CN103687848A - Sustainable chemical process for isolation of naphthalene sulphonic acid compounds with inherent recycle of all acidic streams generated during isolation and washing - Google Patents

Sustainable chemical process for isolation of naphthalene sulphonic acid compounds with inherent recycle of all acidic streams generated during isolation and washing Download PDF

Info

Publication number
CN103687848A
CN103687848A CN201280031697.8A CN201280031697A CN103687848A CN 103687848 A CN103687848 A CN 103687848A CN 201280031697 A CN201280031697 A CN 201280031697A CN 103687848 A CN103687848 A CN 103687848A
Authority
CN
China
Prior art keywords
acid
reaction medium
circulation
reaction
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201280031697.8A
Other languages
Chinese (zh)
Other versions
CN103687848B (en
Inventor
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
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of CN103687848A publication Critical patent/CN103687848A/en
Application granted granted Critical
Publication of CN103687848B publication Critical patent/CN103687848B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Isolation of Naphthalene Sulphonic Acid Compounds is achieved with acidification of alkali fusion mixture with dilute sulphuric acid to precipitation at the predetermined conditions temperature, time and p H and Naphthalene Sulphonic Acid Compounds is separated as a partial alkali metal salt by precipitation and separated by filtration. The resulting filtrate after recycle treatment containing soluble Naphthalene Sulphonic Acid Compounds and/or a salt thereof after recycle treatment is used as a starting reaction medium, top up reaction medium, dilution reaction medium for said subsequent isolation of Naphthalene Sulphonic Acid Compounds. Isolation of Naphthalene Sulphonic Acids can be achieved by two methods viz. forward isolation and Reverse isolate.

Description

The sustainable chemistry method of utilization separated naphthene sulfonic acid compound of eigenmode recirculation of all acid stream of generation during separated and washing
Technical field
The present invention relates to utilize the eigenmode recirculation of all acid stream produce to carry out the method for the naphthene sulfonic acid compound of separated (isolate) part alkali metal salt.
More specifically, the present invention relates to by melting agglomerate is mixed with acid with the H of acquisition part alkali metal salt sour (for simplicity, by melting agglomerate is mixed to produce to be deposited in below with acid, be called as " acid precipitation ") make alkali fusion mixture experience precipitation carry out the method for separated naphthene sulfonic acid compound, it is characterized in that by described melting agglomerate is mixed and carries out acid precipitation with described diluted acid, the naphthene sulfonic acid part an alkali metal salt of precipitation passes through filtering separation, and the eigenmode recirculation of the resulting filtrate of containing solubility naphthene sulfonic acid compound and/or its salt is used as the reaction medium of described separation method.
Background technology
Separated (being defined as widely separated product) carrying out with acidic solution, forming alkaline matter after the chemical process of soluble product by currently known methods separation.Separation is a kind of important chemical process, is widely used in very polymolecular preparation.
Being separated in various chemical groups (comprising medicine, dyestuff and pigment, agrochemicals, speciality chemical, quiet thin chemical and explosive) of molecule found to apply.
The shortcoming of existing separation method:
Naphthene sulfonic acid compound is produced and is used as the intermediate of producing dyestuff and pigment for a long time.General method for separating of naphthene sulfonic acid compound comprises by naphthalene acquisition alkali fusion amine, uses subsequently diluted acid acidifying and precipitation.
The problem of the method is that the overall yield of the naphthene sulfonic acid compound that made by naphthalene is lower and need a large amount of bronsted lowry acids and bases bronsted lowries etc.
According to the methods of above describing as the 533rd to 536 pages of Yutaka HOSODA " Senryo Kagaku (Dye Chemistry) ", the amount that is used for the caustic soda of 1 mole of Koch's acid trisodium salt of alkali fusion is 8.6 moles, and it is corresponding to 4.3 times of theoretical aequum (2 moles).Therefore,, for the Koch's acid of 1 mole, the amount obtaining with the required sulfuric acid of the H acid of single sodium-salt form from melting agglomerate reaches 5.8 moles.
The shortcoming of these methods is, these methods produce a large amount of acid waste liquids, and they are difficult to recirculation.These methods need the reaction conditions about pH, temperature, concentration, reaction reagent and medium etc. unsustainable on environment, and on environment, especially our water body is left to unsustainable impact.
These methods have the shortcoming such as low-conversion and low-yield, cause on the uneconomical and environment of these methods unsustainable.
In addition, above-described methodical other shortcoming is, as the result of these methods, always to form unwanted organic and inorganic byproduct.The type of formed by product and their amount are according to method and molecule and difference.This difficulty during recirculation mother liquor causes producing a large amount of liquid efflunents.
Another shortcoming of above-mentioned method is in some cases, also to produce a large amount of inoganic solids refuses.These solid waste by organic compound as parent material, product and by-product contamination and cause severe contamination problem.Conventionally these refuses are viscous solids, process loaded down with trivial detailsly, are difficult to throw aside, and be industrial known as non-green solid refuse.
Above method still has other shortcoming.Because the generation of a large amount of liquid efflunents and non-green solid refuse, so aforesaid method need to be for the large equipment of effluent treatment and disposal solid waste.These factors are forced the constraint that place is relevant, force these methods only in being suitable for processing the appointment manufacturing district of speciality chemical, to be carried out.
Therefore, these methods are non-green, unsustainable, uneconomic, and in very large degree welding, this has worldwide become focal point.
Therefore, need to provide the method for utilizing the eigenmode recirculation of acid mother liquid to carry out green separation naphthene sulfonic acid compound, avoid thus above-mentioned defect and shortcoming, and recirculation solution continuable and economic on environment is provided.
Summary of the invention
Contriver is the commercially available customization preparation of application, and for example R-Cat1 and R-Cat2 utilize the eigenmode recirculation of the washes that produces during method and mother liquor to carry out the novel method of separated naphthene sulfonic acid compound.
According to following up a case by regular visits to of contriver, in each separating step, using these type of excessive subsidiary material (for example acid) is inevitable to a certain extent.Finding, is almost impossible in the amount of not damaging these subsidiary material that under other advantage of the method, significantly minimizing is used, although still have living space improvement the method.
In separating step, use excessive subsidiary material (for example, acid) for example to cause using, in a large amount of another kind of subsidiary material (, alkali) and the liquid producing after naphthene sulfonic acid compound separation stream.Therefore, for the preparation of the starting material of naphthene sulfonic acid compound and most of cost of processed material, by the cost of bronsted lowry acids and bases bronsted lowry, taken.Meanwhile, produce and contain in a large number draining thing and can not ignoring for the treatment of their economical load of spent acid or inorganic salt.
The object of the inventive method is to provide friendly (green) method on the environment of the problem that a large amount of acid(ic)wastes that the ordinary method that overcomes by naphthene sulfonic acid compound separation causes produce.
Therefore, avoiding the restriction that separated naphthene sulfonic acid compound runs into from alkali fusion agglomerate is main purpose of the present invention.
Another object is to provide not only not expensive in operation but also generates the green method for separating of naphthene sulfonic acid of high-quality product.
Another object of the present invention is to provide utilizes the recirculation of the acid stream producing during separation, separation and washed product to produce naphthene sulfonic acid, causes improving one's methods of Zero discharge.
Another object of the present invention be to provide by utilize the recirculation of the acid stream produce during precipitation, separation and washed product reduce subsidiary material as acid and for and acidic liquid flow out the economy that the consumption of the alkali of stream brings.
Another object of the present invention is to provide a kind of method, wherein relies on reaction medium recyclability significantly to reduce the content of unwanted by product, organic and inorganic impurity, and this causes the purer product forming continuously.
Advantage of the present invention is, since organic relative less with amount with the quantity of inorganic impurity, so the possibility that during recirculation produces by product in acid mother liquid is because being used proprietary preparation R-Cat-1 & R-Cat2 less.This fact makes the acid mother liquid circulation of unlimited amount in our method become possibility effectively.
Another advantage of the inventive method is that product separation method disclosed herein is guaranteed that the solid with crossing forming in the inventive method unexpectedly has low-level organic compound and is therefore green in essence.Therefore, method as herein described flows out treatment facility or does not need to use Solid waste disposal equipment without any need for liquid.The inventive method is that the method is unrestricted with regard to factory location, because it not necessarily must carry out in manufacturing district than another advantage of prior art.
Another advantage of the present invention is, method disclosed herein is carried out under the reaction conditions of milder and barometric point, safer like this.
Another advantage of the present invention is that using the patent response preparation of contriver's exploitation is that any other similar formulations of using in R-Cat1 & R-Cat2 or the inventive method makes complete recirculation acidic liquid stream become possibility.
An advantage again of the inventive method is, the condition that defined its internal heat mechanical condition of pressure, temperature, pH, concentration and various reagent by reactive component occurs close to each comfortable occurring in nature, and making thus the inventive method is optimum and environmental friendliness.
Under this type of temperature and pH value, carry out described method so that its conserve energy and therefore cause method economy, and it is more green, because the generation of energy causes a batch pollution conventionally.
Summary of the invention:
By producing precipitation with dilute sulphuric acid acidizing alkali molten mixture under the temperature in predetermined condition, time and pH, realize the separated of naphthene sulfonic acid compound, and naphthene sulfonic acid compound is separated and pass through filtering separation as part an alkali metal salt by precipitation.By the resulting filtrate of containing solubility naphthene sulfonic acid compound and/or its salt after recycling processing as the initial action medium of the later separation of described naphthene sulfonic acid compound, fill it up with reaction medium, diluting reaction medium.
Can be the separated and reverse separated separation that realizes naphthene sulfonic acid of forward by two kinds of methods.Forward is described clear being shown in A & B respectively with oppositely separated detailed method.
Accompanying drawing explanation
Fig. 1 has shown the diagram of complete method of the present invention.
Fig. 2 has shown the response procedures (sequence) of the forward separate part of method.
Fig. 3 has shown the simplified illustration relation between separation of the present invention and cycling program.
Fig. 4 has shown the diagram of complete method, wherein produces in the method various stream and product.
Fig. 5 has shown the response procedures of the single circulation of reverse separation of a large amount of recirculation loops.
Fig. 6 has shown the schematic diagram of cycling program.
Embodiment
First we will define some Key Terms.
The term that invention is used in describing:
In order to help to understand method described herein, some terms have clearly been defined.
. forward separation-forward separation can be defined as " at fresh water or reaction medium and sulfuric acid, be regarded as starting reaction medium and under predetermined separation condition, add subsequently in the response procedures of melting agglomerate (parent material), to add continuously or to add or to carry out adding of melting agglomerate by any other known method that adds in batches.
. oppositely separated-oppositely separation can be defined as that " fresh water or reaction medium and melting agglomerate (parent material) are regarded as the separating reaction program that starts reaction medium and add subsequently sulfuric acid under predetermined separation condition, to add continuously or to add or to carry out adding of sulphuric acid soln by any other known method that adds in batches.
Reaction medium (RM) is mother liquor or diluted acid or acid water or its combination of using in separation method.
Fresh reactant medium (FRM) is fresh water or fresh diluted acid or fresh acid water or its combination of using in reaction.
The reaction medium factor (RMF) is the FRM that uses in method or the ratio of the weight of RM and the weight of melting agglomerate.
Mother liquor (ML) is that the liquid that carries out producing after particular step flows., in the circulation after its first circulation, in the various stages of the inventive method, use mother liquor as reaction medium (RM).
Separated RM is the mixture of the acid pH in the separated stated limit of H acid, and it is water and easily miscible for being separated.
Cooling curve (CC) is the curve of temperature to the time.
PH curve is the curve of pH to the amount of the required sulfuric acid of separated H acid.
Seeding-be crystallization or the separated initiator that obtains results needed.
Salt adding-be for improving the outside salt that adds of the rate of saltouing.
In the present invention, disclosed method is to utilize the sustainable chemistry method of the separated naphthene sulfonic acid compound of eigenmode recirculation of all acid stream of generation during separated and washing.
The available two kinds of methods of separation of naphthene sulfonic acid compound are carried out, that is:
a: forward is separatedthe separation of-forward can be defined as " at fresh water or reaction medium and sulfuric acid, be regarded as starting reaction medium and under predetermined separation condition, add subsequently in the response procedures of melting agglomerate (parent material) ".
The separated naphthene sulfonic acid compound from melting agglomerate forward, with two kinds of different methods (add continuously, add) in batches, melting agglomerate is added to startup acid solution.
B: oppositely separated-reverse separation can be defined as " fresh water or reaction medium and melting agglomerate (parent material) are regarded as the separating reaction program that starts reaction medium and add subsequently sulfuric acid under predetermined separation condition ".
The reverse separated naphthene sulfonic acid compound from melting agglomerate, with two kinds of different methods (add continuously, add) in batches, sulphuric acid soln is added to and starts melting agglomerate solution.
The inventive method is used patent chemicals be R-Cat1 & R-Cat2 for separating of and recirculation.R-Cat1 & R-Cat2 is multifunctional chemical recirculation preparation, it mainly comprises thin iron powder (scope is that 0% (w/w) is to 95% (w/w)), tin, copper, titanium and zinc or its arbitrary combination, depends on the melting agglomerate (scope is that 0% (w/w) is to 10% (w/w)) for the treatment of acidifying.The purity range of all components is that 50% (w/w) is to 100% (w/w).These patent catalyzer are being implemented and are being optimized after R-Cat A, Al, A2, A3, A4, A5,1,2 remove the various researchs of organic and inorganic impurity effectively.
R-Cat1 & R-Cat2 also contains at 0% (w/w) to the electrolytic salt of sodium, magnesium, calcium, iron, nickel, cobalt, tin, zinc, titanium, copper, manganese and any other metal for example of the various metals with a plurality of valence states in 50% (w/w) scope.The purity of salt be variable and at 50% (w/w) to the scope of 100% (w/w).R-Cat1 & R-Cat2 also contains the activated carbon to the customization level in 5% (w/w) scope at 0% (w/w); Flocculating aids within the scope of 0%-95% and at 0% (w/w) to the discoloring agent in 5% (w/w) scope.
R-Cat1 & R-Cat2 also contain 0% (w/w) to the calcium in 95% (w/w) scope or basic metal as the oxyhydroxide of magnesium, barium, sodium, potassium; Activated carbon at 0.5% (w/w) to the customization level in 5% (w/w) scope; 5% (w/w) to the flocculating aids in 95% (w/w) scope and 0.5% (w/w) to the discoloring agent in 5% (w/w) scope and at 5% (w/w) to the iron powder in 25% (w/w) scope.
R-Cat1 & R-Cat2 also contains specialist additive as polyelectrolyte, defoamer, dispersion agent, emulsifying agent, mass transfer toughener, anti-caking agent, UV stablizer, solubilizing agent and antioxidant and the reagent other.
The inventive method is also used the sodium salt to the commercial grade in 95% (w/w) scope at 0% (w/w), depends at 0% (w/w) to the melting agglomerate for the treatment of acidifying for saltouing from mother liquor in 10% (w/w) scope.The purity of the salt of separating out is that 10% (w/w) is to the scope of 90% (w/w), the more precisely scope of 30-60%.By preordering method, at predetermined amount of time, at preset temperature, from mother liquor, separate out sodium salt.At predefined phase and the salt recirculation of this being separated out at preordering method, get back in method.0% to 50% (w/w) scope that present invention resides in is interior, more preferably the sodium salt in 10-40% (w/w) scope is used.
This application also discloses the sustainable chemistry method of the eigenmode recirculation green separation naphthene sulfonic acid compound that utilizes all acidic liquid streams that produce under the same terms.
Chemical process of the present invention comprises a large amount of recirculation in inside of all streams of processing acid mother liquid and producing in any cycle period substantially.Each circulation also comprises two program-green reaction programs and green separation program.
One of new feature of the inventive method is the reaction medium using about in the various stages of method.
Mention Fig. 1, in first circulation of method of the present invention, FRM is as the reaction medium starting in (step 1.1) and reaction (step 1.2) step, and the step for comprising that stirring & is cooling, stirring & is separated, filter & washing (step 2.1,2.2,2.3,2.4).As key feature of the present invention, in follow-up circulation, the liquid stream producing in the various steps of the recirculation of the first circulation is as reaction medium.Yet these liquid stream is optional as the purposes of reaction medium and FRM can be used as the reaction medium in all circulations.
Be defined in now the stream that the various stage of the present invention produces.As shown in Fig. 1, after filtering in (step 2.3) of stream A after reactions steps, produce.Stream B produces after washed product in step 2.4.With the stream producing after R-Cat1 convection current A & B co-treatment, be defined as flowing C and be transferred to the 2nd and process.Convection current C carry out the 2nd process after, produced stream is stored in storage tank and it is defined as flowing D.Treated mother liquor stream D be used in the various stages for example start, react, stir & cooling, stir & separated, be separated into stream E.
The FRM of certain tittle or any other suitable liquid stream or its are combined in and in washing step, are used as the various loss of liquids that liquid make-up causes by operation, evaporation etc. with compensation.
The details of related step in two programs of the typical recycling of formation the inventive method is described below with reference to Fig. 1,2,3 and 4.
The preferred embodiments of the invention and various other embodiment are described now.
In the distinct program described in embodiment A, add therein in raw-material another embodiment of the present invention, in these two embodiments produce in steps and destiny is identical.
Make variation in the program that starting material add to understand and to optimize naphthene sulfonic acid compound separation method parameter, to set up and to maintain the sustainability of method, to set the unlimited recirculation loop in inside of reaction medium and the consistence of product quality.
Program 1.0-green reaction program:
With two kinds of different methods, carry out green reaction program, as oppositely separated in (A) forward separated (B).The detailed description of the inventive method below.These two kinds of methods only start in (step 1.1) and reaction (step 1.2) different in step, all the other all other steps (1.3,1.4,2.1,2.2,2.3,2.4,3.1 & 3.2) are common in these two kinds of separation methods.
the separation of A:-forward-
As shown in Fig. 2, this program comprises four steps, starts, reaction, separation of AM P.AMp.Amp be separated.Each in these steps is described below.
One in the key feature of this program is the reaction medium using in various steps.Take the circumstances into consideration to add the reaction medium of predetermined amount.Reaction medium causes unique inside recyclability of the inventive method together with the produced actual conditions as by temperature, pressure, pH, stirring and other this type of parameter-definition.
The total amount of the reaction medium needing in this program for typical recycling (is below called as Q rT) requirement by melting agglomerate to the conversion of naphthene sulfonic acid compound determines.Q rTweight ratio (weight ratio) R by reaction medium adetermine, it is the weight W of the reaction medium that needs in the single circulation of the inventive method rAweight W with the total amount of the melting agglomerate for the treatment of to transform in single circulation nratio.For single circulation, be:
(weight ratio) rA=W rA/ W nformula 1
Q rTbe such, its weight equals from the definite W of formula 1 rA.
In a preferred embodiment of the invention, (weight ratio) R apreferably, in 0.25 to 25 scope, preferred scope is 0.5 to 2.5.
Step 1.1-starts: this step is carried out in the reaction vessel with agitator and required annex well known by persons skilled in the art.As shown in Fig. 2, the inventive method first circulation beginning time, the RM of suitable amount is added to reaction vessel.
In a preferred embodiment of the invention, FRM is as reaction medium.Total amount for the required reaction medium of typical recycling (below refers to Q rMT) by the solubleness of naphthene sulfonic acid compound, determined.This amount (is designated as (weight ratio) by the weight ratio of FRM or reaction medium rM) determine, it is the weight W of FRM or reaction medium required in single circulation rMweight W with the total amount of the melting agglomerate for the treatment of to transform in single circulation nratio.-
(weight ratio) rM=W rM/ W nformula 2
Q rMTbe such, its weight equals from the definite W of formula 2 rM.
The FRM using in step 1.1 or the amount of reaction medium (are designated as Q rM1.1) be variable.
In preferred embodiments, (weight ratio) rMpreferably, in 5 to 100 scope, preferred scope is 10 to 75, and Q rM1.1the Q using in this circulation rMTthe scope of 0% (w/w)-40% (w/w) in.
The applicable acid of adding suitable amount and applicable form keeps the temperature of reaction mixture in reaction vessel in the scope of 0 ℃ to 200 ℃ simultaneously, and preferred scope is 30 ℃ to 100 ℃.In a preferred embodiment of the invention, use sulfuric acid.In another embodiment of the present invention, the temperature while adding acid 10 ℃ to 100 ℃, more preferably in the scope of 50 ℃ to 100 ℃.
Mixture is stirred to the scheduled time, its 0 minute to 5 hours, more preferably in the scope of 0.5 hour to 2.5 hours.In agitation phases, the pH of reaction mixture is remained on to predeterminated level, its scope is 1 to 9, preferable range is 1 to 7, most preferably is 1 to 2.
When agitation phases finishes, add the melting agglomerate of suitable amount.It is with its whole required amounts or with any amount of batch of arbitrary size or continuously, or its arbitrary combination is added.Within scheduled period, under preset temperature and predetermined pH, add melting agglomerate.The time of adding melting agglomerate is 0 minute to 5 hours, more preferably in the scope of 0.5 hour to 2.5 hours.Temperature while adding melting agglomerate is in the scope of 0 ℃ to 200 ℃.PH while adding melting agglomerate in 1 to 9 scope, be preferably 1 to 7 scope, more preferably 1 to 2.
In the follow-up circulation of the inventive method, stream E, as reaction medium, replaces starting the FRM in (step 1.1).
In another embodiment of the present invention, the temperature while adding reaction medium 10 ℃ to 100 ℃, more preferably in the scope of 30 ℃ to 70 ℃.
In another embodiment of the present invention, with any program, add reaction medium and/or acid and melting agglomerate.
Step 1.2-reaction: all measure or add melting agglomerate to be transformed with any amount of batch to reaction vessel with it continuously.0 to 5 hour, the total amount of more preferably adding melting agglomerate to be transformed with the interval (depending on molecule to be separated) being applicable in 0.5-1.5 hour.
The reaction medium of suitable amount is added to reaction vessel keeps the pH of temperature and mixture in their pre-determined ranges separately simultaneously.Temperature while adding reaction medium is the scope of 0 ℃ to 200 ℃, more preferably in the scope of 50-100 ℃.PH while adding reaction medium is in 1 to 9 scope, preferably in 2 to 5 scope.In a preferred embodiment of the invention, FRM is as the reaction medium in the step 1.2 of first circulation of the inventive method.For follow-up circulation, stream E is as the reaction medium of this step.
The FRM using in step 1.2 or the amount of reaction medium (are designated as Q rM1.2) the total amount Q that can use in this circulation rMTthe scope of 0% (w/w)-40% (w/w) in change.
By being applicable to acid, be added into alternatively reaction vessel with the required pH level of realization response mixture.The acid of adding applicable form keeps the temperature of reaction mixture in reaction vessel in the scope of 0 ℃ to 200 ℃ simultaneously.
In the pH of reaction mixture is in 1 to 9 scope, preferably during the preset value in 1 to 2 scope, in certain hour section, the preset temperature in the scope of 0 ℃ to 200 ℃ is added to reaction mixture by melting agglomerate.With single batch in batches or continuously or any combination of these addition meanss add the required melting agglomerate of step 1.2.
The agitator that the reaction mixture in all stages in this step is rotated in order to 0 to 500RPM speed alternatively stirs.This step even can successfully carried out under stirring.
oppositely separation of B:--
In the reverse separation of naphthene sulfonic acid compound, only in step No.1.1 & 1.2, change, as shown in Figure 5, the step during all other steps in response procedures 1.3 & 1.4 are separated with forward is identical.This program comprises four steps, starts, reaction, separation of AM P.AMp.Amp be separated.
One in the key feature of this program is the reaction medium using in various steps.Take the circumstances into consideration to add the reaction medium of predetermined amount.Reaction medium causes unique inside recyclability of the inventive method together with the produced actual conditions as by temperature, pressure, pH, stirring and other this type of parameter-definition.
The total amount of the reaction medium needing in this program for typical recycling (is below called as Q rT) requirement by melting agglomerate to the conversion of naphthene sulfonic acid compound determines.Q rTweight ratio (weight ratio) R by reaction medium adetermine, it is the weight W of the reaction medium that needs in the single circulation of the inventive method rAweight W with the total amount of the melting agglomerate for the treatment of to transform in single circulation nratio.For single circulation, be:
(weight ratio) rA=W rA/ W nformula 1
Q rTbe such, its weight equals from the definite W of formula 1 rA.
In a preferred embodiment of the invention, (weight ratio) R apreferably, in 0.25 to 25 scope, preferred scope is 0.5 to 2.5.
Step 1.1-starts: this step is carried out in the reaction vessel with agitator and required annex well known by persons skilled in the art.As shown in Figure 5, the inventive method first circulation beginning time, the RM of suitable amount is added to reaction vessel.
In a preferred embodiment of the invention, FRM is as reaction medium.Total amount for the required reaction medium of typical recycling (below refers to Q rMT) by the solubleness of naphthene sulfonic acid compound, determined.This amount (is designated as (weight ratio) by the weight ratio of FRM or reaction medium rM) determine, it is the weight W of FRM or reaction medium required in single circulation rMweight W with the total amount of the melting agglomerate for the treatment of to transform in single circulation nratio.?
(weight ratio) rM=W rM/ W nformula 2
Q rMTbe such, its weight equals from the definite W of formula 2 rM.
The FRM using in step 1.1 or the amount of reaction medium (are designated as Q rM1.1) be variable.
In preferred embodiments, (weight ratio) rMpreferably, in 5 to 100 scope, preferred scope is 10 to 75, and Q rM1.1the Q using in this circulation rMTthe scope of 0% (w/w)-40% (w/w) in.
The applicable acid of adding suitable amount and applicable form keeps the temperature of reaction mixture in reaction vessel in the scope of 0 ℃ to 200 ℃ simultaneously, and preferred scope is 30 ℃ to 100 ℃.In a preferred embodiment of the invention, use sulfuric acid.In another embodiment of the present invention, the temperature while adding acid 10 ℃ to 100 ℃, more preferably in the scope of 50 ℃ to 100 ℃.
Mixture is stirred to the scheduled time, its 0 minute to 5 hours, more preferably in the scope of 0.5 hour to 2.5 hours.In agitation phases, the pH of reaction mixture is remained on to predeterminated level, its scope is 1 to 9, preferable range is 1 to 7, most preferably is 1 to 2.
When agitation phases finishes, add the melting agglomerate of suitable amount.It is with its whole required amounts or with any amount of batch of arbitrary size or continuously, or its arbitrary combination is added.Within scheduled period, under preset temperature and predetermined pH, add melting agglomerate.The time of adding melting agglomerate is 0 minute to 5 hours, more preferably in the scope of 0.5 hour to 2.5 hours.Temperature while adding melting agglomerate is in the scope of 0 ℃ to 200 ℃.PH while adding melting agglomerate in 1 to 9 scope, be preferably 1 to 7 scope, more preferably 1 to 2.
In the follow-up circulation of the inventive method, stream E, as reaction medium, replaces starting the FRM in (step 1.1).
In another embodiment of the present invention, the temperature while adding reaction medium 10 ℃ to 100 ℃, more preferably in the scope of 30 ℃ to 70 ℃.
In another embodiment of the present invention, with any program, add reaction medium and/or acid and melting agglomerate.
Step 1.2-reaction: all measure or add melting agglomerate to be transformed with any amount of batch to reaction vessel with it.The total amount of adding melting agglomerate to be transformed with the interval (depending on molecule to be separated) being applicable within the time of 0 to 5 hour.
The reaction medium of suitable amount is added to reaction vessel keeps the pH of temperature and mixture in their pre-determined ranges separately simultaneously.Temperature while adding reaction medium is the scope of 0 ℃ to 200 ℃, more preferably in the scope of 50-100 ℃.PH while adding reaction medium is in 1 to 9 scope, preferably in 1 to 2 scope.In a preferred embodiment of the invention, FRM is as the reaction medium in the step 1.2 of first circulation of the inventive method.For follow-up circulation, stream E is as the reaction medium of this step.
The FRM using in step 1.2 or the amount of reaction medium (are designated as Q rM1.2) the total amount Q that can use in this circulation rMTthe scope of 0% (w/w)-40% (w/w) in change.
By being applicable to acid, be added into alternatively reaction vessel with the required pH level of realization response mixture.The acid of adding applicable form keeps the temperature of reaction mixture in reaction vessel in the scope of 0 ℃ to 200 ℃ simultaneously.
In the pH of reaction mixture is in 1 to 9 scope, preferably during the preset value in 1 to 2 scope, in certain hour section, the preset temperature in the scope of 0 ℃ to 200 ℃ is added to reaction mixture by melting agglomerate.With single batch in batches or continuously or any combination of these addition meanss add the required melting agglomerate of step 1.2.
The agitator that the reaction mixture in all stages in this step is rotated in order to 0 to 500RPM speed alternatively stirs.This step even can successfully carried out under stirring.
Forward is with oppositely separated only different in step 1.1 & 1.2 and be identical with all the other methods of carrying out in step 1.4 (separated) in step 1.3 (separation) in these two kinds of separation, with reference to figure 2 & 5.
Step 1.3-is separated: when step 1.2 finishes, complete after the adding of melting agglomerate, alternatively the applicable reaction medium of suitable amount is added to reaction vessel.The consistence of solid is depended in the decision of adding reaction medium.The amount of the reaction medium using in step 1.3 (is designated as QRM 1.3) the total amount Q that can use in this circulation rMTthe scope of 0% (w/w)-40% (w/w) in change.
In a preferred embodiment of the invention, FRM is as the reaction medium in the first circulation of this program, and for the follow-up circulation that stands the inventive method, FRM is flowed E and replaces.
The agitator that the reaction mixture in all stages in this step is rotated in order to 0 to 500RPM speed alternatively stirs.This step even can successfully carried out under stirring.
Remove completely during separating reaction, produce SO 2in the preferred embodiment of (sulfurous gas) gas, then reaction being under agitation heated to scope is 0 to 200 ℃, preferably 0 to 100 ℃, the more preferably preset temperature of 70 to 100 ℃, and lasting scope is 0 hour to 10 hours, preferably 30 minutes to 8 hours, more preferably scheduled time of 30 minutes to 5 hours.
Step 1.4-is separated: in a preferred embodiment of the invention, FRM is as the reaction medium in the first circulation of this program.The consistence of production concentration and crystal formation is uniformly depended in the decision of adding reaction medium.The amount of the reaction medium using in step 1.4 (is designated as QRM 1.4) the total amount Q that can use in this circulation rMTthe scope of 0% (w/w)-40% (w/w) in change.The mixture forming is thus called as separating mixture (seperation mixture).
In a preferred embodiment of the invention, separation temperature is in the scope of 0 to 200 ℃, and separated pH is 1 to 12, preferably in the scope of l to 2.
In preferred embodiments, make pH and temperature condition remain on pH and the temperature of predeterminated level, lasting scope is that 0 hour to 24 hours, preferable range are the time of 30 minutes to 5 hours.
For the follow-up circulation of experience the inventive method, FRM is flowed E and is replaced.
In step 1.1, to 1.4 all above step, sulfuric acid is as preferred applicable acid alternatively.
In another embodiment of the present invention, FRM is as the reaction medium in the first circulation of this program.The FRM using in step 1.4 or the amount (QRM of reaction medium 1.4) Q that can use in this circulation rMTthe scope of 0% (w/w)-40% (w/w) in change.
The agitator that the reaction mixture in all stages in this step is rotated in order to 0 to 500RPM speed alternatively stirs.This step even can successfully carried out under stirring.
The green reaction program of single circulation completes when the end of step 1.4.
In another embodiment of the present invention, separation temperature is preferably 0 ℃ to 100 ℃.
Program 2.0-green separation program:
As shown in Fig. 3, this program comprises four steps, that is, stir & cooling, stir that & is separated, filtration and washing step.Describe each in these steps in detail.
it is cooling that step 2.1-stirs &:as shown in Fig. 3, the mixture obtaining when step 1.4 finishes in the reaction medium of suitable amount (being called as the first sedimentation RM) being added as for reaction vessel alternatively under applicable temperature and pH, described temperature at the scope of 0 to 200 ℃ and described pH in 1 to 11, preferably 2 to 5 and more preferably 1 to 2 scope.Allow the mixture forming thus to stir, by making it keep certain churning time at the first whipping temp.
In a preferred embodiment of the invention, first stir pH in 1 to 11, preferably 2 to 5, more preferably 1 to 2 scope; The first whipping temp 0 ℃ to 200 ℃, preferably in the scope of 0 ℃ to 100 ℃; And under the temperature range of 0 ℃ to 100 ℃, the first churning time is 1 minute to 10 hours, preferably 30 minutes to 3 hours.
The liquid level forming due to stirring means is at the first cooling temperature, the first cooling pH and cooling under the first cooling time.
In a preferred embodiment of the invention, FRM is as the reaction medium in the first circulation, and for the follow-up circulation of experiencing the inventive method, FRM is flowed E and replaces.
The FRM using in step 2.1 or the amount of reaction medium (are designated as Q rM2.1) Q that can use in this circulation rMTthe scope of 0% (w/w)-60% (w/w) in change.
Step 2.2-stirs with separated: when step 2.1 end of the first circulation, add the reaction medium (be called as and stir the separated RM of &) of predetermined amount under predetermined the first whipping temp and predetermined the first stirring pH, in predetermined the first churning time to the cooling agglomerate of stirring &.Stir the mixture.By making mixture keep predetermined first to stir continuity temperature, predetermined first and stir continuity pH and reach predetermined first and stir and continue perdurability to stir.
In a preferred embodiment of the invention, FRM in the first circulation with mixing and separated RM, and for experience the inventive method follow-up circulation, FRM is flowed C and is replaced; The numerical value of whipping temp 0 ℃ to 200 ℃, preferably in the scope of 0 ℃ to 100 ℃; The numerical value of separated pH is 1 to 11, preferably in 2 to 5, more preferably 1 to 2 scope; The numerical value of time and disengaging time 5 minutes to 5 hours, preferably in the scope of 30 minutes to 3 hours.
The FRM using in step 2.2 or the amount of reaction medium (are designated as Q rM2.2) Q that can use in this circulation rMTthe scope of 0% (w/w)-40% (w/w) in change.
Step 2.3-filters:
Then predetermined filtration temperature, predetermined filtration under pH, the separated agglomerate forming when the step 2.2 of the first circulation finishes filters by solid-liquid separating method well known by persons skilled in the art; Continue predetermined filtration time.The liquid stream obtaining when step 2.3 finishes is added to mother liquor storage tank as stream A.
In a preferred embodiment of the invention, separated agglomerate 0 ℃ to 200 ℃, preferably under the numerical value of filtration temperature scope of 40 ℃ to 100 ℃, filter; Filtration time is 5 minutes to 5 hours; Preferably in the scope of 30 minutes to 3 hours.
Step 2.4-washing and filtration: in predetermined separation temperature, then by method known to those skilled in the art, washed and filtered with the total agglomerate obtaining from step 2.3 under predetermined separated pH, wherein the FRM of suitable amount is defined as flowing B.
Initial at Arbitrary cyclic, by liquid, (stream A & B) is stored in the storage tank that contains liquid together with washes, is then transferred to recycling processing container and processes for R-Cat1, processes subsequently for R-Cat2.
In preferred embodiments, separation temperature is 0 ℃ to 200 ℃, is preferably 40 ℃ to 100 ℃, and pH is 1 to 11, is preferably 2 to 5.
The feature that key of the present invention is favourable is that the part storage liquid (described part is defined as flowing E) of suitable amount is recycled in the various steps (step 1.1 is to 1.3 and 2.2) of the ensuing circulation of the inventive method.
The amount of the FRM using in step 2.2 (is designated as Q rM2.2) Q that can use in this circulation rMTthe scope of 0% (w/w)-40% (w/w) in change.
The circulation that the typical recycling of the inventive method is comprised of green reaction program and green separation program is so far.Key feature of the present invention is that the institute of typical recycling carries out at barometric point in steps.
As the favourable feature of key of the present invention, reaction medium is used green reaction program and green separation program, the various streams of taking from mother liquor in the circulation after the first circulation and producing during the inventive method.In other words, the FRM using in the various stages (step 1.1 is to 1.4 and 2.1 to 2.4) of the first circulation by all follow-up circulations in applicable reaction medium substitute.
In step 2.4, FRM all be cycled to used in supplementary copy inventive method in the previously loss of circulation.
The present inventor finds, and the purity of the product naphthene sulfonic acid compound so forming after any cyclic drying changes in 75% to 100%, preferably 78% to 80% scope.
Storage mother liquor and the aqueous cleaning thing that obtains during various steps described above be for processing in another circulation, the quantity of recirculation conventionally in 5 to 100 scope and more than.
Surprisingly, contriver has found that by above-described method, carrying out separated naphthene sulfonic acid compound from melting agglomerate can produce inorganic byproduct in any circulation, the scope of the ratio of the melting agglomerate to be transformed of its weight and above program is 0.25 to 25, and it is crystallization and is inviscid in essence.The color of these by products to light yellow variation, is especially off-white color from white to off-white color.The pH of inorganic byproduct is in 4.0 to 6.0 scope.The moisture content of inorganic byproduct is in 5% to 50% scope, and specified range is 10% to 30%.
Recycling processing to naphthene sulfonic acid compound mother liquor and washes
Collect the recirculation that sick mixing mother liquor and washes are processed for source.Then, according to the first treatment agent (R-Cat1) for the method for below discussing at this and the second treatment agent (R-Cat2), together with sodium sulfate, process the mother liquor merging.For single circulation of the present invention, with reference to the cycle for the treatment of of figure 6.
The recycling processing of R-Cat1 for step No.3.1-
Filtrate flow A & scrub stream B in step 2.3 & 2.4 merges respectively, and be added to R-Cat processing vessel, then predetermined filtration temperature, predetermined filtration under pH, predetermined filtration time, carry out solid-liquid separating method well known by persons skilled in the art, as shown in Fig. 6.
In a preferred embodiment of the invention, the mother liquor of merging being heated in processing vessel to scope is 0 ℃ to 200 ℃, the preferred preset temperature of 40 ℃ to 100 ℃; Its pre-determined process-time 5 minutes to 5 hours, preferably in the scope of 30 minutes to 3 hours.Reach temperature required after, predetermined add temperature and stir under, within the predetermined joining day, add R-Cat1 and the salt of predetermined amount completely or in batches.
The R-Catl of recycling processing and the amount of salt for step 3.1 (are designated as Q r-Cat3.1) Q that can use in this circulation rMTthe scope of 0% (w/v)-40% (w/v) in, more preferably in the scope of 0% (w/v)-20% (w/v), change.
In a preferred embodiment of the invention, fresh salt is only used in fresh circulation and ensuing circulation, from step 3.2, is that the salt of recovery R-Cat2 processes is in treatment step 3.1 & 3.2 recirculation in both.
In preferable range, be under 1 to 7, more preferably 2 to 5 predetermined pH, under agitation whole treated agglomerate remained on to preferable range and be 0 ℃ to 200 ℃, the preferred preset temperature of 40 ℃ to 100 ℃; Lasting scope is 5 minutes to 5 hours, the preferred pre-determined process-time of 30 minutes to 3 hours.
In a preferred embodiment of the invention, being preferably 0 ℃ to 200 ℃, preferably under the temperature range of 40 ℃ to 100 ℃; In preferable range, be under 1 to 7, more preferably 2 to 5 predetermined pH, the Baume of treated slurry to be adjusted to scope to be preferably 0 to 50, more preferably 10 to 35 predetermined Baume.
In a preferred embodiment of the invention, under preferable range is 1 to 7, more preferably 2 to 5 predetermined filtration pH, be 0 ℃ to 200 ℃, preferably filter total mother liquor by known filter method under the predetermined filtration temperature of 40 ℃ to 100 ℃ in preferable range; Lasting scope is 5 minutes to 5 hours, the preferred predetermined filtration time of 30 minutes to 3 hours.The R-Cat1 with crossing with resistates separation is put aside for safe disposal.
The filtrate mother liquor stream that R-Cat1 obtains after processing is defined as flowing C, is then transferred to another processing vessel and processes for R-Cat2.
The recycling processing of R-Cat2 for step No.3.2-
Under preset temperature, predetermined pH, the filtrate mother liquor stream C accepting from a R-Cat treatment step 3.1 is added to R-Cat2 processing vessel, as shown in Fig. 6.
In a preferred embodiment of the invention, stream C being cooled to scope is 0 ℃ to 50 ℃, the preferred preset temperature of 10 ℃ to 40 ℃; Lasting scope is 5 minutes to 5 hours, the preferred predetermined freezing time of 30 minutes to 3 hours.Reach temperature required after, predetermined add temperature and stir under, within the predetermined joining day, add R-Cat2 and the salt of predetermined amount completely or in batches.
The R-Cat2 using in step 3.2 and the amount of salt (are designated as C r-Cat3.2) Q that can use in this circulation rMTthe scope of 0% (w/w)-20% (w/w) in change.
In a preferred embodiment of the invention, fresh salt is only used in fresh circulation and ensuing circulation, salt recirculation in treatment step 3.2 of reclaiming the step 3.2 of fresh circulation and ensuing circulation from same steps.
In preferable range, be under 1 to 7, more preferably 4 to 6 predetermined pH, it is 0 ℃ to 50 ℃, the preferred preset temperature of 10 ℃ to 40 ℃ that whole treated agglomerate is remained on to preferable range; Lasting scope is 5 minutes to 5 hours, the preferred pre-determined process-time of 30 minutes to 3 hours.
In a preferred embodiment of the invention, being preferably 0 ℃ to 50 ℃, preferably under the temperature range of 10 ℃ to 40 ℃; In preferable range, be under 1 to 7, more preferably 4 to 6 predetermined pH, the Baume of treated slurry to be adjusted to scope to be preferably 0 to 50, more preferably 10 to 35 predetermined Baume.
In a preferred embodiment of the invention, under preferable range is 1 to 7, more preferably 4 to 6 predetermined filtration pH, be 0 ℃ to 50 ℃, preferably filter treated mother liquor by known filter method under the predetermined filtration temperature of 10 ℃ to 40 ℃ in preferable range; Lasting scope is 5 minutes to 5 hours, the preferred predetermined filtration time of 30 minutes to 3 hours.The salt reclaiming together with R-Cat2 with crossing is separated and preserve the recycling processing for next circulation by known filter method.
Filtrate mother liquor stream after R-Cat2 processes is defined as flowing D, is then transferred to mother liquor storage tank, and then it returns as flowing E recirculation in next circulation.
It should be noted that in method as described above, by melting agglomerate and/or acid with its whole amount or batch be added into step 1.2 with any interval with arbitrary size.
Further note, in method mentioned above, described the first and second treatment agents are selected from the group that comprises alkali-metal independent oxyhydroxide, carbonate or supercarbonate or their combination; The preferred sodium hydroxide of described oxyhydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide; The preferred sodium carbonate of described carbonate, salt of wormwood, calcium carbonate or Quilonum Retard; The preferred sodium of described supercarbonate, saleratus, lithium bicarbonate.
It shall yet further be noted that method mentioned above is applicable to the sulfonic acid product of separating analogous kind, comprise 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-sulfonic acid (Xue Fo Shi acid), 2-amino-5-naphthol-1,7-disulphonic acid (J-disulfonic acid), 2-phenyl amino-5-naphthols-7-sulfonic acid (phenyl J-acid), 1-ALPHA-NAPHTHYL 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-ALPHA-NAPHTHYL AMINE-3,6,8-trisulfonic acid (Koch's acid), 1-ALPHA-NAPHTHYL AMINE-6-sulfonic acid (Ke Liefu acid), 1-ALPHA-NAPHTHYL AMINE-7-sulfonic acid (Ke Liefu acid), R-acid, G-acid, amino G-acid, 2-amido-8-naphthol-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-ALPHA-NAPHTHYL AMINE-4,7-disulfonic acid and having as amino, nitro, halogen, hydroxyl, sulfonic group, carboxyl, benzyl, phenyl, ketone, the all similar naphthene sulfonic acid of the functional group of aldehyde etc. and 2-Naphthol derivative.
Some advantages that following examples explanation is mentioned herein.
A lot of dyes and dyestuffses (dyestuff), fine chemicals have as the naphthalenesulfonate of one of structural unit and at present for the preparation of various dyes and dyestuffses and pharmaceutical intermediate.
In conventional H-sour preparation method, for the amount of the caustic soda of the Koch's acid trisodium salt of 1 mole of alkali fusion, be 8.6 moles, it is corresponding to 4.3 times of theoretical aequum (2 moles).Therefore,, for the Koch's acid of 1 mole, the amount obtaining with the required sulfuric acid of the H acid of single sodium-salt form from melting agglomerate reaches 5.8 moles.
In order to overcome the above-mentioned shortcoming of current methods, development environment close friend, the safe and nontoxic method of contriver, as shown in the embodiment above.
Embodiment 1:
The forward separating reaction program of H-acid is described with following recirculation in this embodiment.
Fresh circulation: add 181ml water and 50g sulfuric acid in the 0.5 liter of 4 neck round-bottomed flask that is equipped with stirring rod, condenser, thermometer and interpolation hole in being arranged in applicable heating/cooling system, be heated to 60 ℃.Under continuously stirring in 90 ℃, in 20 minutes, 125g melting agglomerate is slowly added in diluted acid.Reactive material is further heated to 95 ℃ to 100 ℃ overflows for SO2 gas and confirms.By Congo red test, check completing of SO2 effusion.Reactive material is cooled to 70 ℃ and filter after the Baume of agglomerate is adjusted to 25 ° of Be.Wet cake with 125ml water washing H-acid.H-acid is dried to the extremely pink H-acid of off-white color to be dried 17g with 80% nitrated value (NV) at 110 ℃.Collecting total filtrate is reaction medium and washes and recirculation in follow-up batch after processing.
the first recirculation (R1): in identical assembling as previously discussed, 61ml fresh water, the treated mother liquor producing of 120ml and 48g sulfuric acid are heated to 60 ℃ in fresh circulation.Under continuously stirring in 90 ℃, in 20 minutes, 125g melting agglomerate is slowly added in diluted acid.Reactive material is further heated to 95 ℃-100 ℃ overflows for SO2 gas and confirms.By Congo red test, check completing of SO2 effusion.Reactive material is cooled to 70 ℃ and filter after the Baume of agglomerate is adjusted to 28 ° of Be.Wet cake with 125ml water washing H-acid.H-acid is dried to the extremely pink H-acid of off-white color acid to be dried 18.0g with 79.40% nitrated value (NV) at 110 ℃.Collecting total filtrate is reaction medium and washes and recirculation in follow-up batch after processing.
the 5th recirculation (R5): in identical assembling as previously discussed, washing mother liquor and 49g sulfuric acid that 33ml fresh water, the treated mother liquor of 148ml and 76ml are produced in the 4th recirculation are heated to 60 ℃.Under continuously stirring in 90 ℃, in 20 minutes, 125g melting agglomerate is slowly added in diluted acid.Reactive material is further heated to 95 ℃-100 ℃ overflows for SO2 gas and confirms.By Congo red test, check completing of SO2 effusion.Reactive material is cooled to 70 ℃ and filter after the Baume of agglomerate is adjusted to 28 ° of Be.Wet cake with 125ml water washing H-acid.H-acid is dried to the deep pink H-acid to be dried 17.5g with 76.63% nitrated value (NV) at 110 ℃.Collecting total filtrate is reaction medium and washes and recirculation in follow-up batch after processing.
the tenth recirculation (R10): in identical assembling as previously discussed, 26ml fresh water, the treated mother liquor producing of 155ml and 48g sulfuric acid are heated to 60 ℃ in the 9th recirculation.Under continuously stirring in 90 ℃, in 20 minutes, 125g melting agglomerate is slowly added in diluted acid.Reactive material is further heated to 95 ℃-100 ℃ overflows for SO2 gas and confirms.By Congo red test, check completing of SO2 effusion.Reactive material is cooled to 70 ℃ and filter after the Baume of agglomerate is adjusted to 28 ° of Be.Wet cake with 125ml water washing H-acid.H-acid is dried to the light brown H-acid to be dried 22g with 76.3% nitrated value (NV) at 110 ℃.Collecting total filtrate is reaction medium and washes and recirculation in follow-up batch after processing.
the 15 recirculation (R15): in identical assembling as previously discussed, 32ml fresh water, the treated mother liquor producing of 149ml and 48g sulfuric acid are heated to 60 ℃ in the 14 recirculation.Under continuously stirring in 90 ℃, in 20 minutes, 125g melting agglomerate is slowly added in diluted acid.Reactive material is further heated to 95 ℃-100 ℃ overflows for SO2 gas and confirms.By Congo red test, check completing of SO2 effusion.Reactive material is cooled to 70 ℃ and filter after the Baume of agglomerate is adjusted to 27 ° of Be.Wet cake with 125ml water washing H-acid.H-acid is dried to the brown H-acid of L. to be dried 19.5g with 74.11% nitrated value (NV) at 110 ℃.Collecting total filtrate is reaction medium and washes and recirculation in follow-up batch after processing.
the 20 recirculation (R20):in identical assembling as previously discussed, 74ml fresh water, the treated mother liquor producing of 107ml, 74ml water and 48g sulfuric acid are heated to 60 ℃ in the 19 recirculation.Under continuously stirring in 90 ℃, in 20 minutes, 125g melting agglomerate is slowly added in diluted acid.Reactive material is further heated to 95 ℃-100 ℃ overflows for SO2 gas and confirms.By Congo red test, check completing of SO2 effusion.Reactive material is cooled to 70 ℃ and filter after the Baume of agglomerate is adjusted to 27 ° of Be.Wet cake with 125ml water washing H-acid.H-acid is dried to the light brown H-acid to be dried 20.5g with 72.64% nitrated value (NV) at 110 ℃.Collecting total filtrate is reaction medium and washes and recirculation in follow-up batch after processing.
Following table (table 01) shows amount economical of the fresh water using in the present invention reaction, separated (the melting group of forward adding continuously of piece)
Figure BDA0000447280910000181
The mother liquor producing in each circulation of forward separable programming is processed with R-Cat1 & sodium sulfate; The 1st details of processing is mentioned in following table 2.
Impurity separating out in the 1st recirculation while carrying out source processing with R-Cat1 & sodium sulfate in the present invention's reaction that following table 02 shows in forward separation.
Figure BDA0000447280910000182
Figure BDA0000447280910000191
Then the 1st processes the rear mother liquor producing processes with R-Cat2 & sodium sulfate, then recirculation in other circulation of the present invention.Its details is mentioned in table 3.
Following table 03 show with R-Cat2 carry out source while processing impurity in the 2nd recirculation, separate out economical with the amount of the fresh water using in the separated the present invention's reaction of forward.
Figure BDA0000447280910000192
Figure BDA0000447280910000201
embodiment 2:
The reverse separating reaction program of H-acid is described with following recirculation in this embodiment.
fresh circulation:the moisture of 1086g is altogether become to two equal portions, is respectively 543ml.The water dilution of a 543ml for 200.0g98% sulfuric acid, makes 640ml volume.By remaining that part of water dilution for 500.0g melting agglomerate, make 840ml volume.
The melting agglomerate that adds dilution in the 2.0 liter of 4 neck round-bottomed flask that is equipped with stirring rod, condenser, thermometer and interpolation hole in being arranged in applicable heating/cooling system, is heated to 90 ℃.Then with 10 grades, (respectively contain 64ml) in batches and add diluted acid slurry, each batch adds 5 minutes.Reactive material is further heated to 95 ℃ to 100 ℃ overflows for SO2 gas and confirms.By Congo red test, check completing of SO2 effusion.Reactive material is cooled to 70 ℃ and filter after the Baume of agglomerate being adjusted to 30 ° of Be by further evaporation agglomerate.Wet cake with 500ml water washing H-acid.H-acid is dried to the extremely peach H-acid of off-white color acid to be dried 86g with 77.03% nitrated value (NV) at 110 ℃.Collecting total filtrate is reaction medium and washes and recirculation in follow-up batch after processing.
the first recirculation (R1): to the treated mother liquor producing of 386.4g, fill it up with 699.6g water in fresh circulation, make 1086g total mass.The volume that makes 1045ml is divided into two equal batch, is respectively 522.5ml.ML dilution by 194.77g98% sulfuric acid with a 522.5ml, makes 610ml volume.By remaining that part of ML dilution for 500.0g melting agglomerate, make 830ml volume.The melting agglomerate that adds dilution in identical assembling as previously discussed, is heated to 90 ℃.Then with 10 grades, (respectively contain 61ml) in batches and add diluted acid slurry, each batch adds 5 minutes.Reactive material is further heated to 95 ℃ to 100 ℃ overflows for SO2 gas and confirms.By Congo red test, check completing of SO2 effusion.Reactive material is cooled to 70 ℃ and filter after the Baume of agglomerate being adjusted to 30 ° of Be by further evaporation agglomerate.Wet cake with 500ml water washing H-acid.H-acid is dried to the extremely pink H-acid of off-white color to be dried 88g with 76.36% nitrated value (NV) at 110 ℃.Collecting total filtrate is reaction medium and washes and recirculation in follow-up batch after processing.
the 5th recirculation (R5): to the treated mother liquor producing of 489.3g, fill it up with 596.7g water in the 3rd recirculation, make 1086g total mass.The volume that makes 1000ml is divided into two equal batch, is respectively 500ml.ML dilution by 189.92g98% sulfuric acid with a 500ml, makes 600ml volume.By remaining that part of ML dilution for 500.0g melting agglomerate, make 850ml volume.
The melting agglomerate that adds dilution in identical assembling as previously discussed, is heated to 90 ℃.Then diluted acid slurry (respectively contains 60ml) in batches with 10 grades and adds diluted acid slurry, and each batch adds 5 minutes.Reactive material is further heated to 95 ℃ to 100 ℃ overflows for SO2 gas and confirms.By Congo red test, check completing of SO2 effusion.Reactive material is further heated to 95 ℃ to 100 ℃ overflows for SO2 gas and confirms.By Congo red test, check completing of SO2 effusion.Reactive material is cooled to 70 ℃ and filter after the Baume of agglomerate is adjusted to 30 ° of Be.Wet cake with 500ml water washing H-acid.H-acid is dried to the extremely pink H-acid of off-white color to be dried 94g with 74.70% nitrated value (NV) at 110 ℃.Collecting total filtrate is reaction medium and washes and recirculation in follow-up batch after processing.
In the present invention's reaction that following table 04 shows in oppositely separation, the amount of the fresh water of use is economical.
Figure BDA0000447280910000221
The mother liquor oppositely producing in each circulation of separable programming is processed with R-Cat1 & sodium sulfate; The 1st details of processing is mentioned in following table 5.
Following table 05 shows impurity separating out in the 1st recirculation while carrying out source processing with R-Cat1 & sodium sulfate in oppositely separated the present invention's reaction.
Then the 1st processes the rear mother liquor producing processes with R-Cat2 & sodium sulfate, then recirculation in other circulation of the present invention.Its details is mentioned in table 6.
Following table 06 show with R-Cat2 carry out source while processing impurity in the 2nd recirculation, separate out economical with the amount of the fresh water of use in the present invention's reaction oppositely separated.
Figure BDA0000447280910000223
Figure BDA0000447280910000231
Be clear that according to the above discussion, the present invention comprises following clause:
1. a chemical process for separated naphthene sulfonic acid from melting agglomerate, the salt that contains described naphthene sulfonic acid in wherein said melting agglomerate, is characterized in that described method is the sustainable method that comprises following program:
Response procedures, wherein said melting agglomerate and acid-respons,
Follow by separable programming, wherein complete the separation of described reaction product,
Follow by recycling processing program, wherein process impure mother liquor for further recirculation in described response procedures and described separable programming, and further, wherein said response procedures and described separable programming are to carry out in a plurality of closed circuits that circulate in lower state, wherein add fresh water only in order to supplement the systematicness loss for example causing due to evaporation, wherein said closed circuit can carry out the recirculation of eigenmode and own type under the level of the source of produced all mother liquors, the described mother liquor using in described method is reaction medium, any in spe medium or washing medium, or its arbitrary combination, as shown in Fig. 4.
2. the method as described in clause 1, the quantity that wherein said melting agglomerate is described a plurality of circulations is preferably greater than 3, more preferably greater than 15, even more preferably greater than 30.
3. the method for claim 1, is characterized in that the described naphthene sulfonic acid in described melting agglomerate is H-acid.
4. the method described in clause 1 to 3, wherein for any single circulation, described response procedures carried out with the stage of preparing respectively the melting agglomerate of dilution and diluted acid, melting agglomerate and the diluted acid of dilution are mixed, and it is characterized in that the described stage carries out in following phases:
Stage 1.1a-is added to the first startup reaction medium to have the first container of agitator and add wherein acid, preferably sulfuric acid, the temperature that simultaneously keeps described acid is 200 ℃ and keep pH between 1 to 7 at the most, 40% (w/w) at the most of the total amount that wherein the first amount that starts reaction medium is the reaction medium that uses in whole circulation, and the first total amount that starts reaction medium of using in whole circulation is in existing circulation, to need 5 to 100 times, preferably 10 to 75 times of separated total melting agglomerate
Stage 1.1b-by the second startup reaction medium be added to there is the second reaction vessel of agitator and add wherein a certain amount of melting agglomerate so that the pH of the mixture in described the second reaction vessel between 8 to 14, preferably between 9 to 13, and 40% (w/w) at the most of the total amount that wherein the second amount that starts reaction medium is the reaction medium that uses in whole circulation, and the second total amount that starts reaction medium of using in whole circulation is in existing circulation, to need 5 to 100 times, preferably 10 to 75 times of separated total melting agglomerate
The mixture that stage 1.1c-stirs the first and second reaction vessels reaches 5 hours at the most, preferred time length of 30 minutes to 2.5 hours, keeps the temperature of mixture to be separately 200 ℃ at the most simultaneously,
Step 1.2-is added to the melting agglomerate of the dilution of described the second reaction vessel the described diluted acid of described the first reaction vessel within time of 5 hours at the most, and the temperature that adds alternatively the first reduction reaction medium and keep this mixture is 200 ℃ and keep pH between 1 to 9 at the most, it is characterized in that all circulations that start for the second circulation from described method, described first and second start reaction medium all takes out from mother liquor storage tank, in described mother liquor storage tank, preserve the mother liquor from the recirculation of recycling processing program, and
The reaction mixture that taking-up obtains when step 1.2 finishes to be to complete described response procedures, and the separated product being obtained by described reaction subsequently further carries out the recycling processing of produced mother liquor subsequently.
5. the method described in clause 1 to 3, wherein for any single circulation, described response procedures carried out with the stage of preparing respectively the melting agglomerate of dilution and diluted acid, melting agglomerate and the diluted acid of dilution are mixed, and it is characterized in that the described stage carries out in the following step:
Stage 1.1a-by the first startup reaction medium be added to there is the first reaction vessel of agitator and add wherein a certain amount of melting agglomerate so that in described the second reaction vessel the pH of mixture between 8 to 14, preferably between 9 to 13, and 40% (w/w) at the most of the total amount that wherein the first amount that starts reaction medium is the reaction medium that uses in whole circulation, and the second total amount that starts reaction medium of using in whole circulation is in existing circulation, to need 5 to 100 times, preferably 10 to 75 times of separated total melting agglomerate
Stage 1.1b-is added to the second startup reaction medium to have the second container of agitator and add wherein acid, preferably sulfuric acid, the temperature that simultaneously keeps described acid is 200 ℃ and keep pH between 1 to 7 at the most, 40% (w/w) at the most of the total amount that wherein the second amount that starts reaction medium is the reaction medium that uses in whole circulation, and the first total amount that starts reaction medium of using in whole circulation is in existing circulation, to need 5 to 100 times, preferably 10 to 75 times of separated total melting agglomerate
The mixture that stage 1.1c-stirs the first and second reaction vessels reaches 5 hours at the most, preferred time length of 30 minutes to 2.5 hours, keeps the temperature of mixture to be separately 200 ℃ at the most simultaneously,
Step 1.2-is added to the diluted acid of described the second reaction vessel the described melting agglomerate of described the first reaction vessel within time of 5 hours at the most, and the temperature that adds alternatively the first reduction reaction medium and keep described mixture is 200 ℃ and keep pH between 1 to 9 at the most, it is characterized in that all circulations that start for the second circulation from described method, described first and second start reaction medium all takes out from mother liquor storage tank, in described mother liquor storage tank, preserve the described mother liquor from the recirculation of recycling processing program, and
The reaction mixture that taking-up obtains when step 1.2 finishes to be to complete described response procedures, and the separated product being obtained by described reaction subsequently further carries out the recycling processing of produced mother liquor subsequently.
6. the method as described in clause 4 to 5, wherein for any circulation of described method, take out the reaction mixture of acquisition when step 1.2 finishes to complete response procedures as described below:
Step 1.3-adds the second reaction medium to described the first reaction vessel alternatively, 40% (w/w) at the most of the total amount that the amount of described the second reaction medium is the reaction medium that uses in whole circulation, with 500RPM at the most, stir the mixture alternatively and the temperature by keeping reaction mixture is 200 ℃ at the most, preferably at the most 100 ℃ simultaneously, and described in carrying out, be stirred to many 10 hours, preferably 30 minutes to 8 hours to remove during reacting the sulfurous gas producing completely, and Baume value is 10 to 50
Step 1.4-is added into described first reaction vessel with fresh reactant form of medium to be no more than the amount of 40% (w/w) of the total amount of the reaction medium using in whole existing circulation by the 3rd reaction medium in the first circulation, thereby formation separating mixture, the temperature that simultaneously keeps described separating mixture is 200 ℃ at the most, preferably at the most 100 ℃ and keep pH between 1 to 7, stir described separating mixture 24 hours at the most simultaneously, preferably at the most 5 hours, it is characterized in that being selected from described mother liquor storage tank for described the 3rd reaction medium of all ensuing circulations.
7. the method described in clause 1 to 6, wherein, for any circulation of described method, described separable programming comprises following steps:
Step 2.1-is added to described first reaction vessel with fresh reactant form of medium to be no more than the amount of 60% (w/w) of the total amount of the reaction medium using in described existing circulation by the first stirring reaction medium, make mixture be cooled to the temperature of 70 ℃ simultaneously, and keep pH between 1 to 7, described in while continuously stirring, mixture is 10 hours at the most, it is characterized in that for all ensuing circulations, described the first stirring reaction medium is taken from described mother liquor storage tank
Step 2.2-by adding alternatively the 4th reaction medium of fresh reactant form of medium to make the temperature of reaction mixture remain on 70 ℃ and pH is remained between 1 to 7 in the first circulation, simultaneously stirred reaction mixture 24 hours at the most, preferably at the most 5 hours, it is characterized in that for all ensuing circulations, described the first stirring reaction medium is taken from described mother liquor storage tank
Step 2.3-filters with under 1 to 7 pH the separated agglomerate forming when step 2.2 finishes the temperature of approximately 70 ℃, and produces the first filtrate flow A as the result of described filtration procedure, the time of 5 hours more than described filtration procedure proceeds to,
Step 2.4-is used fresh reactant medium all agglomerates that washing obtains when step 2.3 finishes under the pH of the temperature of approximately 70 ℃ and 1 to 7, and generation scrub stream B.
8. the method described in clause 1 to 7, wherein, for any circulation of described method, merges the first filtrate flow A and scrub stream B, and carries out following catalytic treatment:
Step 3.1-is heated to 100 ℃ at the most by merging stream A and B in the first processing vessel, the preferred temperature of 70 ℃, continue to many 5 hours, add subsequently the first treatment agent and the first vitriol, 40% (w/v) at the most of the total amount that the amount of wherein said the first treatment agent is the reaction medium that uses in existing circulation, so that the Baume value of mixture remains at the most 50, make to make the temperature of described mixture to remain at the most 50 ℃ and keep pH between 1 to 7 after adding reagent simultaneously, the waste material that wherein produces the second filtrate of mother liquor stream C form and need to dispose, it is characterized in that only in first of this step, recycling fresh vitriol, and in ensuing circulation, use from the salt of step 3.2 generation,
Step 3.2-is added to the second processing vessel by described the second filtrate flow C, wherein described the second filtrate is cooled to the temperature of 25 ℃ at the most, continue to many 5 hours, add subsequently the second treatment agent and vitriol, 20% (w/v) at the most of the total amount that the amount of wherein said the second treatment agent and vitriol is the reaction medium that uses in existing circulation, the Baume value that simultaneously keeps mixture is at the most 50, and keep pH 1 to 7, preferably between 4 to 6, it is characterized in that using fresh salt and in all ensuing circulations, use the salt reclaiming when step 3.2 finishing in the first circulation of described method, wherein
9. the method as described in any one in clause 2 to 8, wherein said acid is sulfuric acid.
10. the method described in clause 9, wherein said the first and second treatment agents are any patent reagent.
11. methods as described in any one in clause 2 to 10, wherein by described melting agglomerate and/or acid with its all amount or arbitrary size with any interval, be added into step 1.2 in batches.
12. the method as described in any one in clause 2 to 11, wherein described the first and second treatment agents of step 3.1 & 3.2 are selected from the group of the combination that comprises alkali-metal oxyhydroxide, carbonate or supercarbonate or alkali-metal oxyhydroxide, carbonate or supercarbonate; The preferred sodium hydroxide of described oxyhydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide; The preferred sodium carbonate of described carbonate, salt of wormwood, calcium carbonate or Quilonum Retard; The preferred sodium bicarbonate of described supercarbonate, saleratus, lithium bicarbonate.
13. methods as described in any one in clause 2 to 12, also applicable to the sulfonic acid product of separating analogous kind, 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-sulfonic acid (Xue Fo Shi acid), 2-amino-5-naphthol-1,7-disulphonic acid (J-disulfonic acid), 2-phenyl amino-5-naphthols-7-sulfonic acid (phenyl J-acid), 1-ALPHA-NAPHTHYL 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-ALPHA-NAPHTHYL AMINE-3,6,8-trisulfonic acid (Koch's acid), 1-ALPHA-NAPHTHYL AMINE-6-sulfonic acid (Ke Liefu acid), 1-ALPHA-NAPHTHYL AMINE-7-sulfonic acid (Ke Liefu acid), R-acid, G-acid, amino G-acid, 2-amido-8-naphthol-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-ALPHA-NAPHTHYL AMINE-4,7-disulfonic acid and having as amino, nitro, halogen, hydroxyl, sulfonic group, carboxyl, benzyl, phenyl, ketone, the all similar naphthene sulfonic acid of the functional group of aldehyde etc. and 2-Naphthol derivative.
14. methods as described in any one in clause 1-6 and 6-12, wherein said loop number is greater than 100.
15. methods as described in any one in clause 8-14, wherein when the temperature of described reaction mixture reaches 0 ℃ to 100 ℃, preferably described the first and second treatment agents added together with short run 70 to 20 ℃ time, once or temperature reach 0 ℃ to 100 ℃, preferably 70 to 20 ℃ just add together this two kinds of reagent.
Although more than describe, contain a lot of specificitys, these should not be construed as and limit the scope of the invention, but as the example of its preferred embodiment.Must it should be understood that lower without departing from the spirit and scope of the present invention disclosing of modifying and more than change basis provide be possible.Therefore, scope of the present invention should not determined by exemplified embodiment, but be determined by claims and legal equivalents thereof.

Claims (15)

1. a chemical process for separated naphthene sulfonic acid from melting agglomerate, the salt that contains described naphthene sulfonic acid in wherein said melting agglomerate, is characterized in that described method is the sustainable method that comprises following program:
Response procedures, wherein said melting agglomerate and acid-respons,
Follow by separable programming, wherein complete the separation of described reaction product,
Follow by recycling processing program, wherein process impure mother liquor for further recirculation in described response procedures and described separable programming,
And further, wherein said response procedures and described separable programming are to carry out in a plurality of closed circuits that circulate in lower state, wherein add fresh water only in order to supplement the systematicness loss for example causing due to evaporation, wherein said closed circuit can carry out the recirculation of eigenmode and own type under the level of the source of produced all mother liquors, the described mother liquor using in described method is any in reaction medium, spe medium or washing medium, or its arbitrary combination, as shown in Fig. 4.
2. the method for claim 1, is characterized in that wherein said melting agglomerate is, the quantity of described a plurality of circulations is preferably greater than 3, more preferably greater than 15, even more preferably greater than 30.
3. the method for claim 1, is characterized in that the described naphthene sulfonic acid in described melting agglomerate is H-acid.
4. the method described in claims 1 to 3, wherein for any single circulation, described response procedures carried out with the stage of preparing respectively the melting agglomerate of dilution and diluted acid, melting agglomerate and the diluted acid of dilution are mixed, and it is characterized in that the described stage carries out in following phases:
Stage 1.1a-is added to the first startup reaction medium to have the first container of agitator and add wherein acid, preferably sulfuric acid, the temperature that simultaneously keeps described acid is 200 ℃ and keep pH between 1 to 7 at the most, 40% (w/w) at the most of the total amount that wherein the first amount that starts reaction medium is the reaction medium that uses in whole circulation, and the first total amount that starts reaction medium of using in whole circulation is in existing circulation, to need 5 to 100 times, preferably 10 to 75 times of separated total melting agglomerate
Stage 1.1b-by the second startup reaction medium be added to there is the second reaction vessel of agitator and add wherein a certain amount of melting agglomerate so that the pH of the mixture in described the second reaction vessel between 8 to 14, preferably between 9 to 13, and 40% (w/w) at the most of the total amount that wherein the second amount that starts reaction medium is the reaction medium that uses in whole circulation, and the second total amount that starts reaction medium of using in whole circulation is in existing circulation, to need 5 to 100 times, preferably 10 to 75 times of separated total melting agglomerate
The mixture that stage 1.1c-stirs the first and second reaction vessels reaches 5 hours at the most, preferred time length of 30 minutes to 2.5 hours, keeps the temperature of mixture to be separately 200 ℃ at the most simultaneously,
Step 1.2-is added to the melting agglomerate of the dilution of described the second reaction vessel the described diluted acid of described the first reaction vessel within time of 5 hours at the most, and the temperature that adds alternatively the first reduction reaction medium and keep this mixture is 200 ℃ and keep pH between 1 to 9 at the most, it is characterized in that all circulations that start for the second circulation from described method, described first and second start reaction medium all takes out from mother liquor storage tank, in described mother liquor storage tank, preserve the mother liquor from the recirculation of recycling processing program, and
The reaction mixture that taking-up obtains when step 1.2 finishes to be to complete described response procedures, and the separated product being obtained by described reaction subsequently further carries out the recycling processing of produced mother liquor subsequently.
5. the method described in claims 1 to 3, wherein for any single circulation, described response procedures carried out with the stage of preparing respectively the melting agglomerate of dilution and diluted acid, melting agglomerate and the diluted acid of dilution are mixed, and it is characterized in that the described stage carries out in the following step:
Stage 1.1a-by the first startup reaction medium be added to there is the first reaction vessel of agitator and add wherein a certain amount of melting agglomerate so that the pH of the mixture in described the second reaction vessel between 8 to 14, preferably between 9 to 13, and 40% (w/w) at the most of the total amount that wherein the first amount that starts reaction medium is the reaction medium that uses in whole circulation, and the second total amount that starts reaction medium of using in whole circulation is in existing circulation, to need 5 to 100 times, preferably 10 to 75 times of separated total melting agglomerate
Stage 1.1b-is added to the second startup reaction medium to have the second container of agitator and add wherein acid, preferably sulfuric acid, the temperature that simultaneously keeps described acid is 200 ℃ and keep pH between 1 to 7 at the most, 40% (w/w) at the most of the total amount that wherein the second amount that starts reaction medium is the reaction medium that uses in whole circulation, and the first total amount that starts reaction medium of using in whole circulation is in existing circulation, to need 5 to 100 times, preferably 10 to 75 times of separated total melting agglomerate
The mixture that stage 1.1c-stirs the first and second reaction vessels reaches 5 hours at the most, preferred time length of 30 minutes to 2.5 hours, keeps the temperature of mixture to be separately 200 ℃ at the most simultaneously,
Step 1.2-is added to the diluted acid of described the second reaction vessel the described melting agglomerate of described the first reaction vessel within time of 5 hours at the most, and the temperature that adds alternatively the first reduction reaction medium and keep described mixture is 200 ℃ and keep pH between 1 to 9 at the most, it is characterized in that all circulations that start for the second circulation from described method, described first and second start reaction medium all takes out from mother liquor storage tank, in described mother liquor storage tank, preserve the described mother liquor from the recirculation of recycling processing program, and
The reaction mixture that taking-up obtains when step 1.2 finishes to be to complete described response procedures, and the separated product being obtained by described reaction subsequently further carries out the recycling processing of produced mother liquor subsequently.
6. the method as described in claim 4 to 5, wherein for any circulation of described method, take out the reaction mixture of acquisition when step 1.2 finishes to complete response procedures as described below:
Step 1.3-adds the second reaction medium to described the first reaction vessel alternatively, 40% (w/w) at the most of the total amount that the amount of described the second reaction medium is the reaction medium that uses in whole circulation, with 500RPM at the most, stir the mixture alternatively and the temperature by keeping reaction mixture is 200 ℃ at the most, preferably at the most 100 ℃ simultaneously, and described in carrying out, be stirred to many 10 hours, preferably 30 minutes to 8 hours to remove during reacting the sulfurous gas producing completely, and Baume value is 10 to 50
Step 1.4-is added into described first reaction vessel with fresh reactant form of medium to be no more than the amount of 40% (w/w) of the total amount of the reaction medium using in whole existing circulation by the 3rd reaction medium in the first circulation, thereby formation separating mixture, the temperature that simultaneously keeps described separating mixture is 200 ℃ at the most, preferably at the most 100 ℃ and keep pH between 1 to 7, stir described separating mixture 24 hours at the most simultaneously, preferably at the most 5 hours, it is characterized in that being selected from described mother liquor storage tank for described the 3rd reaction medium of all ensuing circulations.
7. the method described in claim 1 to 6, wherein, for any circulation of described method, described separable programming comprises following steps:
Step 2.1-is added to described first reaction vessel with fresh reactant form of medium to be no more than the amount of 60% (w/w) of the total amount of the reaction medium using in described existing circulation by the first stirring reaction medium, make gained mixture be cooled to the temperature of 70 ℃ simultaneously, and keep pH between 1 to 7, described in while continuously stirring, mixture is 10 hours at the most, it is characterized in that for all ensuing circulations, described the first stirring reaction medium is taken from described mother liquor storage tank
Step 2.2-by adding alternatively the 4th reaction medium of fresh reactant form of medium to make the temperature of reaction mixture remain on 70 ℃ and pH is remained between 1 to 7 in the first circulation, simultaneously stirred reaction mixture 24 hours at the most, preferably at the most 5 hours, it is characterized in that for all ensuing circulations, described the first stirring reaction medium is taken from described mother liquor storage tank
Step 2.3-filters with under 1 to 7 pH the separated agglomerate forming when step 2.2 finishes the temperature of approximately 70 ℃, and produces the first filtrate flow A as the result of described filtration procedure, the time of 5 hours more than described filtration procedure proceeds to,
Step 2.4-is used fresh reactant medium all agglomerates that washing obtains when step 2.3 finishes under the pH of the temperature of approximately 70 ℃ and 1 to 7, and generation scrub stream B.
8. the method described in claim 1 to 7, wherein, for any circulation of described method, merges the first filtrate flow A and scrub stream B, and carries out following catalytic treatment:
Step 3.1-is heated to 100 ℃ at the most by merging stream A and B in the first processing vessel, the preferred temperature of 70 ℃, continue to many 5 hours, add subsequently the first treatment agent and the first vitriol, 40% (w/v) at the most of the total amount that the amount of wherein said the first treatment agent is the reaction medium that uses in existing circulation, so that the Baume value of mixture remains at the most 50, make the temperature of described mixture after adding reagent remain at the most 50 ℃ and keep pH between 1 to 7 simultaneously, the waste material that wherein produces the second filtrate of mother liquor stream C form and need to dispose, it is characterized in that only in first of this step, recycling fresh vitriol, and in ensuing circulation, use from the salt of step 3.2 generation,
Step 3.2-is added to the second processing vessel by described the second filtrate flow C, wherein described the second filtrate is cooled to the temperature of 25 ℃ at the most, continue to many 5 hours, add subsequently the second treatment agent and vitriol, 20% (w/v) at the most of the total amount that the amount of wherein said the second treatment agent and vitriol is the reaction medium that uses in existing circulation, the Baume value that simultaneously keeps mixture is at the most 50, and keep pH 1 to 7, preferably between 4 to 6, it is characterized in that using fresh salt and in all ensuing circulations, use the salt reclaiming when step 3.2 finishing in the first circulation of described method.
9. the method as described in any one in claim 2 to 8, wherein said acid is sulfuric acid.
10. method as described in claim 9, wherein said the first and second treatment agents are any patent reagent.
11. methods as described in any one in claim 2 to 10, wherein by described melting agglomerate and/or acid with its all amount or arbitrary size with any interval, be added into step 1.2 in batches.
12. the method as described in any one in claim 2 to 11, wherein described the first and second treatment agents of step 3.1 & 3.2 are selected from the group of the combination that comprises alkali-metal oxyhydroxide, carbonate or supercarbonate or alkali-metal oxyhydroxide, carbonate or supercarbonate; The preferred sodium hydroxide of described oxyhydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide; The preferred sodium carbonate of described carbonate, salt of wormwood, calcium carbonate or Quilonum Retard; The preferred sodium bicarbonate of described supercarbonate, saleratus, lithium bicarbonate.
13. methods as described in any one in claim 1 to 12, also applicable to the sulfonic acid product of separating analogous kind, 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-sulfonic acid (Xue Fo Shi acid), 2-amino-5-naphthol-1,7-disulphonic acid (J-disulfonic acid), 2-phenyl amino-5-naphthols-7-sulfonic acid (phenyl J-acid), 1-ALPHA-NAPHTHYL 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-ALPHA-NAPHTHYL AMINE-3,6,8-trisulfonic acid (Koch's acid), 1-ALPHA-NAPHTHYL AMINE-6-sulfonic acid (Ke Liefu acid), 1-ALPHA-NAPHTHYL AMINE-7-sulfonic acid (Ke Liefu acid), R-acid, G-acid, amino G-acid, 2-amido-8-naphthol-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-ALPHA-NAPHTHYL AMINE-4,7-disulfonic acid and having as amino, nitro, halogen, hydroxyl, sulfonic group, carboxyl, benzyl, phenyl, ketone, the all similar naphthene sulfonic acid of the functional group of aldehyde etc. and 2-Naphthol derivative.
14. methods as described in any one in claim 1-6 and 7-12, wherein said loop number is greater than 100.
15. methods as described in any one in claim 8-14, wherein when the temperature of described reaction mixture reaches 0 ℃ to 100 ℃, preferably described the first and second treatment agents added together with short run 70 to 20 ℃ time, once or temperature reach 0 ℃ to 100 ℃, preferably 70 to 20 ℃ just add together this two kinds of reagent.
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)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
IN2975/MUM/2010 2011-04-26
IN2975MU2010 2011-04-26
PCT/IB2012/052072 WO2012147037A2 (en) 2011-04-26 2012-04-26 Sustainable chemical process for isolation of naphthalene sulphonic acid compounds with inherent recycle of all acidic streams generated during isolation and washing

Publications (2)

Publication Number Publication Date
CN103687848A true CN103687848A (en) 2014-03-26
CN103687848B CN103687848B (en) 2018-04-24

Family

ID=46317457

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201280031697.8A Active CN103687848B (en) 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

Country Status (2)

Country Link
CN (1) CN103687848B (en)
WO (1) WO2012147037A2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108358819A (en) * 2018-03-14 2018-08-03 荆门市熊兴化工有限公司 A method of it is produced from K acid and recycles R salt in mother liquor

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108358819A (en) * 2018-03-14 2018-08-03 荆门市熊兴化工有限公司 A method of it is produced from K acid and recycles R salt in mother liquor
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

Also Published As

Publication number Publication date
WO2012147037A3 (en) 2012-12-27
CN103687848B (en) 2018-04-24
WO2012147037A2 (en) 2012-11-01

Similar Documents

Publication Publication Date Title
CN216662498U (en) System for preparing battery-grade lithium hydroxide and lithium carbonate
CN100558636C (en) SODIUMNITRATE and Repone K replacement(metathesis)reaction are produced the method for saltpetre
CN100497304C (en) Method of synthesizing sulfonation paraposition ester
CN103687848A (en) Sustainable chemical process for isolation of naphthalene sulphonic acid compounds with inherent recycle of all acidic streams generated during isolation and washing
CN102020316B (en) Method for preparing chromic anhydride from potassium chromate
CN1304684C (en) Synthesis technology of polyester dying modifier SIPM
CN110330439A (en) A kind of zinc-glycine complex and preparation method thereof not introducing foreign ion
WO2023169432A1 (en) Method and system for preparing battery-grade lithium hydroxide and lithium carbonate
CN104086398B (en) A kind of method of oxalic acid waste liquid Separation and Recovery oxalic acid
CN109336177A (en) A method of with hydrogen peroxide and ammonium hydroxide clean manufacturing high purity vanadic anhydride
CN107934999A (en) A kind of method that battery-level lithium carbonate is recycled in the catalyst waste slag from polyphenylene sulfide
KR101952060B1 (en) Method for preparing furan-2,5-dicarboxylic acid (FDCA) from solid salt
US4808342A (en) Production of sulfonated amines
CN109534369A (en) A kind of film is integrated to prepare lithium chloride device and method thereof
CN104016890A (en) Method for preparing 1-amino-4-sodium naphthalene sulfonate through solid-phase continuous reaction
CN108675919A (en) A kind of method that double trimethylolpropane is extracted in trimethylolpropane heavy constituent
CN205933523U (en) High salt organic wastewater of EDTA and resources recovery system
CN107827821B (en) Continuous flow clean production process of pyrazolone series products
JPS61178971A (en) Manufacture of sulfuric acid semiester compound
US2902448A (en) Manufacture of organic calcium sulfonates
CN102001708A (en) Clean method for preparing sodium chromate from chromite by liquid-phase oxidation
CN105315177B (en) A kind of DSD acid synthesis technique
CN104495931B (en) A kind of potassium chromate liquid phase reactor crystallizes the production method of chromic anhybride
CN109292796B (en) Method for separating caustic alkali and chromate from solid mixture of caustic alkali and chromate
CN103641568A (en) Comprehensive treatment method for waste sulfuric acid of sulfonated products

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant