CN110357775A - A kind of preparation method and preparation facilities of phthalic acid - Google Patents
A kind of preparation method and preparation facilities of phthalic acid Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of phthalic acid and preparation facilities, S1, the concentrated hydrochloric acid that 245~255 parts by weight are added into reaction flask put into the phthalylhydrazine of 48~52 parts by weight into reaction flask；S2, the hydrogen peroxide that 167~173 parts by weight and concentration are 30% is added dropwise into reaction flask；Temperature filters after 2 hours stirred below at 50 DEG C in S3, control reaction flask, and the filter cake obtained after filtering is O-phthalic acid crude；S4, the pure water that 8M parts by weight are added into purification bottle, O-phthalic acid crude in step S3 is added in purification bottle, solid impurity is excluded and obtains filtrate, phthalic acid soaking wet product are obtained by filtration after filtrate slow cooling is carried out crystallization 2 hours to 10 DEG C or less；S5, drying at a temperature of 100~110 DEG C by the phthalic acid soaking wet product of step S4.The present invention turns waste into wealth phthalylhydrazine, so that the cost for preparing phthalic acid substantially reduces, production method is convenient for manipulating, while stable product quality.
Description
Technical field
The present invention relates to phthalic acid preparation field more particularly to the preparation methods and preparation dress of a kind of phthalic acid
It sets.
Background technique
Phthalic acid (molecular formula C8H6O4, physicochemical property are white needle-like crystals, and fusing point is 227 DEG C) is benzene two
One in formic acid isomers, phthalic acid is mainly used for producing phthalic anhydride, and the latter is production dyestuff, perfume, sugar
The precursor of the chemicals such as essence, phthalic acid ester, phenolphthalein.O-methyl-benzene is generally used in existing phthalic acid preparation method
Formic acid, ortho-xylene or naphthalene are raw material, are prepared by vanadic anhydride catalysis oxidation；Or it is hydrolyzed and is prepared with phthalic anhydride.
The cost of the raw materials such as o-toluic acid, ortho-xylene or naphthalene employed in above-mentioned phthalic acid preparation method is relatively high,
Technique is also more complicated.Passing through phthalyl-L- alanyl in pharmaceutical factory -- glutamine, methanol, hydrazine hydrate synthesize the third ammonia of L-
When acyl-L-Glutamine, a large amount of phthalylhydrazine can be generated in reaction process, general medicine enterprise is by phthalylhydrazine
It is handled as waste impurity, processing phthalylhydrazine needs are additionally paid compared with high cost, and treatment process can be to ring
Border generates serious pollution.Therefore, how phthalylhydrazine is subjected to waste utilization, is always that look forward to technology to be solved difficult for medicine
Point.
Summary of the invention
Place in view of the shortcomings of the prior art, the purpose of the present invention is to provide a kind of preparation sides of phthalic acid
Method and preparation facilities, using by-product phthalylhydrazine caused by synthesis Ala-Gln as raw material next life
Production prepares phthalic acid, not only without to by-product phthalylhydrazine caused by synthesis Ala-Gln
It is handled, while phthalylhydrazine being turned waste into wealth, so that the cost for preparing phthalic acid substantially reduces.
The purpose of the invention is achieved by the following technical solution:
A kind of preparation method of phthalic acid, method and step are as follows:
S1, the concentrated hydrochloric acid that 245~255 parts by weight are added into reaction flask, to1348~52 parts by weight are put into reaction flask
Phthalylhydrazine is stirred the mixture in reaction flask, and salt water is added while agitating will be mixed in reaction flask
It closes object and is cooled to 3~8 DEG C；
S2, the hydrogen peroxide that 167~173 parts by weight and concentration are 30% is added dropwise into reaction flask, controls temperature in reaction flask
At 50 DEG C or less；
After S3, step S2 are added dropwise, control temperature in reaction flask and filtered after 2 hours stirred below at 50 DEG C, after filtering
Obtained filter cake is O-phthalic acid crude, and O-phthalic acid crude of weighing is M；
S4, the pure water that 8M parts by weight are added into purification bottle, the O-phthalic acid crude of M parts by weight in step S3 is added
It refines in bottle, fluidized state is heated to the mixture in purification bottle and is kept for 3~4 hours, then in purification bottle
Mixture is filtered processing, excludes solid impurity and obtains filtrate, and filtrate slow cooling crystallize 2 hours to 10 DEG C or less
After filter, by crystal using ice water wash 10 minutes, phthalic acid soaking wet product are obtained after crystal is washed；
S5, by the phthalic acid soaking wet product of step S4 forced air drying 8 hours at a temperature of 100~110 DEG C, and it is final
To phthalic acid dry product.
In order to which the present invention is better achieved, the present invention provides a kind of preferred phthalic acid preparation method, method step
It is rapid as follows:
S1, the concentrated hydrochloric acid that 250 parts by weight are added into reaction flask, the phthalyl of 50 parts by weight is put into reaction flask
Hydrazine is stirred the mixture in reaction flask, and salt water is added while agitating, the mixture in reaction flask is cooled to 3
~8 DEG C；
S2, the hydrogen peroxide that 170 parts by weight and concentration are 30% is added dropwise into reaction flask, temperature is at 50 DEG C in control reaction flask
Below；
After S3, step S2 are added dropwise, control temperature in reaction flask and filtered after 2 hours stirred below at 50 DEG C, after filtering
Obtained filter cake is O-phthalic acid crude, and O-phthalic acid crude of weighing is M；
S4, the pure water that 8M parts by weight are added into purification bottle, the O-phthalic acid crude of M parts by weight in step S3 is added
It refines in bottle, fluidized state is heated to the mixture in purification bottle and is kept for 3~4 hours, then in purification bottle
Mixture is filtered processing, excludes solid impurity and obtains filtrate, and filtrate slow cooling crystallize 2 hours to 10 DEG C or less
After filter, by crystal using ice water wash 10 minutes, phthalic acid soaking wet product are obtained after crystal is washed；
S5, by the phthalic acid soaking wet product of step S4 forced air drying 8 hours at a temperature of 105 DEG C, and finally obtain neighbour
Phthalic acid dry product.
Preferably, the phthalylhydrazine in step S1 of the present invention is in synthesis Ala-Gln reaction
By-product.
Preferably, phthalyl in step S1 of the present invention to obtain method as follows:
S11, phthalyl-L- alanyl -- glutamine, the Xiang Sikou that 120 parts by weight are added into four mouthfuls of reaction flasks
80% hydrazine hydrate of concentration of methanol and 23 parts by weight is added in reaction flask, then stirs, to reaction solution be warming up to interior temperature for 65~
At 67 DEG C, fluidized state is warming up to reaction solution and is kept for 4 hours；
S12, stop heating, be cooled to 10 DEG C hereinafter, filtering to reaction solution, filter cake is washed with methanol；Filter cake subtracts at 60 DEG C
It press dry dry 4 hours, filter cake is transferred in beaker, pure water is added into beaker, beaker internal temperature is then warming up to interior temperature
It is 25~30 DEG C, then stirs 3 hours, filters, filter cake is washed with water, and collects filtrate；
S13, the filtrate in step S12 is transferred in beaker, medicinal carbon, stirring decoloration 30 minutes, filtering is added
Processing obtains filter cake and filtrate, collects filtrate, and filtrate is -1 one glutamine solution of L- alanyl, is collected to filter cake, filters
Cake is washed with water, and filter cake is phthalylhydrazine.
Chlorine is carried out preferably, reacting tail gas generated in step S2 of the present invention and being collected and be passed through in liquid alkaline solution
It absorbs, tail gas includes chlorine and nitrogen.
A kind of preparation facilities of phthalic acid, including heat insulation tank, reaction vessel, agitating device and dropwise addition system, it is described
Reaction vessel is placed in heat insulation tank, and the reaction vessel interior has reaction cavity, is provided with feed opening at the top of the reaction vessel,
The feed opening of the reaction vessel by seal cap sealing connect, the agitating device include stirring motor and be fixed on stirring electricity
Agitating shaft on the output shaft of machine, the agitating shaft of the agitating device are placed in the reaction cavity of reaction vessel through sealing cover
In, the shaft bottom of the agitating device is fixed with stirrer paddle；The dropwise addition system includes dropping tank and is connected to dropwise addition
The drop tube of the drop tube of pot bottom, the dropwise addition system is placed in the reaction cavity of reaction vessel through sealing cover；It is described
Through being equipped with thermometer on the sealing cover of reaction vessel, through being equipped with and reaction vessel on the sealing cover of the reaction vessel
The escape pipe that reaction vessel is connected.
The present invention compared with the prior art, have the following advantages that and the utility model has the advantages that
(1) present invention will synthesize by-product phthalylhydrazine caused by Ala-Gln as raw material
Phthalic acid is prepared to produce, not only without to by-product O-phthalic caused by synthesis Ala-Gln
Hydrazides is handled, while phthalylhydrazine being turned waste into wealth, so that the cost for preparing phthalic acid substantially reduces.
(2) process of preparing of the present invention is easily manipulated, phthalic acid low production cost, and phthalic acid
Stable product quality.
Detailed description of the invention
Fig. 1 is the structural diagram of the present invention.
Wherein, title corresponding to the appended drawing reference in attached drawing are as follows:
1- heat insulation tank, 2- reaction vessel, 21- sealing cover, 3- agitating device, 4- dropwise addition system, 41- drop tube,
5- thermometer, 6- escape pipe.
Specific embodiment
The present invention is described in further detail below with reference to embodiment:
Embodiment one
A kind of preparation method of phthalic acid, method and step are as follows:
S1, the concentrated hydrochloric acid that 245g is added into 500ml reaction flask put into the phthalylhydrazine of 48g into reaction flask, right
Mixture in reaction flask is stirred, and salt water is added while agitating, the mixture in reaction flask is cooled to 3~8
℃；
S2,167g and concentration is added dropwise into reaction flask as 30% hydrogen peroxide, temperature is at 50 DEG C or less in control reaction flask；
After S3, step S2 are added dropwise, control temperature in reaction flask and filtered after 2 hours stirred below at 50 DEG C, after filtering
Obtained filter cake is O-phthalic acid crude, and O-phthalic acid crude of weighing is 103g；
Purification bottle is added in the O-phthalic acid crude of 103g in step S3 by S4, the pure water that 824g is added into purification bottle
In, fluidized state is heated to the mixture in purification bottle and is kept for 3~4 hours, then to the mixture in purification bottle
It is filtered processing, solid impurity is excluded and obtains filtrate, mistake after filtrate slow cooling is carried out crystallization 2 hours to 10 DEG C or less
Filter washs crystal 10 minutes using ice water, and phthalic acid soaking wet product, phthalic acid essence are obtained after crystal is washed
Wet product is 74.5g；
S5, by the phthalic acid soaking wet product of step S4 forced air drying 8 hours at a temperature of 100~110 DEG C, and it is final
To phthalic acid dry product, phthalic acid dry product weight is 48g, and phthalic acid dry product yield reaches 96.0%, adjacent benzene two
Phthalate content is 99.1% in formic acid dry product.
Phthalyl in the present embodiment step S1 is by-product when synthesizing Ala-Gln, adjacent benzene
Two formyls generated by-product when can be using synthesis Ala-Gln, in synthesis L- alanyl-L- glutamy
When amine, phthalyl is excluded as by-product impurities, and the method for synthesizing Ala-Gln is as follows:
120g phthalyl-L- alanyl -- glutamine is added into four mouthfuls of reaction flasks of 2000ml, methanol is added
80% hydrazine hydrate 23g is added in 1300ml, opens stirring.It is 65-67 DEG C of reflux 4h that reaction solution, which is warming up to interior temperature, after having flowed back
HPLC sample detection carries out next-step operation after qualified.Reaction solution is cooled to t≤10 DEG C suction filtration, and filter cake is washed with 200m1 methanol.
Filter cake is drained, and filter cake is collected, and filter cake is dried under reduced pressure 4 hours at 60 DEG C, filter cake is transferred in the beaker of 500ml, into beaker
157ml water is added, being warming up to interior temperature is 25-30 DEG C, is stirred 3 hours, is filtered, filter cake 20ml water washing, and filtrate is collected.Filtrate
It is transferred in the beaker of 500ml, medicinal carbon 5.8g, stirring decoloration 30min, filtering, filter cake 10ml water washing, receipts is added
Collect filtrate.Filter cake is collected as phthalylhydrazine；Filtrate is transferred in the four-hole boiling flask of 3000ml, opens stirring, reaction solution liter
Temperature to interior temperature is 40-50 DEG C, and product is precipitated in the addition ethyl alcohol 600ml into four-hole boiling flask slowly.Reaction solution heating most temperature be
65-75 DEG C of reflux 2h；Reaction solution is cooled to t≤20 DEG C after having flowed back, and temperature fall time is 2 hours.It filters, filter cake 200ml second
Alcohol washing, filters, and collects filter cake.60 DEG C of filter cake are dried under reduced pressure 5-6 hours.Filter cake is collected, -1 one glutamy of L- alanyl is obtained
Amine 64.0g, yield 85.0%.
Phthalyl is prepared phthalic acid as waste utilization by the present embodiment；Phthalyl obtains method
It is as follows:
S11, phthalyl-L- alanyl -- glutamine, the Xiang Sikou that 120 parts by weight are added into four mouthfuls of reaction flasks
80% hydrazine hydrate of concentration of methanol and 23 parts by weight is added in reaction flask, then stirs, to reaction solution be warming up to interior temperature for 65~
At 67 DEG C, fluidized state is warming up to reaction solution and is kept for 4 hours；
S12, stop heating, be cooled to 10 DEG C hereinafter, filtering to reaction solution, filter cake is washed with methanol；Filter cake subtracts at 60 DEG C
It press dry dry 4 hours, filter cake is transferred in beaker, pure water is added into beaker, beaker internal temperature is then warming up to interior temperature
It is 25~30 DEG C, then stirs 3 hours, filters, filter cake is washed with water, and collects filtrate；
S13, the filtrate in step S12 is transferred in beaker, medicinal carbon, stirring decoloration 30 minutes, filtering is added
Processing obtains filter cake and filtrate, collects filtrate, and filtrate is -1 one glutamine solution of L- alanyl, is collected to filter cake, filters
Cake is washed with water, and filter cake is phthalylhydrazine.
As shown in Figure 1, a kind of preparation facilities of phthalic acid, including heat insulation tank 1, reaction vessel 2,3 and of agitating device
Dropwise addition system 4, reaction vessel 2 are placed in heat insulation tank 1, are had reaction cavity inside reaction vessel 2, are provided at the top of reaction vessel 2
Feed opening, the feed opening of reaction vessel 2 are tightly connected by sealing cover 21, and agitating device 3 includes that stirring motor and being fixed on stirs
The agitating shaft on the output shaft of motor is mixed, the agitating shaft of agitating device 3 is placed in the reaction chamber of reaction vessel 2 through sealing cover 21
In body, the shaft bottom of agitating device 3 is fixed with stirrer paddle.Dropwise addition system 4 includes dropping tank and is connected to dropping tank bottom
The drop tube of the drop tube in portion, dropwise addition system 4 is placed in the reaction cavity of reaction vessel 2 through sealing cover 21.Reaction vessel 2
Sealing cover 21 on through being equipped with thermometer 5, reacted with reaction vessel 2 on the sealing cover 21 of reaction vessel 2 through being equipped with
The escape pipe 6 that container 2 is connected.
Embodiment two
A kind of preparation method of phthalic acid, method and step are as follows:
S1, the concentrated hydrochloric acid that 250g is added into 500ml reaction flask put into the phthalylhydrazine of 50g into reaction flask, right
Mixture in reaction flask is stirred, and salt water is added while agitating, the mixture in reaction flask is cooled to 3~8
℃；
S2,170g and concentration is added dropwise into reaction flask as 30% hydrogen peroxide, temperature is at 50 DEG C or less in control reaction flask；
Tail gas generated is reacted in step S2 being collected and being passed through in liquid alkaline solution and carry out chlorine absorption, tail gas includes chlorine and nitrogen
Gas.
After S3, step S2 are added dropwise, control temperature in reaction flask and filtered after 2 hours stirred below at 50 DEG C, after filtering
Obtained filter cake is O-phthalic acid crude, and O-phthalic acid crude of weighing is 105g；
S4, the pure water that 840g is added into 1000ml purification bottle, the O-phthalic acid crude of 105g in step S3 is added
It refines in bottle, fluidized state is heated to the mixture in purification bottle and is kept for 3~4 hours, then in purification bottle
Mixture is filtered processing, excludes solid impurity and obtains filtrate, and filtrate slow cooling crystallize 2 hours to 10 DEG C or less
After filter, by crystal using ice water wash 10 minutes, phthalic acid soaking wet product, O-phthalic are obtained after crystal is washed
Sour soaking wet product are 75g；
S5, by the phthalic acid soaking wet product of step S4 forced air drying 8 hours at a temperature of 100~110 DEG C, and it is final
To phthalic acid dry product, phthalic acid dry product weight is 49.5g, and phthalic acid dry product yield reaches 96.6%, adjacent benzene
Phthalate content is 99.7% in dioctyl phthalate dry product.
The material proportion of the present embodiment is as follows:
| Name of material | Inventory/g | Weight ratio |
| Phthalylhydrazine | 50 | 1 |
| Concentrated hydrochloric acid | 250 | 5.0 |
| Hydrogen peroxide (30%) | 170 | 3.4 |
The operation note of the present embodiment is as follows:
Phthalyl in the present embodiment step S1 is by-product when synthesizing Ala-Gln, adjacent benzene
Two formyls generated by-product when can be using synthesis Ala-Gln, in synthesis L- alanyl-L- glutamy
When amine, phthalyl is excluded as by-product impurities, and phthalyl is prepared adjacent benzene as waste utilization by the present embodiment
Dioctyl phthalate；Phthalyl to obtain method as follows:
S11, phthalyl-L- alanyl -- glutamine, the Xiang Sikou that 120 parts by weight are added into four mouthfuls of reaction flasks
80% hydrazine hydrate of concentration of methanol and 23 parts by weight is added in reaction flask, then stirs, to reaction solution be warming up to interior temperature for 65~
At 67 DEG C, fluidized state is warming up to reaction solution and is kept for 4 hours；
S12, stop heating, be cooled to 10 DEG C hereinafter, filtering to reaction solution, filter cake is washed with methanol；Filter cake subtracts at 60 DEG C
It press dry dry 4 hours, filter cake is transferred in beaker, pure water is added into beaker, beaker internal temperature is then warming up to interior temperature
It is 25~30 DEG C, then stirs 3 hours, filters, filter cake is washed with water, and collects filtrate；
S13, the filtrate in step S12 is transferred in beaker, medicinal carbon, stirring decoloration 30 minutes, filtering is added
Processing obtains filter cake and filtrate, collects filtrate, and filtrate is -1 one glutamine solution of L- alanyl, is collected to filter cake, filters
Cake is washed with water, and filter cake is phthalylhydrazine.
Embodiment three
A kind of preparation method of phthalic acid, method and step are as follows:
S1, the concentrated hydrochloric acid that 255g is added into 500ml reaction flask put into the phthalylhydrazine of 52g into reaction flask, right
Mixture in reaction flask is stirred, and salt water is added while agitating, the mixture in reaction flask is cooled to 3~8
℃；
S2,173g and concentration is added dropwise into reaction flask as 30% hydrogen peroxide, temperature is at 50 DEG C or less in control reaction flask；
Tail gas generated is reacted in step S2 being collected and being passed through in liquid alkaline solution and carry out chlorine absorption, tail gas includes chlorine and nitrogen
Gas.
After S3, step S2 are added dropwise, control temperature in reaction flask and filtered after 2 hours stirred below at 50 DEG C, after filtering
Obtained filter cake is O-phthalic acid crude, and O-phthalic acid crude of weighing is 106.5g；
S4, the pure water that 852g is added into 1000ml purification bottle, the O-phthalic acid crude of 106.5g in step S3 is added
Enter to refine in bottle, fluidized state is heated to the mixture in purification bottle and is kept for 3~4 hours, then in purification bottle
Mixture be filtered processing, exclude solid impurity and obtain filtrate, filtrate slow cooling to 10 DEG C or less is carried out crystallizing 2 small
When after filter, by crystal using ice water wash 10 minutes, phthalic acid soaking wet product, adjacent benzene two are obtained after crystal is washed
Formin wet product is 76.5g；
S5, by the phthalic acid soaking wet product of step S4 forced air drying 8 hours at a temperature of 100~110 DEG C, and it is final
To phthalic acid dry product, phthalic acid dry product weight is 50.4g, and phthalic acid dry product yield reaches 96.5%, adjacent benzene
Phthalate content is 99.5% in dioctyl phthalate dry product.
Phthalyl in the present embodiment step S1 is by-product when synthesizing Ala-Gln, adjacent benzene
Two formyls generated by-product when can be using synthesis Ala-Gln, in synthesis L- alanyl-L- glutamy
When amine, phthalyl is excluded as by-product impurities, and phthalyl is prepared adjacent benzene as waste utilization by the present embodiment
Dioctyl phthalate；Phthalyl to obtain method as follows:
S11, phthalyl-L- alanyl -- glutamine, the Xiang Sikou that 120 parts by weight are added into four mouthfuls of reaction flasks
80% hydrazine hydrate of concentration of methanol and 23 parts by weight is added in reaction flask, then stirs, to reaction solution be warming up to interior temperature for 65~
At 67 DEG C, fluidized state is warming up to reaction solution and is kept for 4 hours；
S12, stop heating, be cooled to 10 DEG C hereinafter, filtering to reaction solution, filter cake is washed with methanol；Filter cake subtracts at 60 DEG C
It press dry dry 4 hours, filter cake is transferred in beaker, pure water is added into beaker, beaker internal temperature is then warming up to interior temperature
It is 25~30 DEG C, then stirs 3 hours, filters, filter cake is washed with water, and collects filtrate；
S13, the filtrate in step S12 is transferred in beaker, medicinal carbon, stirring decoloration 30 minutes, filtering is added
Processing obtains filter cake and filtrate, collects filtrate, and filtrate is -1 one glutamine solution of L- alanyl, is collected to filter cake, filters
Cake is washed with water, and filter cake is phthalylhydrazine.
Example IV
A kind of preparation method of phthalic acid, method and step are as follows:
S1, the concentrated hydrochloric acid that 250g is added into 500ml reaction flask put into the phthalylhydrazine of 50g into reaction flask, right
Mixture in reaction flask is stirred, and salt water is added while agitating, the mixture in reaction flask is cooled to 3~8
℃；
S2,170g and concentration is added dropwise into reaction flask as 30% hydrogen peroxide, temperature is at 50 DEG C or less in control reaction flask；
Tail gas generated is reacted in step S2 being collected and being passed through in liquid alkaline solution and carry out chlorine absorption, tail gas includes chlorine and nitrogen
Gas.
After S3, step S2 are added dropwise, control temperature in reaction flask and filtered after 2 hours stirred below at 50 DEG C, after filtering
Obtained filter cake is O-phthalic acid crude, and O-phthalic acid crude of weighing is 101g；
S4, the pure water that 808g is added into 1000ml purification bottle, the O-phthalic acid crude of 101g in step S3 is added
It refines in bottle, fluidized state is heated to the mixture in purification bottle and is kept for 3~4 hours, then in purification bottle
Mixture is filtered processing, excludes solid impurity and obtains filtrate, and filtrate slow cooling crystallize 2 hours to 10 DEG C or less
After filter, by crystal using ice water wash 10 minutes, phthalic acid soaking wet product, O-phthalic are obtained after crystal is washed
Sour soaking wet product are 84g；
S5, by the phthalic acid soaking wet product of step S4 forced air drying 8 hours at a temperature of 100~110 DEG C, and it is final
To phthalic acid dry product, phthalic acid dry product weight is 50.5g, and phthalic acid dry product yield reaches 97.6%, adjacent benzene
Phthalate content is 99.8% in dioctyl phthalate dry product.
Phthalyl in the present embodiment step S1 is by-product when synthesizing Ala-Gln, adjacent benzene
Two formyls generated by-product when can be using synthesis Ala-Gln, in synthesis L- alanyl-L- glutamy
When amine, phthalyl is excluded as by-product impurities, and phthalyl is prepared adjacent benzene as waste utilization by the present embodiment
Dioctyl phthalate；Phthalyl to obtain method as follows:
S11, phthalyl-L- alanyl -- glutamine, the Xiang Sikou that 120 parts by weight are added into four mouthfuls of reaction flasks
80% hydrazine hydrate of concentration of methanol and 23 parts by weight is added in reaction flask, then stirs, to reaction solution be warming up to interior temperature for 65~
At 67 DEG C, fluidized state is warming up to reaction solution and is kept for 4 hours；
S12, stop heating, be cooled to 10 DEG C hereinafter, filtering to reaction solution, filter cake is washed with methanol；Filter cake subtracts at 60 DEG C
It press dry dry 4 hours, filter cake is transferred in beaker, pure water is added into beaker, beaker internal temperature is then warming up to interior temperature
It is 25~30 DEG C, then stirs 3 hours, filters, filter cake is washed with water, and collects filtrate；
S13, the filtrate in step S12 is transferred in beaker, medicinal carbon, stirring decoloration 30 minutes, filtering is added
Processing obtains filter cake and filtrate, collects filtrate, and filtrate is -1 one glutamine solution of L- alanyl, is collected to filter cake, filters
Cake is washed with water, and filter cake is phthalylhydrazine.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (6)
1. a kind of preparation method of phthalic acid, it is characterised in that: its method and step is as follows:
S1, the concentrated hydrochloric acid that 245~255 parts by weight are added into reaction flask, the adjacent benzene of 48~52 parts by weight is put into reaction flask
Diformylhydrazine is stirred the mixture in reaction flask, and salt water is added while agitating by the mixture in reaction flask
It is cooled to 3~8 DEG C；
S2, the hydrogen peroxide that 167~173 parts by weight and concentration are 30% is added dropwise into reaction flask, temperature is 50 in control reaction flask
DEG C or less；
After S3, step S2 are added dropwise, control temperature in reaction flask and filtered after 2 hours stirred below at 50 DEG C, obtained after filtering
Filter cake be O-phthalic acid crude, and weigh O-phthalic acid crude be M；
S4, the pure water that 8M parts by weight are added into purification bottle, are added purification for the O-phthalic acid crude of M parts by weight in step S3
In bottle, fluidized state is heated to the mixture in purification bottle and is kept for 3~4 hours, then to the mixing in purification bottle
Object is filtered processing, excludes solid impurity and obtains filtrate, mistake after filtrate slow cooling is carried out crystallization 2 hours to 10 DEG C or less
Crystal is washed 10 minutes using ice water, phthalic acid soaking wet product is obtained after crystal is washed by filter；
S5, by the phthalic acid soaking wet product of step S4 forced air drying 8 hours at a temperature of 100~110 DEG C, and finally obtain neighbour
Phthalic acid dry product.
2. a kind of preparation method of phthalic acid described in accordance with the claim 1, it is characterised in that: its method and step is as follows:
S1, the concentrated hydrochloric acid that 250 parts by weight are added into reaction flask, the phthalylhydrazine of 50 parts by weight is put into reaction flask,
Mixture in reaction flask is stirred, and salt water is added while agitating, the mixture in reaction flask is cooled to 3~8
℃；
S2, the hydrogen peroxide that 170 parts by weight and concentration are 30% is added dropwise into reaction flask, control in reaction flask temperature 50 DEG C with
Under；
After S3, step S2 are added dropwise, control temperature in reaction flask and filtered after 2 hours stirred below at 50 DEG C, obtained after filtering
Filter cake be O-phthalic acid crude, and weigh O-phthalic acid crude be M；
S4, the pure water that 8M parts by weight are added into purification bottle, are added purification for the O-phthalic acid crude of M parts by weight in step S3
In bottle, fluidized state is heated to the mixture in purification bottle and is kept for 3~4 hours, then to the mixing in purification bottle
Object is filtered processing, excludes solid impurity and obtains filtrate, mistake after filtrate slow cooling is carried out crystallization 2 hours to 10 DEG C or less
Crystal is washed 10 minutes using ice water, phthalic acid soaking wet product is obtained after crystal is washed by filter；
S5, by the phthalic acid soaking wet product of step S4 forced air drying 8 hours at a temperature of 105 DEG C, and finally obtain adjacent benzene two
Formic acid dry product.
3. a kind of preparation method of phthalic acid according to claim 1 or 2, it is characterised in that: the neighbour in step S1
Phenyl-diformyl hydrazine is the by-product synthesized in Ala-Gln reaction.
4. a kind of preparation method of phthalic acid described in accordance with the claim 3, it is characterised in that: the adjacent benzene two in step S1
Formyl to obtain method as follows:
S11, phthalyl-L- alanyl -- the glutamine that 120 parts by weight are added into four mouthfuls of reaction flasks are reacted to four mouthfuls
80% hydrazine hydrate of concentration of methanol and 23 parts by weight is added in bottle, then stirs, being warming up to interior temperature to reaction solution is 65~67 DEG C
When, fluidized state is warming up to reaction solution and is kept for 4 hours；
S12, stop heating, be cooled to 10 DEG C hereinafter, filtering to reaction solution, filter cake is washed with methanol；Filter cake is dry in 60 DEG C of decompressions
Dry 4 hours, filter cake is transferred in beaker, pure water is added into beaker, it is 25 that beaker internal temperature, which is then warming up to interior temperature,
It~30 DEG C, then stirs 3 hours, filters, filter cake is washed with water, and collects filtrate；
S13, the filtrate in step S12 being transferred in beaker, medicinal carbon is added, stirring is decolourized 30 minutes, filtration treatment,
Filter cake and filtrate are obtained, filtrate is collected, filtrate is -1 one glutamine solution of L- alanyl, is collected to filter cake, and filter cake is used
Water washing, filter cake are phthalylhydrazine.
5. a kind of preparation method of phthalic acid according to claim 1 or 2, it is characterised in that: in the step S2
It reacts tail gas generated and is collected and is passed through in liquid alkaline solution and carry out chlorine absorption, tail gas includes chlorine and nitrogen.
6. a kind of preparation facilities of phthalic acid, it is characterised in that: including heat insulation tank (1), reaction vessel (2), agitating device
(3) and system (4) are added dropwise, the reaction vessel (2) is placed in heat insulation tank (1), has reaction chamber inside the reaction vessel (2)
Body, reaction vessel (2) top are provided with feed opening, and the feed opening of the reaction vessel (2) is connected by sealing cover (21) sealing
It connects, the agitating device (3) includes stirring motor and the agitating shaft that is fixed on the output shaft of stirring motor, the agitating device
(3) agitating shaft is placed in the reaction cavity of reaction vessel (2) through sealing cover (21), the stirring of the agitating device (3)
Axis bottom is fixed with stirrer paddle；The dropwise addition system (4) includes dropping tank and is connected to the drop tube that pot bottom is added dropwise, described
The drop tube of dropwise addition system (4) is placed in the reaction cavity of reaction vessel (2) through sealing cover (21)；The reaction vessel
(2) through being equipped with thermometer (5) on sealing cover (21), on the sealing cover (21) of the reaction vessel (2) through be equipped with
The escape pipe (6) that the reaction vessel (2) of reaction vessel (2) is connected.
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| CN115057767A (en) * | 2022-07-06 | 2022-09-16 | 山东泓瑞医药科技股份公司 | Preparation method of phthalic acid |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61155383A (en) * | 1984-12-27 | 1986-07-15 | Nippon Zeon Co Ltd | Production of phthalic acid compound |
| CN102372626A (en) * | 2011-11-23 | 2012-03-14 | 济南诚汇双达化工有限公司 | Preparation method of phthalic acid |
| CN104650178A (en) * | 2015-02-05 | 2015-05-27 | 南京理工大学 | Technical preparation method of glycyl glutamine |
| CN105483750A (en) * | 2015-11-27 | 2016-04-13 | 北京工业大学 | Method for preparing phthalic acid through phthalylhydrazine in electrochemical oxidation manner |
| CN105646176A (en) * | 2016-01-05 | 2016-06-08 | 郑州轻工业学院 | Preparation method of 4,5-dibromophthalic acid |
| CN105693507A (en) * | 2016-03-18 | 2016-06-22 | 浙江大学 | Synthesis method of 3, 4, 5, 6-tetrafluorophthalic acid |
| CN209076672U (en) * | 2018-09-13 | 2019-07-09 | 河南环宇石化装备科技股份有限公司 | A kind of high-efficiency adsorbent preparation facilities of nitrogen-methane |
-
2019
- 2019-08-23 CN CN201910781037.5A patent/CN110357775A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61155383A (en) * | 1984-12-27 | 1986-07-15 | Nippon Zeon Co Ltd | Production of phthalic acid compound |
| CN102372626A (en) * | 2011-11-23 | 2012-03-14 | 济南诚汇双达化工有限公司 | Preparation method of phthalic acid |
| CN104650178A (en) * | 2015-02-05 | 2015-05-27 | 南京理工大学 | Technical preparation method of glycyl glutamine |
| CN105483750A (en) * | 2015-11-27 | 2016-04-13 | 北京工业大学 | Method for preparing phthalic acid through phthalylhydrazine in electrochemical oxidation manner |
| CN105646176A (en) * | 2016-01-05 | 2016-06-08 | 郑州轻工业学院 | Preparation method of 4,5-dibromophthalic acid |
| CN105693507A (en) * | 2016-03-18 | 2016-06-22 | 浙江大学 | Synthesis method of 3, 4, 5, 6-tetrafluorophthalic acid |
| CN209076672U (en) * | 2018-09-13 | 2019-07-09 | 河南环宇石化装备科技股份有限公司 | A kind of high-efficiency adsorbent preparation facilities of nitrogen-methane |
Non-Patent Citations (2)
| Title |
|---|
| 李元菁: "清洁氯化制备氯苯的实验研究", 《广州化工》 * |
| 李先栓主编: "《高中化学创新实验课程》", 30 June 2011, 东北师范大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115057767A (en) * | 2022-07-06 | 2022-09-16 | 山东泓瑞医药科技股份公司 | Preparation method of phthalic acid |
| CN115057767B (en) * | 2022-07-06 | 2023-12-12 | 山东泓瑞医药科技股份公司 | Preparation method of phthalic acid |
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