CN103687848B - Utilize the sustainable chemistry method of the Intrinsical recycling separation naphthalene sulfonic acids compound of all acid streams produced during separation and washing - Google Patents

Utilize the sustainable chemistry method of the Intrinsical recycling separation naphthalene sulfonic acids compound of all acid streams produced during separation and washing Download PDF

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CN103687848B
CN103687848B CN201280031697.8A CN201280031697A CN103687848B CN 103687848 B CN103687848 B CN 103687848B CN 201280031697 A CN201280031697 A CN 201280031697A CN 103687848 B CN103687848 B CN 103687848B
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acid
mother liquor
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CN103687848A (en
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布哈德莱什·K·帕迪亚
尼特什·H·梅塔
科玛尔·马赫什瓦里
瑞杰施·莫哈勒卡尔
阿什维尼·贡纳尔
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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

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Abstract

By producing the separation precipitated to realize naphthalene sulfonic acids compound with dilute sulfuric acid acidizing alkali molten mixture under predetermined condition temperature, time and pH, and naphthalene sulfonic acids compound is separated and is isolated by filtration by being precipitated as partial alkaline-metal salts.The obtained filtrate containing soluble naphthalene sulfonic acids compound and/or its salt is used as the initial action medium of the later separation naphthalene sulfonic acids compound after recycling processing, fills it up with reaction medium, diluting reaction medium after recycling processing.It can be the separation that naphthalene sulfonic acids is realized in positive separation and reverse separation by two methods.

Description

Utilize the Intrinsical recycling point of all acid streams produced during separation and washing From the sustainable chemistry method of naphthalene sulfonic acids compound
Technical field
The Intrinsical that the present invention relates to the use of caused all acid streams is recycled for separating（isolate）Part alkali gold Belong to the method for the naphthalene sulfonic acids compound of salt form.
More particularly it relates to mixed by the way that agglomerate will be melted with acid to obtain the H acid of part alkali metal salt (for simplicity, be hereinafter referred to as " acid precipitation " by the way that melting agglomerate and acid are blended to produce precipitation) makes alkali fusion Melt mixture experience precipitation the method that separates naphthalene sulfonic acids compound, it is characterised in that by by the melting agglomerate with it is described dilute Acid mixing and carry out acid precipitation, the naphthalene sulfonic acid moieties alkali metal salt of precipitation is isolated by filtration, and obtained containing can The Intrinsical recycling of the filtrate of dissolubility naphthalene sulfonic acids compound and/or its salt is used as the reaction medium of the separation method.
Background technology
Separation (being broadly defined as separation product) passes through the separated chemical method of known method in progress soluble product Afterwards alkaline matter is formed with acid solution.Separation is a kind of important chemical method, is widely used in very polymolecular preparation.
The separation of molecule various chemicals group (including medicine, dyestuff and pigment, agricultural chemicals, speciality chemical, Quiet thin chemicals and explosive) in find application.
The shortcomings that existing separation method：
Naphthalene sulfonic acids compound is produced for a long time and the intermediate as production dyestuff and pigment.For separating naphthalene sulfonic acids The conventional method of compound includes obtaining alkali fusion amine by naphthalene, is then acidified and is precipitated with diluted acid.
The problem of this method is that the gross production rate of the naphthalene sulfonic acids compound as made from naphthalene is relatively low and need a large amount of bronsted lowry acids and bases bronsted lowries etc..
According to page 533 to 536 of such as Yutaka HOSODA " Senryo Kagaku (Dye Chemistry) " upper description Method, the amount for the caustic soda of 1 mole of Koch's acid trisodium salt of alkali fusion is 8.6 moles, it corresponds to theoretical aequum (2 Mole) 4.3 times.Therefore, for 1 mole of Koch's acid, from melting agglomerate obtain in the form of mono-sodium salt H acid it is required The amount of sulfuric acid reaches 5.8 moles.
The shortcomings that these methods is that these methods produce substantial amounts of acid waste liquid, they are difficult to recycle.These methods need Will the environmentally unsustainable reaction condition on pH, temperature, concentration, reaction reagent and medium etc., and to environment, outstanding It is that unsustainable influence is left to our water body.
These methods have the shortcomings that such as low-conversion and low-yield, do not cause these methods uneconomical and environmentally not It is sustainable.
In addition, other shortcomings of all the above method are, as being not required as a result, always being formed for these methods Organic and inorganic byproduct.The type of the accessory substance formed and their the amount difference according to method and molecule.Following again This difficulty during ring mother liquor causes to produce a large amount of liquid efflunents.
The further drawback of above-mentioned method is in some cases, also to produce substantial amounts of inoganic solids waste.These Solid waste is by organic compound such as starting material, product and by-product contamination and causes serious pollution problem.Usually these Waste is viscous solid, and processing is cumbersome, it is difficult to throw aside, and as non-green solid waste for known to industry.
Above method still has other shortcomings.Because the generation of substantial amounts of liquid efflunent and non-green solid waste, The above method needs the big equipment for effluent processing and disposal of solid waste.These factors force the relevant constraint in place, These methods are forced only to be carried out in the specified industrial area for being suitable for handling speciality chemical.
Therefore, these methods are non-green, unsustainable, uneconomic, and are destroyed in very big degree Environment, this worldwide becomes focal point.
Accordingly, it is desirable to provide the method for green separation naphthalene sulfonic acids compound is recycled for using the Intrinsical of acid mother liquid, Thus drawbacks described above and shortcoming are avoided, and environmentally sustainable and economic recirculation solution is provided.
The content of the invention
Inventor has been developed using commercially available customization preparation, such as R-Cat1 and R-Cat2, is produced using during method Raw washings and the Intrinsical of mother liquor are recycled for the new method of separation naphthalene sulfonic acids compound.
According to the follow-up of inventor, using such excessive auxiliary material (such as acid) in certain journey in each separating step It is inevitable on degree.It has been found that these auxiliary materials used are greatly decreased in the case where not damaging the further advantage of this method Amount be nearly impossible, although still thering is space to improve this method.
Caused in separating step using excessive auxiliary material (for example, acid) using substantial amounts of another auxiliary material The liquid flow produced during (for example, alkali) comes and after the separation of naphthalene sulfonic acids compound.Therefore, it is used to prepare the original of naphthalene sulfonic acids compound Most of cost of material and processed materials is taken by the cost of bronsted lowry acids and bases bronsted lowry.Meanwhile produce and largely contain spent acid or inorganic salts Drain thing and cannot ignore for handling their financial burden.
The purpose of the method for the present invention, which is to provide, overcomes a large amount of acidity as caused by the separated conventional method of naphthalene sulfonic acids compound Environmentally friendly (green) method for the problem of waste produces.
Therefore, avoid separating the main mesh that the limitation that naphthalene sulfonic acids compound is run into is the present invention from alkali fusion agglomerate 's.
Another object be to provide it is not only operationally not expensive and also generation high quality product be used for separate naphthalene sulfonic acids Green method.
It is a further object of the present invention to provide following again using the acid stream produced during separation, separation and washed product Ring produces naphthalene sulfonic acids, causes the improved method of Zero discharge.
It is a further object of the present invention to provide by using the acid stream produced during precipitation, separation and washed product It is recycled for reducing the economy that auxiliary material is brought such as the consumption of acid and the alkali for neutralizing acidic liquid flowing out stream.
It is a further object of the present invention to provide a kind of method, it is not required to wherein being greatly reduced by reaction medium recyclability The accessory substance wanted, organic and inorganic impurity content, this causes the purer product being formed continuously.
It is an advantage of the invention that because the organic and quantity of inorganic impurity and amount are relatively fewer, during recirculation The possibility of accessory substance is produced in acid mother liquid because of the smaller using proprietary preparation R-Cat-1＆R-Cat2.The fact is effectively Make it possible an infinite number of acid mother liquid circulation in our methods.
Another advantage of the method for the present invention is that product separation method disclosed herein ensures the use formed in the method for the present invention The solid crossed unexpectedly has low-level organic compound and is therefore substantially green.Therefore, it is as described herein Method is not required any liquid flow to go out processing equipment or need not use solid waste disposal equipment.The method of the present invention is compared to existing Another advantage for having technology is that this method is unrestricted for factory location because its not necessarily must in industrial area into OK.
The another advantage of the present invention is that method disclosed herein carries out under the reaction condition and atmospheric pressure of milder, It is so safer.
Another advantage is that the patent response preparation, that is, R-Cat1＆R-Cat2 or this hair that are developed using inventor Any other like preparation used in bright method makes it possible to recycle acid liquid flow completely.
The another advantage of the method for the present invention is to pass through the pressure of reactive component, temperature, pH, concentration and various reactants institute Its internal thermodynamic condition of definition close to the condition occurred in each comfortable nature, thus make the method for the present invention to be benign and It is environmental-friendly.
The method is carried out at such temperature and pH value so that therefore it, which is saved, energy and causes method economy, and It is more green, because the generation of energy typically results in batch pollution.
Summary of the invention：
By producing precipitation with dilute sulfuric acid acidizing alkali molten mixture and real under the temperature of predetermined condition, time and pH The separation of existing naphthalene sulfonic acids compound, and naphthalene sulfonic acids compound is used as partial alkaline-metal salts by precipitation and is separated and pass through filtering Separation.The obtained filtrate containing soluble naphthalene sulfonic acids compound and/or its salt after recycling processing is used as the naphthalene sulphur The initial action medium of the later separation of acid compound, fill it up with reaction medium, diluting reaction medium.
It can be the separation that naphthalene sulfonic acids is realized in positive separation and reverse separation by two methods.Forward and reverse is separated in detail Thin method description is clearly shown in A＆B respectively.
Brief description of the drawings
Fig. 1 shows the diagram of the complete method of the present invention.
Fig. 2 shows the response procedures of the positive separate section of method（sequence）.
Fig. 3 shows the simplification graphic relation between the separation of the present invention and cyclic program.
Fig. 4 shows the diagram of complete method, wherein producing various streams and product in the method.
Fig. 5 shows the response procedures of the reverse separation single loop of a large amount of recirculation circuits.
Fig. 6 shows the schematic diagram of cyclic program.
Embodiment
We will define some Key Terms first.
The term used in invention description：
In order to help to understand method described herein, some terms are exactly defined.
·Forward direction separation-Forward direction separation can be defined as " to be considered as starting reaction in fresh water or reaction medium and sulfuric acid Medium and then added under predetermined separation condition in the response procedures of melting agglomerate (starting material), to be continuously added to or in batches Add or carried out by any other known Adding Way the addition of melting agglomerate.
·Reversely separation- reversely separate and can be defined as " fresh water or reaction medium and melting agglomerate (starting material) quilt It is considered as the separation response procedures for starting reaction medium and sulfuric acid then being added under predetermined separation condition, to be continuously added to or in batches Add or carried out by any other known Adding Way the addition of sulfuric acid solution.
Reaction medium (RM) is the mother liquor or diluted acid or acid water phase or its combination used in separation method.
Fresh reactant medium (FRM) is the fresh water or fresh diluted acid or fresh acidic water phase or its group used in reaction Close.
The reaction medium factor (RMF) is the ratio of the weight and the weight of melting agglomerate of the FRM or RM used in method.
Mother liquor (ML) is the liquid flow produced after particular step.In the circulation after its first circulation, The various stages of the method for the present invention use mother liquor as reaction medium (RM).
Separation RM is the mixture of the acid pH in the separated specified range of H acid, it is the use of water phase and miscible In phase separation.
Cooling curve (CC) is curve of the temperature to the time.
PH curves are the curves of the amount of the pH sulfuric acid required to separation H acid.
Seeding-it is to obtain crystallization or the separation initiator of required result.
Add salt-be to improve rate of saltouing and exterior addition salt.
Method disclosed in the present invention is followed again using the Intrinsical of all acid streams produced during separation and washing Ring separates the sustainable chemistry method of naphthalene sulfonic acids compound.
The separation of naphthalene sulfonic acids compound can be carried out with two methods, i.e.,：
A：Forward direction separation- positive separate can be defined as " to be considered as starting and reacts in fresh water or reaction medium with sulfuric acid Medium and then under predetermined separation condition add melting agglomerate (starting material) response procedures in ".
From the positive separation naphthalene sulfonic acids compound of melting agglomerate, (it is continuously added to, is added in batches with two kinds of distinct methods Enter) melting agglomerate is added to startup acid solution.
B：The reversely separation of separation-reversely can be defined as " fresh water or reaction medium and melting agglomerate (starting material) quilt It is considered as the separation response procedures for starting reaction medium and sulfuric acid then being added under predetermined separation condition ".
In naphthalene sulfonic acids compound is reversely separated from melting agglomerate, (it is continuously added to, is added in batches with two kinds of distinct methods Enter) sulfuric acid solution is added to startup melting agglomerate solution.
The method of the present invention also uses the sodium salt of the commerical grade in the range of 0% (w/w) to 95% (w/w), depending in 0% (w/ W) to the melting agglomerate to be acidified in the range of 10% (w/w) for saltouing from mother liquor.The purity of the salt of precipitation is 10% (w/w) To the scope of the scope, more precisely 30-60% of 90% (w/w).By preordering method predetermined amount of time, predetermined temperature from Sodium salt is separated out in mother liquor.The salt of the precipitation is recycled back into method in predefined phase and in preordering method.The present invention includes Sodium salt in the range of 0% to 50% (w/w), more preferably in the range of 10-40% (w/w) uses.
This application also discloses the Intrinsical recycling green point using all acidic liquid streams produced under the same terms From the sustainable chemistry method of naphthalene sulfonic acids compound.
The chemical method of the present invention basically comprises processing acid mother liquid and all streams for being produced during any circulation Internal a large amount of recycling.Each circulation also includes two programs-green reaction program and green separation program.
One of new feature of the method for the present invention is the reaction medium on being used in the various stages of method.
Refer to Fig. 1, in first circulation of the method for the present invention, FRM is used as starting (step 1.1) and reaction (step 1.2) reaction medium in step, and for include stir ＆ cooling, stirring ＆ separation, filtering ＆ wash (step 2.1,2.2, 2.3rd, 2.4) the step of.As the present invention key feature, in following cycle, in the various steps of the recycling of first circulation The liquid flow of generation is used as reaction medium.However, these liquid flows are optional as the purposes of reaction medium and FRM can be used as Reaction medium in all circulations.
The stream of the generation of various stages of the present invention is defined on now.As shown in Fig. 1, (steps of the stream A after reactions steps Produced after rapid 2.3) middle filtering.Stream B is produced in step 2.4 after washed product.Produced after being jointly processed by with R-Cat1 convection current A＆B Stream be defined as flow C and be transferred to the 2nd processing.After convection current C carries out the 2nd processing, caused stream is stored in storage In tank and it is defined as flowing D.Treated mother liquor stream D for example starts, reacts used in the various stages, stirs ＆ coolings, stirs Mix ＆ separation, be separated into stream E.
Liquid flow suitable certain amount of FRM or any other or its combination be used as in washing step liquid make-up with Compensation passes through various loss of liquid caused by operation, evaporation etc..
Described below with reference to Fig. 1,2,3 and 4, involved step in two programs of the typical recycling for forming the method for the present invention Rapid details.
The preferred embodiments of the invention and various other embodiments will now be described.
The another embodiment of the present invention of raw material is added in the distinct program wherein described in embodiment A In, all steps in the two embodiments whiles, produces and destiny is identical.
The change in the program of raw material addition is made to understand and optimize naphthalene sulfonic acids compound separation method parameter, to build Sustainability that is vertical and maintaining method, to set the consistent of the unlimited recirculation circuit in the inside of reaction medium and product quality Property.
Program 1.0- green reaction programs：
Green reaction program is carried out with two kinds of distinct methods, such as (A) positive separation (B) reversely separates.Here is the present invention The detailed description of method.Both approaches are only different in step starts (step 1.1) and reaction (step 1.2), remaining is all other Step (1.3,1.4,2.1,2.2,2.3,2.4,3.1＆3.2) in both separation methods be common.
A：- forward direction separation-
As shown in Fig. 2, which includes four steps, that is, starts, reacts, separation separation.These steps are described below In each.
One in the key feature of the program is the reaction medium used in various steps.The anti-of scheduled volume is added as one sees fit Answer medium.Reaction medium is together with caused such as by the specific bar of temperature, pressure, pH, stirring and other such parameter definitions Part causes unique inside recyclability of the method for the present invention.
Total amount (the hereinafter referred to as Q of the reaction medium needed for typical recycling in the programRT) by melting agglomerate Requirement to the conversion of naphthalene sulfonic acids compound determines.QRTBy weight rate (weight rate) R of reaction mediumADetermine, its be The weight W of the reaction medium needed in the single loop of the method for the present inventionRAWith staying in the melting agglomerate converted in single loop The weight W of total amountNRatio.It is for single loop：
(weight rate)RA=WRA/WNFormula 1
QRTIt is such, its weight is equal to the W determined from formula 1RA。
In a preferred embodiment of the invention, (weight rate) RAIt is preferred that in the range of 0.25 to 25, more preferably Scope is 0.5 to 2.5.
Step 1.1- starts：The step is held in the reaction with blender and required annex well known by persons skilled in the art Carried out in device.As shown in Fig. 2, at the beginning of the first circulation of the method for the present invention, the RM of suitable amount is added to reaction and is held Device.
In a preferred embodiment of the invention, FRM is used as reaction medium.For the reaction medium needed for typical recycling Total amount (hereafter refers to QRMT) determined by the solubility of naphthalene sulfonic acids compound.The amount (is referred to by the weight rate of FRM or reaction medium It is shown as (weight rate)RM) determine, it is the weight W of FRM needed for single loop or reaction mediumRMWith staying in single loop The weight W of the total amount of the melting agglomerate of middle conversionNRatio.I.e.-
(weight rate)RM=WRM/WNFormula 2
QRMTIt is such, its weight is equal to the W determined from formula 2RM。
The FRM or the amount of reaction medium used in step 1.1 (is designated as QRM1.1) it is variable.
In preferred embodiments, (weight rate)RMIt is preferred that in the range of 5 to 100, preferred scope for 10 to 75, and QRM1.1The Q used in the cycleRMT0% (w/w) -40% (w/w) in the range of.
The suitable acid of addition suitable amount and suitable form keep at the same time the temperature of reaction mixture in reaction vessel at 0 DEG C extremely In the range of 200 DEG C, preferable scope is 30 DEG C to 100 DEG C.In a preferred embodiment of the invention, using sulfuric acid.At this In the another embodiment of invention, temperature when adding sour is in the range of 10 DEG C to 100 DEG C, more preferably 50 DEG C to 100 DEG C.
Stir the mixture for the scheduled time, when it is when 0 minute small to 5, more preferably 0.5 hour small to 2.5 in the range of. In agitation phases, the pH of reaction mixture is maintained at predeterminated level, in the range of 1 to 9, preferred scope is 1 to 7, optimal Elect 1 to 2 as.
At the end of agitation phases, the melting agglomerate of suitable amount is added.It is with its whole required amount or with arbitrary size Any amount of batch or continuously, or its any combination addition.Within the expected time of arrival, add under predetermined temperature and predetermined pH Add melting agglomerate.Addition melting agglomerate time for 0 minute to 5 it is small when, more preferably 0.5 hour to 2.5 it is small when in the range of.Add Add temperature during melting agglomerate in the range of 0 DEG C to 200 DEG C.Addition melting agglomerate when pH 1 to 9 scope, be preferably 1 To 7 scope, more preferably 1 to 2.
In the following cycle of the method for the present invention, stream E is used as reaction medium, instead of starting the FRM in (step 1.1).
In another embodiment of the present invention, temperature during addition reaction medium is at 10 DEG C to 100 DEG C, more preferably 30 DEG C To in the range of 70 DEG C.
In another embodiment of the present invention, reaction medium and/or acid and melting agglomerate are added with any program.
Step 1.2- reacts：Continuously to be transformed melt is added to reaction vessel with its whole amount or with any amount of batch Melt agglomerate.It is interior when 0 to 5 is small, more preferably when 0.5-1.5 is small to be treated with suitable interval (depending on molecule to be separated) addition The total amount of the melting agglomerate of conversion.
The reaction medium of suitable amount is added to reaction vessel and keeps the pH of temperature and mixture at the same time in each of which Preset range in.Temperature when adding reaction medium 0 DEG C to 200 DEG C scope, more preferably in the range of 50-100 DEG C. Add reaction medium when pH in the range of 1 to 9, preferably 2 to 5 scope.In a preferred embodiment of the invention, FRM is used as the reaction medium in the step 1.2 of the first circulation of the method for the present invention.For following cycle, stream E is used as the step Reaction medium.
The FRM or the amount of reaction medium used in step 1.2 (is designated as QRM1.2) the total amount Q that can use in the cycleRMT 0% (w/w) -40% (w/w) in the range of change.
Suitable acid is alternatively added to reaction vessel to realize the required pH of reaction mixture levels.Addition is adapted to form Acid at the same time keep the temperature of reaction mixture in reaction vessel in the range of 0 DEG C to 200 DEG C.
When the pH of reaction mixture is in the predetermined value in the range of 1 to 9, in the range of preferably 1 to 2, certain In period, the predetermined temperature in the range of 0 DEG C to 200 DEG C is added agglomerate is melted to reaction mixture.With single batch or In batches or the melting agglomerate needed for continuous or these adding methods any combinations addition steps 1.2.
By the reaction mixture in all stages of the step alternatively to 0 to 500RPM the rotating blender of speed Stirring.The step even can successfully carry out under without mixing.
B：- reversely separate-
In the reverse separation of naphthalene sulfonic acids compound, only changed in step No.1.1＆1.2, as shown in Figure 5, instead Answer all other step in program 1.3＆1.4 identical with the step in positive separate.The program includes four steps, that is, opens Dynamic, reaction, separation ＆ separation.
One in the key feature of the program is the reaction medium used in various steps.The anti-of scheduled volume is added as one sees fit Answer medium.Reaction medium is together with caused such as by the specific bar of temperature, pressure, pH, stirring and other such parameter definitions Part causes unique inside recyclability of the method for the present invention.
Total amount (the hereinafter referred to as Q of the reaction medium needed for typical recycling in the programRT) by melting agglomerate Requirement to the conversion of naphthalene sulfonic acids compound determines.QRTBy weight rate (weight rate) R of reaction mediumADetermine, its be The weight W of the reaction medium needed in the single loop of the method for the present inventionRAWith staying in the melting agglomerate converted in single loop The weight W of total amountNRatio.It is for single loop：
(weight rate)RA=WRA/WNFormula 1
QRTIt is such, its weight is equal to the W determined from formula 1RA。
In a preferred embodiment of the invention, (weight rate) RAIt is preferred that in the range of 0.25 to 25, more preferably Scope is 0.5 to 2.5.
Step 1.1- starts：The step is held in the reaction with blender and required annex well known by persons skilled in the art Carried out in device.As shown in Figure 5, at the beginning of the first circulation of the method for the present invention, the RM of suitable amount is added to reaction and is held Device.
In a preferred embodiment of the invention, FRM is used as reaction medium.For the reaction medium needed for typical recycling Total amount (hereafter refers to QRMT) determined by the solubility of naphthalene sulfonic acids compound.The amount (is referred to by the weight rate of FRM or reaction medium It is shown as (weight rate)RM) determine, it is the weight W of FRM needed for single loop or reaction mediumRMWith staying in single loop The weight W of the total amount of the melting agglomerate of middle conversionNRatio.I.e.
(weight rate)RM=WRM/WNFormula 2
QRMTIt is such, its weight is equal to the W determined from formula 2RM。
The FRM or the amount of reaction medium used in step 1.1 (is designated as QRM1.1) it is variable.
In preferred embodiments, (weight rate)RMIt is preferred that in the range of 5 to 100, preferred scope for 10 to 75, and QRM1.1The Q used in the cycleRMT0% (w/w) -40% (w/w) in the range of.
The suitable acid of addition suitable amount and suitable form keep at the same time the temperature of reaction mixture in reaction vessel at 0 DEG C extremely In the range of 200 DEG C, preferable scope is 30 DEG C to 100 DEG C.In a preferred embodiment of the invention, using sulfuric acid.At this In the another embodiment of invention, temperature when adding sour is in the range of 10 DEG C to 100 DEG C, more preferably 50 DEG C to 100 DEG C.
Stir the mixture for the scheduled time, when it is when 0 minute small to 5, more preferably 0.5 hour small to 2.5 in the range of. In agitation phases, the pH of reaction mixture is maintained at predeterminated level, in the range of 1 to 9, preferred scope is 1 to 7, optimal Elect 1 to 2 as.
At the end of agitation phases, the melting agglomerate of suitable amount is added.It is with its whole required amount or with arbitrary size Any amount of batch or continuously, or its any combination addition.Within the expected time of arrival, add under predetermined temperature and predetermined pH Add melting agglomerate.Addition melting agglomerate time for 0 minute to 5 it is small when, more preferably 0.5 hour to 2.5 it is small when in the range of.Add Add temperature during melting agglomerate in the range of 0 DEG C to 200 DEG C.Addition melting agglomerate when pH 1 to 9 scope, be preferably 1 To 7 scope, more preferably 1 to 2.
In the following cycle of the method for the present invention, stream E is used as reaction medium, instead of starting the FRM in (step 1.1).
In another embodiment of the present invention, temperature during addition reaction medium is at 10 DEG C to 100 DEG C, more preferably 30 DEG C To in the range of 70 DEG C.
In another embodiment of the present invention, reaction medium and/or acid and melting agglomerate are added with any program.
Step 1.2- reacts：Melting group to be transformed is added to reaction vessel with its whole amount or with any amount of batch Block.The total of melting agglomerate to be transformed is added in time when 0 to 5 is small with suitable interval (depending on molecule to be separated) Amount.
The reaction medium of suitable amount is added to reaction vessel and keeps the pH of temperature and mixture at the same time in each of which Preset range in.Temperature when adding reaction medium 0 DEG C to 200 DEG C scope, more preferably in the range of 50-100 DEG C. Add reaction medium when pH in the range of 1 to 9, preferably 1 to 2 scope.In a preferred embodiment of the invention, FRM is used as the reaction medium in the step 1.2 of the first circulation of the method for the present invention.For following cycle, stream E is used as the step Reaction medium.
The FRM or the amount of reaction medium used in step 1.2 (is designated as QRM1.2) the total amount Q that can use in the cycleRMT 0% (w/w) -40% (w/w) in the range of change.
Suitable acid is alternatively added to reaction vessel to realize the required pH of reaction mixture levels.Addition is adapted to form Acid at the same time keep the temperature of reaction mixture in reaction vessel in the range of 0 DEG C to 200 DEG C.
When the pH of reaction mixture is in the predetermined value in the range of 1 to 9, in the range of preferably 1 to 2, certain In period, the predetermined temperature in the range of 0 DEG C to 200 DEG C is added agglomerate is melted to reaction mixture.With single batch or In batches or the melting agglomerate needed for continuous or these adding methods any combinations addition steps 1.2.
By the reaction mixture in all stages of the step alternatively to 0 to 500RPM the rotating blender of speed Stirring.The step even can successfully carry out under without mixing.
Forward and reverse separation is different only in step 1.1＆1.2 and in step 1.3 (separation) and step 1.4 (separation) Remaining method of middle progress is identical in both separation, with reference to figure 2＆5.
Step 1.3- is separated：After the addition that melting agglomerate is completed at the end of the step 1.2, alternatively by the suitable of suitable amount The reaction medium of conjunction is added to reaction vessel.Add uniformity of the decision of reaction medium depending on solid.Used in step 1.3 The amount of reaction medium (be designated as QRM1.3) the total amount Q that can use in the cycleRMT0% (w/w) -40% (w/w) scope Interior change.
In a preferred embodiment of the invention, the reaction medium in first circulations of the FRM as the program, and for The following cycle of the method for the present invention is subjected to, FRM is replaced by stream E.
By the reaction mixture in all stages of the step alternatively to 0 to 500RPM the rotating blender of speed Stirring.The step even can successfully carry out under without mixing.
In the complete SO for removing and being produced during reaction is separated2In the preferred embodiment of (sulfur dioxide) gas, Then it will react and be heated to the pre- constant temperature that scope is 0 to 200 DEG C, preferably 0 to 100 DEG C, more preferably 70 to 100 DEG C under agitation Degree, duration ranges for 0 hour to 10 when small, preferably 30 minutes to 8 when small, more preferably 30 minutes to 5 scheduled times when small.
Step 1.4- is separated：In a preferred embodiment of the invention, FRM is used as the reaction in the first circulation of the program Medium.Add uniformity and uniform Crystallization of the decision of reaction medium depending on production concentration.Used in step 1.4 The amount of reaction medium (is designated as QRM1.4) the total amount Q that can use in the cycleRMT0% (w/w) -40% (w/w) in the range of Change.The mixture being consequently formed is referred to as separating mixture（seperation mixture）.
In a preferred embodiment of the invention, separation temperature is in the range of 0 to 200 DEG C, and separate pH 1 to 12nd, in the range of preferably l to 2.
In preferred embodiments, pH and temperature conditionss are made to be maintained at the pH and temperature of predeterminated level, duration ranges 0 Hour to 24 when small, preferred scope be 30 minutes to 5 times when small.
Following cycle for undergoing the method for the present invention, FRM are replaced by stream E.
In all above steps of step 1.1 to 1.4, alternatively sulfuric acid is used as preferable suitable acid.
In another embodiment of the present invention, FRM is used as the reaction medium in the first circulation of the program.Step 1.4 Amount (the QRM of the middle FRM used or reaction medium1.4) Q that can use in the cycleRMT0% (w/w) -40% (w/w) scope Interior change.
By the reaction mixture in all stages of the step alternatively to 0 to 500RPM the rotating blender of speed Stirring.The step even can successfully carry out under without mixing.
The green reaction program of single loop is completed at the end of step 1.4.
In another embodiment of the present invention, separation temperature is preferably 0 DEG C to 100 DEG C.
Program 2.0- green separation programs：
As shown in Fig. 3, which includes four steps, i.e. stirring cooling, stirring separation, filtering and washing step. Each in these steps is described in detail.
Step 2.1- stirring ＆ coolings：As shown in Fig. 3, by the reaction medium (quilt of suitable amount at suitable temperature and pH Referred to as first sedimentation RM) it is optionally added into and exists as the mixture obtained in reaction vessel at the end of step 1.4, the temperature 0 to 200 DEG C of the scope and pH is in the range of 1 to 11, preferably 2 to 5 and more preferably 1 to 2.Allow to be consequently formed mixed Compound stirs, by making it keep certain mixing time in the first whipping temp.
In a preferred embodiment of the invention, scopes of the first stirring pH 1 to 11, preferably 2 to 5, more preferably 1 to 2 It is interior；First whipping temp at 0 DEG C to 200 DEG C, preferably in the range of 0 DEG C to 100 DEG C；And in 0 DEG C to 100 DEG C of temperature model Under enclosing, the first mixing time for 1 minute to 10 it is small when, preferably 30 minutes to 3 it is small when.
The liquid level formed due to stirring means the first cooling temperature, first cooling pH and under the first cooling time it is cold But.
In a preferred embodiment of the invention, FRM is used as the reaction medium in first circulation, and for being sent out through almanac The following cycle of bright method, FRM are replaced by stream E.
The FRM or the amount of reaction medium used in step 2.1 (is designated as QRM2.1) Q that can use in the cycleRMT0% (w/w) change in the range of -60% (w/w).
Step 2.2- is stirred and separation：At the end of the step 2.1 of first circulation, in predetermined first whipping temp and make a reservation for (it is referred to as stirring to the reaction medium for stirring ＆ cooling agglomerate addition scheduled volumes under first stirring pH, in predetermined first mixing time Mix ＆ separation RM).Stir mixture.By keeping mixture, predetermined first stirring continues temperature, predetermined first stirring continues pH Continue to stir up to predetermined first stirring perdurabgility.
In a preferred embodiment of the invention, FRM in first circulation with mixing and separate RM, and for experience The following cycle of the method for the present invention, FRM are replaced by stream C；The numerical value of whipping temp at 0 DEG C to 200 DEG C, preferably at 0 DEG C to 100 DEG C In the range of；The numerical value of pH is separated 1 to 11, preferably in the range of 2 to 5, more preferably 1 to 2；Time and the number of disengaging time Value when 5 minutes small to 5, when preferably 30 minutes small to 3 in the range of.
The FRM or the amount of reaction medium used in step 2.2 (is designated as QRM2.2) Q that can use in the cycleRMT0% (w/w) change in the range of -40% (w/w).
Step 2.3- is filtered：
Then under predetermined filtration temperature, predetermined filtering pH, the separation group that is formed at the end of the step 2.2 of first circulation Block is filtered by solid-liquid separating method well known by persons skilled in the art；Persistently predetermined filtration time.Will be at the end of step 2.3 The liquid flow of acquisition is added to mother liquor storage tank as stream A.
In a preferred embodiment of the invention, agglomerate is separated in 0 DEG C to 200 DEG C, preferably 40 DEG C to 100 DEG C of filtering temperature Spend under the numerical value of scope and filter；Filtration time for 5 minutes to 5 it is small when；It is preferred that 30 minutes to 3 it is small when in the range of.
Step 2.4- is washed and filtering：The total agglomerate obtained under predetermined separation temperature and predetermined separation pH from step 2.3 Then wash and filter by method known to those skilled in the art, the FRM of wherein suitable amount is defined as flowing B.
It is initial in Arbitrary cyclic, liquid and washings (are flowed into A＆B) together and are stored in the storage tank containing liquid, then It is transferred to recycling processing container and is used for R-Cat1 processing, is used subsequently to R-Cat2 processing.
In preferred embodiments, separation temperature be 0 DEG C to 200 DEG C, be preferably 40 DEG C to 100 DEG C, and pH for 1 to 11, it is preferably 2 to 5.
The key of the present invention is advantageous feature is that make a part of storage of liquid of suitable amount (part is defined as flowing E) It is recycled in the various steps (step 1.1 to 1.3 and 2.2) of the ensuing circulation of the method for the present invention.
The amount of the FRM used in step 2.2 (is designated as QRM2.2) Q that can use in the cycleRMT0% (w/w) -40% (w/w) change in the range of.
The circulation that the typical recycling of the method for the present invention is made of green reaction program and green separation program, is to this Only.The key feature of the present invention is that all steps of typical recycling are carried out in atmospheric pressure.
As the crucial favourable feature of the present invention, reaction medium uses green reaction program and green separation program two Person, the various streams that mother liquor is derived from circulation after the first cycle and is produced during the method for the present invention.In other words, The reaction that the FRM used in the various stages (step 1.1 to 1.4 and 2.1 to 2.4) of one circulation is adapted in all following cycles Medium substitutes.
In step 2.4, FRM is in loss of all circulations for supplementing previous loops in the method for the present invention.
Present inventor have found that the purity for the product naphthalene sulfonic acids compound being thusly-formed after any cyclic drying Change in the range of 75% to 100%, preferably 78% to 80%.
Storage mother liquor and the aqueous cleaning thing obtained during kind described above step are used in another circulation Processing, the quantity of recycling usually in the range of 5 to 100 and more than.
Carried out separating naphthalene sulfonic acids chemical combination from melting agglomerate with the process described above surprisingly, inventor has found Thing can produce inorganic byproduct in any circulation, the scope of the ratio of the melting agglomerate to be transformed of its weight and procedure above For 0.25 to 25, it is crystallization and is substantially inviscid.The color of these accessory substances is from white to off-white color to light yellow Change, in particular off-white color.The pH of inorganic byproduct is in the range of 4.0 to 6.0.The moisture of inorganic byproduct 5% to In the range of 50%, particular range is 10% to 30%.
To the recycling processing of naphthalene sulfonic acids compound stock solutions and washings
Collect the recycling that disease mixing both mother liquor and washings are used for source processing.Then, according to being herein discussed below The mother liquor that method is merged with the first inorganic agent (R-Cat1) and second processing agent (R-Cat2) together with sodium sulphate processing.For this hair Bright single loop, with reference to the processing cycle of figure 6.
The recycling processing of step No.3.1- R-Cat1
Filtrate stream A＆ scrub streams B in step 2.3＆2.4 merges respectively, and adds to R-Cat process containers, then pre- Determine to carry out solid-liquid separating method well known by persons skilled in the art under filtration temperature, predetermined filtering pH, predetermined filtration time, such as scheme Shown in 6.
In a preferred embodiment of the invention, the mother liquor of merging is heated to scope as 0 DEG C to 200 in process container DEG C, preferably 40 DEG C to 100 DEG C of predetermined temperature；When its pre-determined process-time is when 5 minutes small to 5, preferably 30 minutes small to 3 In the range of.After the desired temperature has been reached, add completely or in batches at predetermined addition temperature and stirring, in predetermined add in the time Enter the R-Cat1 and salt of scheduled volume.
(Q is designated as the R-Catl of the recycling processing in step 3.1 and the amount of saltR-Cat3.1) can make in the cycle QRMT0% (w/v) -40% (w/v) in the range of, change in the range of more preferably 0% (w/v) -20% (w/v).
In a preferred embodiment of the invention, fresh salt only uses in fresh circulation and ensuing circulation, from step The salt recycled after rapid 3.2 i.e. R-Cat2 processing recycles in both processing step 3.1＆3.2.
In the case where preferred scope is 1 to 7, more preferably 2 to 5 predetermined pH, whole treated agglomerate is protected under agitation Hold preferred scope be 0 DEG C to 200 DEG C, preferably 40 DEG C to 100 DEG C of predetermined temperature；Duration ranges for 5 minutes to 5 it is small when, it is excellent 30 minutes are selected to 3 pre-determined process-times when small.
In a preferred embodiment of the invention, in preferably 0 DEG C to 200 DEG C, preferably 40 DEG C to 100 DEG C of temperature range Under；The Baume of treated slurry adjusted in the case where preferred scope is 1 to 7, more preferably 2 to 5 predetermined pH preferred to scope For 0 to 50, more preferably 10 to 35 predetermined Baume.
In a preferred embodiment of the invention, preferred scope be 1 to 7, more preferably 2 to 5 predetermined filtering pH under, Total mother is filtered by known filter method under the predetermined filtration temperature that preferred scope is 0 DEG C to 200 DEG C, preferably 40 DEG C to 100 DEG C Liquid；Duration ranges for 5 minutes to 5 when small, preferably 30 minutes to 3 predetermined filtration times when small.Will be with the separated use of residue The R-Cat1 crossed is put aside for safe disposal.
The filtrate mother liquor stream obtained after R-Cat1 processing is defined as flowing C, is then transferred to another process container and is used for R- Cat2 processing.
The recycling processing of step No.3.2- R-Cat2
Under predetermined temperature, predetermined pH, the filtrate mother liquor stream C received from the first R-Cat processing steps 3.1 is added to R- Cat2 process containers, as shown in Fig. 6.
In a preferred embodiment of the invention, will flow C to be cooled to scope is 0 DEG C to 50 DEG C, preferably 10 DEG C to 40 DEG C Predetermined temperature；Duration ranges for 5 minutes to 5 when small, preferably 30 minutes to 3 predetermined cooling times when small.Reaching required temperature After degree, it is predetermined add under temperature and stirring, in the predetermined R-Cat2 for adding in the time completely or being added portionwise scheduled volume and Salt.
The R-Cat2 and the amount of salt used in step 3.2 (is designated as CR-Cat3.2) Q that can use in the cycleRMT0% (w/w) change in the range of -20% (w/w).
In a preferred embodiment of the invention, fresh salt only uses in fresh circulation and ensuing circulation, slave phase It is that the salt recycled in the step 3.2 of fresh circulation and ensuing circulation recycles in processing step 3.2 with step.
In the case where preferred scope is 1 to 7, more preferably 4 to 6 predetermined pH, whole treated agglomerate is maintained at preferred Scope is 0 DEG C to 50 DEG C, preferably 10 DEG C to 40 DEG C of predetermined temperature；Duration ranges for 5 minutes to 5 it is small when, preferably 30 minutes to 3 The pre-determined process-time of hour.
In a preferred embodiment of the invention, in preferably 0 DEG C to 50 DEG C, preferably 10 DEG C to 40 DEG C of temperature range Under；The Baume of treated slurry adjusted in the case where preferred scope is 1 to 7, more preferably 4 to 6 predetermined pH preferred to scope For 0 to 50, more preferably 10 to 35 predetermined Baume.
In a preferred embodiment of the invention, preferred scope be 1 to 7, more preferably 4 to 6 predetermined filtering pH under, Place is filtered through by known filter method under the predetermined filtration temperature that preferred scope is 0 DEG C to 50 DEG C, preferably 10 DEG C to 40 DEG C The mother liquor of reason；Duration ranges for 5 minutes to 5 when small, preferably 30 minutes to 3 predetermined filtration times when small.Will be with used R- The salt that Cat2 is recycled together is separated by known filter method and stores the recycling processing for subsequent cycle.
Filtrate mother liquor stream after R-Cat2 processing is defined as flowing D, is then transferred to mother liquor storage tank, then it is next It is recirculated back in circulation as stream E.
It should be noted that in method as described above, by melting agglomerate and/or acid with its whole amount or with arbitrary size Batch is added to step 1.2 at any interval.
It is further noted that in method as discussed above, first and second inorganic agent is selected from the list comprising alkali metal Only hydroxide, carbonate or bicarbonate or the group of combinations thereof；The preferred sodium hydroxide of the hydroxide, hydrogen-oxygen Change potassium, calcium hydroxide, lithium hydroxide；Carbonate preferred sodium carbonate, potassium carbonate, calcium carbonate or the lithium carbonate；The bicarbonate The preferred sodium of salt, saleratus, lithium bicarbonate.
It shall yet further be noted that sulfonic acid product of the method as discussed above suitable for separation similar kind, including 1,8- dihydroxy naphthlene- 4- sulfonic acid, 1- amino-8-naphthol -5,7- disulfonic acid, 1- amino-8-naphthol -2,4- disulfonic acid (chicago acid), 2- amino -8- Naphthols -3,6- disulfonic acid (γ disulfonic acid), 2- amino -5- naphthols -7- sulfonic acid (J- acid), beta naphthal -6- sulfonic acid (Xue Fo Shi acid), 2- amino -5- naphthols -1,7- disulfonic acid (J- disulfonic acid), 2- phenyl amino -5- naphthols -7- sulfonic acid (phenyl J- acid), 1- naphthyls Amine -8- sulfonic acid (Schollkopf acid), 2- amino naphthalenes -4,8- disulfonic acid (C- acid), 1 amino 8 naphthol 4,6 disulfonic acid (K- acid), 1, 8- dihydroxy naphthlene -3,6- disulfonic acid (chromotropic acid), 1- naphthylamine -3,6,8- trisulfonic acids (Koch's acid), 1- naphthylamine -6- sulfonic acid (Ke Liefu acid), 1- naphthylamine -7- sulfonic acid (Ke Liefu acid), R- acid, G- acid, amino G- acid, 2- amido-8-naphthol-6-sulfonic acids (γ acid), 2- amino -5- naphthols -7- sulfonic acid (different γ acid), M- acid, 1- amino -8- naphthols -5- sulfonic acid, 1- naphthylamines -4,7- Disulfonic acid and functional group with such as amino, nitro, halogen, hydroxyl, sulfonic group, carboxyl, benzyl, phenyl, ketone, aldehyde own Similar naphthalene sulfonic acids and betanaphthol derivative.
Following embodiments illustrate some advantages being mentioned above.
Many dyes and dyestuffs (dyestuff), fine chemicals have as one of construction unit naphthalene sulfonate simultaneously And currently used for preparing various dyes and dyestuffs and pharmaceutical intermediate.
In conventional H-acid preparation method, the amount for the caustic soda of 1 mole of Koch's acid trisodium salt of alkali fusion is rubbed for 8.6 You, it corresponds to 4.3 times of theoretical aequum (2 moles).Therefore, for 1 mole of Koch's acid, obtained from melting agglomerate The amount of the sour required sulfuric acid of H in the form of mono-sodium salt reaches 5.8 moles.
In order to overcome the disadvantages mentioned above of current methods, inventor's friendly, safe and nontoxic method of development environment, such as Shown in the following examples.
Embodiment 1：
In this embodiment, with the positive separation response procedures of following recycling description H- acid.
Fresh circulation：In suitable heating/cooling system is arranged in equipped with stirring rod, condenser, thermometer and 181ml water and 50g sulfuric acid are added in 0.5 liter of 4 neck round-bottom flask of added holes, is heated to 60 DEG C.With continuous stirring in 90 DEG C, 125g melting agglomerates are slowly added in diluted acid in 20 minutes.Reactive material is further heated to 95 DEG C to 100 DEG C to be used for SO2 gases are escaped and confirmed.The completion of SO2 effusions is checked by Congo red test.By reactive material be cooled to 70 DEG C and Filtered after the Baume of agglomerate is adjusted to 25 ° of Be.With the wet cake of 125ml water washings H- acid.By H- acid 110 DEG C it is dry with Dry off-white colors of the 17g with 80% nitration value (NV) is sour to pink H-.Collect total filtrate i.e. reaction medium and washings and Recycled after treatment in subsequent batches.
First recycling (R1)：It is in identical assembling as described above, 61ml fresh waters, 120ml is treated The mother liquor and 48g sulfuric acid produced in fresh circulation is heated to 60 DEG C.With continuous stirring in 90 DEG C, in 20 minutes by 125g Melting agglomerate is slowly added in diluted acid.Reactive material is further heated to 95 DEG C -100 DEG C and is used for the effusion of SO2 gases and confirmation. The completion of SO2 effusions is checked by Congo red test.By reactive material be cooled to 70 DEG C and by the Baume of agglomerate adjust to Filtered after 28 ° of Be.With the wet cake of 125ml water washings H- acid.H- acid is had 79.40% in 110 DEG C of dryings to dry 18.0g The off-white color acid of nitration value (NV) is sour to pink H-.Collect total filtrate i.e. reaction medium and washings and after treatment rear Recycled in continuous batch.
5th recycling (R5)：It is in identical assembling as described above, 33ml fresh waters, 148ml is treated The washing mother liquor and 49g sulfuric acid that mother liquor and 76ml are produced in the 4th recycling are heated to 60 DEG C.With continuous stirring in 90 DEG C, 125g melting agglomerates are slowly added in diluted acid in 20 minutes.Reactive material is further heated to 95 DEG C -100 DEG C to be used for SO2 gases are escaped and confirmed.The completion of SO2 effusions is checked by Congo red test.By reactive material be cooled to 70 DEG C and Filtered after the Baume of agglomerate is adjusted to 28 ° of Be.With the wet cake of 125ml water washings H- acid.By H- acid 110 DEG C it is dry with Dry 17.5g has the deep pink H- acid of 76.63% nitration value (NV).Collect total filtrate i.e. reaction medium and washings and Recycled after processing in subsequent batches.
Tenth recycling (R10)：It is in identical assembling as described above, 26ml fresh waters, 155ml is treated The mother liquor and 48g sulfuric acid produced in the 9th recycling is heated to 60 DEG C.With continuous stirring will in 90 DEG C, in 20 minutes 125g melting agglomerates are slowly added in diluted acid.By reactive material be further heated to 95 DEG C -100 DEG C be used for SO2 gases effusion and Confirm.The completion of SO2 effusions is checked by Congo red test.Reactive material is cooled to 70 DEG C and by the Baume of agglomerate Filtered after adjusting to 28 ° of Be.With the wet cake of 125ml water washings H- acid.H- acid is had in 110 DEG C of dryings to dry 22g The light brown H- acid of 76.3% nitration value (NV).Collect total filtrate i.e. reaction medium and washings and subsequently criticizing after treatment Secondary middle recycling.
15th recycling (R15)：In identical assembling as described above, by 32ml fresh waters, 149ml by processing The mother liquor that produces and 48g sulfuric acid in the 14th recycling be heated to 60 DEG C.With continuous stirring in 90 DEG C, in 20 minutes 125g melting agglomerates are slowly added in diluted acid.Reactive material is further heated to 95 DEG C -100 DEG C and is used for the effusion of SO2 gases And confirmation.The completion of SO2 effusions is checked by Congo red test.Reactive material is cooled to 70 DEG C and by agglomerate Baume is filtered after adjusting to 27 ° of Be.With the wet cake of 125ml water washings H- acid.H- acid is dried to dry 19.5g at 110 DEG C L. browns H- acid with 74.11% nitration value (NV).Collect total filtrate i.e. reaction medium and washings and after treatment rear Recycled in continuous batch.
20th recycling (R20)：In identical assembling as described above, by 74ml fresh waters, 107ml by processing The mother liquor, 74ml water and the 48g sulfuric acid that produce in the 19th recycling be heated to 60 DEG C.With continuous stirring in 90 DEG C, 125g melting agglomerates are slowly added in diluted acid in 20 minutes.Reactive material is further heated to 95 DEG C -100 DEG C and is used for SO2 Gas is escaped and confirmed.The completion of SO2 effusions is checked by Congo red test.Reactive material is cooled to 70 DEG C and will rolled into a ball The Baume of block is filtered after adjusting to 27 ° of Be.With the wet cake of 125ml water washings H- acid.H- acid is dry with drying at 110 DEG C 20.5g has the light brown H- acid of 72.64% nitration value (NV).Collect total filtrate i.e. reaction medium and washings and handling Recycled afterwards in subsequent batches.
Following table (table 01) shows the economical of the amount of the fresh water used in present invention reaction,Forward direction separation (melting agglomerate Be continuously added to)
The mother liquor produced in each circulation of positive separable programming is handled with R-Cat1＆ sodium sulphate；1st processing it is thin Section refers in table 2 below.
Following table 02 shows that impurity exists when carrying out source processing with R-Cat1＆ sodium sulphate during the positive separated present invention reacts Precipitation in 1st recycling.
Then the mother liquor produced after 1st processing is handled with R-Cat2＆ sodium sulphate, then in other circulations of the present invention Middle recycling.Its details refers in table 3.
Precipitation in the 2nd recycling of following table 03 is shown when carrying out source processing with R-Cat2 impurity and positive separated The amount of fresh water used in present invention reaction it is economical.
Embodiment 2：
In this embodiment, with the reverse separation response procedures of following recycling description H- acid.
Fresh circulation：It is respectively 543ml by the moisture of 1086g altogether into two equal portions.200.0g98% sulfuric acid portion 543ml Water dilution, 640ml volumes are made.500.0g melting remaining that part of water of agglomerate is diluted, 840ml volumes are made.
In suitable heating/cooling system is arranged in equipped with stirring rod, condenser, thermometer and added holes Diluted melting agglomerate is added in 2.0 liter of 4 neck round-bottom flask, is heated to 90 DEG C.Then with 10 grades in batches (respectively containing 64ml) Diluted acid slurry is added, each batch is added 5 minutes.Reactive material is further heated to 95 DEG C to 100 DEG C and is used for SO2 gases ease Go out and confirm.The completion of SO2 effusions is checked by Congo red test.Reactive material is cooled to 70 DEG C and by into one Step evaporation agglomerate filters after the Baume of agglomerate is adjusted to 30 ° of Be.With the wet cake of 500ml water washings H- acid.H- acid is existed 110 DEG C of dryings are sour to the H- of pink to dry off-white color acid of the 86g with 77.03% nitration value (NV).It is i.e. anti-to collect total filtrate Answer medium and washings and recycled after treatment in subsequent batches.
First recycling (R1)：699.6g water is filled it up with to the treated mother liquors produced in fresh circulation of 386.4g, 1086g gross masses are made.The volume of obtained 1045ml is divided into two equal batches, is respectively 522.5ml.By 194.77g98% sulphur The ML dilutions of acid portion 522.5ml, are made 610ml volumes.500.0g meltings remaining that part of ML of agglomerate is diluted, is made 830ml volumes.Diluted melting agglomerate is added in identical assembling as described above, is heated to 90 DEG C.Then with 10 etc. Diluted acid slurry is added (respectively containing 61ml) in batches, each batch is added 5 minutes.Reactive material is further heated to 95 DEG C extremely 100 DEG C are used for SO2 gases and escape and confirm.The completion of SO2 effusions is checked by Congo red test.Reactive material is cooled to 70 DEG C and filtered after the Baume of agglomerate is adjusted to 30 ° of Be by further evaporating agglomerate.With 500ml water washings H- acid Wet cake.H- acid is dry sour to pink H- to dry off-white colors of the 88g with 76.36% nitration value (NV) at 110 DEG C.Receive Lump filtrate, that is, reaction medium and washings and recycled after treatment in subsequent batches.
5th recycling (R5)：596.7g is filled it up with to the treated mother liquors produced in the 3rd recycling of 489.3g Water, is made 1086g gross masses.The volume of obtained 1000ml is divided into two equal batches, is respectively 500ml.By 189.92g98% The ML dilutions of sulfuric acid portion 500ml, are made 600ml volumes.500.0g meltings remaining that part of ML of agglomerate is diluted, is made 850ml volumes.
Diluted melting agglomerate is added in identical assembling as described above, is heated to 90 DEG C.Diluted acid slurry then with 10 grades add diluted acid slurry (respectively containing 60ml) in batches, and each batch is added 5 minutes.Reactive material is further heated to 95 DEG C to 100 DEG C be used for SO2 gases escape and confirm.The completion of SO2 effusions is checked by Congo red test.By reactive material into one Step is heated to 95 DEG C to 100 DEG C and is used for the effusion of SO2 gases and confirms.The completion of SO2 effusions is checked by Congo red test.Will be anti- Answer material to be cooled to 70 DEG C and filtered after the Baume of agglomerate is adjusted to 30 ° of Be.With the wet filter of 500ml water washings H- acid Cake.H- acid is dry sour to pink H- to dry off-white colors of the 94g with 74.70% nitration value (NV) at 110 DEG C.Collect total Filtrate, that is, reaction medium and washings and recycled after treatment in subsequent batches.
Following table 04 shows the economical of the amount of the fresh water used in reversely separated present invention reaction.
The mother liquor produced in each circulation of reverse separable programming is handled with R-Cat1＆ sodium sulphate；1st processing it is thin Section refers in table 5 below.
Following table 05 shows that impurity exists when carrying out source processing with R-Cat1＆ sodium sulphate during the reversely separated present invention reacts Precipitation in 1st recycling.
Then the mother liquor produced after 1st processing is handled with R-Cat2＆ sodium sulphate, then in other circulations of the present invention Middle recycling.Its details refers in table 6.
Precipitation in the 2nd recycling of following table 06 is shown when carrying out source processing with R-Cat2 impurity and reversely separated The amount of fresh water used in present invention reaction it is economical.
According to the above discussion it is clear that the present invention includes following clause：
1. the chemical method of naphthalene sulfonic acids is separated in a kind of agglomerate from melting, wherein containing the naphthalene sulphur in the melting agglomerate The salt of acid, it is characterised in that the method is to include the sustainable method of following procedure：
Response procedures, wherein the melting agglomerate is reacted with acid,
Separable programming is followed by, wherein the separation of the reaction product is completed,
Recycling processing program is followed by, wherein handling impure mother liquor in the response procedures and the separation journey Further recycled in sequence, and further, wherein the response procedures and the separable programming circulate in stable state shape with multiple Carried out in the closed circuit of state, wherein addition fresh water loses only for supplementing the systematicness for example caused by evaporation, its Described in closed circuit the recycling of Intrinsical and own type can be carried out under the source level of caused all mother liquors, it is described The mother liquor used in method is any of for reaction medium, spe medium or washing medium, or its any combination, such as schemes Shown in 4.
2. the method as described in clause 1, wherein the quantity that the melting agglomerate is the multiple circulation is preferably greater than 3, more Preferably greater than 15,30 are even more preferably greater than.
3. the method as described in claim 1, it is characterised in that the melting group naphthalene sulfonic acids in the block is H- acid.
4. the method as described in clause 1 to 3, wherein for any single loop, the response procedures to prepare respectively Diluted melting agglomerate and diluted acid, the stage progress for mixing diluted melting agglomerate and diluted acid, it is characterised in that institute State the stage carries out in following phases：
First startup reaction medium is added to the first container with blender and added thereto by stage 1.1a- Acid, preferably sulfuric acid, while keep the sour temperature to be at most 200 DEG C and keep pH between 1 to 7, wherein first starts instead The amount for answering medium is at most 40% (w/w) of the total amount of the reaction medium used in whole circulation, and is used in entirely circulating The first startup reaction medium total amount be needed in existing circulation 5 to 100 times of separated total melting agglomerate, preferably 10 to 75 Times,
Stage 1.1b- adds the second startup reaction medium to the second reaction vessel with blender and thereto Add a certain amount of melting agglomerate so that mixture in second reaction vessel pH between 8 to 14, preferably 9 to 13 it Between, and the at most 40% (w/ for the total amount that the amount of the wherein second startup reaction medium is the reaction medium used in whole circulation W), the total amount of the second startup reaction medium used in and entirely circulating is that separated total melting agglomerate is needed in existing circulation 5 to 100 times, preferably 10 to 75 times,
Stage 1.1c- stir the first and second reaction vessels mixture up at most 5 it is small when, it is preferably 30 minutes to 2.5 small When duration, while it is at most 200 DEG C to keep the temperature of respective mixture,
Step 1.2- adds the diluted melting agglomerate of second reaction vessel to institute in the time when at most 5 is small The diluted acid of the first reaction vessel is stated, and is optionally added into the first reduction reaction medium and keeps the temperature of the mixture to be And pH is kept between 1 to 9, it is characterised in that followed for all since the second circulation of the method by most 200 DEG C Ring, described first and second start reaction medium all takes out from mother liquor storage tank, is stored in the mother liquor storage tank from recycling The mother liquor of processing routine recycling, and
The reaction mixture obtained at the end of step 1.2 is taken out to complete the response procedures, is subsequently isolated by described Obtained product is reacted, then the recycling processing of mother liquor caused by further progress.
5. the method as described in clause 1 to 3, wherein for any single loop, the response procedures to prepare respectively Diluted melting agglomerate and diluted acid, the stage progress for mixing diluted melting agglomerate and diluted acid, it is characterised in that institute State the stage carries out in the following steps：
First startup reaction medium is added to the first reaction vessel with blender and added thereto by stage 1.1a- Enter it is a certain amount of melting agglomerate so that in second reaction vessel pH of mixture between 8 to 14, preferably 9 to 13, and And wherein first startup reaction medium amount be the reaction medium used in whole circulation total amount at most 40% (w/w), and And the total amount of the second startup reaction medium used in whole circulation be needed in existing circulation the 5 of separated total melting agglomerate to 100 times, preferably 10 to 75 times,
Second startup reaction medium is added to the second container with blender and added thereto by stage 1.1b- Acid, preferably sulfuric acid, while keep the sour temperature to be at most 200 DEG C and keep pH between 1 to 7, wherein second starts instead The amount for answering medium is at most 40% (w/w) of the total amount of the reaction medium used in whole circulation, and is used in entirely circulating The first startup reaction medium total amount be needed in existing circulation 5 to 100 times of separated total melting agglomerate, preferably 10 to 75 Times,
Stage 1.1c- stir the first and second reaction vessels mixture up at most 5 it is small when, it is preferably 30 minutes to 2.5 small When duration, while it is at most 200 DEG C to keep the temperature of respective mixture,
Step 1.2- adds the diluted acid of second reaction vessel to the described first reaction in the time when at most 5 is small The melting agglomerate of container, and be optionally added into the first reduction reaction medium and keep the temperature of the mixture to be at most And pH is kept between 1 to 9, it is characterised in that for all circulations since the second circulation of the method, institute by 200 DEG C State the first and second startup reaction mediums all to take out from mother liquor storage tank, stored in the mother liquor storage tank from recycling processing The mother liquor of program recycling, and
The reaction mixture obtained at the end of step 1.2 is taken out to complete the response procedures, is subsequently isolated by described Obtained product is reacted, then the recycling processing of mother liquor caused by further progress.
6. the method as described in clause 4 to 5, wherein any circulation for the method, takes out at the end of step 1.2 The reaction mixture of acquisition is to complete response procedures as described below：
Step 1.3- alternatively adds the second reaction medium, the amount of second reaction medium to first reaction vessel At most 40% (w/w) for the total amount of reaction medium used in whole circulation, at the same it is alternatively mixed with most 500RPM stirrings Compound and be at most 200 DEG C, preferably up to 100 DEG C by keeping the temperature of reaction mixture, and carry out the stirring extremely It is more 10 it is small when, preferably 30 minutes to 8 when small to remove the sulfur dioxide produced during react, and Baume values completely For 10 to 50,
Step 1.4- in first circulation by the 3rd reaction medium with fresh reactant form of medium with no more than entirely existing The amount of 40% (w/w) of the total amount of the reaction medium used in row circulation is added to first reaction vessel, so as to form separation Mixture, while keep the temperature of the separating mixture to be at most 200 DEG C, preferably up to 100 DEG C and keep pH 1 to 7 Between, at the same stir the separating mixture at most 24 it is small when, preferably up to 5 it is small when, it is characterised in that for it is all next The 3rd reaction medium of circulation be selected from the mother liquor storage tank.
7. the method as described in clause 1 to 6, wherein any circulation for the method, the separable programming include Following steps：
Step 2.1- is by the first stirring reaction medium with fresh reactant form of medium with no more than in the existing circulation The amount of 60% (w/w) of the total amount of the reaction medium used is added to first reaction vessel, while mixture is cooled to 70 DEG C temperature, and keep pH between 1 to 7, at the same continuously stir the mixture at most 10 it is small when, it is characterised in that for All ensuing circulations, the first stirring reaction medium are derived from the mother liquor storage tank,
Step 2.2- is made instead by alternatively adding the 4th reaction medium of fresh reactant form of medium in first circulation Between answering the temperature of mixture to be maintained at 70 DEG C and pH being maintained at 1 to 7, at the same stir reaction mixture at most 24 it is small when, it is excellent When choosing at most 5 is small, it is characterised in that for all ensuing circulations, the first stirring reaction medium is derived from the mother liquor storage Hide tank,
The separation agglomerate that step 2.3- is formed at the end of being filtered at about 70 DEG C of temperature and 1 to 7 pH in step 2.2, And produced as the result of the filter process the first filtrate stream A, the filter process be carried out within 5 it is small when time,
At the end of step 2.4- is washed in step 2.3 using fresh reactant medium at about 70 DEG C of temperature and 1 to 7 pH All agglomerates obtained, and produce scrub stream B.
8. the method as described in clause 1 to 7, wherein any circulation for the method, by the first filtrate stream A and is washed Wash stream B to merge, and carry out following catalytic treatment：
Step 3.1- will merge stream A and B in the first process container and be heated at most 100 DEG C, preferably 70 DEG C of temperature, hold It is continuous at most 5 it is small when, the first inorganic agent and the first sulfate are then added, wherein the amount of first inorganic agent is in existing circulation At most 40% (w/v) of the total amount of the middle reaction medium used, so that the Baume values of mixture are maintained at most 50, while makes The temperature of the mixture is set to be maintained at most 50 DEG C and keep pH between 1 to 7 after addition reagent, wherein producing mother liquor stream C The waste material that second filtrate of form and needs are disposed, it is characterised in that only use fresh sulfuric acid in the first circulation of the step Salt, and the salt produced from step 3.2 is used in ensuing circulation,
Step 3.2- adds second filtrate stream C to second processing container, wherein second filtrate is cooled to At most 25 DEG C of temperature, be continued up to 5 it is small when, then add second processing agent and sulfate, wherein the second processing agent and The amount of sulfate is at most 20% (w/v) of the total amount of the reaction medium used in existing circulation, while keeps mixture Baume values are at most 50, and keep pH between 1 to 7, preferably 4 to 6, it is characterised in that in the first circulation of the method The salt recycled at the end of being used using fresh salt and in all ensuing circulations in step 3.2, wherein
9. the method as any one of clause 2 to 8, wherein the acid is sulfuric acid.
10. such as the method described in clause 9, wherein first and second inorganic agent is any patent reagent.
11. the method as any one of clause 2 to 10, wherein by the melting agglomerate and/or acid with its whole amount Or arbitrary size is added to step 1.2 at any interval in batches.
12. first and second processing of the method as any one of clause 2 to 11, wherein step 3.1＆3.2 Agent is selected from hydroxide, carbonate or the bicarbonate of the hydroxide comprising alkali metal, carbonate or bicarbonate or alkali metal The group of the combination of salt；The preferred sodium hydroxide of the hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide；The carbonate is excellent Select sodium carbonate, potassium carbonate, calcium carbonate or lithium carbonate；The preferred sodium acid carbonate of the bicarbonate, saleratus, lithium bicarbonate.
13. the method as any one of clause 2 to 12, is equally applicable to the sulfonic acid product of separation similar kind, such as 1,8- dihydroxy naphthlene -4- sulfonic acid, 1- amino-8-naphthol -5,7- disulfonic acid, 1- amino-8-naphthol -2,4- disulfonic acid (Chicago Acid), 2- amino-8-naphthol -3,6- disulfonic acid (γ disulfonic acid), 2- amino -5- naphthols -7- sulfonic acid (J- acid), beta naphthal -6- sulphurs Acid (Xue Fo Shi acid), 2- amino -5- naphthols -1,7- disulfonic acid (J- disulfonic acid), 2- phenyl amino -5- naphthols -7- sulfonic acid (phenyl J- acid), 1- naphthylamine -8- sulfonic acid (Schollkopf acid), 2- amino naphthalenes -4,8- disulfonic acid (C- acid), 1- amino-8-naphthols -4,6- two Sulfonic acid (K- acid), 1,8- dihydroxy naphthlene -3,6- disulfonic acid (chromotropic acid), 1- naphthylamine -3,6,8- trisulfonic acids (Koch's acid), 1- naphthalenes Base amine -6- sulfonic acid (Ke Liefu acid), 1- naphthylamine -7- sulfonic acid (Ke Liefu acid), R- acid, G- acid, amino G- acid, 2- amino -8- Naphthols -6- sulfonic acid (γ acid), 2- amino -5- naphthols -7- sulfonic acid (different γ acid), M- acid, 1- amino-8-naphthol -5- sulfonic acid, 1- naphthalenes Base amine -4,7- disulfonic acid and the official with such as amino, nitro, halogen, hydroxyl, sulfonic group, carboxyl, benzyl, phenyl, ketone, aldehyde All similar naphthalene sulfonic acids and betanaphthol derivative that can be rolled into a ball.
14. such as the method any one of clause 1-6 and 6-12, wherein the loop number is more than 100.
15. such as the method any one of clause 8-14, wherein when the temperature of the reaction mixture reaches 0 DEG C extremely First and second inorganic agent is added together with small lot at 100 DEG C, preferably 70 to 20 DEG C, once or temperature reach 0 DEG C both reagents are just added together to 100 DEG C, preferably 70 to 20 DEG C.
Although above description contains many specificity, these should not be construed as limiting the scope of the invention, but make For the example of its preferred embodiment.It must should be understood that and modify and change root without departing from the spirit and scope of the invention It is possible according to being given above open.Therefore, the scope of the present invention should not be determined by exemplified embodiment, but by Appended claims and its legal equivalents determine.

Claims (17)

1. the chemical method of naphthyl sulphonic acids is separated in a kind of agglomerate from melting, wherein containing the naphthyl sulphur in the melting agglomerate The salt of acid, it is characterised in that the method is to include the sustainable method of following procedure：
Green reaction program, wherein the green reaction program since forward direction separation or reversely separation, wherein it is described melting group Block and sulfuric acid reaction, diluted melting agglomerate and dilute sulfuric acid are mixed, and gained reaction mixture is used to complete to react, It is characterized in that, fresh water is used in the first circulation of the step, and use is handled in step 3.2 in subsequent circulation It is defined as the filtrate mother liquor stream for flowing D and being stored in mother liquor storage tank afterwards, wherein positive separation is defined as in fresh water Or the filtrate mother liquor stream and sulfuric acid are considered as starting reaction medium and melting agglomerate are then added under predetermined separation condition In response procedures, to be continuously added to or be added portionwise or be carried out by any other known Adding Way the addition of melting agglomerate, Reversely separation is defined as fresh water or the filtrate mother liquor stream and melting agglomerate is considered as starting reaction medium and then pre- Determine to add the separation response procedures of sulfuric acid under separation condition, to be continuously added to or be added portionwise or by any other known addition Method carries out the addition of sulfuric acid solution,
Green separation program is followed by, wherein the separation of the reaction product is completed, wherein adding mother liquor to form separation mixing Thing, and separation agglomerate and the first filtrate stream A are obtained after stirring and filtering, it is characterised in that in the first circulation of the step It is middle to use fresh water, and using being defined as flowing D and being stored in mother liquor after step 3.2 processing storing in subsequent circulation The filtrate mother liquor stream in tank is hidden, and using fresh supplement water to clean obtained separation agglomerate and scrub stream B,
Recycling processing program is followed by, wherein handling impure mother liquor in the green reaction program and the green point Further recycled from program, wherein any circulation for the method, flows A and scrub stream B by filtrate and merge, and carry out It is following with the first inorganic agent recycling processing and with second processing agent recycling processing：
Step 3.1- will merge stream A and B in the first process container and be heated at most 100 DEG C of temperature, be continued up to 5 it is small when, First inorganic agent and sulfate are then added, wherein the amount of first inorganic agent and sulfate is to make in existing circulation At most 40% (w/v) of the total amount of reaction medium, so that the Baume values of mixture are maintained at 10 to 35, while makes adding The temperature of the mixture is maintained at 40 DEG C to 100 DEG C and keeps pH between 1 to 7 after reagent adding, wherein producing mother liquor stream C-shaped The waste material that second filtrate of formula and needs are disposed, it is characterised in that fresh sulfuric acid salt only is used in the first circulation of the step, And the salt produced from step 3.2 is used in ensuing circulation,
Step 3.2- adds second filtrate stream C to second processing container, wherein second filtrate is cooled to 10 DEG C To 40 DEG C of temperature, be continued up to 5 it is small when, the second processing agent and sulfate are then added, wherein the second processing agent Amount with sulfate is 0% (w/v) to 20% (w/v) of the total amount of the reaction medium used in existing circulation, is kept at the same time The Baume values of mixture are 10 to 50, and keep pH between 1 to 7, it is characterised in that are made in the first circulation of the method The salt recycled at the end of being used with fresh salt and in all ensuing circulations in step 3.2,
Filtrate mother liquor stream after step 3.2 processing is defined as flowing D, is then transferred in the mother liquor storage tank of purifying, with Continued cycling through afterwards in the green reaction program and green separation program in this Posterior circle,
And further, wherein the green reaction program and the green separation program circulate in closing for lower state with multiple Carried out in cyclization road, wherein addition fresh water loses only for supplementing the systematicness for example caused by evaporation, wherein described Closed circuit can carry out the recycling of Intrinsical and own type under the source level of caused all mother liquors, in the method The mother liquor used is any of for reaction medium, spe medium or washing medium, or its any combination, and
First and second inorganic agent wherein in step 3.1 and 3.2 be selected from the hydroxide comprising alkali metal, carbonate or The group of the combination of the hydroxide of bicarbonate or alkali metal, carbonate or bicarbonate.
2. the method as described in claim 1, it is characterised in that the quantity of wherein the multiple circulation is more than 3.
3. the method as described in claim 1, wherein dilute to prepare respectively for any single loop, the green reaction program The melting agglomerate and dilute sulfuric acid released, the stage progress for mixing diluted melting agglomerate and dilute sulfuric acid, it is characterised in that The stage carries out in following phases：
First startup reaction medium is added to the first container with blender and adds sulfuric acid thereto by stage 1.1a-, The temperature of the sulfuric acid is kept to be at most 200 DEG C and keep pH between 1 to 7 at the same time, wherein first starts the amount of reaction medium At most 40% (w/w) for the total amount of reaction medium used in whole circulation, and first used in entirely circulating is opened The total amount of dynamic reaction medium is 5 to 100 times that separated total melting agglomerate is needed in existing circulation,
Second startup reaction medium is added to the second reaction vessel with blender and adds one thereto by stage 1.1b- Quantitative melts agglomerate so that the pH of the mixture in second reaction vessel is between 8 to 14, and wherein second opens The amount of dynamic reaction medium is at most 40% (w/w) of the total amount of the reaction medium used in whole circulation, and entirely circulates The total amount of middle the second startup reaction medium used is 5 to 100 times that separated total melting agglomerate is needed in existing circulation,
Stage 1.1c- stirs the mixture of the first and second reaction vessels up at most 5 duration when small, while keeps respective The temperature of mixture is at most 200 DEG C,
Step 1.2- adds the diluted melting agglomerate of second reaction vessel to described in the time when at most 5 is small The dilute sulfuric acid of one reaction vessel, it is characterised in that described for all circulations since the second circulation of the method First and second start reaction medium all takes out from mother liquor storage tank, is stored in the mother liquor storage tank from recycling processing program The mother liquor of recycling, and
The reaction mixture obtained at the end of step 1.2 is taken out to complete the response procedures, is subsequently isolated by the reaction The recycling processing of obtained product, then mother liquor caused by further progress.
4. the method as described in claim 1, wherein dilute to prepare respectively for any single loop, the green reaction program The melting agglomerate and dilute sulfuric acid released, the stage progress for mixing diluted melting agglomerate and dilute sulfuric acid, it is characterised in that The stage carries out in the following steps：
First startup reaction medium is added to the first reaction vessel with blender and adds one thereto by stage 1.1a- Quantitative melts agglomerate so that the pH of the mixture in second reaction vessel is between 8 to 14, and wherein first starts instead The amount for answering medium is at most 40% (w/w) of the total amount of the reaction medium used in whole circulation, and makes in entirely circulating The total amount of second startup reaction medium is 5 to 100 times that separated total melting agglomerate is needed in existing circulation,
Second startup reaction medium is added to the second container with blender and adds sulfuric acid thereto by stage 1.1b-, The temperature of the sulfuric acid is kept to be at most 200 DEG C and keep pH between 1 to 7 at the same time, wherein second starts the amount of reaction medium At most 40% (w/w) for the total amount of reaction medium used in whole circulation, and first used in entirely circulating is opened The total amount of dynamic reaction medium is 5 to 100 times that separated total melting agglomerate is needed in existing circulation,
Stage 1.1c- stirs the mixture of the first and second reaction vessels up at most 5 duration when small, while keeps respective The temperature of mixture is at most 200 DEG C,
Step 1.2-, which adds the dilute sulfuric acid of second reaction vessel to the described first reaction in the time when at most 5 is small, to be held The melting agglomerate of device, it is characterised in that for all circulations since the second circulation of the method, first He Second starts reaction medium all takes out from mother liquor storage tank, stores in the mother liquor storage tank and is recycled from recycling processing program The mother liquor, and
The reaction mixture obtained at the end of step 1.2 is taken out to complete the response procedures, is subsequently isolated by the reaction The recycling processing of obtained product, then mother liquor caused by further progress.
5. the method as described in claim 3 or 4, wherein any circulation for the method, takes out at the end of step 1.2 The reaction mixture of acquisition is to complete response procedures as described below：
Step 1.3- adds the second reaction medium to first reaction vessel, and second reaction medium is store selected from the mother liquor Tank is hidden, the amount of second reaction medium is at most 40% (w/w) of the total amount of the reaction medium used in whole circulation, together When mixture and be at most 200 DEG C by keeping the temperature of reaction mixture is alternatively stirred with most 500RPM, and into To remove the sulfur dioxide produced during react completely when the row stirring at most 10 is small, and Baume values be 10 to 50,
Step 1.4- in first circulation by the 3rd reaction medium with fresh reactant form of medium existing to be followed no more than whole The amount of 40% (w/w) of the total amount of the reaction medium used in ring is added to first reaction vessel, so that it is mixed to form separation Compound, while keep the temperature of the separating mixture to be at most 200 DEG C and keep pH between 1 to 7, while described in stirring When separating mixture at most 24 is small, it is characterised in that the 3rd reaction medium for all ensuing circulations is selected from described Mother liquor storage tank.
6. method according to any one of claims 1 to 4, wherein any circulation for the method, the green point Comprised the steps of from program：
Step 2.1- is by the first stirring reaction medium with fresh reactant form of medium to be used no more than in the existing circulation The amount of 60% (w/w) of total amount of reaction medium add to first reaction vessel, while be cooled to gained mixture 70 DEG C of temperature, and keep pH between 1 to 7, at the same continuously stir the mixture at most 10 it is small when, it is characterised in that it is right In all ensuing circulations, the first stirring reaction medium is derived from the mother liquor storage tank,
Step 2.2- is anti-by the fresh reactant form of medium for being derived from the mother liquor storage tank is added in first circulation the 4th Between answering medium and the temperature of reaction mixture is maintained at 70 DEG C and pH is maintained at 1 to 7, while stir reaction mixture at most 24 it is small when, it is characterised in that for all ensuing circulations, it is described first stirring reaction medium is derived from the mother liquor storage tank,
The separation agglomerate that step 2.3- is formed at the end of being filtered at 70 DEG C of temperature and 1 to 7 pH in step 2.2, and make For the filter process result produce the first filtrate flow A, the filter process be carried out within 5 it is small when time,
Step 2.4- is obtained at the end of being washed using fresh reactant medium at about 70 DEG C of temperature and 1 to 7 pH in step 2.3 All agglomerates, and produce scrub stream B.
7. method according to any one of claims 1 to 4, wherein by the melting agglomerate and/or sulfuric acid with its whole amount Or arbitrary size is added to step 1.2 at any interval in batches.
8. the chemical method for separating sulfonic acid product, the sulfonic acid product are selected from 1- hydroxyl -8- amino -3,6- naphthalenedisulfonic acids (H- acid), 1,8- dihydroxy naphthlene -4- sulfonic acid, 1- amino-8-naphthol -5,7- disulfonic acid, 1- amino-8-naphthol -2,4- disulfonic acid (chicago acid), 2- amino-8-naphthol -3,6- disulfonic acid (γ disulfonic acid), 2- amino -5- naphthols -7- sulfonic acid (J- acid), 2- naphthalenes Phenol -6- sulfonic acid (Xue Fo Shi acid), 2- amino -5- naphthols -1,7- disulfonic acid (J- disulfonic acid), 2- phenyl amino -5- naphthols -7- sulphurs Acid (phenyl J- acid), 1- naphthylamine -8- sulfonic acid (Schollkopf acid), 2- amino naphthalenes -4,8- disulfonic acid (C- acid), 1- amino-8-naphthols - 4,6- disulfonic acid (K- acid), 1,8- dihydroxy naphthlene -3,6- disulfonic acid (chromotropic acid), 1- naphthylamine -3,6,8- trisulfonic acid (kocks Acid), 1- naphthylamine -6- sulfonic acid, 1- naphthylamine -7- sulfonic acid, R- acid, G- acid, amino G- acid, 2- amido-8-naphthol-6-sulfonic acids (γ acid), M- acid, 1- amino-8-naphthol -5- sulfonic acid, 1- naphthylamine -4,7- disulfonic acid and with such as amino, nitro, halogen, hydroxyl All similar naphthyl sulphonic acids and betanaphthol derivative of the functional group of base, sulfonic group, carboxyl, benzyl, phenyl, ketone, aldehyde etc., its It is to include the sustainable method of following procedure to be characterized in that the method：
Green reaction program, wherein the green reaction program since forward direction separation or reversely separation, wherein it is described melting group Block and sulfuric acid reaction, diluted melting agglomerate and dilute sulfuric acid are mixed, and gained reaction mixture is used to complete to react, It is characterized in that, fresh water is used in the first circulation of the step, and use is handled in step 3.2 in subsequent circulation It is defined as the filtrate mother liquor stream for flowing D and being stored in mother liquor storage tank afterwards, wherein positive separation is defined as in fresh water Or the filtrate mother liquor stream and sulfuric acid are considered as starting reaction medium and melting agglomerate are then added under predetermined separation condition In response procedures, to be continuously added to or be added portionwise or be carried out by any other known Adding Way the addition of melting agglomerate, Reversely separation is defined as fresh water or the filtrate mother liquor stream and melting agglomerate is considered as starting reaction medium and then pre- Determine to add the separation response procedures of sulfuric acid under separation condition, to be continuously added to or be added portionwise or by any other known addition Method carries out the addition of sulfuric acid solution,
Green separation program is followed by, wherein the separation of the reaction product is completed, wherein adding mother liquor to form separation mixing Thing, and separation agglomerate and the first filtrate stream A are obtained after stirring and filtering, it is characterised in that in the first circulation of the step It is middle to use fresh water, and using being defined as flowing D and being stored in mother liquor after step 3.2 processing storing in subsequent circulation The filtrate mother liquor stream in tank is hidden, and using fresh supplement water to clean obtained separation agglomerate and scrub stream B,
Recycling processing program is followed by, wherein handling impure mother liquor in the green reaction program and the green point Further recycled from program, wherein any circulation for the method, flows A and scrub stream B by filtrate and merge, and carry out Following circular treatment：
Step 3.1- will merge stream A and B in the first process container and be heated at most 100 DEG C of temperature, be continued up to 5 it is small when, The first inorganic agent and sulfate are then added, wherein the amount of first inorganic agent and sulfate uses in existing circulation At most 40% (w/v) of the total amount of reaction medium, so that the Baume values of mixture are maintained at 10 to 35, while makes to try in addition The temperature of the mixture is maintained at 40 DEG C to 100 DEG C and keeps pH between 1 to 7 after agent, wherein producing mother liquor stream C-shaped formula Second filtrate and the waste material disposed of needs, it is characterised in that only fresh sulfuric acid salt is used in the first circulation of the step, and The salt produced from step 3.2 is used in ensuing circulation,
Step 3.2- adds second filtrate stream C to second processing container, wherein second filtrate is cooled to 10 DEG C To 40 DEG C of temperature, be continued up to 5 it is small when, second processing agent and sulfate are then added, wherein the second processing agent and sulphur The amount of hydrochlorate is 0% (w/v) to 20% (w/v) of the total amount of the reaction medium used in existing circulation, while keeps mixing The Baume values of thing are 10 to 50, and keep pH between 1 to 7, it is characterised in that using new in the first circulation of the method Fresh salt and in all ensuing circulations using the salt recycled at the end of in step 3.2,
Filtrate mother liquor stream after step 3.2 processing is defined as flowing D, is then transferred in the mother liquor storage tank of purifying, with Continued cycling through afterwards in the green reaction program and green separation program in this Posterior circle,
And further, wherein the green reaction program and the green separation program circulate in closing for lower state with multiple Carried out in cyclization road, wherein addition fresh water loses only for supplementing the systematicness for example caused by evaporation, wherein described Closed circuit can carry out the recycling of Intrinsical and own type under the source level of caused all mother liquors, in the method The mother liquor used is any of for reaction medium, spe medium or washing medium, or its any combination.
9. method as claimed in claim 8, it is characterised in that the quantity of wherein the multiple circulation is more than 3.
10. method as claimed in claim 8, wherein for any single loop, the green reaction program to prepare respectively Diluted melting agglomerate and dilute sulfuric acid, the stage progress for mixing diluted melting agglomerate and dilute sulfuric acid, its feature exist Carried out in the stage in following phases：
First startup reaction medium is added to the first container with blender and adds sulfuric acid thereto by stage 1.1a-, The temperature of the sulfuric acid is kept to be at most 200 DEG C and keep pH between 1 to 7 at the same time, wherein first starts the amount of reaction medium At most 40% (w/w) for the total amount of reaction medium used in whole circulation, and first used in entirely circulating is opened The total amount of dynamic reaction medium is 5 to 100 times that separated total melting agglomerate is needed in existing circulation,
Second startup reaction medium is added to the second reaction vessel with blender and adds one thereto by stage 1.1b- Quantitative melts agglomerate so that the pH of the mixture in second reaction vessel is between 8 to 14, and wherein second opens The amount of dynamic reaction medium is at most 40% (w/w) of the total amount of the reaction medium used in whole circulation, and entirely circulates The total amount of middle the second startup reaction medium used is 5 to 100 times that separated total melting agglomerate is needed in existing circulation,
Stage 1.1c- stirs the mixture of the first and second reaction vessels up at most 5 duration when small, while keeps respective The temperature of mixture is at most 200 DEG C,
Step 1.2- adds the diluted melting agglomerate of second reaction vessel to described in the time when at most 5 is small The dilute sulfuric acid of one reaction vessel, it is characterised in that described for all circulations since the second circulation of the method First and second start reaction medium all takes out from mother liquor storage tank, is stored in the mother liquor storage tank from recycling processing program The mother liquor of recycling, and
The reaction mixture obtained at the end of step 1.2 is taken out to complete the response procedures, is subsequently isolated by the reaction The recycling processing of obtained product, then mother liquor caused by further progress.
11. method as claimed in claim 8, wherein for any single loop, the green reaction program to prepare respectively Diluted melting agglomerate and dilute sulfuric acid, the stage progress for mixing diluted melting agglomerate and dilute sulfuric acid, its feature exist Carried out in the following steps in the stage：
First startup reaction medium is added to the first reaction vessel with blender and adds one thereto by stage 1.1a- Quantitative melts agglomerate so that the pH of the mixture in second reaction vessel is between 8 to 14, and wherein first starts instead The amount for answering medium is at most 40% (w/w) of the total amount of the reaction medium used in whole circulation, and makes in entirely circulating The total amount of second startup reaction medium is 5 to 100 times that separated total melting agglomerate is needed in existing circulation,
Second startup reaction medium is added to the second container with blender and adds sulfuric acid thereto by stage 1.1b-, The temperature of the sulfuric acid is kept to be at most 200 DEG C and keep pH between 1 to 7 at the same time, wherein second starts the amount of reaction medium At most 40% (w/w) for the total amount of reaction medium used in whole circulation, and first used in entirely circulating is opened The total amount of dynamic reaction medium is 5 to 100 times that separated total melting agglomerate is needed in existing circulation,
Stage 1.1c- stirs the mixture of the first and second reaction vessels up at most 5 duration when small, while keeps respective The temperature of mixture is at most 200 DEG C,
Step 1.2-, which adds the dilute sulfuric acid of second reaction vessel to the described first reaction in the time when at most 5 is small, to be held The melting agglomerate of device, it is characterised in that for all circulations since the second circulation of the method, first He Second starts reaction medium all takes out from mother liquor storage tank, stores in the mother liquor storage tank and is recycled from recycling processing program The mother liquor, and
The reaction mixture obtained at the end of step 1.2 is taken out to complete the response procedures, is subsequently isolated by the reaction The recycling processing of obtained product, then mother liquor caused by further progress.
12. the method as described in claim 10 or 11, wherein any circulation for the method, takes out in step 1.2 knot The reaction mixture obtained during beam is to complete response procedures as described below：
Step 1.3- adds the second reaction medium to first reaction vessel, and second reaction medium is store selected from the mother liquor Tank is hidden, the amount of second reaction medium is at most 40% (w/w) of the total amount of the reaction medium used in whole circulation, together When mixture and be at most 200 DEG C by keeping the temperature of reaction mixture is alternatively stirred with most 500RPM, and into To remove the sulfur dioxide produced during react completely when the row stirring at most 10 is small, and Baume values be 10 to 50,
Step 1.4- in first circulation by the 3rd reaction medium with fresh reactant form of medium existing to be followed no more than whole The amount of 40% (w/w) of the total amount of the reaction medium used in ring is added to first reaction vessel, so that it is mixed to form separation Compound, while keep the temperature of the separating mixture to be at most 200 DEG C and keep pH between 1 to 7, while described in stirring When separating mixture at most 24 is small, it is characterised in that the 3rd reaction medium for all ensuing circulations is selected from described Mother liquor storage tank.
13. the method as any one of claim 8 to 11, wherein any circulation for the method, the green Separable programming comprises the steps of：
Step 2.1- is by the first stirring reaction medium with fresh reactant form of medium to be used no more than in the existing circulation The amount of 60% (w/w) of total amount of reaction medium add to first reaction vessel, while be cooled to gained mixture 70 DEG C of temperature, and keep pH between 1 to 7, at the same continuously stir the mixture at most 10 it is small when, it is characterised in that it is right In all ensuing circulations, the first stirring reaction medium is derived from the mother liquor storage tank,
Step 2.2- is anti-by the fresh reactant form of medium for being derived from the mother liquor storage tank is added in first circulation the 4th Between answering medium and the temperature of reaction mixture is maintained at 70 DEG C and pH is maintained at 1 to 7, while stir reaction mixture at most 24 it is small when, it is characterised in that for all ensuing circulations, it is described first stirring reaction medium is derived from the mother liquor storage tank,
The separation agglomerate that step 2.3- is formed at the end of being filtered at 70 DEG C of temperature and 1 to 7 pH in step 2.2, and make For the filter process result produce the first filtrate flow A, the filter process be carried out within 5 it is small when time,
Step 2.4- is obtained at the end of being washed using fresh reactant medium at about 70 DEG C of temperature and 1 to 7 pH in step 2.3 All agglomerates, and produce scrub stream B.
14. the method as any one of claim 8 to 11, wherein by the melting agglomerate and/or sulfuric acid with its whole Amount or arbitrary size are added to step 1.2 at any interval in batches.
15. the method as any one of claim 8 to 11, wherein step 3.1 and 3.2 first and second processing Agent is selected from hydroxide, carbonate or the bicarbonate of the hydroxide comprising alkali metal, carbonate or bicarbonate or alkali metal The group of the combination of salt.
16. such as the method any one of claim 1-4 and 8-11, wherein the loop number is more than 100.
17. such as the method any one of claim 1-4 and 8-11, wherein when the temperature of the reaction mixture reaches 0 DEG C first and second inorganic agent is added together with small lot at 100 DEG C, once or temperature reach 0 DEG C to 100 DEG C Both reagents are just added together.
CN201280031697.8A 2011-04-26 2012-04-26 Utilize the sustainable chemistry method of the Intrinsical recycling separation naphthalene sulfonic acids compound of all acid streams produced during separation and washing Active CN103687848B (en)

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CN108358819B (en) * 2018-03-14 2020-11-13 荆门市丽康源纺织科技有限公司 Method for recovering R salt from K acid production mother liquor
CN112174858A (en) * 2020-09-28 2021-01-05 安徽生源化工有限公司 Beta-naphthalenesulfonic acid and refining method, filtrate and application thereof
CN113698323B (en) * 2021-09-02 2023-09-05 昌邑瑞新化学工业有限公司 Method for producing tobias acid by reducing yield of acid precipitation mother liquor wastewater

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB109709A (en) * 1916-12-07 1917-09-27 Louis Munroe Dennis Improvements in or relating to Methods of Producing Sulphonic Acids or their Salts.
GB907612A (en) * 1960-09-22 1962-10-10 Allied Chem Improvements relating to the production of 2-naphthalene sulphuric acid
CN101811745A (en) * 2009-12-28 2010-08-25 天津吉星聚化工科技有限公司 Treating device for extracting naphthalene sulfonic acid waste liquor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB109709A (en) * 1916-12-07 1917-09-27 Louis Munroe Dennis Improvements in or relating to Methods of Producing Sulphonic Acids or their Salts.
GB907612A (en) * 1960-09-22 1962-10-10 Allied Chem Improvements relating to the production of 2-naphthalene sulphuric acid
CN101811745A (en) * 2009-12-28 2010-08-25 天津吉星聚化工科技有限公司 Treating device for extracting naphthalene sulfonic acid waste liquor

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