CN109503348A - A kind of preparation method of anthraquinone - Google Patents
A kind of preparation method of anthraquinone Download PDFInfo
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- CN109503348A CN109503348A CN201910007306.2A CN201910007306A CN109503348A CN 109503348 A CN109503348 A CN 109503348A CN 201910007306 A CN201910007306 A CN 201910007306A CN 109503348 A CN109503348 A CN 109503348A
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- water
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/24—Anthracenes; Hydrogenated anthracenes
Abstract
The invention discloses a kind of preparation methods of anthraquinone, including condensation, hydrolysis, closed loop, dilution process, mother liquor reprocessing process, sulfur waste sour water reprocessing process.It using relatively simple technique, recycles, turns waste into wealth, business industrial chemicals is separately recovered from aluminium scrap salt water and sulfur waste sour water, reduce comprehensive preparation cost by a relatively large margin, reduce environmental pollution.Hydrolyzing process can generate a kind of waste water containing aluminium salt, that is mother liquor, contain a certain amount of o-benzoylbenzoic acid in the mother liquor, by being improved to hydrolyzing process, o-benzoylbenzoic acid unsegregated in lower layer's mother liquor can not only be separated, the yield of anthraquinone is improved, and improves the purity of the composite water purifying agent prepared in mother liquor, composite water purifying agent is without variegated.In addition, the composite water purifying agent water purification turbidity removal ability of the application preparation significantly improves.
Description
Technical field
The present invention relates to chemical technology field, in particular to a kind of preparation method of anthraquinone.
Background technique
Anthraquinone is a kind of important industrial chemicals, it, which is widely used in synthetic dyestuff, papermaking and agricultural production, prevents birds
It eats the fields such as fruit.Whole world annual output is about at 90,000 tons or so at present.Prior art synthesize anthraquinone preparation, be with phthalic anhydride with
Benzene is condensed under Catalyzed by Anhydrous Aluminium Chloride, is generated benzoylbenzoic acid aluminium complex salt, is obtained benzoylbenzoic acid through hydrolysis acidification,
Manufactured goods are obtained by dehydrating agent dehydration closed-loop of oleum again.The technique of prior art preparation synthesis anthraquinone successively includes: polymerization
→ hydrolysis → acidification → distillation → granulation → suction filtration → centrifugal dehydration → packs → feeding intake → and is dehydrated → closed loop → dilution → filtering
→ dehydration → drying → obtain manufactured goods.
The preparation method of prior art synthesis anthraquinone is made a general survey of, not only complex technical process, the production cycle is long, preparation cost
Height, and since its discharge water generated fails to obtain redevelopment utilization, and resource is wasted, it polluted environment.In phthalic anhydride
During method produces anthraquinone, a kind of waste water containing aluminium salt is generated, which has due to certain o-benzoylbenzoic acid etc.
The presence of machine object and aobvious brown, thus due to being sold containing the variegated product that cannot function as in gained composite water purifying agent.Cause China
The producer of overwhelming majority Phthalic Anhydrides production anthraquinones is by the discharge of wastewater at present.Certain pollution is not only caused to environment in this way, together
When one ton of anthraquinone of every production will have 0.6 ton of Al2O3Wasting is fallen in vain.
The purpose of the present invention is to provide a kind of preparation methods of anthraquinone, using relatively simple technique, circulation benefit
With turning waste into wealth, business industrial chemicals be separately recovered from aluminium scrap salt water and sulfur waste sour water, to reduce comprehensive preparation by a relatively large margin
Cost reduces environmental pollution.
Summary of the invention
In order to solve the above-mentioned technical problem, one aspect of the present invention provides a kind of preparation method of anthraquinone, including condensation, water
Solution, closed loop, dilution process；
(1) the condensation process are as follows:
By benzene: alchlor: phthalic anhydride=1:(2-10): benzene is first sent into condensation kettle by the weight part ratio of (1-6), and unlatching is stirred
Addition alchlor is mixed, phthalic anhydride is then put into, temperature in the kettle is maintained at 20-50 DEG C when feeding intake, and makes to react the adjacent benzene first of thoroughly generation
Acyl benzoic acid aluminium salt is warming up to 55-65 DEG C after reaction, keeps the temperature 1-5 hours；
(2) hydrolyzing process are as follows:
A. hydrolysis acidification: the o-benzoylbenzoic acid aluminium salt that condensation reaction finishes is put into the hydrolysis kettle for filling bottom water,
The dilute sulfuric acid that mass concentration is 10-25% is added, reaction generates o-benzoylbenzoic acid；
B. it separates: carrying out static layering after completion of the reaction, lower layer's mother liquor is discharged by reaction kettle bottom after layering, must be deposited in anti-
Answer the o-benzoylbenzoic acid for being dissolved in benzene in bottom portion；
C. it distills: being passed through 2-8kg/cm in reaction kettle2The steam of pressure, the steaming when reactor temperature reaches 90-110 DEG C
Fraction enters benzene tank recycling from benzo；Water is added into reaction kettle to be crystallized, o-benzoylbenzoic acid is obtained after filtering,
And it puts it into measuring tank；
D. it is dehydrated: the o-benzoylbenzoic acid in measuring tank being imported in closed loop dehydrating kettle and carries out vacuum dehydration to get liquid
State BB acid；
(3) the closed loop process are as follows:
Dewatered o-benzoylbenzoic acid liquid meter is put into closed loop pot, 100% sulfuric acid of mass concentration is added, opens
Stirring is opened, steam is led in collet makes the temperature in kettle rise to 150-200 DEG C, and heat preservation reaction in 1-5 hours generates anthraquinone；
(4) the dilution process are as follows:
The closed loop material of end of reaction is put into the dilution kettle for having turned on stirring, thread be added dilute sulfuric acid 20min, then plus
Big flow, the weight percent for controlling dilute sulfuric acid is 10%-50%；Stop stirring after continuing stirring 20-40 minutes, is diluted
Anthraquinone；It is conducted into dehydration equipment and implements anthraquinone and the separation of Waste Sulfuric Acid water, obtain solid-state anthraquinone and sulfur waste sour water；
Wherein, the hydrogen chloride that condensation process and hydrolyzing process generate collects falling film absorption and obtains hydrochloric acid.
As a kind of perferred technical scheme, in the hydrolysis acidification step of hydrolyzing process, the weight of the bottom water and dilute sulfuric acid
Amount part is compared for 7:(1-10), and the weight part ratio of benzene is (2-10) in dilute sulfuric acid and condensation step: 1.
As a kind of perferred technical scheme, in the distilation steps of hydrolyzing process, it is pure in condensation process that the amount of water, which is added,
1-10 times of benzene dosage.
As a kind of perferred technical scheme, in closed loop process, 100% sulfuric acid of mass concentration is pure in condensation process
0.5-10 times of benzene dosage.
As a kind of perferred technical scheme, it dilutes in process, the mass concentration of the dilute sulfuric acid is 10%~50%.
As a kind of perferred technical scheme, further include mother liquor reprocessing process:
Mother liquor and aluminium hydroxide that hydrolyzing process generates are put into polymerization reaction kettle, are warming up to 80 DEG C with steam
Start polymerization reaction and keep the temperature 4 hours, polymerization reactant is sent in standing and curing tank stands 6 hours later, supernatant is sent
After being dried to spray dryer, composite water purifying agent product is obtained.
As a kind of perferred technical scheme, in the mother liquor reprocessing process, the weight part ratio of mother liquor and aluminium hydroxide
For (5-20): 1.
As a kind of perferred technical scheme, further include sulfur waste sour water reprocessing process:
The sulfur waste sour water for diluting process generation and magnesium powder are measured in proportion, water or wash water or sulfuric acid are added in neutralizing tank
Mother liquor after magnesium crystallization, is first added magnesium powder under stiring, adds sulfuric acid and carries out neutralization reaction, controls pH, the temperature of neutralization reaction
Degree and reaction time, react fully progress；Solution after reaction is filtered through leaf-type filter, clear liquid is squeezed into crystallization
Device is cooled to 30 DEG C or less and is centrifuged, and wet feed is sent into vibratory liquefaction drying bed, is made seven in 50 DEG C of -55 DEG C of dryings
Water magnesium sulfate.
As a kind of perferred technical scheme, in sulfur waste sour water reprocessing process, magnesium powder, sulfur waste sour water, mother liquor
Weight part ratio is 1:(1-10): 2.
As a kind of perferred technical scheme, in the Waste Sulfuric Acid water process process, the pH of neutralization reaction is 6.5-7.5,
75-100 DEG C of the temperature of neutralization reaction, reaction time are 1.0-10.0 hours.
Compared with prior art, the invention has the benefit that a kind of preparation method of anthraquinone provided by the invention, circulation
It utilizes, turns waste into wealth.Using relatively simple technique, it is former that business chemical industry is separately recovered from aluminium scrap salt water and sulfur waste sour water
Material reduces environmental pollution to reduce comprehensive preparation cost by a relatively large margin.By being improved to hydrolyzing process, can not only incite somebody to action
Unsegregated o-benzoylbenzoic acid is separated in lower layer's mother liquor, improves the yield of anthraquinone, and is improved in mother liquor and prepared
Composite water purifying agent purity, composite water purifying agent is without variegated.In addition, the turbidity removal water purification energy of the composite water purifying agent of the application preparation
Power significantly improves.
Specific embodiment
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this hair can be more easily to understand
Bright content.Unless otherwise defined, all technologies used herein and scientific term have common with fields of the present invention
The normally understood identical meaning of technical staff.When there is a conflict, the definition in this specification shall prevail.
For the purpose of following detailed description, it should be understood that the present invention can be used various substitutions variation and step it is suitable
Sequence, unless specifically stated on the contrary.In addition, being indicated in the case where in addition in any operational instances or otherwise pointing out
Such as all numbers of the amount of ingredient used in description and claims should be understood in all cases by term
" about " it modifies.Therefore, unless indicated to the contrary, the numerical parameter otherwise illustrated in the following description and appended dependent claims is root
The approximation changed according to the expected performance of the invention to be obtained.It is at least not intended to for the applicable of doctrine of equivalents being limited in
In the scope of the claims, each numerical parameter should at least be given up according to the number of the effective digital of report and by the way that application is common
Enter technology to explain.
Although illustrating that broad range of numberical range and parameter of the invention are approximations, listed in specific example
Numerical value is reported as accurately as possible.However, any numerical value inherently includes the standard deviation by finding in its each self-test measurement
The certain errors necessarily led to.
When a numberical range disclosed herein, above range is considered as continuously, and the minimum value including the range and most
Big value and each value between this minimum value and maximum value.Further, when range refers to integer, including the model
Each integer between minimum value and maximum value enclosed.In addition, when providing multiple range Expressive Features or characteristic, Ke Yihe
And the range.In other words, unless otherwise specified, otherwise all ranges disclosed herein are understood to include and are wherein included into
Any and all subrange.For example, should be regarded as including between minimum value 1 and maximum value 10 from the specified range of " 1 to 10 "
Any and all subrange.The Exemplary range of range 1 to 10 include but is not limited to 1 to 6.1,3.5 to 7.8,5.5 to
10 etc..
The present invention provides a kind of preparation methods of anthraquinone, including condensation, hydrolysis, closed loop, dilution process；
It is condensed process
In the application, the condensation process are as follows:
By benzene: alchlor: phthalic anhydride=1:(2-10): benzene is first sent into condensation kettle by the weight part ratio of (1-6), and unlatching is stirred
Addition alchlor is mixed, phthalic anhydride is then put into, temperature in the kettle is maintained at 20-50 DEG C when feeding intake, and makes to react the adjacent benzene first of thoroughly generation
Acyl benzoic acid aluminium salt is warming up to 55-65 DEG C after reaction, keeps the temperature 1-5 hours；
As a kind of perferred technical scheme, the condensation process are as follows:
By benzene: alchlor: benzene is first sent into condensation kettle by phthalic anhydride=1:3-4:2 weight part ratio, is opened stirring and is added three
Then aluminium chloride puts into phthalic anhydride, temperature in the kettle is maintained at 30-40 DEG C when feeding intake, and makes to react thoroughly generation o-benzoylbenzoic acid
Aluminium salt is warming up to 60-65 DEG C after reaction, keeps the temperature 1-2 hours；
Hydrolyzing process
In the application, as a kind of perferred technical scheme, the hydrolyzing process are as follows:
A. hydrolysis acidification: the o-benzoylbenzoic acid aluminium salt that condensation reaction finishes is put into the hydrolysis kettle for filling bottom water,
The dilute sulfuric acid that concentration is 10-15% or so is added, reaction generates o-benzoylbenzoic acid；
B. it separates: carrying out static layering after completion of the reaction, lower layer's mother liquor is discharged by reaction kettle bottom after layering, must be deposited in anti-
Answer the o-benzoylbenzoic acid for being dissolved in benzene in bottom portion；
C. it distills: being passed through 3~6kg/cm in reaction kettle2The steam of pressure, when reactor temperature reaches 100~103 DEG C
When distillation Separation of Benzene and enter benzene tank recycle；Water is added into reaction kettle to be crystallized, o-benzoyl benzene is obtained after filtering
Formic acid, and put it into measuring tank；
D. it is dehydrated: the o-benzoylbenzoic acid in measuring tank being imported in closed loop dehydrating kettle and carries out vacuum dehydration to get liquid
State BB acid；
As a kind of perferred technical scheme, the hydrolyzing process are as follows:
A. hydrolysis acidification: the o-benzoylbenzoic acid aluminium salt that condensation reaction finishes is put into the hydrolysis kettle for filling bottom water,
The dilute sulfuric acid that mass concentration is 10% is added, reaction generates o-benzoylbenzoic acid；
B. it separates: carrying out static layering after completion of the reaction, lower layer's mother liquor is discharged by reaction kettle bottom after layering, must be deposited in anti-
Answer the o-benzoylbenzoic acid for being dissolved in benzene in bottom portion；Lower layer's mother liquor is collected, sodium citrate, stirring to citric acid are added thereto
Sodium is completely dissolved, and continues to stir 20-40min, and ether is added and is extracted, first carries out ether and mother liquor sufficiently at room temperature
Then contact stands water phase extracted and organic phase, layering then separates.Isolated organic phase is distilled
Separation obtains ether and o-benzoylbenzoic acid, and ether enters ether tank recycling, and o-benzoylbenzoic acid is merged into reaction
Kettle.
It is described that carry out coming into full contact at room temperature by ether and mother liquor realized by way of stirring or vibrating,
The purpose is to so that remaining o-benzoylbenzoic acid in water phase is entered organic phase to the maximum extent.
As a kind of perferred technical scheme, the weight part ratio of the sodium citrate and dilute sulfuric acid in hydrolysis acidification step is
1:(30-50), preferably 1:40.
As a kind of perferred technical scheme, the volume ratio of the ether and mother liquor is (1-3): 1, preferably 2:1.
C. it distills: being passed through 3~6kg/cm in reaction kettle2The steam of pressure, when reactor temperature reaches 100~103 DEG C
When distillation Separation of Benzene and enter benzene tank recycle；Water is added into reaction kettle to be crystallized, o-benzoyl benzene is obtained after filtering
Formic acid, and put it into measuring tank；
D. it is dehydrated: the o-benzoylbenzoic acid in measuring tank being imported in closed loop dehydrating kettle and carries out vacuum dehydration to get liquid
State BB acid；
As a kind of perferred technical scheme, in the hydrolysis acidification step of hydrolyzing process, the weight of the bottom water and dilute sulfuric acid
Amount part is compared for 7:(1-3), preferably 7:2；The weight part ratio of benzene is (4-8) in dilute sulfuric acid and condensation step: 1, preferably 6.3:
1。
As a kind of perferred technical scheme, in the distilation steps of hydrolyzing process, the amount that water is added into reaction kettle is contracting
5-8 times, preferably 6 times for closing purified petroleum benzin dosage in process.
In a kind of preparation method of anthraquinone of the application, hydrolyzing process can generate a kind of waste water containing aluminium salt, i.e. mother liquor,
Contain a certain amount of o-benzoylbenzoic acid in the mother liquor, on the one hand will affect the yield of anthraquinone, on the other hand due to adjacent benzene first
The presence of the organic matters such as acyl benzoic acid makes mother liquor show brown, and the composite water purifying agent purity for causing mother liquor to prepare is not high, containing variegated.
Inventors have found that the application carries out the separation of ether reextraction by the way that sodium citrate is added into the lower layer's mother liquor being discharged after separation
Method, o-benzoylbenzoic acid unsegregated in lower layer's mother liquor can not only be separated, improve the yield of anthraquinone, and
The purity of the composite water purifying agent prepared in mother liquor is improved, composite water purifying agent is without variegated.Moreover, inventor unexpectedly sends out
Existing, after sodium citrate progress ether reextraction separation is added in lower layer's mother liquor, the composite water purifying agent water purification ability of preparation is significant
It improves.Inventor's supposition, the possible reason is, the sulfuric acid reaction in sodium citrate and mother liquor generates sodium sulphate, one side sulphur
Sour sodium polarity is larger, can promote the separation of water phase and organic phase；Another aspect sodium sulphate is soluble easily in water, greatly reduces adjacent benzene first
Solubility of the acyl benzoic acid in water phase helps to separate yield of the o-benzoylbenzoic acid to improve anthraquinone.In addition, lemon
The citric acid that sulfuric acid reaction in sour sodium and mother liquor generates stays in mother liquor, when preparing polyaluminium sulfate by mother liquor, improves
The storage stability and turbidity removal water purification ability of polyaluminium sulfate, not only strengthen Al3+And SO4 2-Coordination ability, be formed simultaneously
With the bigger complex of acid group hydrogen bond connection polyhydroxy complex ion, adsorption capacity is bigger.
Closed loop process
As a kind of perferred technical scheme, the closed loop process are as follows:
Dewatered o-benzoylbenzoic acid liquid meter is put into closed loop pot, 100% sulfuric acid of mass concentration is added, opens
Stirring is opened, leading to steam in collet makes the temperature in kettle rise to 165 DEG C, keeps the temperature reaction in 2 hours and generates anthraquinone；
As a kind of perferred technical scheme, in closed loop process, 100% sulfuric acid is about condensed purified petroleum benzin dosage in process
0.8-3 times, preferably 1.2 times.
Dilute process
As a kind of perferred technical scheme, the dilution process are as follows:
The closed loop material of end of reaction is put into the dilution kettle for having turned on stirring, thread be added dilute sulfuric acid 20min, then plus
Big flow, the weight percent for controlling dilute sulfuric acid is 30%~50%；Continue stirring 30~stopping stirring after forty minutes, obtains dilute
The anthraquinone released；It is conducted into dehydration equipment and implements anthraquinone and the separation of Waste Sulfuric Acid water, obtain solid-state anthraquinone and sulfur waste sour water；
The purpose that dilute sulfuric acid is added in thread is that originally material in reactor temperature is high, if addition is too fast to will lead to material knot
Block dilutes insufficient.As a kind of perferred technical scheme, it diluting in process, the mass concentration of the dilute sulfuric acid is 10%~
30%.Dilute acid concentration is excessively high to damage filter cloth, and the too low waste acid quantity of concentration is excessive to be unfavorable for heavy burden utilization.Wherein, condensation process and
The hydrogen chloride that hydrolyzing process generates collects falling film absorption and obtains hydrochloric acid.
Mother liquor reprocesses process
As a kind of perferred technical scheme, the application further includes mother liquor reprocessing process:
Mother liquor and aluminium hydroxide that hydrolyzing process generates are put into polymerization reaction kettle, are warming up to 80 DEG C with steam
Start polymerization reaction and keep the temperature 4 hours, polymerization reactant is sent in standing and curing tank stands 6 hours later, supernatant is sent
After being dried to spray dryer, composite water purifying agent product is obtained.
As a kind of perferred technical scheme, in the mother liquor reprocessing process, the weight part ratio of mother liquor and aluminium hydroxide
For (6-10): 1, preferably=8:1.
Sulfur waste sour water reprocesses process
As a kind of perferred technical scheme, the application further includes sulfur waste sour water reprocessing process:
The sulfur waste sour water for diluting process generation and magnesium powder are measured in proportion, water or wash water or sulfuric acid are added in neutralizing tank
Mother liquor after magnesium crystallization, is first added magnesium powder under stiring, adds sulfuric acid and carries out neutralization reaction, controls pH, the temperature of neutralization reaction
Degree and reaction time, react fully progress；Solution after reaction is filtered through leaf-type filter, clear liquid is squeezed into crystallization
Device is cooled to 30 DEG C or less and is centrifuged, and wet feed is sent into vibratory liquefaction drying bed, is made seven in 50 DEG C of -55 DEG C of dryings
Water magnesium sulfate；
In the application, the magnesium powder is ore (dolomite, magnesia, snake aragonite) or its calcining powder containing magnesia.Make
For a preferred technical solution, in the sulfur waste sour water reprocessing process, magnesium powder, sulfur waste sour water, mother liquor weight part ratio be
1:(2-4): 2, preferably 1:3.2:2.As a kind of perferred technical scheme, it in the Waste Sulfuric Acid water process process, neutralizes anti-
The pH control answered is 6.5-7.5, preferably pH=5, it is therefore an objective to accelerate magnesium powder dissolution conversion；85-95 DEG C of the temperature of neutralization reaction,
Reaction time is 2.0-3.0 hours.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
The some nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
Embodiment
Embodiment 1
Embodiment 1 provides a kind of preparation method of anthraquinone, including condensation, hydrolysis, closed loop, dilution process, mother liquor are located again
Science and engineering sequence, sulfur waste sour water reprocess process.
It is condensed process
By benzene: alchlor: benzene is first sent into condensation kettle by phthalic anhydride=1:3.4:2 weight part ratio, is opened stirring and is added three
Then aluminium chloride puts into phthalic anhydride, temperature in the kettle is maintained at 30 DEG C when feeding intake, and makes to react thoroughly generation o-benzoylbenzoic acid aluminium
Salt is warming up to 60 DEG C after reaction, keeps the temperature 1 hour；
Hydrolyzing process
A. hydrolysis acidification: the o-benzoylbenzoic acid aluminium salt that condensation reaction finishes is put into the hydrolysis kettle for filling bottom water,
The dilute sulfuric acid that mass concentration is 10% is added, reaction generates o-benzoylbenzoic acid；
B. it separates: carrying out static layering after completion of the reaction, lower layer's mother liquor is discharged by reaction kettle bottom after layering, must be deposited in anti-
Answer the o-benzoylbenzoic acid for being dissolved in benzene in bottom portion；Lower layer's mother liquor is collected, sodium citrate, stirring to citric acid are added thereto
Sodium is completely dissolved, and continues to stir 30min, and ether is added and is extracted, is first sufficiently connect ether at room temperature with mother liquor
Then touching stands water phase extracted and organic phase, layering then separates.Water phase after separation is final mother liquor.It will separation
Obtained organic phase carries out distillation separation, obtains ether and o-benzoylbenzoic acid, and ether enters ether tank recycling, adjacent benzene
Carbamoyl benzoate is merged into reaction kettle.
It is described that carry out coming into full contact at room temperature by ether and mother liquor realized by way of stirring or vibrating,
The purpose is to so that remaining o-benzoylbenzoic acid in water phase is entered organic phase to the maximum extent.The sodium citrate and hydrolysis acid
The weight part ratio for changing dilute sulfuric acid in step is 1:40.The volume ratio of the ether and mother liquor is 2:1.
C. it distills: being passed through 5kg/cm in reaction kettle2The steam of pressure, the distillation point when reactor temperature reaches 100 DEG C
Enter benzene tank recycling from benzo；Water is added into reaction kettle to be crystallized, o-benzoylbenzoic acid is obtained after filtering, and will
It is put into measuring tank；
D. it is dehydrated: the o-benzoylbenzoic acid in measuring tank being imported in closed loop dehydrating kettle and carries out vacuum dehydration to get liquid
State BB acid；
In the hydrolysis acidification step of hydrolyzing process, the weight part ratio of the bottom water and dilute sulfuric acid is 7:2；Dilute sulfuric acid and condensation
The weight part ratio of benzene is 6.3:1 in step.
In the distilation steps of hydrolyzing process, the amount that water is added into reaction kettle is 6 times for being condensed purified petroleum benzin dosage in process.
Closed loop process
Dewatered o-benzoylbenzoic acid liquid meter is put into closed loop pot, 100% sulfuric acid of mass concentration is added, opens
Stirring is opened, leading to steam in collet makes the temperature in kettle rise to 165 DEG C, keeps the temperature reaction in 2 hours and generates anthraquinone；
As a kind of perferred technical scheme, in closed loop process, 100% sulfuric acid is purified petroleum benzin dosage in condensation process
1.2 again.
Dilute process
The closed loop material of end of reaction is put into the dilution kettle for having turned on stirring, thread be added dilute sulfuric acid 20min, then plus
Big flow, the weight percent for controlling dilute sulfuric acid is 40%；Stop stirring after continuing stirring 300 minutes, obtains diluted anthraquinone；
It is conducted into dehydration equipment and implements anthraquinone and the separation of Waste Sulfuric Acid water, obtain solid-state anthraquinone and sulfur waste sour water；
It dilutes in process, the mass concentration of the dilute sulfuric acid is 20%.
The hydrogen chloride that condensation process and hydrolyzing process generate collects falling film absorption and obtains hydrochloric acid.
Mother liquor reprocesses process
Final mother liquor and aluminium hydroxide that hydrolyzing process generates are put into polymerization reaction kettle, are warming up to steam
80 DEG C of beginning polymerization reactions simultaneously keep the temperature 4 hours, polymerization reactant are sent in standing and curing tank stand 6 hours later, supernatant
Liquid is sent to spray dryer drying process, obtains composite water purifying agent product.
The weight part ratio of the final mother liquor and aluminium hydroxide is 8:1.
Sulfur waste sour water reprocesses process
The sulfur waste sour water for diluting process generation and magnesium powder are measured in proportion, after magnesium sulfate crystallization is added in neutralizing tank
Magnesium powder is first added in mother liquor under stiring, adds sulfuric acid and carries out neutralization reaction, controls pH, temperature and the reaction of neutralization reaction
Time, react fully progress；Solution after reaction is filtered through leaf-type filter, clear liquid is squeezed into crystallizer, is cooled to 30
DEG C or less be centrifuged, wet feed is sent into vibratory liquefaction drying bed, in 50 DEG C of dry obtained epsom salts；
The magnesium powder is the ore calcination powder containing magnesia；
In sulfur waste sour water reprocessing process, magnesium powder, sulfur waste sour water, mother liquor weight part ratio be 1:3.2:2.It neutralizes anti-
The pH control answered is 5；90 DEG C of the temperature of neutralization reaction, reaction time are 2.5 hours.
Embodiment 2
Embodiment 2 provides a kind of preparation method of anthraquinone, including condensation, hydrolysis, closed loop, dilution process, mother liquor are located again
Science and engineering sequence, sulfur waste sour water reprocess process.
Embodiment 2 is difference from example 1 is that hydrolyzing process, the hydrolyzing process of embodiment 2 are as follows:
Hydrolyzing process
A. hydrolysis acidification: the o-benzoylbenzoic acid aluminium salt that condensation reaction finishes is put into the hydrolysis kettle for filling bottom water,
The dilute sulfuric acid that mass concentration is 10% is added, reaction generates o-benzoylbenzoic acid；
B. it separates: carrying out static layering after completion of the reaction, lower layer's mother liquor is discharged by reaction kettle bottom after layering, must be deposited in anti-
Answer the o-benzoylbenzoic acid for being dissolved in benzene in bottom portion；Lower layer's mother liquor is collected, sodium citrate, stirring to citric acid are added thereto
Sodium is completely dissolved, and continues to stir 30min, and ether is added and is extracted, is first sufficiently connect ether at room temperature with mother liquor
Then touching stands water phase extracted and organic phase, layering then separates.Water phase after separation is final mother liquor.It will separation
Obtained organic phase carries out distillation separation, obtains ether and o-benzoylbenzoic acid, and ether enters ether tank recycling, adjacent benzene
Carbamoyl benzoate is merged into reaction kettle.
It is described that carry out coming into full contact at room temperature by ether and mother liquor realized by way of stirring or vibrating,
The purpose is to so that remaining o-benzoylbenzoic acid in water phase is entered organic phase to the maximum extent.The sodium citrate and hydrolysis acid
The weight part ratio for changing dilute sulfuric acid in step is 1:30.The volume ratio of the ether and mother liquor is 1:1.
C. it distills: being passed through 5kg/cm in reaction kettle2The steam of pressure, the distillation point when reactor temperature reaches 100 DEG C
Enter benzene tank recycling from benzo；Water is added into reaction kettle to be crystallized, o-benzoylbenzoic acid is obtained after filtering, and will
It is put into measuring tank；
D. it is dehydrated: the o-benzoylbenzoic acid in measuring tank being imported in closed loop dehydrating kettle and carries out vacuum dehydration to get liquid
State BB acid；
In the hydrolysis acidification step of hydrolyzing process, the weight part ratio of the bottom water and dilute sulfuric acid is 7:1；Dilute sulfuric acid and condensation
The weight part ratio of benzene is 4:1 in step.
In the distilation steps of hydrolyzing process, the amount that water is added into reaction kettle is 5 times for being condensed purified petroleum benzin dosage in process.
Embodiment 3
Embodiment 3 provides a kind of preparation method of anthraquinone, including condensation, hydrolysis, closed loop, dilution process, mother liquor are located again
Science and engineering sequence, sulfur waste sour water reprocess process.
Embodiment 3 is difference from example 1 is that hydrolyzing process, the hydrolyzing process of embodiment 3 are as follows:
Hydrolyzing process
A. hydrolysis acidification: the o-benzoylbenzoic acid aluminium salt that condensation reaction finishes is put into the hydrolysis kettle for filling bottom water,
The dilute sulfuric acid that mass concentration is 10% is added, reaction generates o-benzoylbenzoic acid；
B. it separates: carrying out static layering after completion of the reaction, lower layer's mother liquor is discharged by reaction kettle bottom after layering, must be deposited in anti-
Answer the o-benzoylbenzoic acid for being dissolved in benzene in bottom portion；Lower layer's mother liquor is collected, sodium citrate, stirring to citric acid are added thereto
Sodium is completely dissolved, and continues to stir 30min, and ether is added and is extracted, is first sufficiently connect ether at room temperature with mother liquor
Then touching stands water phase extracted and organic phase, layering then separates.Water phase after separation is final mother liquor.It will separation
Obtained organic phase carries out distillation separation, obtains ether and o-benzoylbenzoic acid, and ether enters ether tank recycling, adjacent benzene
Carbamoyl benzoate is merged into reaction kettle.
It is described that carry out coming into full contact at room temperature by ether and mother liquor realized by way of stirring or vibrating,
The purpose is to so that remaining o-benzoylbenzoic acid in water phase is entered organic phase to the maximum extent.The sodium citrate and hydrolysis acid
The weight part ratio for changing dilute sulfuric acid in step is 1:50.The volume ratio of the ether and mother liquor is 3:1.
C. it distills: being passed through 5kg/cm in reaction kettle2The steam of pressure, the distillation point when reactor temperature reaches 100 DEG C
Enter benzene tank recycling from benzo；Water is added into reaction kettle to be crystallized, o-benzoylbenzoic acid is obtained after filtering, and will
It is put into measuring tank；
D. it is dehydrated: the o-benzoylbenzoic acid in measuring tank being imported in closed loop dehydrating kettle and carries out vacuum dehydration to get liquid
State BB acid；
In the hydrolysis acidification step of hydrolyzing process, the weight part ratio of the bottom water and dilute sulfuric acid is 7:3；Dilute sulfuric acid and condensation
The weight part ratio of benzene is 8:1 in step.
In the distilation steps of hydrolyzing process, the amount that water is added into reaction kettle is 8 times for being condensed purified petroleum benzin dosage in process.
Embodiment 4
Embodiment 4 provides a kind of preparation method of anthraquinone, including condensation, hydrolysis, closed loop, dilution process, mother liquor are located again
Science and engineering sequence, sulfur waste sour water reprocess process.
Embodiment 4 is difference from example 1 is that hydrolyzing process, the hydrolyzing process of embodiment 4 are as follows:
Hydrolyzing process
A. hydrolysis acidification: the o-benzoylbenzoic acid aluminium salt that condensation reaction finishes is put into the hydrolysis kettle for filling bottom water,
The dilute sulfuric acid that mass concentration is 10% is added, reaction generates o-benzoylbenzoic acid；
B. it separates: carrying out static layering after completion of the reaction, lower layer's mother liquor is discharged by reaction kettle bottom after layering, must be deposited in anti-
Answer the o-benzoylbenzoic acid for being dissolved in benzene in bottom portion；Lower layer's mother liquor is collected, sodium citrate, stirring to citric acid are added thereto
Sodium is completely dissolved, and continues to stir 30min, and ether is added and is extracted, is first sufficiently connect ether at room temperature with mother liquor
Then touching stands water phase extracted and organic phase, layering then separates.Water phase after separation is final mother liquor.It will separation
Obtained organic phase carries out distillation separation, obtains ether and o-benzoylbenzoic acid, and ether enters ether tank recycling, adjacent benzene
Carbamoyl benzoate is merged into reaction kettle.
It is described that carry out coming into full contact at room temperature by ether and mother liquor realized by way of stirring or vibrating,
The purpose is to so that remaining o-benzoylbenzoic acid in water phase is entered organic phase to the maximum extent.The sodium citrate and hydrolysis acid
The weight part ratio for changing dilute sulfuric acid in step is 0.1:40.The volume ratio of the ether and mother liquor is 2:1.
C. it distills: being passed through 5kg/cm in reaction kettle2The steam of pressure, the distillation point when reactor temperature reaches 100 DEG C
Enter benzene tank recycling from benzo；Water is added into reaction kettle to be crystallized, o-benzoylbenzoic acid is obtained after filtering, and will
It is put into measuring tank；
D. it is dehydrated: the o-benzoylbenzoic acid in measuring tank being imported in closed loop dehydrating kettle and carries out vacuum dehydration to get liquid
State BB acid；
In the hydrolysis acidification step of hydrolyzing process, the weight part ratio of the bottom water and dilute sulfuric acid is 7:2；Dilute sulfuric acid and condensation
The weight part ratio of benzene is 6.3:1 in step.
In the distilation steps of hydrolyzing process, the amount that water is added into reaction kettle is 6 times for being condensed purified petroleum benzin dosage in process.
Embodiment 5
Embodiment 5 provides a kind of preparation method of anthraquinone, including condensation, hydrolysis, closed loop, dilution process, mother liquor are located again
Science and engineering sequence, sulfur waste sour water reprocess process.
Embodiment 5 is difference from example 1 is that hydrolyzing process, the hydrolyzing process of embodiment 5 are as follows:
Hydrolyzing process
A. hydrolysis acidification: the o-benzoylbenzoic acid aluminium salt that condensation reaction finishes is put into the hydrolysis kettle for filling bottom water,
The dilute sulfuric acid that mass concentration is 10% is added, reaction generates o-benzoylbenzoic acid；
B. it separates: carrying out static layering after completion of the reaction, lower layer's mother liquor is discharged by reaction kettle bottom after layering, must be deposited in anti-
Answer the o-benzoylbenzoic acid for being dissolved in benzene in bottom portion；Lower layer's mother liquor is collected, sodium citrate, stirring to citric acid are added thereto
Sodium is completely dissolved, and continues to stir 30min, and ether is added and is extracted, is first sufficiently connect ether at room temperature with mother liquor
Then touching stands water phase extracted and organic phase, layering then separates.Water phase after separation is final mother liquor.It will separation
Obtained organic phase carries out distillation separation, obtains ether and o-benzoylbenzoic acid, and ether enters ether tank recycling, adjacent benzene
Carbamoyl benzoate is merged into reaction kettle.
It is described that carry out coming into full contact at room temperature by ether and mother liquor realized by way of stirring or vibrating,
The purpose is to so that remaining o-benzoylbenzoic acid in water phase is entered organic phase to the maximum extent.The sodium citrate and hydrolysis acid
The weight part ratio for changing dilute sulfuric acid in step is 1:40.The volume ratio of the ether and mother liquor is 0.1:1.
C. it distills: being passed through 5kg/cm in reaction kettle2The steam of pressure, the distillation point when reactor temperature reaches 100 DEG C
Enter benzene tank recycling from benzo；Water is added into reaction kettle to be crystallized, o-benzoylbenzoic acid is obtained after filtering, and will
It is put into measuring tank；
D. it is dehydrated: the o-benzoylbenzoic acid in measuring tank being imported in closed loop dehydrating kettle and carries out vacuum dehydration to get liquid
State BB acid；
In the hydrolysis acidification step of hydrolyzing process, the weight part ratio of the bottom water and dilute sulfuric acid is 7:2；Dilute sulfuric acid and condensation
The weight part ratio of benzene is 6.3:1 in step.
In the distilation steps of hydrolyzing process, the amount that water is added into reaction kettle is 6 times for being condensed purified petroleum benzin dosage in process.
Embodiment 6
Embodiment 6 provides a kind of preparation method of anthraquinone, including condensation, hydrolysis, closed loop, dilution process, mother liquor are located again
Science and engineering sequence, sulfur waste sour water reprocess process.
Embodiment 6 is difference from example 1 is that hydrolyzing process, the hydrolyzing process of embodiment 6 are as follows:
Hydrolyzing process
A. hydrolysis acidification: the o-benzoylbenzoic acid aluminium salt that condensation reaction finishes is put into the hydrolysis kettle for filling bottom water,
The dilute sulfuric acid that mass concentration is 10% is added, reaction generates o-benzoylbenzoic acid；
B. it separates: carrying out static layering after completion of the reaction, lower layer's mother liquor is discharged by reaction kettle bottom after layering, must be deposited in anti-
Answer the o-benzoylbenzoic acid for being dissolved in benzene in bottom portion；Lower layer's mother liquor is collected, sodium tartrate, stirring to tartaric acid are added thereto
Sodium is completely dissolved, and continues to stir 30min, and ether is added and is extracted, is first sufficiently connect ether at room temperature with mother liquor
Then touching stands water phase extracted and organic phase, layering then separates.Water phase after separation is final mother liquor.It will separation
Obtained organic phase carries out distillation separation, obtains ether and o-benzoylbenzoic acid, and ether enters ether tank recycling, adjacent benzene
Carbamoyl benzoate is merged into reaction kettle.
It is described that carry out coming into full contact at room temperature by ether and mother liquor realized by way of stirring or vibrating,
The purpose is to so that remaining o-benzoylbenzoic acid in water phase is entered organic phase to the maximum extent.The sodium tartrate and hydrolysis acid
The weight part ratio for changing dilute sulfuric acid in step is 1:40.The volume ratio of the ether and mother liquor is 2:1.
C. it distills: being passed through 5kg/cm in reaction kettle2The steam of pressure, the distillation point when reactor temperature reaches 100 DEG C
Enter benzene tank recycling from benzo；Water is added into reaction kettle to be crystallized, o-benzoylbenzoic acid is obtained after filtering, and will
It is put into measuring tank；
D. it is dehydrated: the o-benzoylbenzoic acid in measuring tank being imported in closed loop dehydrating kettle and carries out vacuum dehydration to get liquid
State BB acid；
In the hydrolysis acidification step of hydrolyzing process, the weight part ratio of the bottom water and dilute sulfuric acid is 7:2；Dilute sulfuric acid and condensation
The weight part ratio of benzene is 6.3:1 in step.
In the distilation steps of hydrolyzing process, the amount that water is added into reaction kettle is 6 times for being condensed purified petroleum benzin dosage in process.
Embodiment 7
Embodiment 7 provides a kind of preparation method of anthraquinone, including condensation, hydrolysis, closed loop, dilution process, mother liquor are located again
Science and engineering sequence, sulfur waste sour water reprocess process.
For embodiment 7 difference from example 1 is that mother liquor reprocesses process, the mother liquor of embodiment 7 reprocesses process
Are as follows:
Final mother liquor and aluminium hydroxide that hydrolyzing process generates are put into polymerization reaction kettle, are warming up to steam
80 DEG C of beginning polymerization reactions simultaneously keep the temperature 4 hours, polymerization reactant are sent in standing and curing tank stand 6 hours later, supernatant
Liquid is sent to spray dryer drying process, obtains composite water purifying agent product.
The weight part ratio of the final mother liquor and aluminium hydroxide is 2:1.
Embodiment 8
Embodiment 8 provides a kind of preparation method of anthraquinone, including condensation, hydrolysis, closed loop, dilution process, mother liquor are located again
Science and engineering sequence, sulfur waste sour water reprocess process.
For embodiment 8 difference from example 1 is that mother liquor reprocesses process, the mother liquor of embodiment 8 reprocesses process
Are as follows:
Final mother liquor and aluminium hydroxide that hydrolyzing process generates are put into polymerization reaction kettle, are warming up to steam
80 DEG C of beginning polymerization reactions simultaneously keep the temperature 4 hours, polymerization reactant are sent in standing and curing tank stand 6 hours later, supernatant
Liquid is sent to spray dryer drying process, obtains composite water purifying agent product.
The weight part ratio of the final mother liquor and aluminium hydroxide is 30:1.
Embodiment 9
Embodiment 9 provides a kind of preparation method of anthraquinone, including condensation, hydrolysis, closed loop, dilution process, mother liquor are located again
Science and engineering sequence, sulfur waste sour water reprocess process.
For embodiment 9 difference from example 1 is that mother liquor reprocesses process, the mother liquor of embodiment 9 reprocesses process
Are as follows:
Final mother liquor and aluminium hydroxide that hydrolyzing process generates are put into polymerization reaction kettle, are warming up to steam
40 DEG C of beginning polymerization reactions simultaneously keep the temperature 2 hours, polymerization reactant are sent in standing and curing tank stand 7 hours later, supernatant
Liquid is sent to spray dryer drying process, obtains composite water purifying agent product.
The weight part ratio of the final mother liquor and aluminium hydroxide is 8:1.
Embodiment 10
Embodiment 10 provides a kind of preparation method of anthraquinone, including condensation, hydrolysis, closed loop, dilution process, mother liquor are located again
Science and engineering sequence, sulfur waste sour water reprocess process.
Embodiment 10 is difference from example 1 is that hydrolyzing process, the hydrolyzing process of embodiment 10 are as follows:
A. hydrolysis acidification: the o-benzoylbenzoic acid aluminium salt that condensation reaction finishes is put into the hydrolysis kettle for filling bottom water,
The dilute sulfuric acid that mass concentration is 10% is added, reaction generates o-benzoylbenzoic acid；
B. it separates: carrying out static layering after completion of the reaction, lower layer's mother liquor is discharged by reaction kettle bottom after layering, must be deposited in anti-
Answer the o-benzoylbenzoic acid for being dissolved in benzene in bottom portion；
C. it distills: being passed through 5kg/cm in reaction kettle2The steam of pressure, the distillation point when reactor temperature reaches 100 DEG C
Enter benzene tank recycling from benzo；Water is added into reaction kettle to be crystallized, o-benzoylbenzoic acid is obtained after filtering, and will
It is put into measuring tank；
D. it is dehydrated: the o-benzoylbenzoic acid in measuring tank being imported in closed loop dehydrating kettle and carries out vacuum dehydration to get liquid
State BB acid；
In the hydrolysis acidification step of hydrolyzing process, the weight part ratio of the bottom water and dilute sulfuric acid is 7:2；Dilute sulfuric acid and condensation
The weight part ratio of benzene is 6.3:1 in step.
In the distilation steps of hydrolyzing process, the amount that water is added into reaction kettle is 6 times for being condensed purified petroleum benzin dosage in process.
Performance evaluation
1. turbidity removal ability
The 200mL diatomite simulated water sample for taking 10 equivalent parts, be separately added into 10mg embodiment 1-10 be prepared it is compound
Water purification agent is stirred 30s on six electric mixer of JJ-4A with the revolving speed of 350r/min, is then stirred with the revolving speed of 100r/min
10min is mixed, after standing 15min, the Aspirate supernatant at away from supernatant liquid face 2cm surveys the turbidity of its supernatant respectively.Turbidity
Measurement use≤water turbidity measurement >=(GB13200-1991) in spectrophotometry, the results are shown in Table 1.
2. composite water purifying agent appearance
The embodiment 1-10 composite water purifying agent being prepared is visually observed, evaluation criterion is the face of composite water purifying agent
Whether color is uniform, there is non-variegation, determines to the results are shown in Table 1 whether containing organic impurities in composite water purifying agent with this.
Table 1:
| Turbidity removal rate | Appearance | |
| Embodiment 1 | 89.20% | Color is uniform, non-variegation |
| Embodiment 2 | 78.30% | Color is uniform, non-variegation |
| Embodiment 3 | 79.20% | Color is uniform, non-variegation |
| Embodiment 4 | 35.70% | Have variegated |
| Embodiment 5 | 42.10% | Have variegated |
| Embodiment 6 | 56.70% | Have variegated |
| Embodiment 7 | 36.80% | Color is uniform, non-variegation |
| Embodiment 8 | 31.20% | Color is uniform, non-variegation |
| Embodiment 9 | 36.90% | Color is uniform, non-variegation |
| Embodiment 10 | 29.60% | Have variegated |
Embodiment above-mentioned is merely illustrative, and is used to explain the present invention some features of the method.Appended right
It is required that the range as wide as possible for being intended to require to be contemplated that, and embodiments as presented herein is only according to all possible reality
Apply the explanation of the embodiment of the combined selection of example.Therefore, the purpose of applicant is that the attached claims are not illustrated this
The exemplary selectional restriction of the feature of invention.Some numberical ranges used also include son in the claims
Range, the variation in these ranges should also be construed to be covered by the attached claims in the conceived case.
Claims (10)
1. a kind of preparation method of anthraquinone, which is characterized in that including condensation, hydrolysis, closed loop, dilution process；
(1) the condensation process are as follows:
By benzene: alchlor: phthalic anhydride=1:(2-10): benzene is first sent into condensation kettle by the weight part ratio of (1-6), is opened stirring and is added
Enter alchlor, then put into phthalic anhydride, temperature in the kettle is maintained at 20-50 DEG C when feeding intake, and makes to react thoroughly generation o-benzoyl benzene
Formic acid aluminium salt is warming up to 55-65 DEG C after reaction, keeps the temperature 1-5 hours；
(2) hydrolyzing process are as follows:
A. hydrolysis acidification: the o-benzoylbenzoic acid aluminium salt that condensation reaction finishes is put into the hydrolysis kettle for filling bottom water, is added
Mass concentration is the dilute sulfuric acid of 10-25%, and reaction generates o-benzoylbenzoic acid；
B. it separates: carrying out static layering after completion of the reaction, lower layer's mother liquor is discharged by reaction kettle bottom after layering, reaction kettle must be deposited in
The o-benzoylbenzoic acid for being dissolved in benzene of bottom；
C. it distills: being passed through 2-8kg/cm in reaction kettle2The steam of pressure, the distillation point when reactor temperature reaches 90-110 DEG C
Enter benzene tank recycling from benzo；Water is added into reaction kettle to be crystallized, o-benzoylbenzoic acid is obtained after filtering, and will
It is put into measuring tank；
D. it is dehydrated: the o-benzoylbenzoic acid in measuring tank being imported in closed loop dehydrating kettle and carries out vacuum dehydration to get liquid BB
Acid；
(3) the closed loop process are as follows:
Dewatered o-benzoylbenzoic acid liquid meter is put into closed loop pot, 100% sulfuric acid of mass concentration is added, unlatching is stirred
It mixes, steam is led in collet makes the temperature in kettle rise to 150-200 DEG C, and heat preservation reaction in 1-5 hours generates anthraquinone；
(4) the dilution process are as follows:
The closed loop material of end of reaction is put into the dilution kettle for having turned on stirring, dilute sulfuric acid 20min is added in thread, then increases stream
Amount, the weight percent for controlling dilute sulfuric acid is 10%-50%；Stop stirring after continuing stirring 20-40 minutes, obtains diluted anthracene
Quinone；It is conducted into dehydration equipment and implements anthraquinone and the separation of Waste Sulfuric Acid water, obtain solid-state anthraquinone and sulfur waste sour water；
Wherein, the hydrogen chloride that condensation process and hydrolyzing process generate collects falling film absorption and obtains hydrochloric acid.
2. a kind of preparation method of anthraquinone according to claim 1, which is characterized in that the hydrolysis acidification step of hydrolyzing process
In, the weight part ratio of the bottom water and dilute sulfuric acid is 7:(1-10), the weight part ratio of dilute sulfuric acid and benzene in condensation step is (2-
10): 1.
3. a kind of preparation method of anthraquinone according to claim 1, which is characterized in that in the distilation steps of hydrolyzing process,
The amount that water is added is 1-10 times for being condensed purified petroleum benzin dosage in process.
4. a kind of preparation method of anthraquinone according to claim 1, which is characterized in that in closed loop process, the quality is dense
Spending 100% sulfuric acid is 0.5-10 times for being condensed purified petroleum benzin dosage in process.
5. a kind of preparation method of anthraquinone according to claim 1, which is characterized in that in dilution process, the dilute sulfuric acid
Mass concentration be 10%~50%.
6. a kind of preparation method of anthraquinone according to claim 1, which is characterized in that further include mother liquor reprocessing process:
Mother liquor and aluminium hydroxide that hydrolyzing process generates are put into polymerization reaction kettle, are warming up to 80 DEG C of beginnings with steam
Polymerization reaction simultaneously keeps the temperature 4 hours, polymerization reactant is sent in standing and curing tank stands 6 hours later, supernatant is sent to spray
After mist drier is dried, composite water purifying agent product is obtained.
7. a kind of preparation method of anthraquinone according to claim 1, which is characterized in that in the mother liquor reprocessing process,
The weight part ratio of mother liquor and aluminium hydroxide is (5-20): 1.
8. a kind of preparation method of anthraquinone according to claim 1, which is characterized in that further include sulfur waste sour water reprocessing work
Sequence:
The sulfur waste sour water for diluting process generation and magnesium powder are measured in proportion, water or wash water or magnesium sulfate knot are added in neutralizing tank
Mother liquor after crystalline substance, is first added magnesium powder under stiring, add sulfuric acid carry out neutralization reaction, control pH, the temperature of neutralization reaction with
And the reaction time, react fully progress；Solution after reaction is filtered through leaf-type filter, clear liquid is squeezed into crystallizer, it is cold
But it is centrifuged to 30 DEG C or less, wet feed is sent into vibratory liquefaction drying bed, seven water sulfuric acid are made in 50 DEG C of -55 DEG C of dryings
Magnesium.
9. a kind of preparation method of anthraquinone according to claim 5, which is characterized in that the sulfur waste sour water reprocesses process
In, magnesium powder, sulfur waste sour water, mother liquor weight part ratio be 1:(1-10): 2.
10. a kind of preparation method of anthraquinone according to claim 5, which is characterized in that the Waste Sulfuric Acid water process process
In, the pH of neutralization reaction is 6.5-7.5, and 75-100 DEG C of the temperature of neutralization reaction, the reaction time is 1.0-10.0 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109809447A (en) * | 2019-03-27 | 2019-05-28 | 宋纯 | The recovery method of Waste Sulfuric Acid |
| CN109928871A (en) * | 2019-04-11 | 2019-06-25 | 山东昌邑海能化学有限责任公司 | A kind of method of high-purity synthesis anthraquinone coproduction of ammonia sulfate |
| CN109928872A (en) * | 2019-04-11 | 2019-06-25 | 山东昌邑海能化学有限责任公司 | A kind of method of high-purity synthesis anthraquinone co-producing sulfuric acid magnesium |
| CN109503348B (en) * | 2019-01-04 | 2019-10-25 | 辽宁坤泰化工有限公司 | A kind of preparation method of anthraquinone |
| CN112279755A (en) * | 2020-09-17 | 2021-01-29 | 岳阳振兴中顺新材料科技有限公司 | Energy-saving production method and device for anthraquinone |
| CN115368227B (en) * | 2022-09-13 | 2023-09-19 | 黎明化工研究设计院有限责任公司 | Method for producing 2-ethyl anthraquinone |
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| CN102659551A (en) * | 2012-04-23 | 2012-09-12 | 张晗 | Preparation method of synthetic anthraquinone |
| CN103908870A (en) * | 2012-12-29 | 2014-07-09 | 天津市旗东化工厂 | Treatment method for acyl-chlorination reaction tail gas |
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| CN102659551A (en) * | 2012-04-23 | 2012-09-12 | 张晗 | Preparation method of synthetic anthraquinone |
| CN103908870A (en) * | 2012-12-29 | 2014-07-09 | 天津市旗东化工厂 | Treatment method for acyl-chlorination reaction tail gas |
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|---|---|---|---|---|
| CN109503348B (en) * | 2019-01-04 | 2019-10-25 | 辽宁坤泰化工有限公司 | A kind of preparation method of anthraquinone |
| CN109809447A (en) * | 2019-03-27 | 2019-05-28 | 宋纯 | The recovery method of Waste Sulfuric Acid |
| CN109928871A (en) * | 2019-04-11 | 2019-06-25 | 山东昌邑海能化学有限责任公司 | A kind of method of high-purity synthesis anthraquinone coproduction of ammonia sulfate |
| CN109928872A (en) * | 2019-04-11 | 2019-06-25 | 山东昌邑海能化学有限责任公司 | A kind of method of high-purity synthesis anthraquinone co-producing sulfuric acid magnesium |
| CN109928871B (en) * | 2019-04-11 | 2022-06-21 | 山东昌邑海能化学有限责任公司 | Method for high-purity anthraquinone synthesis and ammonium sulfate co-production |
| CN109928872B (en) * | 2019-04-11 | 2022-06-21 | 山东昌邑海能化学有限责任公司 | Method for high-purity synthesis of anthraquinone and co-production of magnesium sulfate |
| CN112279755A (en) * | 2020-09-17 | 2021-01-29 | 岳阳振兴中顺新材料科技有限公司 | Energy-saving production method and device for anthraquinone |
| CN115368227B (en) * | 2022-09-13 | 2023-09-19 | 黎明化工研究设计院有限责任公司 | Method for producing 2-ethyl anthraquinone |
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