CN102320930B - Method for preparing alkylphenol products and method for effectively governing wastewater - Google Patents
Method for preparing alkylphenol products and method for effectively governing wastewater Download PDFInfo
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Abstract
The invention relates to a method for preparing high-selectivity ortho-substituent alkylphenol product mixed liquid, in particular to a method for preparing the mixed liquid containing ortho-substituent alkylphenol products. In the method, phenol and isobutene are used as raw materials, phenoxyl aluminum is used as catalysts, and homogeneous catalytic alkylation reaction is adopted. A low-pressure process method is adopted for preparing organo-aluminum compound catalysts, and impurities in the catalysts are effectively removed, so the high-selectivity ortho-substituent alkylphenol product mixed liquid is obtained in the catalytic alkylation reaction process. The phenoxyl aluminum catalysts are decomposed, inorganic aqueous alkali prepared from alkaline-earth metal oxide takes reaction with aluminum hydroxide hydrates, aluminum salt mixtures insoluble in water are generated, a water layer in a suspending liquid state is formed in a still standing state, and the water layer is removed through sedimentation and filtration. Therefore, the obtained process water can be cyclically used, the goal of effectively governing wastewater discharge is reached, and an oil layer is the alkylphenol product mixed liquid after the catalyst removal.
Description
Technical field
The present invention is the preparation method of a kind of highly selective ortho position substituted alkyl phenol product mixed solution.Be specifically related to take phenol and iso-butylene as raw material, adopting phenoxy group aluminium is catalyzer, and homogeneous catalysis alkylated reaction, prepares a kind of mixed solution that contains ortho position substituted alkyl phenol product, and effective improvement method of the waste water producing.
Background technology
The catalyzed reaction of phenol or phenol compound and olefines alkylating reagent is the electrophilic substitution reaction of alkylating reagent on aromatic ring, oh group is as first kind substituting group, making reaction product is mainly a contraposition and two isomer that ortho position is replaced by alkylating reagent of phenolic hydroxyl group, complete after an alkyl replacement, make aromatic ring passivation, after being replaced by two alkyl, further passivation, therefore obtain a substituted alkylated product relatively easy, two substituted alkylated products take second place, and obtaining three substituted alkylated products will be difficult to.
Select an acidic catalyst, while using protonic acid, phenol or phenol compound react what first obtain with olefines alkylating reagent be that para-orientation product is 4-alkyl substituted phenol, continues next stage reaction and obtain ortho position substitution product 2-alkyl substituted phenol in the time that contraposition is occupied by major part; Be that catalyzer carries out alkylated reaction with Lewis acid, 2-alkyl substituted phenol product has precedence over 4-alkyl substituted phenol, but its catalysis is not as proton, and the product obtaining is ortho para substitution product, and ratio in mixture is suitable.When making phenoxy group aluminium with metallic aluminium and phenol reactant, during as the catalyzer of phenol and iso-butylene alkylation substitution reaction, more much higher than other lewis acidic ortho position selectivity, preferential o-tert-butylphenol or the 2-TBP (being called for short 2-phenol) of generating, then be two substituted products in ortho position of hydroxyl, as 2,6 di t butyl phenol (being called for short 2,6-phenol).From theory significance, make catalyzer with phenoxy group aluminium, the alkylphenol product reaction solution obtaining is ortho position substituted alkyl phenol product, as, 2-phenol, a small amount of 2,6-phenol, almost there is no 2,4-DTBP (being called for short 2,4-phenol), 4-TBP (being called for short 4-phenol), 2,4,6-tri-butyl-phenol (abbreviation 2,4,6-phenol) by product generates, and further illustrating it is that a kind of good ortho position replaces catalyzer.But in actual production process, not like this, make catalyzer with phenoxy group aluminium, if the selection of raw material and preparation technology are unreasonable, the selectivity of the alkylphenol product of ortho position replacement is reduced greatly, in alkylphenol product reaction solution, remove 2-phenol, 2, beyond 6-phenol product, also in various degree contain 2, 4, 6-phenol, 2, 4-phenol, 4-phenol by product, cause by product to increase, production process complexity, raw material consumption and production cost increase, people research is take phenol and iso-butylene as raw material for this reason, phenoxy group aluminium is catalyzer, alkylated reaction is prepared 2-phenol or a small amount of 2, the production technique of 6-phenol product, take the selectivity that improves ortho position substituted alkyl phenol as target.
Chinese patent CN 1193007A discloses phenol and iso-butylene is raw material, phenoxy group aluminium be catalyzer to carry out catalytic alkylation reaction preparation be main alkylphenol product mixed solution with 2,6-phenol, its weak point be in reaction solution, contain more 2,4-phenol.Due to 2, 6-phenol and 2, the boiling-point difference of 4-phenol is less, make to bring very large difficulty to alkylphenol mixed solution rectifying, obtain 2 of required purity by the method for unrestricted increase rectifying tower plates number, 6-phenolic product, but can not guarantee the feasibility of suitability for industrialized production, illustrate that this technology could not make good use of phenoxy group aluminium product, cause catalyst performance to occur deviation, do not reach the effect of phenol ortho highly selective alkylated reaction, in addition, before the rectifying of alkylation mixed solution, decompose phenoxy group aluminium with 5% aqueous sulfuric acid and wash alkylation liquid method meeting waste water with water, free-phenol in alkylation liquid is dissolved in wherein, phenolic wastewater is difficult to effectively process, if process and reach emission standard, the economic cost of its running cost and consumption is that institute of manufacturing enterprise is unacceptable, directly discharge, the environment of periphery is caused to very large injury.
Chinese patent CN1868992A discloses alkylphenol coproduction technology technology, phenol and iso-butylene are raw material, phenoxy group aluminium is that catalyzer carries out catalytic alkylation reaction preparation with 2,6-phenol, o-tert-butylphenol are main mixed alkylphenol product, its weak point be in gained alkylated reaction liquid containing have an appointment 10% 2,4,6-phenol, other by product of approximately 10%, make the raw materials cost of production process higher; Water decomposes phenoxy group aluminium, has equally the emission problem of phenolic wastewater.
Chinese patent CN101628854A discloses take phenol metallic aluminium as raw material, prepare phenol ortho alkylation substitution reaction catalyzer phenoxy group aluminium, its weak point is to adopt traditional normal pressure processing method, and the phenol that the hydrogen of discharging in back flow reaction process is entrained with in still causes significant loss and contaminate environment; Unlimited system is difficult to avoid airborne oxygen or moisture to enter in still to cause the oxidation of phenol and the hydrolysis of catalyzer, makes to obtain can contain trace impurity Al (OH) in the mixed solution of phenol, phenoxy group Al catalysts
3, Al
2o
3and affect the selectivity of substituted alkyl phenol product in ortho position in alkylation process; Water decomposes phenoxy group aluminium, and with adopting so-called flash evaporation technology to remove impurities H aluminum oxide, obviously, flash evaporation technology is removed impurities H aluminum oxide and do not had feasibility.
Chinese patent CN101747156A, CN1844071A disclose employing high-pressure process method and have prepared phenoxy group Al catalysts, prepare ortho-substituent phenol product for phenol with isopentene or iso-butylene catalytic alkylation reaction, its weak point phenol and this strong heat release of metallic aluminium bits, self-accelerating reaction while releasing hydrogen gas, that will be dangerous can not to remove in time reaction heat if carry out in airtight reactor, especially prepare the reaction solution of high phenoxy group aluminium content, the design pressure of its reactor can be higher, reaches 3.5 ~ 4.0MPa.Facility investment strengthens, even bring a lot of drawbacks to running cost and production management.Nonetheless, the fixing impurity in the micro-moisture in raw material phenol and metallic aluminium still makes to contain in phenoxy group Al catalysts trace impurity Al (OH)
3, Al
2o
3and affect the selectivity of substituted alkyl phenol product in ortho position in alkylation process.In addition, water decomposes phenoxy group aluminium, if do not take effective treatment process, has the emission problem of phenolic wastewater.
Industrial Catalysis, 2008,16(9): 68-70, the synthetic of the tertiary octyl phenol of 2-cumyl-4-disclosed, the special octyl phenol of 4-and alpha-methyl styrene are raw material, and phenoxy group aluminium is that catalyzer carries out catalytic alkylation reaction, and its weak point remains discharge of wastewater problem.
Other correlation technique have 3-methylphenol and iso-butylene be raw material prepare the 6-tertiary butyl-3-methylphenol, 2-methylphenol and iso-butylene be raw material to prepare substituted alkylated reactions the in ortho position such as the 6-tertiary butyl-2-methylphenol be that phenoxy group aluminium is catalyzer substantially, its weak point remains the impurity problem in catalyzer and has the emission problem of phenolic wastewater.
Preparing 2-phenol mechanism of catalytic reaction take phenoxy group aluminium as catalyzer, is first that phenoxy group aluminium and iso-butylene effect form phenyl tertbutyl ether, and phenyl tertbutyl ether is reset and formed o-tert-butylphenol, if iso-butylene is excessive, continues reaction and generates 2,6-phenol.The phenoxy group aluminium made from metallic aluminium and phenol reactant according to a conventional method, inevitably contains micro-Al (OH)
3, Al
2o
3, Fe
2o
3, SiO
2deng impurity, this is because contain Al in metallic aluminium
2o
3, Fe
2o
3, SiO
2deng impurity, in phenol, reactive system, there is micro-water in addition, make the phenoxy group aluminum portions hydrolysis generating form Al (OH)
3, be suspended in wherein with other impurity, to cause be the ortho position elective reduction of alkylated reaction in the existence of these impurity just, causes a small amount of 4-phenol and 2,4-phenol to generate reason.Effectively removing the impurity in reaction system, improve phenoxy group aluminium purity, is to improve optionally effective ways of ortho position substituted alkyl phenol product.
The method of the phenoxy group aluminium that technology is in the past made with metallic aluminium and phenol reactant is that metallic aluminium and phenol are in the normal-pressure reaction kettle with reflux exchanger, 140 ~ 180 ℃ of temperature of reaction, reach the reflux temperature of phenol and carried out back flow reaction, reaction is emitted a large amount of heats and is generated hydrogen and emits, reaction process can be aggravated along with the rising of temperature, in short period of time, may have little time cooling for reflux by condenser, hydrogen is carried phenol secretly and is discharged from condensator outlet, causes loss and the environmental pollution of a large amount of phenol; Even if control proper, carry out reflux course stably, discharge hydrogen from reactor time, can carry in various degree a certain amount of phenol secretly equally, in addition, minor amount of water branch in reflux course repeatedly in atmosphere brings in reactor, causes the hydrolysis of phenoxy group aluminium and generates Al (OH)
3, Al
2o
3, the elective reduction that the existence of these impurity causes alkylated reaction ortho position to replace.
Take phenol, iso-butylene as raw material, phenoxy group aluminium is catalyzer, alkylated reaction is prepared with 2,6-phenol, 2-phenol are main mixed alkylphenol product, water decomposes phenoxy group Al catalysts, hydrolysate is comparatively complicated, and the aluminium hydroxide conventionally generating is actual in containing AlOOH (boehmite), Al (OH)
3(surge aluminium stone), Al (OH)
3the mixture of (gibbsite) etc., is scattered in water with white colloidality floss, is difficult to simple filter method, aluminium hydroxide be separated with water.
Water of the present invention decomposes phenoxy group Al catalysts, and the inorganic base aqueous solution of simultaneously making with alkaline earth metal oxide or oxyhydroxide and aluminium hydroxide hydrate carry out neutralization reaction, generates the aluminium salt mixture that is insoluble in water, as: 3CaOAl
2o
36H
2o, 12CaO7Al
2o
3, Al (OH)
3ca (OH)
2, Al
2o
3in mixture, therewith mutually roughly the same can be also barium metal or MAGNESIUM METAL saline admixture.Under static condition is deposited in water layer, adopt settlement separate processing method to isolate aluminium salt mixture, clear water layer; Top oil reservoir is the alkylphenol product mixed solution of deviating from catalyzer, obtains 2-phenolic product or 2,6-phenolic product after rectifying.The water layer that a few batch reaction materials are obtained is collected in storage tank, sedimentation, filters to isolate aluminium salt mixture, and molten with alkali after concentrating, carbon separating method reclaims aluminum oxide; On storage tank, the clear water layer of part or accurate clear water layer, again for modulating inorganic base aqueous solution, use this part process water iterative cycles with this, reach the object of effective improvement discharge of wastewater.
The present invention reacts metallic aluminium and prepares phenoxy group Al catalysts with phenol in low pressure reaction still, phenol reacts and releasing hydrogen gas with metallic aluminium bits, airtight reacting kettle inner pressure is constantly increased, utilize rated pressure in the automatic control pressure limiting valve goalkeeper still on reactor to be made as definite value, in the time that still internal pressure exceedes rated pressure value, the manual operation hydrogen of opening and release is opened or adopted to autocontrol valve, set pressure is higher, the gaseous phase partial pressure of reactor top phenol is lower, and the phenol that in the still of discharge, hydrogen is carried secretly is just fewer.Hydrogen outlet in reactor installs metal liquid removing net or packing layer additional, prevents from causing phenol loss by entrainment; Reactor, without installing reflux exchanger additional, as long as simple tail gas trapper is housed at hydrogen outer vent, obtains in the mixed solution of phenol, phenoxy group Al catalysts trace impurity Al (OH) thus
3, Al
2o
3the more traditional normal pressure processing method of content low; In addition, adopt charcoal absorption, filtration process method, further remove the Al (OH) only depositing in phenol, phenoxy group aluminium mixture
3, Al
2o
3deng impurity.
Summary of the invention
The present invention is for overcoming above-mentioned deficiency of the prior art, adopts effective improvement method of the waste water producing in the preparation method of a kind of highly selective ortho position substituted alkyl phenol product mixed solution and preparation process.
Be specifically related to take phenol compound and olefines alkylating reagent as raw material, employing organo-aluminium compound is catalyzer, adopt low pressure process method to be prepared with machine aluminium compound catalyzer and effectively remove the impurity in catalyzer, in catalytic alkylation reaction process, obtain highly selective ortho position substituted alkyl phenol product mixed solution thus.Before rectifying, need from alkylphenol product mixed solution, remove organo aluminum catalyst, except effectively having solved the emission problem of phenolic wastewater in organo aluminum catalyst process.
The preparation method of a kind of highly selective of the present invention ortho position substituted alkyl phenol product mixed solution, take phenol as raw material, iso-butylene is as alkylating reagent, phenoxy group aluminium are catalyzer, adopt with the low pressure reaction still A modulation catalyst of automatically controlling pressure limiting valve; In filter B, remove impurity; Catalytic alkylation reaction carries out in autoclave C; In catalyst separating still D, separate aluminum compound; In slurry tank E, F, complete the separation of suspension water layer; Oil reservoir is ortho position substituted alkyl phenol product mixed solution, enters in storage tank G.
The preparation method of a kind of highly selective of the present invention ortho position substituted alkyl phenol product mixed solution, carries out according to following step:
(1) prepare the process of phenoxy group aluminium: add in proportion phenol compound, metallic aluminium bits with automatically controlling in the low pressure reaction still A of pressure limiting valve, air in nitrogen replacement still, heat up, stir, heat up, phenol compound reacts and releasing hydrogen gas with metallic aluminium bits, still internal pressure constantly increases, when reaching rated pressure value, the autocontrol valve hydrogen of opening and release; In still, metallic aluminium bits dissolve in phenol compound completely, and reaction completes, and obtains the mixed solution of phenol, phenoxy group Al catalysts;
(2) remove Impurities In Catalyst process: in low pressure reaction still A, add in proportion gac, under steady temperature, stir certain hour, in filter B, filter, filtrate enters in alkylated reaction still C.
(3) alkylation process: in autoclave C, carry out in advance nitrogen replacement air wherein, add after the mixed solution of phenol compound, phenoxy group Al catalysts and be pressurized to definite value with nitrogen, stir, heat up, adopt continuously feeding mode to drip olefines alkylating reagent; Catalytic alkylation reaction, after the reaction times of regulation completes, stirs, cooling, emits nitrogen and returns to normal pressure, obtains the ortho position substituted alkyl phenol product mixed solution that contains phenoxy group Al catalysts, enters into catalyst separating still D;
(4) separating catalyst process: add inorganic base aqueous solution in catalyst separating still D, stir under steady temperature, leave standstill layering.Separate, the water layer that is suspension below is successively put into slurry tank E, F; The oil reservoir of clarification is o-tert-butylphenol product mixed solution, enters in storage tank G, and rectification under vacuum obtains product.
(5) process water removal process completes the separation of suspension water layer in slurry tank E, F, adopts sedimentation, filtering separation processing method, and suspension water layer is separated into supernatant liquor and solids mixture.Analyze the massfraction of alkali in supernatant liquor, with the inorganic base aqueous solution in this preparation steps (4).
Phenol compound of the present invention refers to phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2-isopropyl-phenol, 3-isopropyl-phenol, 4-isopropyl-phenol, 2-octyl phenol, 4-octyl phenol, 2-nonylphenol or 4-nonylphenol;
Olefines alkylating reagent of the present invention refers to iso-butylene, isopentene, propylene;
Organo-aluminium compound catalyzer of the present invention refers to phenol compound and reacts with metallic aluminium, and releasing hydrogen gas generates phenoxy group aluminium or alkyl phenoxy aluminum compound.
Wherein the bits of the metallic aluminium described in step (1) refer to industrial aluminium ingot mechanical means are cut into about (8 ~ 12mm) × (1 ~ 3mm) × (20 ~ 30mm) irregular bar.
Wherein, in the process of preparing phenoxy group aluminium described in step (1), phenol and metallic aluminium bits mass ratio are 1:0.001 ~ 0.02; Suitable mass ratio is 1:0.002 ~ 0.008; Suitable temperature of reaction is 140 ~ 180 ℃; The suitable reaction times is 60 ~ 90min;
Wherein in the still described in step (1), rated pressure is set by autocontrol valve, and suitable rated pressure is 0.1 ~ 0.2MPa.While exceeding rated pressure, valve opening, emits the hydrogen that reaction produces, and then returns to suitable rated pressure.
Wherein in the reactor described in step (1), hydrogen outlet pipe place is provided with stainless steel liquid removing net or packing layer, prevents from causing phenol loss by entrainment; The outer hydrogen outer vent of reactor is equipped with tail gas trapper.
Wherein in the process of preparing phenoxy group aluminium described in step (1), due to heat release in reaction process releasing hydrogen gas, according to the variation of rated pressure in still, regulate heating and cooling intensity, maintain reaction and carry out in gentle speed, keep as far as possible the release of hydrogen continous-stable in still.
Wherein, in the process of preparing phenoxy group aluminium described in step (1), the pressure of emission hydrogen is 0 ~ 0.2MPa, is convenient to recycle.
Wherein the Impurities In Catalyst described in step (2) refers to the Al (OH) of trace in phenol, phenoxy group Al catalysts mixture
3, Al
2o
3, Fe
2o
3, SiO
2deng material, swim in liquid with microgranular.
Wherein the Impurities In Catalyst of removing described in step (2) refers to by charcoal absorption Al (OH)
3, Al
2o
3, Fe
2o
3, SiO
2deng material, by filtration process method, impurity in phenol, phenoxy group Al catalysts mixture is separated with gac.
Wherein the gac described in step (2) need be at 160 ~ 200 ℃ of dehydrations, water-content≤0.001% before using.
Wherein removing in Impurities In Catalyst process described in step (2), the mass ratio of phenol and gac is 1:0.005 ~ 0.1; Suitable mass ratio is 1:0.01 ~ 0.04; Optimal temperature is 90 ~ 110 ℃; Suitable mixing time is 30 ~ 90min.
Wherein the filtration process method described in step (2) refers to by filtration under diminished pressure, pressure filtration, power-driven pump circulating filtration method.
Wherein the discharge of the filtration process described in step (2) gac residue can recycling use.
The wherein alkylation process described in step (3), add phenol, phenoxy group Al catalysts mixture, fully replace wherein oxygen with nitrogen, it is 1.0 ~ 1.8MPa that nitrogen is pressurized to still internal pressure, in reactor, nitrogen pressure is advisable higher than the emergent pressure of iso-butylene under temperature of reaction, nitrogen pressure is higher, and in gas phase, the dividing potential drop of iso-butylene is lower, and result improves the transformation efficiency of iso-butylene.
The wherein alkylation process described in step (3), along with the increase of iso-butylene add-on, the transformation efficiency of phenol improves, continuing increases, and partial reaction generates 2,6-phenol product, cause o-tert-butylphenol elective reduction, the mol ratio of phenol and iso-butylene is 1:0.5 ~ 2.5; Suitable mol ratio is 1:0.8 ~ 1.1; Suitable temperature of reaction is 90 ~ 130 ℃.
The wherein alkylation process described in step (3), iso-butylene adopts the charging of continuous dropping mode, and iso-butylene feed time is 120 ~ 240 min; The suitable insulation reaction time is 60 ~ 150min.
Wherein the separating catalyst process described in step (4) refers to by water and inorganic base aqueous solution the hydrolysis of phenoxy group aluminium is generated to phenol and aluminium hydroxide hydrate, and then reacts with inorganic alkali solution, generates the aluminium salt mixture that is insoluble in water, easy precipitation.Stir, after leaving standstill, the oil reservoir of clarification is separated with suspension water layer.
Wherein the inorganic base aqueous solution described in step (4) is prepared by alkaline earth metal oxide magnesium oxide, calcium oxide, barium oxide and tap water, and temperature is 15 ~ 35 ℃; Massfraction is 1 ~ 25%; Suitable massfraction is 2 ~ 6%
Wherein the add-on of the inorganic base aqueous solution described in step (4) is associated with the mole number of metallic aluminium in alkylphenol product mixed solution, and metallic aluminium and alkaline earth metal oxide mol ratio are 1:0.5 ~ 5.0; Suitable mol ratio is 1:1.0 ~ 2.0.
Wherein the steady temperature described in step (4) is 40 ~ 45 ℃; Churning time is 30 ~ 60min; Time of repose is 40 ~ 80min.
Wherein the water layer of suspension described in step (4), is made up of water and aluminium salt mixture, and aluminium salt mixture is by 3CaOAl
2o
36H
2o, 12CaO7Al
2o
3, Al (OH)
3, Ca (OH)
2, Al
2o
3deng composition.Massfraction in suspension water layer is 3 ~ 7%.
The wherein water layer of suspension described in step (4), the process water being obtained by sedimentation, filtering separation can recycle, the calcium oxide massfraction 0.3 ~ 0.6% in its process water.
Wherein the alkylphenol product mixed solution described in step (4) has the 2-phenol product of high quality mark, a small amount of phenol raw material or 2,6-phenol product, and not containing people's less desirable 4-phenol, 2,4-phenol, 2,4,6-phenol by product.
Wherein the oil reservoir of the clarification described in step (4) is alkylphenol product mixed solution, wherein contain the micro-material such as water, alkaline earth metal hydroxides, do not affect rectifying, because slight alkalinity environmental energy effectively prevents from the dealkylation of alkylphenol product in rectification process process from needing some alkaline matters of artificial interpolation in alkylphenol product rectifying in the past.
Wherein the process water removal process described in step (5) refers to suspension water layer described in step (4) is carried out to sedimentation, filtering separation process.Select the quantity of slurry tank to be associated with the settling time, the settling time is long, needs the quantity of sedimentation still tank many, 24 ~ 32 hours suitable settling times, 25 ~ 50 ℃ of sedimentation temperature in the kettle; After completing sedimentation, emit supernatant liquor, remaining slurries filtration obtains solid aluminium salt mixture and supernatant liquor.
Wherein the supernatant liquor described in step (5) merges collected process water at slurry tank E, F top and slurries filtration after having referred to the settling time, contains a small amount of alkaline earth metal hydroxides; Solids mixture has referred to and has obtained after filtering at the accumulation of slurry tank E, F bottom after the settling time, mainly by the mixture of alkaline earth salt, a small amount of alkaline earth metal hydroxides and the impurity that brought by alkaline earth metal oxide raw material etc.
The supernatant liquor wherein obtaining in step (5), analyze the massfraction of alkaline earth metal hydroxides, again the inorganic base aqueous solution described in preparation steps (4), separating catalyst process described in completing steps (4) in the same way, with this iterative cycles, reach the iterative cycles use of preparing alkylphenol product mixed solution process water, in whole process, there is no the discharge of phenolic wastewater and process water.
The solids mixture wherein obtaining in step (5), according to " alumina producing Bayer process Technology ", reclaims aluminum oxide, or for the preparation of the raw material of cement, reaches the object of comprehensive utilization solids with this.
advantage of the present invention
1, the present invention reacts metallic aluminium and prepares phenoxy group Al catalysts with phenol in low pressure reaction still, and without installing reflux exchanger additional, simple liquid removing net or packing layer, tail gas trapper can be controlled the effusion loss of phenol; Tail gas hydrogen is convenient to recycle; Low-pressure process obtains in the mixed solution of phenol, phenoxy group Al catalysts, trace impurity Al (OH)
3, Al
2o
3the relative traditional method of content low, in catalytic alkylation reaction process, can obtain relative highly selective ortho position substituted alkyl phenol product mixed solution thus.
2, take phenol compound and olefines alkylating reagent as raw material, employing organo-aluminium compound is catalyzer, by effectively removing Al in catalyzer (OH)
3, Al
2o
3, Fe
2o
3, SiO
2deng impurity, in catalytic alkylation reaction process, can obtain relative highly selective ortho position substituted alkyl phenol product mixed solution thus.
3, in alkylation process, being pressurized to still internal pressure with nitrogen is 1.0 ~ 1.8MPa, and the transformation efficiency of iso-butylene is improved; Optimize take phenol, iso-butylene, phenoxy group aluminium as catalyzer, carry out the processing parameter of catalytic alkylation reaction, can obtain the high yield of relative iso-butylene, phenol high conversion and highly selective ortho position substituted alkyl phenol product mixed solution, greatly reduce the raw materials cost of producing.
4, before the rectifying of o-tert-butylphenol product mixed solution, need from alkylphenol product mixed solution, remove organo aluminum catalyst, except effectively having solved the emission problem of phenolic wastewater in organo aluminum catalyst process.
5, in o-tert-butylphenol product mixed solution, contain micro-alkaline matter, alkaline environment can effectively prevent the dealkylation of alkylphenol product in rectification process process.
Accompanying drawing explanation
Wherein Fig. 1 is highly selective of the present invention ortho position substituted alkyl phenol product mixed solution preparation technology schematic flow sheet, wherein A. low pressure reaction still, B. strainer, C. autoclave, D. catalyst separating still, E. slurry tank, F. slurry tank, G. storage tank.
Embodiment
Be specifically related to take phenol compound and olefines alkylating reagent as raw material, employing organo-aluminium compound is catalyzer, adopt low pressure process method to be prepared with machine aluminium compound catalyzer and effectively remove the impurity in catalyzer, in catalytic alkylation reaction process, obtain highly selective ortho position substituted alkyl phenol product mixed solution thus.Before rectifying, need from alkylphenol product mixed solution, remove organo aluminum catalyst, except effectively having solved the emission problem of phenolic wastewater in organo aluminum catalyst process.
As shown in Figure 1, effective improvement method of the waste water producing in the preparation method of a kind of highly selective of the present invention ortho position substituted alkyl phenol product mixed solution and preparation process, by phenol compound, metallic aluminium is considered to be worth doing to add in proportion in reactor A and is reacted modulation catalyst, releasing hydrogen gas in reaction process, the reaction solution mixed solution obtaining enters in filter B and filters, phenol compound after despumation and phenoxy group Al catalysts enter in autoclave C, drip olefines alkylating reagent and carry out catalytic alkylation reaction, obtain the ortho position substituted alkyl phenol product mixed solution that contains aluminum compound catalyzer, enter in catalyst separating still D and separate aluminum compound, in catalyst separating still D, add inorganic base aqueous solution, stir, leave standstill, layering, upper strata oil reservoir is ortho position substituted alkyl phenol product mixed solution, enter in storage tank G, lower floor is the water layer of suspension, successively put into slurry tank E, in F, carry out sedimentation, at slurry tank E, in F, completing suspension water layer separates, be separated into supernatant liquor and solids mixture, supernatant liquor iterative cycles uses, outside solids mixture discharge system.
Phenol compound, olefines alkylating reagent that the present invention uses are commercially available prod, and specification is industrial top grade product; Magnesium oxide, calcium oxide, barium oxide are commercially available prod, and specification is industrial top grade product; Process water is ordinary tap water; Metallic aluminium is commercially available industrial goods AL99.85 aluminium ingot; Gac is commercially available prod ZXK-AR, granularity 100 ~ 120 orders.
embodiment 1
Both catalyzer modulation kettle in the GST-2 type 2000mL stainless steel low pressure reaction still A that is connected to filter B at the bottom of trapper and blow-down pipe, emptying valve, still with magnetic stirring apparatus, autocontrol valve, add 600 grams of phenol, 4.0 grams, metallic aluminium bits, with the air in nitrogen replacement reactor.Open heating power supply, material in still is slowly heated up.In the time that temperature in the kettle rises to 50 ℃, start stirring, regulate 80～100 revs/min of mixing speed, when temperature rises to 98～102 ℃, regulate 300～350 revs/min of mixing speed, slowly being warming up to 140～165 ℃ of phenol starts to react and releasing hydrogen gas with metallic aluminium bits, still internal pressure increases gradually, when reaching 0.1 MPa, slightly opens autocontrol valve by manual mode, and the hydrogen of releasing, 165～180 ℃, insulation reaction 70 minutes, still internal pressure is controlled at 0.1 ~ 0.2 MPa during this time, treat that in still, metallic aluminium bits dissolve completely, reaction completes.Reduce reactor temperature to 130 ℃, stop stirring, open emptying valve and reply normal pressure, add 15 grams of gacs, with the air in nitrogen replacement reactor, then nitrogen is pressurized to 0.2 MPa, at 100 ℃, stirs 60 minutes, open Filter valve at the bottom of still, in filter B, complete pressurized heat and filter, get rid of filter residue, filtrate enters in the GST-2 type 2000mL stainless steel autoclave C with magnetic stirring apparatus, 1000mL raw materials tank both alkylated reaction stills.Catalytic alkylation reaction adds 330 grams of iso-butylenes in 1000mL raw materials tank.With the air in nitrogen replacement reactor and to be pressurized to still internal pressure be 1.5MPa, stir, 700～750 revs/min, heating, slowly heats up material in still, in the time that temperature rises to 110 ℃, open the valve of raw materials tank, in reactor, add continuously iso-butylene raw material, reacting kettle inner pressure maintains 1.5MPa left and right, within 200 minutes, adds whole iso-butylenes in feed pot.After having fed in raw material, 110～113 ℃ of temperature of reaction, insulation reaction 80 minutes, make phenol, iso-butylene proceed alkylated reaction, after insulation reaction completes, open reactor bottom valve, reaction solution is pressed into in the GST-2 type 2000mL stainless steel low pressure reaction still of magnetic stirring apparatus, 500mL raw materials tank both catalyst separating still D, carry out catalyst separating.Start stirring, when temperature in the kettle is down to 50 ~ 60 ℃, the calcium oxide aqueous solution of 300 gram 6% in 500mL raw materials tank is added in 20 minutes uniformly, temperature is controlled at 40 ~ 45 ℃, stirs 50 minutes, leaves standstill 60 minutes.Open still bottom valve, the water layer of suspension is put into the 500mL graduated cylinder as slurry tank E, F; Collect in 925.3 grams of 1500mL glass port grinding bottles that pack into as storage tank G. of oil reservoir gas chromatographic analysis composition (in table 1).
Phenol conversion 90.6%, iso-butylene turn yield 98.5%, in phenol 2-phenol selectivity 95.7%, in phenol 2,6-phenol selectivity 2.3%, in phenol ortho position substituted alkyl phenol product selectivity 98.0%.
embodiment 2
By 25 ~ 50 ℃ of the water layers of the suspension of 500mL graduated cylinder splendid attire in embodiment 1, sedimentation 24 hours, inclines and supernatant liquor, and remaining throw out filters and obtains clear liquid and filter cake, merges 276 grams of clear liquids, calcium oxide massfraction 0.4% in clear liquid.Add water and calcium oxide, 300 grams of the calcium oxide aqueous solutions of preparation 3.8% are for subsequent use.
In low pressure reaction still A, add 600 grams of phenol, 3.0 grams, metallic aluminium bits, with the air in nitrogen replacement reactor.Open heating power supply, material in still is slowly heated up.In the time that temperature in the kettle rises to 50 ℃, start stirring, regulate 80～100 revs/min of mixing speed, when temperature rises to 98～102 ℃, regulate 300～350 revs/min of mixing speed, slowly being warming up to 140～165 ℃ of phenol starts to react and releasing hydrogen gas with metallic aluminium bits, still internal pressure increases gradually, when reaching 0.15 MPa, slightly opens autocontrol valve by manual mode, and the hydrogen of releasing, 165～180 ℃, insulation reaction 80 minutes, still internal pressure is controlled at 0.1 ~ 0.2 MPa during this time, treat that in still, metallic aluminium bits dissolve completely, reaction completes.Reduce reactor temperature to 130 ℃, stop stirring, open emptying valve and reply normal pressure, add 10 grams of gacs, with the air in nitrogen replacement reactor, then nitrogen is pressurized to 0.1 MPa, at 110 ℃, stir 70 minutes, open Filter valve at the bottom of still, in filter B, complete pressurized heat and filter, get rid of filter residue, filtrate enters in autoclave C, carries out catalytic alkylation reaction, adds 358 grams of iso-butylenes in 1000mL raw materials tank.With the air in nitrogen replacement reactor and to be pressurized to still internal pressure be 1.2MPa, stir, 700～750 revs/min, heating, slowly heats up material in still, in the time that temperature rises to 120 ℃, open the valve of raw materials tank, in reactor, add continuously iso-butylene raw material, reacting kettle inner pressure maintains 1.5MPa left and right, within 220 minutes, adds whole iso-butylenes in feed pot.After having fed in raw material, 90～95 ℃ of temperature of reaction, insulation reaction 150 minutes, makes phenol, iso-butylene proceed alkylated reaction, after insulation reaction completes, opens reactor bottom valve, and reaction solution is pressed in catalyst separating still D.Start stirring, separate temperature in the kettle while being down to 50～60 ℃, the calcium oxide aqueous solution of 300 gram 3.8% in 500mL raw materials tank is added in 20 minutes uniformly, temperature is controlled at 40 ~ 45 ℃, stirs standing 80 minutes 40 minutes.Open still bottom valve, the water layer of suspension is put into the 500mL graduated cylinder as slurry tank E, F; Collect in 945.3 grams of 1500mL glass port grinding bottles that pack into as storage tank G. of oil reservoir gas chromatographic analysis composition (in table 1).
Phenol conversion 95.1%, iso-butylene turn yield 96.3%, in phenol 2-phenol selectivity 93.0%, in phenol 2,6-phenol selectivity 4.2%, in phenol ortho position substituted alkyl phenol product selectivity 97.2%.
embodiment 3
By 25 ~ 50 ℃ of the water layers of the suspension of 500mL graduated cylinder splendid attire in embodiment 2, sedimentation 32 hours, inclines and supernatant liquor, and remaining throw out filters and obtains clear liquid and filter cake, merges 260 grams of clear liquids, calcium oxide massfraction 0.6% in clear liquid.Add water and calcium oxide, 300 grams of the calcium oxide aqueous solutions of preparation 6.4% are for subsequent use.
In low pressure reaction still A, add 600 grams of phenol, 5.0 grams, metallic aluminium bits, with the air in nitrogen replacement reactor.Open heating power supply, material in still is slowly heated up.In the time that temperature in the kettle rises to 50 ℃, start stirring, regulate 80～100 revs/min of mixing speed, when temperature rises to 98～102 ℃, regulate 300～350 revs/min of mixing speed, slowly being warming up to 140～165 ℃ of phenol starts to react and releasing hydrogen gas with metallic aluminium bits, still internal pressure increases gradually, when reaching 0.20 MPa, slightly opens autocontrol valve by manual mode, and the hydrogen of releasing, 165～180 ℃, insulation reaction 90 minutes (, still internal pressure is controlled at 0.1 ~ 0.2 MPa during this time, treat that in still, metallic aluminium bits dissolve completely, reaction completes.Reduce reactor temperature to 130 ℃, stop stirring, open emptying valve and reply normal pressure, add 20 grams of gacs, with the air in nitrogen replacement reactor, then nitrogen is pressurized to 0.3 MPa, at 100 ℃, stir 80 minutes, open Filter valve at the bottom of still, in filter B, complete pressurized heat and filter, get rid of filter residue, filtrate enters in autoclave C, carries out catalytic alkylation reaction, adds 393 grams of iso-butylenes in 1000mL raw materials tank.With the air in nitrogen replacement reactor and to be pressurized to still internal pressure be 1.8MPa, stir, 700～750 revs/min, heating, slowly heats up material in still, in the time that temperature rises to 90 ℃, open the valve of raw materials tank, in reactor, add continuously iso-butylene raw material, reacting kettle inner pressure maintains 1.8MPa left and right, within 240 minutes, adds whole iso-butylenes in feed pot.After having fed in raw material, 90～95 ℃ of temperature of reaction (, insulation reaction 130 minutes, makes phenol, iso-butylene proceed alkylated reaction, after insulation reaction completes, opens reactor bottom valve, and reaction solution is pressed in catalyst separating still D.Start stirring, separate temperature in the kettle while being down to 50～60 ℃, the calcium oxide aqueous solution of 300 gram 6.4% in 500mL raw materials tank is added in 20 minutes uniformly, temperature is controlled at 40 ~ 45 ℃, stirs standing 80 minutes 60 minutes.Open still bottom valve, the water layer of suspension is put into the 500mL graduated cylinder as slurry tank E, F; Collect in 986.6 grams of 1500mL glass port grinding bottles that pack into as storage tank G. of oil reservoir gas chromatographic analysis composition (in table 1).
Phenol conversion 98.6%, iso-butylene turn yield 95.7%, in phenol 2-phenol selectivity 90.8%, in phenol 2,6-phenol selectivity 7.9%, in phenol ortho position substituted alkyl phenol product selectivity 98.7%.
embodiment 4
By 25 ~ 50 ℃ of the water layers of the suspension of 500mL graduated cylinder splendid attire in embodiment 3, sedimentation 30 hours, inclines and supernatant liquor, and remaining throw out filters and obtains clear liquid and filter cake, merges 282 grams of clear liquids, calcium oxide massfraction 0.3% in clear liquid.Add water and calcium oxide, 300 grams of the calcium oxide aqueous solutions of preparation 2.3% are for subsequent use.
In low pressure reaction still A, add 600 grams of phenol, 1.2 grams, metallic aluminium bits, with the air in nitrogen replacement reactor.Open heating power supply, material in still is slowly heated up.In the time that temperature in the kettle rises to 50 ℃, start stirring, regulate 80～100 revs/min of mixing speed, when temperature rises to 98～102 ℃, regulate 300～350 revs/min of mixing speed, slowly being warming up to 140～165 ℃ of phenol starts to react and releasing hydrogen gas with metallic aluminium bits, still internal pressure increases gradually, when reaching 0.10 MPa, slightly opens autocontrol valve by manual mode, and the hydrogen of releasing, 165～180 ℃, insulation reaction 60 minutes, still internal pressure is controlled at 0.1 ~ 0.2 MPa during this time, treat that in still, metallic aluminium bits dissolve completely, reaction completes.Reduce reactor temperature to 130 ℃, stop stirring, open emptying valve and reply normal pressure, add 6 grams of gacs, with the air in nitrogen replacement reactor, then nitrogen is pressurized to 0.1 MPa, at 90 ℃, stir 90 minutes, open Filter valve at the bottom of still, in filter B, completing pressurized heat filters, get rid of filter residue, filtrate enters in autoclave C, carry out catalytic alkylation reaction, in 1000mL raw materials tank, add 286 grams of iso-butylenes, with the air in nitrogen replacement reactor and open that to be pressurized to still internal pressure be 1.0MPa, stir, 700～750 revs/min, heating, material in still is slowly heated up, in the time that temperature rises to 130 ℃, open the valve of raw materials tank, in reactor, add continuously iso-butylene raw material, reacting kettle inner pressure maintains 1.0MPa left and right, within 220 minutes, add whole iso-butylenes in feed pot.After having fed in raw material, 125～130 ℃ of temperature of reaction, insulation reaction 60 minutes, makes phenol, iso-butylene proceed alkylated reaction, after insulation reaction completes, opens reactor bottom valve, and reaction solution is pressed in catalyst separating still D.Start stirring, separate temperature in the kettle while being down to 50～60 ℃, the calcium oxide aqueous solution of 300 gram 2.3% in 500mL raw materials tank is added in 20 minutes uniformly, temperature is controlled at 40 ~ 45 ℃, stirs standing 60 minutes 30 minutes.Open still bottom valve, the water layer of suspension is put into the 500mL graduated cylinder as slurry tank E, F; Collect in 885.5 grams of 1500mL glass port grinding bottles that pack into as storage tank G. of oil reservoir, gas chromatographic analysis composition (in table 1),
Phenol conversion 79.8%, iso-butylene turn yield 98.1%, in phenol 2-phenol selectivity 98.3%, in phenol 2,6-phenol selectivity 0.0%, in phenol ortho position substituted alkyl phenol product selectivity 98.3%.
embodiment 5
By 25 ~ 50 ℃ of the water layers of the suspension of 500mL graduated cylinder splendid attire in embodiment, sedimentation 30 hours, inclines and supernatant liquor, and remaining throw out filters and obtains clear liquid and filter cake, merges 285 grams of clear liquids, calcium oxide massfraction 0.6% in clear liquid.Add water and calcium oxide, 300 grams of the calcium oxide aqueous solutions of preparation 2.0% are for subsequent use.
In low pressure reaction still A, add 600 grams of phenol, 2.0 grams, metallic aluminium bits, with the air in nitrogen replacement reactor.Open heating power supply, material in still is slowly heated up.In the time that temperature in the kettle rises to 50 ℃, start stirring, regulate 80～100 revs/min of mixing speed, when temperature rises to 98～102 ℃, regulate 300～350 revs/min of mixing speed, slowly being warming up to 140～165 ℃ of phenol starts to react and releasing hydrogen gas with metallic aluminium bits, still internal pressure increases gradually, when reaching 0.15 MPa, slightly opens autocontrol valve by manual mode, and the hydrogen of releasing, 165～180 ℃, insulation reaction 70 minutes, still internal pressure is controlled at 0.1 ~ 0.2 MPa during this time, treat that in still, metallic aluminium bits dissolve completely, reaction completes.Reduce reactor temperature to 130 ℃, stop stirring, open emptying valve and reply normal pressure, add 24 grams of gacs, with the air in nitrogen replacement reactor, then nitrogen is pressurized to 0.2 MPa, at 100 ℃, stir 60 minutes, open Filter valve at the bottom of still, in filter B, completing pressurized heat filters, get rid of filter residue, filtrate enters in autoclave C, carry out catalytic alkylation reaction, in 1000mL raw materials tank, add 310 grams of iso-butylenes, with the air in nitrogen replacement reactor and open that to be pressurized to still internal pressure be 1.5MPa, stir, 700～750 revs/min, heating, material in still is slowly heated up, in the time that temperature rises to 100 ℃, open the valve of raw materials tank, in reactor, add continuously iso-butylene raw material, reacting kettle inner pressure maintains 1.5MPa left and right, within 180 minutes, add whole iso-butylenes in feed pot.After having fed in raw material, 100～105 ℃ of temperature of reaction, insulation reaction 110 minutes, makes phenol, iso-butylene proceed alkylated reaction, after insulation reaction completes, opens reactor bottom valve, and reaction solution is pressed in catalyst separating still D.Start stirring, when separation temperature in the kettle is down to 50～60 ℃, the calcium oxide aqueous solution of 300 gram 2.0% in 500mL raw materials tank is added in 20 minutes uniformly, temperature is controlled at 40 ~ 45 ℃, stir 50 minutes, leave standstill 80 minutes, open still bottom valve, the water layer of suspension is put into the 500mL graduated cylinder as slurry tank E, F; Collect in 904.8 grams of 1500mL glass port grinding bottles that pack into as storage tank G. of oil reservoir gas chromatographic analysis composition (in table 1).
Phenol conversion 85.9%, iso-butylene turn yield 97.5%, in phenol 2-phenol selectivity 98.5%, in phenol 2,6-phenol selectivity 0.0%, in phenol selectivity 98.5%.
Table 1: embodiment 1～5 gas chromatographic analysis ortho position substituted alkyl phenol product mixed solution
Claims (5)
1. a preparation method for highly selective ortho position substituted alkyl phenol product mixed solution, is characterized in that carrying out according to following step:
(1) prepare the process of phenoxy group aluminium: add in proportion phenol compound, metallic aluminium bits with automatically controlling in the low pressure reaction still of pressure limiting valve, air in nitrogen replacement still, heat up, stir, heat up, phenol compound reacts and releasing hydrogen gas with metallic aluminium bits, still internal pressure constantly increases, when reaching rated pressure value, the autocontrol valve hydrogen of opening and release; In still, metallic aluminium bits dissolve in phenol compound completely, and reaction completes, and obtains the mixed solution of phenol, phenoxy group Al catalysts; Wherein in the still described in step (1), rated pressure is set by autocontrol valve, and rated pressure is 0.1 ~ 0.2MPa, and while exceeding rated pressure, valve opening, emits the hydrogen that reaction produces, and then returns to suitable rated pressure;
(2) remove Impurities In Catalyst process: in low pressure reaction still, add in proportion gac, under steady temperature, stir certain hour, in strainer, filter, filtrate enters in alkylated reaction still;
(3) alkylation process: in autoclave, carry out in advance nitrogen replacement air wherein, add after the mixed solution of phenol compound, phenoxy group Al catalysts and be pressurized to definite value with nitrogen, stir, heat up, adopt continuously feeding mode to drip olefines alkylating reagent; Catalytic alkylation reaction, after the reaction times of regulation completes, stirs, cooling, emits nitrogen and returns to normal pressure, obtains the ortho position substituted alkyl phenol product mixed solution that contains phenoxy group Al catalysts, enters into catalyst separating still; Wherein said phenol compound refers to phenol; Wherein the mol ratio of the alkylation process phenol described in step (3) and iso-butylene is 1:0.8 ~ 1.1; Temperature of reaction is 90 ~ 130 ℃; The wherein alkylation process described in step (3), adds phenol, phenoxy group Al catalysts mixture, fully replaces wherein air with nitrogen, and it is 1.0 ~ 1.8MPa that nitrogen is pressurized to still internal pressure;
(4) separating catalyst process: add inorganic base aqueous solution in catalyst separating still, stir under steady temperature, leave standstill layering; Separate, the water layer that is suspension below is successively put into slurry tank; The oil reservoir of clarification is o-tert-butylphenol product mixed solution, enters in storage tank, and rectification under vacuum obtains product;
(5) process water removal process completes the separation of suspension water layer in slurry tank, adopts sedimentation, filtering separation processing method, and suspension water layer is separated into supernatant liquor and solids mixture; Analyze the massfraction of alkali in supernatant liquor, with the inorganic base aqueous solution in this preparation steps (4);
Wherein said olefines alkylating reagent refers to iso-butylene;
Wherein said phenoxy group Al catalysts refers to phenoxy group aluminium;
The wherein alkylation process described in step (3), iso-butylene adopts the charging of continuous dropping mode, and iso-butylene feed time is 120 ~ 240 min; The insulation reaction time is 60 ~ 150min.
2. the preparation method of a kind of highly selective according to claim 1 ortho position substituted alkyl phenol product mixed solution, is characterized in that wherein that the bits of the metallic aluminium described in step (1) refer to industrial aluminium ingot mechanical means is cut into (8 ~ 12mm) × (1 ~ 3mm) × (20 ~ 30mm) irregular bar; Wherein, in the process of preparing phenoxy group aluminium described in step (1), phenol and metallic aluminium bits mass ratio are 1:0.001 ~ 0.02; Temperature of reaction is 140 ~ 180 ℃;
Wherein in the reactor described in step (1), hydrogen outlet pipe place is provided with stainless steel liquid removing net or packing layer; The outer hydrogen outer vent of reactor is equipped with tail gas trapper;
Wherein, in the process of preparing phenoxy group aluminium described in step (1), the pressure of emission hydrogen is 0 ~ 0.2MPa.
3. the preparation method of a kind of highly selective according to claim 1 ortho position substituted alkyl phenol product mixed solution, is characterized in that wherein the Impurities In Catalyst described in step (2) refers to Al (OH) micro-in phenol, phenoxy group Al catalysts mixture
3, Al
2o
3, Fe
2o
3, SiO
2material, swims in liquid with microgranular;
Wherein the Impurities In Catalyst of removing described in step (2) refers to by charcoal absorption Al (OH)
3, Al
2o
3, Fe
2o
3, SiO
2material, separates impurity in phenol, phenoxy group Al catalysts mixture by filtration process method with gac;
Wherein the gac described in step (2) need be at 160 ~ 200 ℃ of dehydrations, water-content≤0.001% before using;
Wherein removing in Impurities In Catalyst process described in step (2), the mass ratio of phenol and gac is 1:0.005 ~ 0.1; Temperature is 90 ~ 110 ℃;
Wherein the filtration process method described in step (2) refers to by filtration under diminished pressure, pressure filtration, power-driven pump circulating filtration method;
Wherein the discharge of the filtration process described in step (2) gac residue can recycling use.
4. the preparation method of a kind of highly selective according to claim 1 ortho position substituted alkyl phenol product mixed solution, it is characterized in that wherein that the separating catalyst process described in step (4) refers to by water and inorganic base aqueous solution generates phenol and aluminium hydroxide hydrate by the hydrolysis of phenoxy group aluminium, and then react with inorganic alkali solution, generation is insoluble in the aluminium salt mixture of water, easy precipitation, stir, after leaving standstill, the oil reservoir of clarification is separated with suspension water layer;
Wherein the inorganic base aqueous solution described in step (4) is prepared by alkaline earth metal oxide magnesium oxide, calcium oxide, barium oxide and tap water, and temperature is 15 ~ 35 ℃; Massfraction is 1 ~ 25%;
Wherein the steady temperature described in step (4) is 40 ~ 45 ℃; Churning time is 30 ~ 60min; Time of repose is 40 ~ 80min;
The wherein water layer of suspension described in step (4), the process water being obtained by sedimentation, filtering separation can recycle, the calcium oxide massfraction 0.3 ~ 0.6% in its process water.
5. the preparation method of a kind of highly selective according to claim 1 ortho position substituted alkyl phenol product mixed solution, it is characterized in that wherein the process water removal process described in step (5) refers to carries out sedimentation, filtering separation process to suspension water layer described in step (4), 24 ~ 32 hours settling times, 25 ~ 50 ℃ of sedimentation temperature in the kettle; After completing sedimentation, emit supernatant liquor, remaining slurries filtration obtains solid aluminium salt mixture and supernatant liquor.
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| JP3733192B2 (en) * | 1997-01-30 | 2006-01-11 | 本州化学工業株式会社 | Method for producing crude 2,6-dialkylphenol |
| CN1868992A (en) * | 2005-05-28 | 2006-11-29 | 淄博万昌科威化工有限公司 | Alkylphenol coproduction technology |
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| US3970708A (en) * | 1974-12-26 | 1976-07-20 | Chevron Research Company | Process for removing aluminum phenoxide catalyst from phenol alkylation products |
| JP3733192B2 (en) * | 1997-01-30 | 2006-01-11 | 本州化学工業株式会社 | Method for producing crude 2,6-dialkylphenol |
| CN1197785A (en) * | 1998-05-09 | 1998-11-04 | 临湘市氨基化学品厂 | Preparation of o-isopropyl phenol |
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