CN110229084A - A kind of preparation method of orthocoll - Google Patents
A kind of preparation method of orthocoll Download PDFInfo
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- CN110229084A CN110229084A CN201910610806.5A CN201910610806A CN110229084A CN 110229084 A CN110229084 A CN 110229084A CN 201910610806 A CN201910610806 A CN 201910610806A CN 110229084 A CN110229084 A CN 110229084A
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- orthocoll
- solution
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- purified water
- potassium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
Abstract
The invention discloses a kind of preparation methods of orthocoll, this method is using guaiacol as raw material, pass through sulfonation, calcification and potassiumization, which are reacted, is made orthocoll crude product, nitrogen is passed through in sulfonation using method of the invention, prevent guaiacol from aoxidizing and polymerizeing, it solves the problems, such as that hydroxyl is easy to be sulfonated the oxidisability that agent has to be aoxidized, CGS Continuous Grain Silicon is concentrated under reduced pressure using heat pump recompression in orthocoll crude product solution and fine work solution be again concentrated under reduced pressure continuous crystallisation and reach reduces the temperature of concentration process and reduces the impurity that concentration process generates by high temperature, the preparation method is simple, it is time-consuming short, orthocoll purity is high, yield is good, suitable for industrial mass production.
Description
Technical field
The present invention relates to the synthesis technical field of compound, the preparation method of specifically a kind of orthocoll.
Background technique
Orthocoll is stimulant expectorant, by stimulating bronchial mucosa glandular secretion, makes the thinning appearance of sputum
Easy expectoration, frequently as one of the main component of compound eliminating phlegm and relieving cough class oral solution.The guaiacol of country's commercial type at present
Potassium sulfonate finished product is that (English name is for 4- hydroxy 3-methoxybenzene potassium sulfonate and 3- hydroxyl -4- methoxy benzenesulfonic acid potassium
potassium 4-hydroxy-3-methoxybenzenesulphonate/potassium 3-hydroxy-4-
Methoxybenzenesulphonate mixture).Orthocoll is recorded at United States Pharmacopeia USP33 editions.At present
The method of synthesizing guaiacol potassium sulfonate mainly carries out sulfonation by guaiacol (o-methoxyphenol) and its derivative and is made.
Sulfonating reaction is traditional conventional organic chemical reactions, is that sulfonating agent directly replaces hydrogen atom to be carried out with sulfonic group
Reaction.Common sulfonating agent has the concentrated sulfuric acid, is dissolved in the different solvents such as chlorohydrocarbon, sulfur dioxide liquid, dioxane and pyridine
In sulfur trioxide, chlorosulfonic acid, the mixture and chlorosulfuric acid etc. of sulfur dioxide and chlorine.Sulfuric acid is a kind of relatively mild sulfonation
Agent, the sulfonation for most of aromatic compounds；Sulfur trioxide is fiercer sulfonating agent, due to that can generate by-product, one
As be dissolved in solvent and use.In addition, the temperature of control sulfonating reaction is extremely important, when temperature is low, sulfonic group easily enters and replaces
The ortho position of base, when temperature is high, sulfonic group easily enters the contraposition of substituent group.
104292136 A of patent CN discloses a kind of preparation method of orthocoll.To produce guaiacol
By-product 1,2-dimethoxy benzene is raw material, using sulfuric acid as solvent and sulfonating agent, cools to -5~10 DEG C, 1,2-dimethoxy benzene is added, stirs
Lower heating, reaction are mixed, calcium oxide is added or calcium carbonate adjusts pH value；Filtering reacting liquid obtains 3,4- dimethoxy benzene sulfonic acid
Calcium is added lewis acid in 3,4- dimethoxy benzene sulfoacid calcium, is warming up to 60~100 DEG C, reacts 2~5 hours, cool to 20
~30 DEG C, obtain the mixture of 3- hydroxyl -4- methoxy benzenesulfonic acid calcium and 4- hydroxy 3-methoxybenzene sulfoacid calcium.In 3- hydroxyl
In base -4- methoxy benzenesulfonic acid calcium and the mixture of 4- hydroxy 3-methoxybenzene sulfoacid calcium be added potassium carbonate, saleratus or
Potassium hydroxide is warming up to 50~100 DEG C, reacts 2~10 hours, cools to -10~0 DEG C, be filtered to remove insoluble matter, be cured
Create the wooden potassium phenolsulfonate.This method is to produce the by-product 1,2-dimethoxy benzene of guaiacol as raw material, cheap, reaction condition temperature
With, it is environmental-friendly, it can be used for industrialized production.But the product that this method obtains is orthocoll crude product, it is pure
Spend lower, the catalyst used is more, and the temperature difference of control is big, and the reaction time is long, unstable products, is not suitable for industrializing big rule
Mould production, what embodiment was write is the method for small lot production, although yield is higher, up to not when being produced in enormous quantities
To this yield.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of orthocoll, and this method solve hydroxyls to be easy quilt
The problem of oxidisability that sulfonating agent has is aoxidized, preparation method is simple, time-consuming short, and orthocoll purity is high is received
Rate is good, is suitable for industrial mass production.
A kind of preparation method of orthocoll, is passed through nitrogen in sulfonation, prevents guaiacol from aoxidizing and polymerizeing,
Intermediate calcicol solution, orthocoll crude product and the filtering of fine work solution use 0.22~0.65 μm of filter membrane
Secondary filter is carried out, and CGS Continuous Grain Silicon reduction thickening temperature is concentrated under reduced pressure using heat pump recompression and shortens heated time,
The purity and yield for reducing the by-product generated when high temperature concentration and improving orthocoll, the specific steps are as follows:
(1) guaiacol is put into reactor, under stirring, is passed through nitrogen 10 minutes, displacement removes in reactor and guaiacol
In air after, slowly instill sulfuric acid, time for adding is 2~3 hours, and sulfuric acid is added dropwise and finishes, continues to be passed through nitrogen, and stirring
Lower reaction 15~25 minutes, then heats to 70~80 DEG C, insulation reaction 5~6 hours；Sulfonation terminal is checked, after reaching home
Stop reacting and stops being passed through nitrogen.
(2) sulfonated liquid that step (1) obtains slowly is pumped into 70~80 DEG C of purified water, the dosage of purified water is sulfonation
1.60~1.64 times of liquid, under stirring, slowly investment calcium carbonate does calcification terminal inspection up to pH5.0~5.5 several times；
(3) calcification terminal reach after, 80~85 DEG C insulation reaction 20~30 minutes, stop heating, stand 15~20 minutes；First use
Centrifuge filtering, then secondary filter is carried out through 0.22~0.65 μm of filter membrane, obtain calcifying solution.
(4) potassium carbonate is weighed, equivalent purified water is added, under stirring, is heated to after all dissolving, it is spare；By calcifying solution, stir
It mixes down, is heated to 70~80 DEG C, slowly instill above-mentioned solution of potassium carbonate, time for adding is 1~1.5 hour, is tried with precision
When paper checks pH value meta-alkalescence, potassium terminal inspection is done.
(5) after potassium terminal reaches, potassium liquid is heated to slightly boiled, is kept for 10~15 minutes, under stirring, it is cooled to 70~
80 DEG C, carry out secondary filter, by filtrate carry out heat pump recompression be concentrated under reduced pressure continuous crystallisation, control vacuum degree be -0.065~-
0.08MPa, 75~85 DEG C of temperature, and crystallization is continuously sent in crystallization cooling tank.
(6) crystallization is cooled to 15~20 DEG C, then carries out centrifugal rejection filter and filters out mother liquor, crystal purifying water washing, inspection
Looking into cleaning solution pH value is 7.5~8.0, and the wet crude product of orthocoll is obtained after drying, is sent to refining step.
(7) the wet crude product of orthocoll of step (6) is refined, into the wet crude product of orthocoll,
It is pumped into purified water, the dosage of purified water is 2~2.4 times of the wet crude product of orthocoll, and under stirring, heating makes to be completely dissolved
To clear, secondary filter then is carried out with 0.22~0.65 μm of filter membrane.
(8) the refined filtration liquid that step (7) film is obtained by filtration carries out heat pump recompression and continuous crystallisation is concentrated under reduced pressure, and controls vacuum
Spending is -0.065~-0.08MPa, 75~85 DEG C of temperature, and crystallization is continuously sent in crystallization cooling tank.
(9) crystallization is cooled to 15~20 DEG C, then carries out centrifugal rejection filter and filter out mother liquor, crystal purifying water washing is used
Precision test paper checks that cleaning solution pH value is 7.0~7.5, after filter cake drying, obtains orthocoll fine work wet product, send back tender
Sequence.
(10) 8~10h is dried in orthocoll fine work wet product in 85~90 DEG C of baking ovens, crush, sieve,
Orthocoll fine work is obtained after inspection.
The method that the step (1) checks sulfonation terminal is to take purified water and react obtained sulfonated liquid with the volume of 9:1
It is to reach sulfonation terminal when no grease is precipitated than being uniformly mixed.
The method of step (2) the calcification terminal inspection includes following two: a small amount of calcifying solution 1) is taken, with pH precision test paper
Check that the pH of calcifying solution, pH are to reach calcification terminal at 5.0~5.5 section；2) a small amount of calcifying solution is taken, a small amount of carbonic acid is added
Calcium, it is to reach calcification terminal that stirring, which does not generate bubble,.
The method of step (4) the potassium terminal inspection the following steps are included:
1) ammonium oxalate is taken, adds purified water dissolution that the ammonium oxalate test solution that concentration is 35mg/mL is made；
2) 2mL potassium liquid is taken, purified water 10mL is added and shakes up；
3) take 2mL potassium liquid, be added purified water 8mL, then plus ammonium oxalate test solution 2mL shake up；
4) solution within one minute, 2) compared with solution 3), 3) should be clarified substantially as solution 2), that is, indicate to arrive
Up to terminal.
The beneficial effects of the present invention are:
The present invention obtains guaiacol-sulfonic acid using guaiacol as raw material, by sulfuric acid sulfonation, calcium carbonate calcification, potassium carbonate potassium
The wet crude product of potassium, orthocoll crude product and fine work solution have been all made of the technology that continuous crystallisation is concentrated under reduced pressure in heat pump recompression
It reduces thickening temperature and shortens heated time, reduce the by-product generated when high temperature concentration and improve the pure of orthocoll
Degree and yield.The present invention is filled with nitrogen in sulfonation and protects to sulfonation process, prevents guaiacol from aoxidizing and polymerizeing, makes to produce
Product color is white without active carbon decoloring, and greatly reduces polymerization jelly, facilitates subsequent filter, yield has also obtained greatly
Big promotion.The present invention has carried out reaction end inspection after sulfonation, calcification, potassiumization reaction, and determination is reached home, and raw material is
Reacted complete just progress next step operation guarantees that raw material largely all becomes product, and the yield of product is high.The present invention is using heat
Pump recompression is concentrated under reduced pressure CGS Continuous Grain Silicon and the wet crude product solution of orthocoll and fine work solution is concentrated under reduced pressure
Continuous crystallisation greatly reduces the generation of impurity in high temperature concentration process, mentions while improving the purity of orthocoll
High its yield, obtained final products reach orthocoll quality company standard, contain C7H7KO5S be 98.5%~
101.0%, moisture is 3.0~6.0%, and the yield of mass production is also up to 82% or more.
Detailed description of the invention
Fig. 1 is that continuous crystalizer, crystallizer composed structure: 01 tubulation is concentrated under reduced pressure in the recompression of orthocoll heat pump
Heat exchanger, 02 evaporator, 03 vapour liquid separator, 04 heat pump, 05 hot recycle pump, 06 Recovery of the hot water tank, 07 electronic continuous discharge
Valve, 08 crystallization cooling tank.
Specific embodiment
For the more detailed introduction present invention, below with reference to embodiment, the present invention will be further described.
Embodiment 1
A kind of preparation method of orthocoll, is passed through nitrogen in sulfonation, prevents guaiacol from aoxidizing and polymerizeing, and adopt
The yield and purity that the technology raising orthocoll of continuous crystallisation is concentrated under reduced pressure are recompressed with heat pump, specific steps are such as
Under:
(1) guaiacol is put into reactor, under stirring, is passed through nitrogen 10 minutes, displacement removes in reactor and guaiacol
In air after, slowly instill sulfuric acid, time for adding is 2 hours, and sulfuric acid is added dropwise and finishes, continues to be passed through nitrogen, and under stiring
Reaction 15 minutes, then heats to 70 DEG C, insulation reaction 6 hours；It checks sulfonation terminal, stops reacting and stopping after reaching home
It is passed through nitrogen.
(2) sulfonated liquid that step (1) obtains slowly is pumped into 70~80 DEG C of purified water, the dosage of purified water is sulfonation
1.60 times of liquid, under stirring, slowly investment calcium carbonate does calcification terminal inspection up to pH5.5 several times.
(3) calcification terminal reach after, 85 DEG C insulation reaction 30 minutes, stop heating, stand 15 minutes；First with centrifuge mistake
Filter, then secondary filter is carried out through 0.22~0.65 μm of filter membrane, obtain calcifying solution.
(4) potassium carbonate is weighed, equivalent purified water is added, under stirring, being heated to 50~60 DEG C makes after all dissolving, spare；
By calcifying solution, under stirring, 70 DEG C are heated to, slowly instills above-mentioned solution of potassium carbonate, time for adding is 1.5 hours, with essence
When close test paper checks pH value meta-alkalescence, potassium terminal inspection is done.
(5) potassium terminal reach after, potassium liquid is heated to it is slightly boiled, keep 15 minutes, under stirring, be cooled to 70~80
DEG C, secondary filter is carried out through 0.22~0.65 μm of filter membrane, filtrate is subjected to heat pump recompression, continuous crystallisation is concentrated under reduced pressure, control is true
Reciprocal of duty cycle is -0.065MPa, and crystallization is simultaneously continuously sent in crystallization cooling tank by 85 DEG C of temperature.
(6) crystallization is cooled to 15 DEG C, then carries out centrifugal rejection filter and filter out mother liquor, crystal purifying water washing, inspection is washed
Washing liquid pH value is 7.5, and the wet crude product of orthocoll is obtained after drying, is sent to refining step.
(7) the wet crude product of orthocoll of step (6) is refined, into the wet crude product of orthocoll,
It is pumped into purified water, the dosage of purified water is 2 times of the wet crude product of orthocoll, and under stirring, heating makes to be completely dissolved to clear,
Then secondary filter is carried out with 0.22~0.65 μm of filter membrane.
(8) the refined filtration liquid that step (7) film is obtained by filtration carries out heat pump recompression and continuous crystallisation is concentrated under reduced pressure, and controls vacuum
Spending is 0.08MPa, 75 DEG C of temperature, and crystallization is continuously sent in crystallization cooling tank.
(9) crystallization is cooled to 20 DEG C, then carries out centrifugal rejection filter and filters out mother liquor, crystal purifying water washing, with precision
Test paper checks that cleaning solution pH value is 7.0, after filter cake drying, obtains orthocoll fine work wet product, send drying process.
(10) 8h is dried in 85~90 DEG C of baking ovens in orthocoll fine work wet product, crushes, screening, examines
Orthocoll fine work is obtained afterwards, and the yield of fine work is 84.93%.
The method that the step (1) checks sulfonation terminal is to take purified water and react obtained sulfonated liquid with the volume of 9:1
It is to reach sulfonation terminal when no grease is precipitated than being uniformly mixed.
The method of step (2) the calcification terminal inspection are as follows: take a small amount of calcifying solution, check calcifying solution with pH precision test paper
PH, pH are to reach calcification terminal at 5.0~5.5 section.
The method of step (4) the potassium terminal inspection the following steps are included:
1) ammonium oxalate is taken, adds purified water dissolution that the ammonium oxalate test solution that concentration is 35mg/mL is made；
2) 2mL potassium liquid is taken, purified water 10mL is added and shakes up；
3) take 2mL potassium liquid, be added purified water 8mL, then plus ammonium oxalate test solution 2mL shake up；
4) solution within one minute, 2) compared with solution 3), 3) should be clarified substantially as solution 2), that is, indicate to arrive
Up to terminal.
Embodiment 2
A kind of preparation method of orthocoll, is passed through nitrogen in sulfonation, prevents guaiacol from aoxidizing and polymerizeing, and adopt
The yield and purity of orthocoll are improved with the technology for carrying out vacuum continuous crystallisation concentration at normal temperature, specific steps are such as
Under:
(1) guaiacol is put into reactor, under stirring, is passed through nitrogen 10 minutes, displacement removes in reactor and guaiacol
In air after, slowly instill sulfuric acid, time for adding is 2.5 hours, and sulfuric acid is added dropwise and finishes, continues to be passed through nitrogen, and stirring
Lower reaction 20 minutes, then heats to 75 DEG C, insulation reaction 5.5 hours；It checks sulfonation terminal, stops reaction simultaneously after reaching home
Stopping is passed through nitrogen.
(2) sulfonated liquid that step (1) obtains slowly is pumped into 70~80 DEG C of purified water, the dosage of purified water is sulfonation
1.62 times of liquid under stirring, slowly divide 3 investment calcium carbonate until pH5.2, does calcification terminal inspection.
(3) calcification terminal reach after, 80~85 DEG C insulation reaction 25 minutes, stop heating, stand 18 minutes；First with centrifugation
Machine filtering, then secondary filter is carried out through 0.22~0.65 μm of filter membrane, obtain calcifying solution.
(4) potassium carbonate is weighed, equivalent purified water is added, under stirring, being heated to 50~60 DEG C makes after all dissolving, spare；
By calcifying solution, under stirring, 70~80 DEG C are heated to, slowly instills above-mentioned solution of potassium carbonate, time for adding is 1.2 hours,
When checking pH value meta-alkalescence with precision test paper, potassium terminal inspection is done.
(5) potassium terminal reach after, potassium liquid is heated to it is slightly boiled, keep 12 minutes, under stirring, be cooled to 70~80
DEG C, secondary filter is carried out through 0.22~0.65 μm of filter membrane, filtrate is subjected to heat pump recompression, continuous crystallisation is concentrated under reduced pressure, control is true
Reciprocal of duty cycle be -0.07MPa, 82 DEG C of temperature, and will crystallization continuously be sent to crystallization cooling tank in.
(6) crystallization is cooled to 18 DEG C, then carries out centrifugal rejection filter and filter out mother liquor, crystal purifying water washing, inspection is washed
Washing liquid pH value is 7.8, and the wet crude product of orthocoll is obtained after drying, is sent to refining step.
(7) the wet crude product of orthocoll of step (6) is refined, into the wet crude product of orthocoll,
Be pumped into purified water, the dosage of purified water is 2.2 times of the wet crude product of orthocoll, under stirring, heating make to be completely dissolved to
Clearly, secondary filter then is carried out with 0.22~0.65 μm of filter membrane.
(8) the refined filtration liquid that step (7) film is obtained by filtration carries out heat pump recompression and continuous crystallisation is concentrated under reduced pressure, and controls vacuum
Spending is -0.075MPa, 78 DEG C of temperature, and crystallization is continuously sent in crystallization cooling tank.
(9) crystallization is cooled to 18 DEG C, then carries out centrifugal rejection filter and filters out mother liquor, crystal purifying water washing, with precision
Test paper checks that cleaning solution pH value is 7.2, after filter cake drying, obtains orthocoll fine work wet product, send drying process.
(10) 9h is dried in 85~90 DEG C of baking ovens in orthocoll fine work wet product, crushes, screening, examines
Orthocoll fine work is obtained afterwards, and the yield of fine work is 92.94%.
The method that the step (1) checks sulfonation terminal is to take purified water and react obtained sulfonated liquid with the volume of 9:1
It is to reach sulfonation terminal when no grease is precipitated than being uniformly mixed.
The method of step (2) the calcification terminal inspection are as follows: take a small amount of calcifying solution, a small amount of calcium carbonate is added, stirring does not produce
Anger bubble is to reach calcification terminal.
The method of step (4) the potassium terminal inspection the following steps are included:
1) ammonium oxalate is taken, adds purified water dissolution that the ammonium oxalate test solution that concentration is 35mg/mL is made；
2) 2mL potassium liquid is taken, purified water 10mL is added and shakes up；
3) take 2mL potassium liquid, be added purified water 8mL, then plus ammonium oxalate test solution 2mL shake up；
4) solution within one minute, 2) compared with solution 3), 3) should be clarified substantially as solution 2), that is, indicate to arrive
Up to terminal.
Embodiment 3
A kind of preparation method of orthocoll, is passed through nitrogen in sulfonation, prevents guaiacol from aoxidizing and polymerizeing, and adopt
The yield and purity of orthocoll are improved with the technology for carrying out vacuum continuous crystallisation concentration at normal temperature, specific steps are such as
Under:
(1) guaiacol is put into reactor, under stirring, is passed through nitrogen 10 minutes, displacement removes in reactor and guaiacol
In air after, slowly instill sulfuric acid, time for adding is 3 hours, and sulfuric acid is added dropwise and finishes, continues to be passed through nitrogen, and under stiring
Reaction 25 minutes, then heats to 80 DEG C, insulation reaction 5 hours；It checks sulfonation terminal, stops reacting and stopping after reaching home
It is passed through nitrogen.
(2) sulfonated liquid that step (1) obtains slowly is pumped into 70~80 DEG C of purified water, the dosage of purified water is sulfonation
1.64 times of liquid, under stirring, slowly investment calcium carbonate does calcification terminal inspection up to pH5.0 several times.
(3) calcification terminal reach after, 85 DEG C insulation reaction 20 minutes, stop heating, stand 20 minutes；First with centrifuge mistake
Filter, then secondary filter is carried out through 0.22~0.65 μm of filter membrane, obtain calcifying solution.
(4) potassium carbonate is weighed, equivalent purified water is added, under stirring, is heated to after all dissolving, it is spare；By calcifying solution, stir
It mixes down, is heated to 75 DEG C, slowly instill above-mentioned solution of potassium carbonate, time for adding is 1.0 hours, checks pH with precision test paper
When being worth meta-alkalescence, potassium terminal inspection is done.
(5) potassium terminal reach after, potassium liquid is heated to it is slightly boiled, keep 10 minutes, under stirring, be cooled to 70~80
DEG C, secondary filter is carried out through 0.22~0.65 μm of filter membrane, filtrate is subjected to heat pump recompression, continuous crystallisation is concentrated under reduced pressure, control is true
Reciprocal of duty cycle be -0.075MPa, 75 DEG C of temperature, and will crystallization continuously be sent to crystallization cooling tank in.
(6) crystallization is cooled to 20 DEG C, then carries out centrifugal rejection filter and filter out mother liquor, crystal purifying water washing, inspection is washed
Washing liquid pH value is 8.0, and the wet crude product of orthocoll is obtained after drying, is sent to refining step.
(7) the wet crude product of orthocoll of step (6) is refined, into the wet crude product of orthocoll,
Be pumped into purified water, the dosage of purified water is 2.4 times of the wet crude product of orthocoll, under stirring, heating make to be completely dissolved to
Clearly, secondary filter then is carried out with 0.22~0.65 μm of filter membrane.
(8) the refined filtration liquid that step (7) film is obtained by filtration carries out heat pump recompression and continuous crystallisation is concentrated under reduced pressure, and controls vacuum
Degree is -0.065MPa, and crystallization is simultaneously continuously sent in crystallization cooling tank by 85 DEG C of temperature.
(9) crystallization is cooled to 20 DEG C, then carries out centrifugal rejection filter and filters out mother liquor, crystal purifying water washing, with precision
Test paper checks that cleaning solution pH value is 7.5, after filter cake drying, obtains orthocoll fine work wet product, send drying process.
(10) 10h is dried in 85~90 DEG C of baking ovens in orthocoll fine work wet product, crushed, screening, inspection
Orthocoll fine work is obtained after testing, the yield of fine work is 83.81%.
The method that the step (1) checks sulfonation terminal is to take purified water and react obtained sulfonated liquid with the volume of 9:1
It is to reach sulfonation terminal when no grease is precipitated than being uniformly mixed.
The method of step (2) the calcification terminal inspection includes following two: a small amount of calcifying solution 1) is taken, with pH precision test paper
Check that the pH of calcifying solution, pH are to reach calcification terminal at 5.0~5.5 section；2) a small amount of calcifying solution is taken, a small amount of carbonic acid is added
Calcium, it is to reach calcification terminal that stirring, which does not generate bubble,.
The method of step (4) the potassium terminal inspection the following steps are included:
1) ammonium oxalate is taken, adds purified water dissolution that the ammonium oxalate test solution that concentration is 35mg/mL is made；
2) 2mL potassium liquid is taken, purified water 10mL is added and shakes up；
3) take 2mL potassium liquid, be added purified water 8mL, then plus ammonium oxalate test solution 2mL shake up；
4) solution within one minute, 2) compared with solution 3), 3) should be clarified substantially as solution 2), that is, indicate to arrive
Up to terminal.
Step (5) and (8) carry out heat pump recompression and continuous crystallisation, orthocoll are concentrated under reduced pressure in above embodiments
Heat pump recompression is concentrated under reduced pressure continuous crystalizer composite structural diagram and sees Fig. 1, its working principles are as follows:
Orthocoll solution to be concentrated is pumped into Tube Heat Exchanger 01, starting hot recycle pump 05 passes through solution
Tube Heat Exchanger 01 recycles, and then opens auxiliary steam tube valve and starts the cycle over heat temperature raising, 75 are risen to solution temperature~
Auxiliary steam tube valve is closed at 85 DEG C, starting heat pump 04 starts to be concentrated under reduced pressure, and the steam that evaporator 02 evaporates is direct
Into heat pump 04, it is molten that the heating orthocoll of Tube Heat Exchanger 01 is directly entered through the compressed high-temperature steam of heat pump 04
Liquid pays attention to observing the concentrate in device and begins with crystallization precipitation, starts electronic continuous discharge valve after largely crystallizing and being precipitated
Crystallization is sent into crystallization cooling tank 08 after suitably cooling down and carries out centrifugal rejection filter, wash, be dried to obtain and more create by 07 continuous discharge valve
The wooden potassium phenolsulfonate fine work.
Claims (4)
1. a kind of preparation method of orthocoll, which is characterized in that the method is passed through nitrogen in sulfonation, prevents from being cured
The wooden phenol oxidation and polymerization are created, intermediate calcicol solution, orthocoll crude product and the filtering of fine work solution are adopted
Secondary filter is carried out with 0.22~0.65 μm of filter membrane, and CGS Continuous Grain Silicon is concentrated under reduced pressure using heat pump recompression to reduce concentration temperature
Degree and shortening heated time reduce the by-product generated when high temperature concentration and the purity and yield that improve orthocoll,
Specific step is as follows:
(1) guaiacol is put into reactor, under stirring, is passed through nitrogen 10 minutes, displacement removes in reactor and guaiacol
In air after, slowly instill sulfuric acid, time for adding is 2~3 hours, and sulfuric acid is added dropwise and finishes, continues to be passed through nitrogen, and stirring
Lower reaction 15~25 minutes, then heats to 70~80 DEG C, insulation reaction 5~6 hours；Sulfonation terminal is checked, after reaching home
Stop reacting and stops being passed through nitrogen；
(2) sulfonated liquid that step (1) obtains slowly is pumped into 70~80 DEG C of purified water, the dosage of purified water is sulfonated liquid
1.60~1.64 times, under stirring, slowly investment calcium carbonate does calcification terminal inspection up to pH5.0~5.5 several times；
(3) calcification terminal reach after, 80~85 DEG C insulation reaction 20~30 minutes, stop heating, stand 15~20 minutes；First use
Centrifuge filtering, then secondary filter is carried out through 0.22~0.65 μm of filter membrane, obtain calcifying solution；
(4) potassium carbonate is weighed, equivalent purified water is added, under stirring, is heated to after all dissolving, it is spare；By calcifying solution, stirring
Under, 70~80 DEG C are heated to, above-mentioned solution of potassium carbonate is slowly instilled, time for adding is 1~1.5 hour, uses precision test paper
When checking pH value meta-alkalescence, potassium terminal inspection is done；
(5) potassium terminal reach after, potassium liquid is heated to it is slightly boiled, keep 10~15 minutes, under stirring, be cooled to 70~80
DEG C, carry out secondary filter, by filtrate carry out heat pump recompression be concentrated under reduced pressure continuous crystallisation, control vacuum degree be -0.065~-
0.08MPa, 75~85 DEG C of temperature, and crystallization is continuously sent in crystallization cooling tank；
(6) crystallization is cooled to 15~20 DEG C, then carries out centrifugal rejection filter and filter out mother liquor, crystal purifying water washing, inspection is washed
Washing liquid pH value is 7.5~8.0, and the wet crude product of orthocoll is obtained after drying, is sent to refining step；
(7) the wet crude product of orthocoll of step (6) is refined, into the wet crude product of orthocoll, is pumped into
Purified water, the dosage of purified water is 2~2.4 times of the wet crude product of orthocoll, under stirring, heating make to be completely dissolved to
Clearly, secondary filter then is carried out with 0.22~0.65 μm of filter membrane；
(8) the refined filtration liquid that step (7) film is obtained by filtration carries out heat pump recompression and continuous crystallisation is concentrated under reduced pressure, and controls vacuum degree
For -0.065~-0.08MPa, 75~85 DEG C of temperature, and crystallization is continuously sent in crystallization cooling tank；
(9) crystallization is cooled to 15~20 DEG C, then carries out centrifugal rejection filter and filters out mother liquor, crystal purifying water washing, with precision
Test paper checks that cleaning solution pH value is 7.0~7.5, after filter cake drying, obtains orthocoll fine work wet product, send drying process；
(10) 8~10h is dried in 85~90 DEG C of baking ovens in orthocoll fine work wet product, crushes, screening, examines
Orthocoll fine work is obtained afterwards.
2. the preparation method of orthocoll according to claim 1, which is characterized in that the step (1) checks sulphur
The method for changing terminal is that the sulfonated liquid for taking purified water and reaction to obtain is uniformly mixed with the volume ratio of 9:1, when no grease is precipitated
When be reach sulfonation terminal.
3. the preparation method of orthocoll according to claim 1, which is characterized in that step (2) calcification is whole
The method that point checks includes following two: 1) take a small amount of calcifying solution, check the pH of calcifying solution with pH precision test paper, pH 5.0~
It is to reach calcification terminal when 5.5 section；2) a small amount of calcifying solution is taken, a small amount of calcium carbonate is added, it is to arrive that stirring, which does not generate bubble,
Up to calcification terminal.
4. the preparation method of orthocoll according to claim 1, which is characterized in that step (4) potassiumization is whole
Point check method the following steps are included:
1) ammonium oxalate is taken, adds purified water dissolution that the ammonium oxalate test solution that concentration is 35mg/mL is made；
2) 2mL potassium liquid is taken, purified water 10mL is added and shakes up；
3) take 2mL potassium liquid, be added purified water 8mL, then plus ammonium oxalate test solution 2mL shake up；
4) solution within one minute, 2) compared with solution 3), 3) should be clarified substantially as solution 2), that is, indicate to arrive
Up to terminal.
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Inventor after: Mo Shanjun Inventor after: Lai Yizhu Inventor after: Lu Qifeng Inventor after: Huang Jingzhou Inventor after: He Zhengjian Inventor after: Qin Xu Inventor after: He Qun Inventor after: Wei Yuezheng Inventor after: Fan Guihong Inventor after: Huang Mincong Inventor after: Xiong Chunmei Inventor after: Wei Taixin Inventor before: Mo Shanjun Inventor before: Lai Yizhu Inventor before: Lu Qifeng Inventor before: Huang Jingzhou Inventor before: He Zhengjian Inventor before: Qin Xu Inventor before: He Qun Inventor before: Wei Yuezheng Inventor before: Fan Guihong Inventor before: Huang Mincong Inventor before: Xiong Chunmei Inventor before: Wei Taixin |