CN107188785A - A kind of 2,4 diamino benzene sulfonic acid and its salt produce the resource utilization method of waste water - Google Patents
A kind of 2,4 diamino benzene sulfonic acid and its salt produce the resource utilization method of waste water Download PDFInfo
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- CN107188785A CN107188785A CN201710262398.XA CN201710262398A CN107188785A CN 107188785 A CN107188785 A CN 107188785A CN 201710262398 A CN201710262398 A CN 201710262398A CN 107188785 A CN107188785 A CN 107188785A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/045—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of a group bound to the ring by nitrogen
- C07C37/05—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of a group bound to the ring by nitrogen by substitution of a NH2 group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/72—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
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Abstract
A kind of 2,4 diamino benzene sulfonic acids and its salt produce the resource utilization method of waste water, including：(1) m-phenylene diamine (MPD) routinely carries out sulfonating reaction with sulfuric acid and/or oleum, obtains acid mother liquor A and an acid crude between sulfur acid；Between acid crude through water washing, sour intermediate products and cleaning solution B between obtaining；Between sour intermediate products neutralized with alkali, isolated hydrochlorate product and neutralize mother solution C；(2) at least one of acid mother liquor A, cleaning solution B, neutralization mother solution C by between, are configured to the pickle that acidity is 3~20%, and the pickle prepared can be directly as material liquid, and through heating up, hydrolysis obtain resorcinol hydrolyzate；Or a certain amount of m-phenylene diamine (MPD) is supplemented into the pickle prepared as material liquid, heating hydrolysis obtains resorcinol hydrolyzate；(3) resorcinol hydrolyzate obtains resorcinol product through extraction, rectifying.The present invention significantly reduces spent acid, the discharge capacity of waste water that 2,4 diamino benzene sulfonic acids and its salt production process are produced, and improves raw material comprehensive utilization ratio.
Description
(1) technical field
The present invention relates to the resource utilization method that one kind 2,4- diamino benzene sulfonic acids and its salt produce waste water, more particularly to
Acid mother liquor, cleaning solution and neutralization mother liquor are used to produce resorcinol in the middle of a kind of 2,4- diamino benzene sulfonic acids and its salt production process
Method.
(2) background technology
2,4- diamino benzene sulfonic acids, sour between being commonly called as, alias m-phenylenediamine -4-sulfonic acid is a kind of important industrial chemicals, often
It is used as dyestuff intermediate or medicine intermediate.Between traditional sour synthesis route be with m-phenylene diamine (MPD) sulfonation prepare between acid,
Such as document 2, the new technique for synthesizing (applying Wei Bin etc., Shanghai Dyestuffs, the 5th phase of volume 36) of 4- diamino benzene sulfonic acids, CN1900058A,
CN102516137A etc., using m-phenylene diamine (MPD) as raw material, with sulfuric acid, oleum or SO3Gas is as sulfonating agent to m-phenylene diamine (MPD)
Sulfonation processing is carried out, acid between product is derived from, an acid is neutralized by alkali lye obtain salt again.
Because the solubility of raw material and product in acid and water is larger, spent acid, waste water can not be recycled, can only be with
Acid is discharged together, is substantially increased the pressure of follow-up spent acid processing, can be caused the serious wasting of resources and environmental pollution.
CN103641568B, Chen Houkai etc. have inquired into the waste acid treatment scheme of 2,4- diamino benzene sulfonic acids, can concentrate place
Manage or for producing sulfate.Although this technique solve the governing problem of a large amount of Waste Sulfuric Acids of sulfonated product, but contains in spent acid
There are a large amount of organic principles not all to be reasonably utilized, cause the waste of resource.
In summary, find the production waste water progress efficient resource utilization of one kind 2,4- diamino benzene sulfonic acids and its salt into
For the key of technological innovation in the industry.
(3) content of the invention
It is an object of the invention to provide the recycling side that a kind of 2,4- diamino benzene sulfonic acids and its salt produce waste water
Method.
To realize the object of the invention, the technical scheme used is as follows：
One kind 2,4- diamino benzene sulfonic acids and its salt produce the resource utilization method of waste water, comprise the following steps：
(1) 2,4- diamino benzene sulfonic acids and its salt production waste water are collected：M-phenylene diamine (MPD) is with sulfuric acid and/or oleum by normal
Rule carry out sulfonating reaction, and sulfonation material dilutes through hydrolysis, cooling, with water or frozen water, separation of solid and liquid, and acid is female between obtaining sulfur acid
Liquid A and an acid crude；Between acid crude through water washing, sour intermediate products and cleaning solution B between obtaining；Between in sour intermediate products alkali
A hydrochlorate product is isolated to, obtained suspension and neutralizes mother solution C；
(2) acidity will be configured to selected from least one of acid mother liquor A, cleaning solution B, neutralization mother solution C between step (1)
For 3~20% pickle, the pickle prepared can obtain resorcinol hydrolysis directly as material liquid through the hydrolysis that heats up
Liquid；Or a certain amount of m-phenylene diamine (MPD) is supplemented into the pickle prepared as material liquid, heating hydrolysis obtains resorcinol hydrolysis
Liquid；
(3) resorcinol hydrolyzate obtains resorcinol product through extraction, rectifying.
In the step (2), an acid mother liquor A is preferably comprised in the pickle of preparation.
In the step (2), in the pickle preferably prepared acidity (with sulphur acid meter) be 6~20%, more preferably 8~
15%.
In the step (2), preferably m-phenylene diamine (MPD) is added into the pickle of preparation.The additional amount of m-phenylene diamine (MPD) preferably makes
The ratio between molal quantity of total mole number and sulfuric acid of m-phenylene diamine (MPD) and m-phenylene diamine (MPD) sulfonated bodies is 1 in material liquid:1.5~3.0, it is more excellent
Select 1:1.7~2.4.
In the step (2), during material liquid hydrolysis, temperature control is 180~260 DEG C, preferably 200~250 DEG C；Water
It is preferably 120~300min to solve the reaction time.
The definition of acidity is in the present invention：The quality of sulfuric acid is converted to according to hydrogen ion content in solution, after conversion
Sulfuric acid mass percent concentration is used as acidity.
The beneficial effect of the present invention compared with prior art is mainly reflected in：
The present invention opens the production utilization of wastewater resource production resorcinol of 2,4- diamino benzene sulfonic acids and its salt
New technology so that sulfuric acid, water and organic principle in spent acid and waste water that an acid and its salt production process are produced are able to abundant profit
With significantly reducing spent acid, the discharge capacity of waste water that 2,4- diamino benzene sulfonic acids and its salt production process are produced, improve raw material and integrate
Utilization rate.
(4) illustrate
Fig. 1 is present invention process schematic flow sheet.
(5) embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
Embodiment 1,
(1) synthesis of 2,4- diamino benzene sulfonic acids and its salt uses common process：108g m-phenylene diamine (MPD)s are added into 378g
In 98% sulfuric acid, within control 120 DEG C of process temperature of charging, charging finishes to form homogeneous salting liquid, is warming up to 150 DEG C, delays
The slow oleums of 271.3g 50% that add carry out sulfonation, and addition is incubated 4h after finishing.Sulfonated liquid is cooled to after 130 DEG C, slowly
Hydrolysis after 32.4g water, insulation 20min is added to complete and cool down to room temperature.The hydrolyzate of cooling is slowly added to 550g frozen water
In, 15 DEG C or so filterings, acid mother liquor A between isolated filter cake and 941g.Filter cake adds 200g water to be washed, and is separated after washing
To sour a solid and 343g cleaning solution B, a sour yield 74.6%, a sour purity (HPLC) 99.5%.By obtained above acid
32% sodium hydrate aqueous solution is added in solid, pH~9 are adjusted, it is a hydrochlorate suspension to neutralize obtained product, through solid-liquid
Separation, is obtained in 2,4- diamino benzene sulfonic acids sodium (double) 152.6g (pure) and 180.2g and mother solution C, a pair product purity
(HPLC) 99.2%, feed molar utilization rate 72.7%.
(2) sulfuric acid of 400g 98% and 3240g water are added 200g and melted by the dilute sulfuric acid that mixed preparing acidity is 11%
The m-phenylene diamine (MPD) melted and pickle mixed preparing metaphenylenediamine sulphate solution.The material liquid prepared is preheated to after 240 DEG C
Add reactor hydrolysis 240min；Resorcinol (pure) 187.4g is obtained through conventional solvent extraction and separation, rectifying after reaction,
Resorcinol product purity (HPLC) 99.5%, m-phenylene diamine (MPD) feed molar utilization rate 92%.
Embodiment 2,
(1) according to double between the method synthesis of step (1) described in embodiment 1, acid mother liquor A, 343g cleaning solution between 941g is obtained
In B, 180g and three strands of waste water of mother solution C；
(2) by step (1) obtain between acid mother liquor A, cleaning solution B, neutralize three strands of waste water of mother solution C and mix and match somebody with somebody with 3900g water
Relieving haperacidity degree is 11% pickle, does not add m-phenylene diamine (MPD), and directly pickle is preheated to after 240 DEG C and adds reactor hydrolysis
240min；After reaction resorcinol (pure) 26g is obtained through extraction, rectifying, resorcinol product purity (HPLC) 99.2%,
Phenylenediamine feed molar utilization rate 97.3%.
Embodiment 3,
(1) according to double between the method synthesis of step (1) described in embodiment 1, acid mother liquor A, 343g cleaning solution between 941g is obtained
In B, 180g and three strands of waste water of mother solution C；
(2) by step (1) obtain between acid mother liquor A and 3900g water mixed preparings acidity be 11% pickle, add
The m-phenylene diamine (MPD) of 270g meltings prepares hydrolysis material liquid；Reactor is added after the hydrolysis material liquid prepared is preheated into 240 DEG C
Hydrolysis 240min obtains resorcinol hydrolyzate, and resorcinol (pure) 276g, resorcinol product purity are obtained through extraction, rectifying
(HPLC) 99.7%, m-phenylene diamine (MPD) feed molar utilization rate 93.7%.
Embodiment 4,
(1) according to double between the method synthesis of step (1) described in embodiment 1, acid mother liquor A, 343g cleaning solution between 941g is obtained
In B, 180g and three strands of waste water of mother solution C；
(2) by step (1) obtain between acid mother liquor A and 4900g water mixed preparings acidity be 8% pickle, add
The m-phenylene diamine (MPD) of 300g meltings prepares hydrolysis material liquid；Reactor is added after the hydrolysis material liquid prepared is preheated into 230 DEG C
Hydrolysis 200min obtains resorcinol hydrolyzate, and resorcinol (pure) 279g, resorcinol product purity are obtained through extraction, rectifying
(HPLC) 99.5%, m-phenylene diamine (MPD) feed molar utilization rate 92.7%.
Embodiment 5,
(1) according to double between the method synthesis of step (1) described in embodiment 1, acid mother liquor A, 343g cleaning solution between 941g is obtained
In B, 180g and three strands of waste water of mother solution C；
(2) by step (1) obtain between acid mother liquor A, cleaning solution B and 3480g water mixed preparing acidity for 12.4% it is dilute
Acid solution, the m-phenylene diamine (MPD) for adding 290g meltings prepares hydrolysis material liquid；The hydrolysis material liquid prepared is preheated to after 220 DEG C and added
Enter reactor hydrolysis 240min and obtain resorcinol hydrolyzate, resorcinol (pure) 291g, resorcinol are obtained through extraction, rectifying
Product purity (HPLC) 99.4%, m-phenylene diamine (MPD) feed molar utilization rate 93.2%.
Embodiment 6,
(1) according to double between the method synthesis of step (1) described in embodiment 1, acid mother liquor A, 343g cleaning solution between 941g is obtained
In B, 180g and three strands of waste water of mother solution C；
(2) by step (1) obtain between acid mother liquor A, neutralize mother solution C and 2000g water mixed preparings acidity be 15% it is dilute
Acid solution, the m-phenylene diamine (MPD) for adding 212g meltings prepares hydrolysis material liquid；The hydrolysis material liquid prepared is preheated to after 200 DEG C and added
Enter reactor hydrolysis 280min and obtain resorcinol hydrolyzate, resorcinol (pure) 197g, resorcinol are obtained through extraction, rectifying
Product purity (HPLC) 99.2%, m-phenylene diamine (MPD) feed molar utilization rate 92.5%.
Embodiment 7
(1) an acid mother liquor A between acidleach cake and 941g is obtained according to the method for step (1) described in embodiment 1, filter cake is without washing
Wash, add 32% sodium hydrate aqueous solution, adjust pH~9, neutralize obtained product be between hydrochlorate suspension, through separation of solid and liquid,
Obtain in 2,4- diamino benzene sulfonic acids sodium (double) 175g (pure) and 600g and mother solution C, a pair product purity (HPLC)
99.5%, yield 83.5%；
(2) by step (1) obtain between acid mother liquor A, neutralize mother solution C and 3700g water mixed preparings acidity be 9.1% it is dilute
Acid solution, the m-phenylene diamine (MPD) for adding 250g meltings prepares hydrolysis material liquid；The hydrolysis material liquid prepared is preheated to after 250 DEG C and added
Enter reactor hydrolysis 160min and obtain resorcinol hydrolyzate, resorcinol (pure) 240g, resorcinol are obtained through extraction, rectifying
Product purity (HPLC) 99.5%, m-phenylene diamine (MPD) feed molar utilization rate 92.5%.
Above-described embodiment Comparative result is as follows：
Note：It is the comparison with embodiment 1 that unit resorcinol, which consumes sulfuric acid decrement,.
By embodiment 1 it can be found that a pairing is during, sour yield reaches 93.2% between crude product, after washing between acid receive
Rate only reaches 74.6%, after neutralization between double yields be reduced to 72.7%.Between acid and its salt production process in can produce waste liquid A, B, C,
Substantial amounts of acid is present in an acid mother liquor A especially in water-washing process, if waste water is not carried out into recycling, a large amount of sulphur
Sour, unreacted raw material m-phenylene diamine (MPD) and the accessory substance of generation are present in waste liquid, it is impossible to rationally utilized.By implementing
Example 1,2,3,4,5, is respectively used to prepare resorcinol by different waste liquids, m-phenylene diamine (MPD) molar yield improve (be 92% with
On), produce resorcinol product per ton and save about 2 tons or so sulfuric acid, the sulfuric acid and organic principle in a twin production waste liquid are able to
Make full use of, realize the recycling of waste liquid.The waste liquid that double production processes are produced between embodiment 2,3,4,5 is used between preparing
Benzenediol, it is suitable that obtained product and the m-phenylene diamine (MPD) acidic hydrolysis of embodiment 1 prepare the product quality that resorcinol obtains, explanation
The method that 2,4- diamino benzene sulfonic acids and its salt production waste water are prepared resorcinol by the application is feasible.
Claims (9)
1. one kind 2,4- diamino benzene sulfonic acids and its salt produce the resource utilization method of waste water, comprise the following steps：
(1) 2,4- diamino benzene sulfonic acids and its salt production waste water are collected：M-phenylene diamine (MPD) routinely enters with sulfuric acid and/or oleum
Row sulfonating reaction, sulfonation material dilutes through hydrolysis, cooling, with water or frozen water, separation of solid and liquid, obtains acid mother liquor A between sulfur acid
With an acid crude；Between acid crude through water washing, sour intermediate products and cleaning solution B between obtaining；Between sour intermediate products neutralized with alkali, obtain
To suspension be isolated to a hydrochlorate product and neutralize mother solution C；
(2) acid mother liquor A, cleaning solution B between step (1) will be selected from, at least one of mother solution C is neutralized, be configured to acidity for 3~
20% pickle, the pickle prepared can be directly as material liquid, and through heating up, hydrolysis obtains resorcinol hydrolyzate；Or to
A certain amount of m-phenylene diamine (MPD) is supplemented in the pickle prepared as material liquid, heating hydrolysis obtains resorcinol hydrolyzate；
(3) resorcinol hydrolyzate obtains resorcinol product through extraction, rectifying.
2. resource utilization method as claimed in claim 1, it is characterised in that：In the step (2), in the pickle of preparation
Contain an acid mother liquor A.
3. resource utilization method as claimed in claim 1, it is characterised in that：In the step (2), in the pickle of preparation
Acidity is 6~20%.
4. resource utilization method as claimed in claim 2, it is characterised in that：In the step (2), in the pickle of preparation
Acidity is 6~20%.
5. resource utilization method as claimed in claim 4, it is characterised in that：In the step (2), in the pickle of preparation
Acidity is 8~15%.
6. the resource utilization method as described in one of Claims 1 to 5, it is characterised in that：In the step (2), to preparation
A certain amount of m-phenylene diamine (MPD) is supplemented in good pickle as material liquid, the additional amount of m-phenylene diamine (MPD) make in material liquid m-phenylene diamine (MPD) and
The ratio between the total mole number of m-phenylene diamine (MPD) sulfonated bodies and the molal quantity of sulfuric acid are 1:1.5~3.0.
7. resource utilization method as claimed in claim 6, it is characterised in that：The additional amount of m-phenylene diamine (MPD) makes in the middle of material liquid
The ratio between molal quantity of total mole number and sulfuric acid of phenylenediamine and m-phenylene diamine (MPD) sulfonated bodies is 1:1.7~2.4.
8. the resource utilization method as described in one of Claims 1 to 5, it is characterised in that：In the step (2), material liquid
During hydrolysis, temperature control is 180~260 DEG C, and hydrolysis time is 120~300min.
9. resource utilization method as claimed in claim 8, it is characterised in that：In the step (2), material liquid hydrolysis
When, temperature control is 200~250 DEG C.
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| CN201710262398.XA CN107188785B (en) | 2017-04-20 | 2017-04-20 | Resource utilization method of 2, 4-diaminobenzene sulfonic acid and salt production wastewater |
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| CN201710262398.XA CN107188785B (en) | 2017-04-20 | 2017-04-20 | Resource utilization method of 2, 4-diaminobenzene sulfonic acid and salt production wastewater |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108863857A (en) * | 2018-06-29 | 2018-11-23 | 浙江龙盛化工研究有限公司 | The serial dilution device and method of N-acetylsulfanilyl chloride cooling crystallization |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3462497A (en) * | 1966-11-14 | 1969-08-19 | Koppers Co Inc | Resorcinol manufacture |
| CN106277477A (en) * | 2016-10-31 | 2017-01-04 | 江苏远征化工有限公司 | The processing method of acid-bearing wastewater in a kind of 2,4 diamino benzene sulfonic acids and salt production process thereof |
-
2017
- 2017-04-20 CN CN201710262398.XA patent/CN107188785B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3462497A (en) * | 1966-11-14 | 1969-08-19 | Koppers Co Inc | Resorcinol manufacture |
| CN106277477A (en) * | 2016-10-31 | 2017-01-04 | 江苏远征化工有限公司 | The processing method of acid-bearing wastewater in a kind of 2,4 diamino benzene sulfonic acids and salt production process thereof |
Non-Patent Citations (1)
| Title |
|---|
| 吴晓宇等: ""利用工业生产废酸制间苯二酚"，吴晓宇等，化工进展，第28卷第2期，第236-353页", 《化工进展》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108863857A (en) * | 2018-06-29 | 2018-11-23 | 浙江龙盛化工研究有限公司 | The serial dilution device and method of N-acetylsulfanilyl chloride cooling crystallization |
| CN108863857B (en) * | 2018-06-29 | 2024-04-30 | 浙江龙盛化工研究有限公司 | Continuous dilution device and method for cooling crystallization of acetamido benzenesulfonyl chloride |
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