouring and fixation effect in food, chocolate, ice-creams, beverage and the daily cosmetics.
Production method:
1, extracts and get by XIANGJIALANDOU.
Be hydrolyzed into methyl catechol by Ortho Anisidine through diazonium, in the presence of nitrosodimethylaniline and catalyzer,, or under potassium hydroxide catalysed, form, get through extracting and separating, vacuum distilling and crystallization and purification again with the trichloromethane reaction with formaldehyde condensation.Also available wood pulp waste liquor, Eugenol, methyl catechol, safrole etc. are made.
2, with the xylogen be raw material
Can utilize that contained xylogen prepares vanillin food grade,1000.000000ine mesh in the sulfurous acid pulping waste liquor in paper mill.Contain solid substance 10%～12% in the general waste liquid, wherein 40%～50% is calcium lignin sulphonate.Earlier waste liquid is concentrated into and contains solid substance 40%～50%, add 25% NaOH of xylogen amount, and be heated to 160～175 ℃ (about 1.1～1.2MPa), blowing air oxidation 2h, transformation efficiency generally can reach 8%～11% of xylogen.Oxide compound extracts vanillin food grade,1000.000000ine mesh with benzene, and reclaims benzene with the method for wet distillation; In oxide compound, add sodium bisulfite and generate hydrosulphite, separate with impurity then, solve crude vanillin with the sulfuric acid branch again, after underpressure distillation and recrystallization get finished product.
3, with the methyl catechol be raw material
Trichoro-aldehyde method methyl catechol and trichoro-aldehyde are heated to 27 ℃ of condensations and generate 3-methoxyl group-4-hydroxy phenyl trichloromethyl methyl alcohol in the presence of soda ash or salt of wormwood, and unreacted methyl catechol is removed with wet distillation.In the presence of caustic soda, make oxygenant with oil of mirbane, be heated to 150 ℃ of oxicrackings and get vanillin food grade,1000.000000ine mesh; Also available Cu-CuO-CoCl2 makes catalyzer, and 100 ℃ of following atmospheric oxidations, reaction back extracts vanillin food grade,1000.000000ine mesh with benzene, through underpressure distillation and recrystallization purify finished product.
The acetaldehyde acid system adds methyl catechol, sodium hydroxide solution and yellow soda ash successively in glyoxylic acid solution, and generates 3-methoxyl group-4-hydroxy phenyl hydroxyethanoic acid 30～33 ℃ of following condensations.After going out unreacted methyl catechol with solvent extraction, add sodium hydroxide solution, asking in the presence of nitrobenzene-sulfonic acid and the calcium hydroxide, be heated to 100 ℃ and carry out oxicracking and get vanillin food grade,1000.000000ine mesh.Oxidation products extracts vanillin food grade,1000.000000ine mesh with ethylene dichloride after neutralizing, crude product through underpressure distillation and recrystallization purify finished product.Nitroso process adds reactor with 30% hydrochloric acid 166kg and water 200kg, be cooled to l0 ℃ after, in 2h, drip xylidine 61.5kg, temperature is no more than 25%, continues to stir 20min afterwards.Be cooled to after 6 ℃ 25% the aqueous solution that drips that the 75kg Sodium Nitrite is made into, temperature is controlled at 7～10 ℃ and continues to stir 1h down.Leach the NDMA hydrochloride, add a certain amount of ethanol and concentrated hydrochloric acid again,, get NDMA with the dilution solid.
Methyl catechol and NDMA condensation: urotropine 26kg is dissolved in the 34kg water, adds 126kg methyl catechol and 63kg alcoholic acid mixed solution again, it is standby to store in header tank.The NDMA hydrochloride and the alcoholic acid mixture 550kg of above-mentioned gained are added reactor, add the metallic salt catalyzer after being heated to 28 ℃, drip methyl catechol mixed solution (3～3.5h) when being heated to 35～36 ℃ then, temperature remains on 40～43 ℃, drips the back and continues stirring reaction 1h.Add the water dilution of 40 ℃ of 100kg then, and stir 15min, the content of vanillin food grade,1000.000000ine mesh should be more than 11% in the condensated liquid.
With benzene is solvent, the above-mentioned condensated liquid of continuous countercurrent extraction in rotating disc type liquid-liquid extraction tower.The benzene extraction liquid contains a large amount of hydrochloric acid, washes with water earlier, is neutralized to Ph=4 with alkali again; Reclaim benzene with the rising-film evaporator distillation, dash with water vapour then and steam 1h to remove remaining benzene; Pressure reducing and steaming moisture steams crude vanillin at last fast under 120～150 ℃ (666.6Pa) again, about 70 ℃ at zero pour.Dissolving crude product in 70 ℃ toluene, is filtered postcooling to 18～20 ℃, suction strainer and with small amount of toluene wash vanillin food grade,1000.000000ine mesh.Then carry out the underpressure distillation second time, (266.6～399.9Pa) cut also is dissolved in it in 60～70 ℃ the Diluted Alcohol, slowly is cooled to 16～18 ℃ and makes its crystallization (1h) to collect 130～140 ℃.Get rid of filter with whizzer, and wash with a little Diluted Alcohol.Under 50～60 ℃, hot gas flow oven dry 12h gets finished product at last.By methyl catechol, yield can reach more than 65%.
4, p-Hydroxybenzaldehyde method
With the p-Hydroxybenzaldehyde is raw material, prepares vanillin food grade,1000.000000ine mesh through single bromination, methoxylation.In the 250mL flask, add 16g (0.131mo1) p-Hydroxybenzaldehyde and 90mL solvent, splash into 6.8mL (0.131mo1) liquid bromine after the dissolving, be heated to 40～45 ℃ of reaction 6h.The decompression take out solvent, residue adds water boil, filtered while hot, filtrate crystallisation by cooling, filtration, dry white crystals 3-bromo-4-hydroxyl-phenyl aldehyde, 123～124 ℃ of fusing points, yield 90%.
The method of vanillin food grade,1000.000000ine mesh production at present exists the serious environmental pollution problem, and working method is loaded down with trivial details, and yield is lower.
Summary of the invention
In order to overcome the shortcoming that existing vanillin food grade,1000.000000ine mesh production technique exists, the present invention proposes a kind of production method of vanillin food grade,1000.000000ine mesh.This method is utilized process by raw material condensation, acidifying, wooden phenol extraction, oxidation, depickling, extraction, distillation, crystallization and catalyst regeneration, the technical problem that contaminated solution and yield are high.
The scheme that technical solution problem of the present invention is adopted is:
With wooden phenol is the raw material production vanillin food grade,1000.000000ine mesh, and production process is:
The raw material condensation: in and drop into water and oxoethanoic acid in the still, freezing, stir, the cooling back drips caustic soda soln, when pH was neutral, reaction finished, and obtained oxoethanoic acid sodium.
Drop into water, wooden phenol and caustic soda soln in the condensation still successively, temperature control stirs, and the oxoethanoic acid sodium solution is put into the condensation still, and control Fu temperature continues to stir, and the back that reacts completely is static, obtains condensated liquid.
Condensated liquid acidifying: condensated liquid is joined the acidifying still, heat up and stir, add dilute sulphuric acid, when the pH of conditioned reaction material reaches set(ting)value, finish the condensated liquid acidifying, form neutralizer.
Wood phenol extraction: neutralizer is joined in the extraction tower, add the toluene extraction, take off benzene by debenzolizing tower then, obtain wooden phenol.
Condensated liquid oxidation: condensated liquid is joined oxidizing reactor, and add alkali lye, add catalyst pulp simultaneously, make condensated liquid obtain oxidation.Filter after the condensated liquid oxidation, the clarification back adds alkali lye, obtains oxidation liquid.
Oxidation liquid decarboxylation: oxidation liquid is joined the decarboxylation still, drip dilute sulphuric acid simultaneously, be transported in the water washing still after stirring, the static layering, lower floor's oil reservoir crude vanillin is put into the washing still, stirring, static, the crude vanillin after obtaining to wash.
The vanillin food grade,1000.000000ine mesh extraction: neutralizer is joined in the extraction tower, add toluene in tower, extraction back liquid takes off benzene through debenzolizing tower, and toluene purifies back vanillin food grade,1000.000000ine mesh extraction crude product and is drawn to crystallization kettle.
The vanillin food grade,1000.000000ine mesh distillation: crude vanillin is sucked in the rectifying tower, and the heating vacuum distillation obtains the vanillin food grade,1000.000000ine mesh distillate.
The vanillin food grade,1000.000000ine mesh crystallization: put into the first alcohol and water at crystallization kettle, the vanillin food grade,1000.000000ine mesh distillate that distillation is obtained adds crystallization kettle, and decrease temperature crystalline obtains crystallization vanillin food grade,1000.000000ine mesh product.
Catalyst regeneration: add alkali lye in the catalyzer that the condensated liquid oxidising process is reclaimed, aerating oxygen in reactor makes spent catalyst regeneration.
Oven dry of vanillin food grade,1000.000000ine mesh product and packing: open the drying bed induced draft fan, open air preheater steam, control preheater outlet wind-warm syndrome waits the charging oven dry of the stable back of drying bed wind-warm syndrome, and dry back discharging is put into vibratory screening apparatus continuously and sieved, the back packing of sieving.
Positively effect, the present invention is the raw material production vanillin food grade,1000.000000ine mesh with wooden phenol, and it is continuous to have reaction process, and auxiliary materials recycle does not have discharge of poisonous waste, environmentally safe, and prepared vanillin food grade,1000.000000ine mesh product yield height, the advantage that impurity is few.Suit in producing vanillin food grade,1000.000000ine mesh spices, to use.
Embodiment
With wooden phenol is the raw material production vanillin food grade,1000.000000ine mesh, and production process is:
1, raw material condensation
In and drop into water and oxoethanoic acid successively in the still, opens freezing and stirs, begin to drip caustic soda soln after the cooling, the control rate of addition, temperature in keeping is often tested pH, when pH is neutral, the reaction end.
In the condensation still, drop into water, wooden phenol and caustic soda soln successively, open and stir, by regulating freezing or steam control temperature in the kettle, and stir in the unlatching of back and still blowing bottom valve, the oxoethanoic acid sodium solution is put into the condensation still, and control Fu temperature continues to stir and heats up, and staticly after stopping to stir finishes to condensation reaction
2, condensated liquid acidifying
Drop into metering water in sulfuric acid preparation still, open and stir and the chuck water coolant, open the sulfuric acid baiting valve, control sulfuric acid dispensing speed and temperature in the kettle all add until sulfuric acid, continue cooling.
Condensated liquid one still is squeezed into the acidifying still, open and stir, rise the Fu temperature, open the dilute sulphuric acid baiting valve, often test pH, note simultaneously observing the condensated liquid colour-change, when the pH value reached set(ting)value, acidifying finished, controlled temperature.
3, wooden phenol extraction
Open extraction liquid pump and respective valves, neutralizer is squeezed into extraction tower after looking the border is appreciable and being lower than the visor height, stop charging, and close feed valve and pump.Open benzene backflash toluene feed respective valves, keep the under meter late gate to be in and close, open the toluene pump, open under meter late gate dominant discharge and advance benzene to extraction tower.Open tower when overflow port has benzene to flow out and stir, hold the respective valves of toluene extraction liquid simultaneously successfully, the control toluene flux to debenzolizing tower; At any time observe discharging of extraction tower toluene and debenzolizing tower toluene liquid level, open gradually to the setting height when debenzolizing tower toluene liquid level and take off the benzene reboiler steam and carry out toluene distillation, hold respective valves and refluxing toluene simultaneously successfully.Strengthen toluene feed solution flow gradually, the benzene reboiler steam is taken off in corresponding increasing simultaneously, and regulate toluene extraction flow and toluene yield and be in equilibrium state, control benzene backflash liquid level, control tower still liquid level is relatively stable, enters the continuous extraction operation.Keep toluene extraction flow, open the neutralizer feed rate gradually, carry out normal continuous extraction at normal temperatures, analyze water outlet and contain wooden phenol amount less than 100PPm, according to the inlet amount that analytical results is regulated toluene and neutralizer, extraction after liquid is put to the condensated liquid scale tank.When the full tower of toluene recovery tower still liquid level, to purifying the groove discharge, the tank liquor position was too high when purifying, and carries out toluene, water azeotropic method piptonychia benzene when the too high or circulation of tower still temperature was smooth, control discharge, the steam regulation size prevents bumping when taking off benzene, takes off about 3 hours of benzene time, take off benzene and finish postcooling sampling carrying out stratographic analysis, put into after qualified and reclaim wooden phenol special barrel, simultaneously overflowing liquid is switched to another and purify groove, continue extraction.
4, condensated liquid oxidation
Open condensation liquid pump and respective valves, condensated liquid is squeezed into oxidizing reactor.Open and stir, put into alkali lye, get in touch with the catalyst regeneration operation, the qualified catalyst pulp of regeneration is squeezed into stills for air blowing with pump, open the condenser valve, open steam, the condenser valve is closed in heating.Regulate heating steam, keep temperature of reaction, pressure, oxidation finishes.Slowly open cold condenser valve is sent the oxidation material into the static still of oxidation liquid with the oxidation cycle pump after the cooling, carries out quiescent settling.Behind the quiescent settling, open static still side baiting valve, earlier liquid is put into filter pocket just, observe visor at any time, after the liquid clarification, switch valve is put into the secondary filtrate receiver with oxidation liquid, the control blowing time, finish the back and open stirring, remaining oxidation liquid is put into filter pocket just, filter.First filter pocket oxidation liquid is once filtered earlier with the pumping plate-and-frame filter press, carry out self-circulation during filtration earlier, treat to put into the salkali waste groove after filtrate is clarified substantially, at any time observe salkali waste tank liquor position, when the salkali waste groove to setting height, open the salkali waste pump, filtrate is squeezed into plate-and-frame filter press carry out secondary filtration, at any time observe filtrate, muddy filtrate is put into static still, clear filtrate is put into the secondary filtrate receiver.Must be noted that device security operation item during the filter press machine operation, filter cloth must be cleaned out and compressed before the press filtration, note during filtration controlling charging valve opening, feed pressure and discharging flow, when just beginning binder, the control feed pressure, continuation along with press filtration, feed pressure increases gradually, when pressure reaches the 0.4MPa left and right sides, shows that the frame inner catalyst is full, can stop this moment filtering, send the catalyst regeneration operation to measure regeneration after washing of recovery catalyzer with water and the air blow drying.
5, oxidation liquid decarboxylation
Open the secondary filtrate pump, the oxidation clear liquid is squeezed into the decarboxylation still, open induced draft fan, drip dilute sulphuric acid simultaneously, note the control rate of addition, prevent to drip and cause too soon that flash, controlled temperature, sulfuric acid drip and stop to drip when setting pH, continue to be stirred to and no longer emit till the bubble, stop stirring static layering.In the washing still, put into water, by observing visor, lower floor's oil reservoir crude vanillin is put into the washing still, when washing still material reaches 6 batches or wash during near upper cover, the intensification melt, control Fu temperature is opened and is stirred, stop after the stirring to stir, obtain crude vanillin after static will the washing and put into head steaming medial launder.Water layer is put to the extraction liquid bath.
6, vanillin food grade,1000.000000ine mesh extraction
Open extraction liquid pump and respective valves, neutralizer is squeezed into extraction tower to stopping charging behind the observable height below the visor, and close feed valve and pump.Open benzene backflash toluene feed valve and toluene pump, advance toluene in tower, when the cat head overflow port has benzene to flow out, open to the valve of debenzolizing tower, the toluene overflow starts extraction tower simultaneously and stirs to debenzolizing tower, regulates toluene flux.At any time observe discharging of extraction tower toluene and debenzolizing tower toluene liquid level, open gradually to the setting height when debenzolizing tower toluene liquid level and take off the benzene reboiler steam and carry out toluene distillation.Strengthen the toluene feed flow gradually, the benzene reboiler steam is taken off in corresponding increasing simultaneously, and regulate toluene extraction flow and toluene yield and be in equilibrium state, control benzene backflash liquid level, control tower still liquid level is relatively stable, enters operate continuously.After the toluene feed operate continuously is stable, keep the toluene feed flow, open oxidative decarboxylation liquid fresh feed pump,, carry out continuous extraction after transferring flow, extract, take off the benzene series system and strengthen toluene and decarboxylated liquid inlet amount after all normal gradually to the normal running flow to the extraction tower charging; Waste water is put into wastewater trough, analyzes waste water vanirone content less than 100PPm, sampling in normal back 1 hour when head is driven, and sample is got in per tour just often one time, regulates toluene and decarboxylated liquid inlet amount according to analytical results.To observe backflash liquid level and extraction tower benzene layer during operation at any time, control benzene backflash liquid level, control extraction tower benzene layer is not higher than the visor center line.When toluene recovery tower still liquid level to setting height, when too high the or circulation of tower still temperature is smooth, still liquid is drained into benzene purify groove, purify the groove tower bottoms when too high, carry out toluene, water azeotropic method piptonychia benzene, use vacuum piptonychia benzene again, at any time control vacuum lifting speed, vacuum prevents that the material bumping is drawn onto toluene in the vacuum pump from low to high, and toluene purifies back vanillin food grade,1000.000000ine mesh extraction crude product and is drawn to crystallization kettle.Purify two of grooves and switch use.Under the driving standard state, change water wash column water once every day continuously.Will be during each orderly shutdown the emptying of tower still material, to prevent that vanillin food grade,1000.000000ine mesh is in the crystallization of tower still.
7, vanillin food grade,1000.000000ine mesh distillation
Start vacuum pump, start water circulating pump, crude vanillin is sucked rectifying Tata still, attention can not be inhaled the people with solid impurity, in order to avoid the infringement pump housing.Charging finishes, close feed valve, open steam and other valve, after checking that a steaming recycle pump is normal, ON cycle pump and vacuum, the control vapor pressure, control discharging speed and backflow, tower top temperature, vacuum tightness go out light constituent to head and steam the light constituent groove, light constituent after rolling, at any time observe discharging color and temperature, respectively difference is expected to head steaming tempering tank and pan tank, each first adopts 1/3 earlier when adopting finished product, change second batch then over to, adopt after full for second batch, two pan tanks switch and use control mixture discharging flow, finished product discharging flow again.After discharging finished, steam off, vacuum and recycle pump were put into tar pool with raffinate, packed with bag behind the crystallisation by cooling, and recycle pump is in time clean with steam flush.
8, vanillin food grade,1000.000000ine mesh crystallization
Steam vanillin food grade,1000.000000ine mesh finished product quantity according to head, put into the first alcohol and water at crystallization kettle, after finishing, close baiting valve, open the suction vacuum pump, the head product that are steamed into are sucked crystallization kettle, put vacuum, open and stir and steam, heat up by proportioning.Open freezingly after the stirring, material in the still is observed in cooling at any time, when crystallization occurring, adds and drips water, the control dropping time, continues to be cooled to crystallization and finishes.Brilliant material is put into whizzer and is carried out centrifugally, washes with a small amount of cold water.Send the drying room drying with crystallization material chemical examination qualified back metering.Mother liquor is put into the crystalline mother solution groove.
With the crystalline mother solution pump methanol mother liquor is sent into the crystallization recovery tower and carry out Methanol Recovery, the earlier little back of control vapor pressure is big, notes observing boiling situation in the still, prevents that bumping from dashing material; Regulate quantity of reflux, the control tower top temperature, the cat head material is adopted into another still and is heavily steamed.The methyl alcohol finished product returns the methyl alcohol scale tank and reuses, and loss methyl alcohol is replenished by methanol pump.The extraction of still liquid is reclaimed.
9, catalyst regeneration
In the making beating still, add water, open and stir, add at solid feed inlet and reclaim catalyzer, with pressurized air slurry is depressed into the catalyst regeneration still after the form slurry.Put into alkali lye in the catalyst regeneration still, open steam heating, intensification back closed reactor is opened oxygen control still internal pressure, and control reaction temperature is closed oxygen behind the reaction certain hour, and restock oxygen after pressure descends is not till descending.
10, oven dry of vanillin food grade,1000.000000ine mesh product and packing
Open the drying bed induced draft fan, open air preheater steam, control preheater outlet wind-warm syndrome waits the stable back of drying bed wind-warm syndrome to prepare charging.
After the drying bed parameters was stable, beginning was controlled input speed to the drying bed continuously feeding.Open the drying bed discharging, exsiccant vanillin food grade,1000.000000ine mesh finished product is put into vibratory screening apparatus continuously filter, sampling send the analyzer room after the assay was approved, packs.After the charging of vanillin food grade,1000.000000ine mesh wet finished product finishes, continue discharging till the not discharging of vanillin food grade,1000.000000ine mesh, close air preheater heating valve then, make drying bed cooling back close induced draft fan.
Characteristics of the present invention
In vanillin food grade,1000.000000ine mesh production process of the present invention, catalyzer can be regenerated, and reuses in Production Flow Chart.
Add toluene in reaction process after, take off benzene again, the toluene after removing is repeated application in process of production.
The methyl alcohol that uses in reaction process also can reclaim and use.
In sulfuric acid that in reaction process, adds and the alkali lye and after, form sodium sulfate, remain in the mother liquor, through the mother liquor concentration and evaporation, obtain the sodium sulfate product.
Through the actual production test, adopting the vanillin food grade,1000.000000ine mesh content of the prepared vanillin food grade,1000.000000ine mesh product of the inventive method is more than 99%.
Claims (1)
1. the production method of a vanillin food grade,1000.000000ine mesh is characterized in that:
With wooden phenol is the raw material production vanillin food grade,1000.000000ine mesh, and production process is:
1), raw material condensation
In and drop into water and oxoethanoic acid successively in the still, opens freezing and stirs, begin to drip caustic soda soln after the cooling, the control rate of addition, temperature in keeping is often tested pH, when pH is neutral, the reaction end;
In the condensation still, drop into water, wooden phenol and caustic soda soln successively, open and stir, by regulating freezing or steam control temperature in the kettle, and stir in the unlatching of back and still blowing bottom valve, the oxoethanoic acid sodium solution is put into the condensation still, control Fu temperature continues to stir and heats up, and staticly after stopping to stir finishes to condensation reaction;
2), condensated liquid acidifying
Drop into metering water in sulfuric acid preparation still, open and stir and the chuck water coolant, open the sulfuric acid baiting valve, control sulfuric acid dispensing speed and temperature in the kettle all add until sulfuric acid, continue cooling;
Condensated liquid one still is squeezed into the acidifying still, open and stir, rise the Fu temperature, open the dilute sulphuric acid baiting valve, often test PH, observe the condensated liquid colour-change at any time simultaneously, when the pH value reached set(ting)value, acidifying finished, controlled temperature;
3), wooden phenol extraction
Open extraction liquid pump and respective valves, neutralizer is squeezed into extraction tower after looking the border is appreciable and being lower than the visor height, stop charging, and close feed valve and pump; Open benzene backflash toluene feed respective valves, keep the under meter late gate to be in and close, open the toluene pump, open under meter late gate dominant discharge and advance benzene to extraction tower; Open tower when overflow port has benzene to flow out and stir, hold the respective valves of toluene extraction liquid simultaneously successfully, the control toluene flux to debenzolizing tower; At any time observe discharging of extraction tower toluene and debenzolizing tower toluene liquid level, open gradually to the setting height when debenzolizing tower toluene liquid level and take off the benzene reboiler steam and carry out toluene distillation, hold respective valves and refluxing toluene simultaneously successfully; Strengthen toluene feed solution flow gradually, the benzene reboiler steam is taken off in corresponding increasing simultaneously, and regulate toluene extraction flow and toluene yield and be in equilibrium state, control benzene backflash liquid level, control tower still liquid level is relatively stable, enters the continuous extraction operation; Keep toluene extraction flow, open the neutralizer feed rate gradually, carry out normal continuous extraction at normal temperatures, analyze water outlet and contain wooden phenol amount less than 100PPm, according to the inlet amount that analytical results is regulated toluene and neutralizer, extraction after liquid is put to the condensated liquid scale tank; When the full tower of toluene recovery tower still liquid level, to purifying the groove discharge, the tank liquor position was too high when purifying, and carries out toluene, water azeotropic method piptonychia benzene when the too high or circulation of tower still temperature was smooth, control discharge, the steam regulation size prevents bumping when taking off benzene, takes off about 3 hours of benzene time, take off benzene and finish postcooling sampling carrying out stratographic analysis, put into after qualified and reclaim wooden phenol special barrel, simultaneously overflowing liquid is switched to another and purify groove, continue extraction;
4), condensated liquid oxidation
Open condensation liquid pump and respective valves, condensated liquid is squeezed into oxidizing reactor; Open and stir, put into alkali lye, get in touch with the catalyst regeneration operation, the qualified catalyst pulp of regeneration is squeezed into stills for air blowing with pump, open the condenser valve, open steam, the condenser valve is closed in heating; Regulate heating steam, keep temperature of reaction, pressure, oxidation finishes; Slowly open cold condenser valve is sent the oxidation material into the static still of oxidation liquid with the oxidation cycle pump after the cooling, carries out quiescent settling; Behind the quiescent settling, open static still side baiting valve, earlier liquid is put into filter pocket just, observe visor at any time, after the liquid clarification, switch valve is put into the secondary filtrate receiver with oxidation liquid, the control blowing time, finish the back and open stirring, remaining oxidation liquid is put into filter pocket just, filter; First filter pocket oxidation liquid is once filtered earlier with the pumping plate-and-frame filter press, carry out self-circulation during filtration earlier, treat to put into the salkali waste groove after filtrate is clarified substantially, at any time observe salkali waste tank liquor position, when the salkali waste groove to setting height, open the salkali waste pump, filtrate is squeezed into plate-and-frame filter press carry out secondary filtration, at any time observe filtrate, muddy filtrate is put into static still, clear filtrate is put into the secondary filtrate receiver; Must be noted that device security operation item during the filter press machine operation, filter cloth must be cleaned out and compressed before the press filtration, note during filtration controlling charging valve opening, feed pressure and discharging flow, when just beginning binder, the control feed pressure, continuation along with press filtration, feed pressure increases gradually, when pressure reaches the 0.4MPa left and right sides, shows that the frame inner catalyst is full, can stop this moment filtering, send the catalyst regeneration operation to measure regeneration after washing of recovery catalyzer with water and the air blow drying;
5), oxidation liquid decarboxylation
Open the secondary filtrate pump, the oxidation stillness of night is squeezed into the decarboxylation still, open induced draft fan, drip dilute sulphuric acid simultaneously, note the control rate of addition, prevent to drip and cause flash too soon, controlled temperature exists, and sulfuric acid drips and stops when setting pH dripping, and continues to be stirred to and no longer emits till the bubble, stop stirring static layering; In the washing still, put into water, by observing visor, lower floor's oil reservoir crude vanillin is put into the washing still, when washing still material reaches 6 batches or wash intensification melt, control Fu temperature during near upper cover, open and stir, stop after the stirring to stir, obtain crude vanillin after static will the washing and put into head steaming medial launder, water layer is put to the extraction liquid bath;
6), vanillin food grade,1000.000000ine mesh extraction
Open extraction liquid pump and respective valves, neutralizer is squeezed into extraction tower to stopping charging behind the observable height below the visor, and close feed valve and pump; Open benzene backflash toluene feed valve and toluene pump, advance toluene in tower, when the cat head overflow port has benzene to flow out, open to the valve of debenzolizing tower, the toluene overflow starts extraction tower simultaneously and stirs to debenzolizing tower, regulates toluene flux; At any time observe discharging of extraction tower toluene and debenzolizing tower toluene liquid level, open gradually to the setting height when debenzolizing tower toluene liquid level and take off the benzene reboiler steam and carry out toluene distillation; Strengthen the toluene feed flow gradually, the benzene reboiler steam is taken off in corresponding increasing simultaneously, and regulate toluene extraction flow and toluene yield and be in equilibrium state, control benzene backflash liquid level, control tower still liquid level is relatively stable, enters operate continuously; After the toluene feed operate continuously is stable, keep the toluene feed flow, open oxidative decarboxylation liquid fresh feed pump,, carry out continuous extraction after transferring flow, extract, take off the benzene series system and strengthen toluene and decarboxylated liquid inlet amount after all normal gradually to the normal running flow to the extraction tower charging; Waste water is put into wastewater trough, analyzes waste water vanirone content less than 100PPm, sampling in normal back 1 hour when head is driven, and sample is got in per tour just often one time, regulates toluene and decarboxylated liquid inlet amount according to analytical results; To observe backflash liquid level and extraction tower benzene layer during operation at any time, control benzene backflash liquid level, control extraction tower benzene layer is not higher than the visor center line; When toluene recovery tower still liquid level to setting height, when too high the or circulation of tower still temperature is smooth, still liquid is drained into benzene purify groove, purify the groove tower bottoms when too high, carry out toluene, water azeotropic method piptonychia benzene, use vacuum piptonychia benzene again, at any time control vacuum lifting speed, vacuum prevents that the material bumping is drawn onto toluene in the vacuum pump from low to high, and toluene purifies back vanillin food grade,1000.000000ine mesh extraction crude product and is drawn to crystallization kettle; Purify two of grooves and switch use; Under the driving standard state, change water wash column water once every day continuously; Will be during each orderly shutdown the emptying of tower still material, to prevent that vanillin food grade,1000.000000ine mesh is in the crystallization of tower still;
7), vanillin food grade,1000.000000ine mesh distillation
Start vacuum pump, start water circulating pump, crude vanillin is sucked rectifying Tata still, attention can not be inhaled the people with solid impurity, in order to avoid the infringement pump housing; Charging finishes, close feed valve, open steam and other valve, after checking that a steaming recycle pump is normal, ON cycle pump and vacuum, the control vapor pressure, control discharging speed and backflow, tower top temperature, vacuum tightness go out light constituent to head and steam the light constituent groove, light constituent after rolling, at any time observe discharging color and temperature, respectively difference is expected to head steaming tempering tank and pan tank, each first adopts 1/3 earlier when adopting finished product, change second batch then over to, adopt after full for second batch, two pan tanks switch and use control mixture discharging flow, finished product discharging flow again; After discharging finished, steam off, vacuum and recycle pump were put into tar pool with raffinate, packed with bag behind the crystallisation by cooling, and recycle pump is in time clean with steam flush;
8), vanillin food grade,1000.000000ine mesh crystallization
Steam vanillin food grade,1000.000000ine mesh finished product quantity according to head, put into the first alcohol and water at crystallization kettle, after finishing, close baiting valve, open the suction vacuum pump, the head product that are steamed into are sucked crystallization kettle, put vacuum, open and stir and steam, heat up by proportioning; Open freezingly after the stirring, material in the still is observed in cooling at any time, when crystallization occurring, adds and drips water, the control dropping time, continues to be cooled to crystallization and finishes; Brilliant material is put into whizzer and is carried out centrifugally, washes with a small amount of cold water, the qualified back of crystallization material chemical examination is measured send the drying room drying, and mother liquor is put into the crystalline mother solution groove;
With the crystalline mother solution pump methanol mother liquor is sent into the crystallization recovery tower and carry out Methanol Recovery, the earlier little back of control vapor pressure is big, notes observing boiling situation in the still, prevents that bumping from dashing material; Regulate quantity of reflux, the control tower top temperature, the cat head material is adopted into another still and is heavily steamed; The methyl alcohol finished product returns the methyl alcohol scale tank and reuses, and loss methyl alcohol is replenished by methanol pump, and the extraction of still liquid is reclaimed;
9), catalyst regeneration
In the making beating still, add water, open and stir, add at solid feed inlet and reclaim catalyzer, with pressurized air slurry is depressed into the catalyst regeneration still after the form slurry; Put into alkali lye in the catalyst regeneration still, open steam heating, intensification back closed reactor is opened oxygen control still internal pressure, and control reaction temperature is closed oxygen behind the reaction certain hour, and restock oxygen after pressure descends is not till descending;
10), oven dry of vanillin food grade,1000.000000ine mesh product and packing
Open the drying bed induced draft fan, open air preheater steam, control preheater outlet wind-warm syndrome waits the stable back of drying bed wind-warm syndrome to prepare charging;
After the drying bed parameters was stable, beginning was controlled input speed to the drying bed continuously feeding; Open the drying bed discharging, exsiccant vanillin food grade,1000.000000ine mesh finished product is put into vibratory screening apparatus continuously filter, sampling send the analyzer room after the assay was approved, packs; After the charging of vanillin food grade,1000.000000ine mesh wet finished product finishes, continue discharging till the not discharging of vanillin food grade,1000.000000ine mesh, close air preheater heating valve then, make drying bed cooling back close induced draft fan.
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