CN107188785B - Resource utilization method of 2, 4-diaminobenzene sulfonic acid and salt production wastewater - Google Patents
Resource utilization method of 2, 4-diaminobenzene sulfonic acid and salt production wastewater Download PDFInfo
- Publication number
- CN107188785B CN107188785B CN201710262398.XA CN201710262398A CN107188785B CN 107188785 B CN107188785 B CN 107188785B CN 201710262398 A CN201710262398 A CN 201710262398A CN 107188785 B CN107188785 B CN 107188785B
- Authority
- CN
- China
- Prior art keywords
- acid
- phenylenediamine
- liquor
- resorcinol
- raw material
- 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.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 27
- 150000003839 salts Chemical class 0.000 title claims abstract description 24
- 239000002351 wastewater Substances 0.000 title claims abstract description 23
- JVMSQRAXNZPDHF-UHFFFAOYSA-N 2,4-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C(N)=C1 JVMSQRAXNZPDHF-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 84
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 78
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 43
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229940018564 m-phenylenediamine Drugs 0.000 claims abstract description 40
- 239000012452 mother liquor Substances 0.000 claims abstract description 39
- 239000000047 product Substances 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 12
- 239000000413 hydrolysate Substances 0.000 claims abstract description 10
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000013067 intermediate product Substances 0.000 claims abstract description 6
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 5
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 5
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 239000012043 crude product Substances 0.000 claims abstract description 3
- 230000001502 supplementing effect Effects 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 31
- 238000006460 hydrolysis reaction Methods 0.000 claims description 29
- 238000000926 separation method Methods 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 3
- 238000007796 conventional method Methods 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 16
- 230000007062 hydrolysis Effects 0.000 description 24
- 239000000243 solution Substances 0.000 description 14
- 238000004128 high performance liquid chromatography Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 108010009736 Protein Hydrolysates Proteins 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LDXYDHGRKFMULJ-UHFFFAOYSA-N (3-azaniumylphenyl)azanium;sulfate Chemical compound OS(O)(=O)=O.NC1=CC=CC(N)=C1 LDXYDHGRKFMULJ-UHFFFAOYSA-N 0.000 description 1
- JVMSQRAXNZPDHF-UHFFFAOYSA-M 2,4-diaminobenzenesulfonate Chemical compound NC1=CC=C(S([O-])(=O)=O)C(N)=C1 JVMSQRAXNZPDHF-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OVDVGECZCGXFJO-UHFFFAOYSA-N benzene-1,3-diamine;sodium Chemical compound [Na].NC1=CC=CC(N)=C1 OVDVGECZCGXFJO-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A resource utilization method of 2, 4-diaminobenzene sulfonic acid and salt production wastewater comprises the following steps: (1) performing sulfonation reaction on m-phenylenediamine and sulfuric acid and/or fuming sulfuric acid conventionally to obtain sulfuric acid-containing m-acid mother liquor A and a crude m-acid product; washing the m-acid crude product with water to obtain an m-acid intermediate product and a washing solution B; neutralizing the intermediate product of the m-acid with alkali, and separating to obtain an m-acid salt product and a neutralization mother liquor C; (2) preparing at least one of the meta-acid mother liquor A, the washing liquor B and the neutralization mother liquor C into a dilute acid liquor with the acidity of 3-20%, wherein the prepared dilute acid liquor can be directly used as a raw material liquor, and heating and hydrolyzing to obtain resorcinol hydrolysate; or supplementing a certain amount of m-phenylenediamine into the prepared dilute acid solution as a raw material solution, and heating and hydrolyzing to obtain resorcinol hydrolysate; (3) the resorcinol hydrolysate is extracted and rectified to obtain the resorcinol product. The invention obviously reduces the discharge amount of waste acid and waste water generated in the production process of the 2, 4-diaminobenzene sulfonic acid and the salt thereof, and improves the comprehensive utilization rate of raw materials.
Description
(I) technical field
The invention relates to a resource utilization method of 2, 4-diaminobenzene sulfonic acid and salt production wastewater, in particular to a method for producing resorcinol by using intermediate acid mother liquor, washing liquor and neutralization mother liquor in the production process of 2, 4-diaminobenzene sulfonic acid and salt.
(II) background of the invention
2, 4-diaminobenzene sulfonic acid, commonly known as meta-acid, is also called m-phenylenediamine-4-sulfonic acid, is an important chemical raw material and is commonly used as a dye intermediate or a medical intermediate. The traditional synthetic process route of meta-acid is to prepare meta-acid by sulfonating m-phenylenediamine, such as a new synthetic process of 2, 4-diaminobenzenesulfonic acid (Shiweibin et al, Shanghai dye, vol. 36, No. 5), CN1900058A, CN102516137A and the like in the literature, wherein m-phenylenediamine is used as a raw material, and sulfuric acid, fuming sulfuric acid or SO is used as a raw material3The gas is used as a sulfonating agent to sulfonate the m-phenylenediamine, thereby obtaining a product, namely m-acid, and the m-acid is neutralized by alkali liquor to obtain salt.
Because the raw materials and the products have high solubility in acid and water, the waste acid and the waste water cannot be recycled and can only be discharged along with the acid, the pressure of subsequent waste acid treatment is greatly increased, and serious resource waste and environmental pollution are caused.
CN103641568B, Chenqian, etc. discuss the waste acid treatment scheme of 2, 4-diaminobenzene sulfonic acid, and can be concentrated or used for producing sulfate. Although the process solves the problem of treatment of a large amount of waste sulfuric acid in sulfonated products, a large amount of organic components contained in the waste acid are not reasonably utilized, and the waste of resources is caused.
In conclusion, the key of the technical innovation in the industry is to find the effective resource utilization of the production wastewater of the 2, 4-diaminobenzene sulfonic acid and the salt thereof.
Disclosure of the invention
The invention aims to provide a resource utilization method of 2, 4-diaminobenzene sulfonic acid and salt production wastewater.
In order to realize the purpose of the invention, the adopted technical scheme is as follows:
a resource utilization method of 2, 4-diaminobenzene sulfonic acid and salt production wastewater comprises the following steps:
(1) collecting 2, 4-diaminobenzene sulfonic acid and salt production wastewater thereof: performing sulfonation reaction on m-phenylenediamine and sulfuric acid and/or fuming sulfuric acid by a conventional method, hydrolyzing and cooling a sulfonated material, diluting the sulfonated material with water or ice water, and performing solid-liquid separation to obtain sulfuric acid-containing m-acid mother liquor A and a crude m-acid product; washing the m-acid crude product with water to obtain an m-acid intermediate product and a washing solution B; neutralizing the intermediate product of the m-acid with alkali, and separating the obtained suspension to obtain an m-acid salt product and a neutralization mother liquor C;
(2) preparing at least one of the meta-acid mother liquor A, the washing liquor B and the neutralization mother liquor C in the step (1) into a dilute acid liquor with the acidity of 3-20%, wherein the prepared dilute acid liquor can be directly used as a raw material liquor and subjected to heating hydrolysis to obtain resorcinol hydrolysate; or supplementing a certain amount of m-phenylenediamine into the prepared dilute acid solution as a raw material solution, and heating and hydrolyzing to obtain resorcinol hydrolysate;
(3) The resorcinol hydrolysate is extracted and rectified to obtain the resorcinol product.
In the step (2), the prepared diluted acid solution preferably contains an isophthalic acid mother liquor A.
In the step (2), the acidity (calculated by sulfuric acid) in the prepared diluted acid solution is preferably 6-20%, and more preferably 8-15%.
In the step (2), m-phenylenediamine is preferably added to the prepared diluted acid solution. The amount of the m-phenylenediamine added is preferably such that the ratio of the total mole number of the m-phenylenediamine and the m-phenylenediamine sulfonate to the mole number of the sulfuric acid in the raw material liquid is 1:1.5 to 3.0, more preferably 1:1.7 to 2.4.
In the step (2), the temperature is controlled to be 180-260 ℃, and preferably 200-250 ℃ during the hydrolysis reaction of the raw material liquid; the hydrolysis reaction time is preferably 120-300 min.
The acidity in the present invention is defined as: and converting the hydrogen ion content of the solution into the mass of the sulfuric acid, and taking the mass percentage concentration of the converted sulfuric acid as the acidity.
Compared with the prior art, the invention has the following beneficial effects:
the invention opens up a new process for producing the resorcinol by recycling the production wastewater of the 2, 4-diaminobenzene sulfonic acid and the salt thereof, so that the waste acid generated in the production process of the m-acid and the salt thereof and the sulfuric acid, water and organic components in the wastewater can be fully utilized, the discharge amount of the waste acid and the wastewater generated in the production process of the 2, 4-diaminobenzene sulfonic acid and the salt thereof is obviously reduced, and the comprehensive utilization rate of raw materials is improved.
(IV) description of the drawings
FIG. 1 is a schematic process flow diagram of the present invention.
(V) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
in the case of the example 1, the following examples are given,
(1) the synthesis of the 2, 4-diaminobenzene sulfonic acid and the salt thereof adopts a conventional process: 108g of m-phenylenediamine is added into 378g of 98% sulfuric acid, the temperature in the charging process is controlled within 120 ℃, a uniform salt solution is formed after charging, the temperature is raised to 150 ℃, 271.3g of 50% fuming sulfuric acid is slowly added for sulfonation, and the temperature is kept for 4 hours after charging. And cooling the sulfonation liquid to 130 ℃, slowly adding 32.4g of water, preserving the temperature for 20min, completing hydrolysis, and cooling to room temperature. And slowly adding the cooled hydrolysate into 550g of ice water, filtering at about 15 ℃, and separating to obtain a filter cake and 941g of the m-acid mother liquor A. 200g of water is added into the filter cake for washing, and after washing, the solid of the m-acid and 343g of washing liquid B are separated, the yield of the m-acid is 74.6 percent, and the purity (HPLC) of the m-acid is 99.5 percent. Adding 32% sodium hydroxide aqueous solution into the obtained m-acid solid, adjusting the pH to 9, neutralizing to obtain a product, namely m-acid salt suspension, and performing solid-liquid separation to obtain 152.6g (pure) of 2, 4-diaminobenzene sodium sulfonate (m-bis) and 180.2g of neutralization mother liquor C, wherein the purity (HPLC) of the m-bis product is 99.2%, and the molar utilization rate of the raw material is 72.7%.
(2) 400g of 98% sulfuric acid and 3240g of water were mixed to prepare a dilute sulfuric acid having an acidity of 11%, and 200g of molten m-phenylenediamine was added and mixed with a dilute acid solution to prepare a m-phenylenediamine sulfate solution. Preheating the prepared raw material liquid to 240 ℃, and adding the raw material liquid into a reactor for hydrolysis for 240 min; after the reaction, the resorcinol (pure) 187.4g is obtained by conventional solvent extraction separation and rectification, the purity (HPLC) of the resorcinol product is 99.5 percent, and the molar utilization rate of the m-phenylenediamine raw material is 92 percent.
In the case of the example 2, the following examples are given,
(1) the m-bis was synthesized according to the procedure of step (1) described in example 1, giving 941g of m-acid mother liquor a, 343g of washing liquor B, 180g of neutralized mother liquor C as three waste waters;
(2) mixing three streams of wastewater of the m-acid mother liquor A, the washing liquid B and the neutralization mother liquor C obtained in the step (1) with 3900g of water to prepare a dilute acid liquor with the acidity of 11%, directly preheating the dilute acid liquor to 240 ℃ without adding m-phenylenediamine, and then adding the dilute acid liquor into a reactor for hydrolysis for 240 min; 26g of resorcinol (purified) is obtained by extraction and rectification after reaction, the purity (HPLC) of the resorcinol product is 99.2 percent, and the molar utilization rate of the m-phenylenediamine raw material is 97.3 percent.
In the case of the example 3, the following examples are given,
(1) the m-bis was synthesized according to the procedure of step (1) described in example 1, giving 941g of m-acid mother liquor a, 343g of washing liquor B, 180g of neutralized mother liquor C as three waste waters;
(2) Mixing the meta-acid mother liquor A obtained in the step (1) with 3900g of water to prepare a dilute acid solution with the acidity of 11%, and adding 270g of molten m-phenylenediamine to prepare a hydrolysis raw material solution; preheating the prepared hydrolysis raw material liquid to 240 ℃, adding the hydrolysis raw material liquid into a reactor for hydrolysis for 240min to obtain resorcinol hydrolysate, extracting and rectifying to obtain 276g of resorcinol (purified), wherein the purity (HPLC) of the resorcinol product is 99.7 percent, and the molar utilization rate of the m-phenylenediamine raw material is 93.7 percent.
In the case of the example 4, the following examples are given,
(1) the m-bis was synthesized according to the procedure of step (1) described in example 1, giving 941g of m-acid mother liquor a, 343g of washing liquor B, 180g of neutralized mother liquor C as three waste waters;
(2) mixing the meta-acid mother liquor A obtained in the step (1) with 4900g of water to prepare a dilute acid liquor with the acidity of 8%, and adding 300g of molten m-phenylenediamine to prepare a hydrolysis raw material liquor; preheating the prepared hydrolysis raw material liquid to 230 ℃, adding the hydrolysis raw material liquid into a reactor for hydrolysis for 200min to obtain resorcinol hydrolysate, extracting and rectifying to obtain 279g of resorcinol (purified), wherein the purity (HPLC) of the resorcinol product is 99.5 percent, and the molar utilization rate of the m-phenylenediamine raw material is 92.7 percent.
In the case of the example 5, the following examples were conducted,
(1) the m-bis was synthesized according to the procedure of step (1) described in example 1, giving 941g of m-acid mother liquor a, 343g of washing liquor B, 180g of neutralized mother liquor C as three waste waters;
(2) Mixing the m-acid mother liquor A obtained in the step (1), a washing solution B and 3480g of water to prepare a dilute acid solution with the acidity of 12.4%, and adding 290g of molten m-phenylenediamine to prepare a hydrolysis raw material solution; preheating the prepared hydrolysis raw material liquid to 220 ℃, adding the hydrolysis raw material liquid into a reactor for hydrolysis for 240min to obtain resorcinol hydrolysate, extracting and rectifying to obtain 291g of resorcinol (purity), wherein the purity (HPLC) of the resorcinol product is 99.4%, and the molar utilization rate of the m-phenylenediamine raw material is 93.2%.
In the case of the example 6, it is shown,
(1) the m-bis was synthesized according to the procedure of step (1) described in example 1, giving 941g of m-acid mother liquor a, 343g of washing liquor B, 180g of neutralized mother liquor C as three waste waters;
(2) mixing the meta-acid mother liquor A and the neutralization mother liquor C obtained in the step (1) with 2000g of water to prepare a dilute acid liquor with the acidity of 15%, and adding 212g of molten m-phenylenediamine to prepare a hydrolysis raw material liquor; preheating the prepared hydrolysis raw material liquid to 200 ℃, adding the hydrolysis raw material liquid into a reactor for hydrolysis for 280min to obtain resorcinol hydrolysate, extracting and rectifying to obtain 197g of resorcinol (purified), 99.2% of resorcinol product purity (HPLC) and 92.5% of m-phenylenediamine raw material molar utilization rate.
Example 7
(1) Obtaining an m-acid filter cake and 941g of m-acid mother liquor A by the method of the step (1) in example 1, adding 32% of sodium hydroxide aqueous solution into the filter cake without washing, adjusting the pH to 9, neutralizing to obtain a product which is an m-acid salt suspension, and performing solid-liquid separation to obtain 175g (sodium metabis) of 2, 4-diaminobenzene sulfonate and 600g of neutralized mother liquor C, wherein the purity (HPLC) of the m-bis product is 99.5 percent, and the yield is 83.5 percent;
(2) Mixing the meta-acid mother liquor A and the neutralization mother liquor C obtained in the step (1) with 3700g of water to prepare a dilute acid liquor with the acidity of 9.1%, and adding 250g of molten m-phenylenediamine to prepare a hydrolysis raw material liquor; preheating the prepared hydrolysis raw material liquid to 250 ℃, adding the hydrolysis raw material liquid into a reactor for hydrolysis for 160min to obtain resorcinol hydrolysate, extracting and rectifying to obtain 240g of resorcinol (purified), wherein the purity (HPLC) of the resorcinol product is 99.5%, and the molar utilization rate of the m-phenylenediamine raw material is 92.5%.
The results of the above examples are compared as follows:
note: the reduction in sulfuric acid consumption per unit of resorcinol is compared to example 1.
From example 1, it can be found that in the process of the m-bis synthesis, the yield of crude m-acid reaches 93.2%, the yield of the m-acid after washing only reaches 74.6%, and the yield of the m-acid after neutralization is reduced to 72.7%. Waste liquid A, B, C is generated in the production process of the m-acid and the salt thereof, especially, a large amount of m-acid exists in the m-acid mother liquid A in the washing process, and if the waste water is not recycled, a large amount of sulfuric acid, unreacted raw material m-phenylenediamine and generated byproducts exist in the waste liquid, so that reasonable utilization cannot be achieved. Through the embodiments 1, 2, 3, 4 and 5, different waste liquids are respectively used for preparing resorcinol, the m-phenylenediamine molar yield is improved (more than 92 percent), about 2 tons of sulfuric acid is saved in each ton of resorcinol products, the sulfuric acid and organic components in the waste liquid in the double-production process are fully utilized, and the resource utilization of the waste liquid is realized. The waste liquid generated in the double production processes of examples 2, 3, 4 and 5 is used for preparing resorcinol, and the obtained product has the quality equivalent to that of the product obtained in the step of preparing resorcinol by performing acid hydrolysis on m-phenylenediamine in example 1, which shows that the method for preparing resorcinol from waste water generated in the production of 2, 4-diaminobenzene sulfonic acid and salts thereof is feasible.
Claims (6)
1. A resource utilization method of 2, 4-diaminobenzene sulfonic acid and salt production wastewater comprises the following steps:
(1) collecting 2, 4-diaminobenzene sulfonic acid and salt production wastewater thereof: performing sulfonation reaction on m-phenylenediamine and sulfuric acid and/or fuming sulfuric acid by a conventional method, hydrolyzing and cooling a sulfonated material, diluting the sulfonated material with water or ice water, and performing solid-liquid separation to obtain sulfuric acid-containing m-acid mother liquor A and a crude m-acid product; washing the m-acid crude product with water to obtain an m-acid intermediate product and a washing solution B; neutralizing the intermediate product of the m-acid with alkali, and separating the obtained suspension to obtain an m-acid salt product and a neutralization mother liquor C;
(2) preparing at least one of the m-phenylenediamine mother liquor A, the washing liquor B and the neutralization mother liquor C in the step (1) into a dilute acid liquor with the acidity of 3-20%, wherein the prepared dilute acid liquor contains the m-phenylenediamine mother liquor A and has the acidity of 6-20%, a certain amount of m-phenylenediamine is supplemented into the prepared dilute acid liquor to serve as a raw material liquor, the adding amount of the m-phenylenediamine enables the ratio of the total mole number of the m-phenylenediamine and the m-phenylenediamine sulfonate in the raw material liquor to the mole number of sulfuric acid to be 1: 1.5-3.0, and heating and hydrolyzing to obtain a resorcinol hydrolysate; or supplementing a certain amount of m-phenylenediamine into the prepared dilute acid solution as a raw material solution, and heating and hydrolyzing to obtain resorcinol hydrolysate;
(3) The resorcinol hydrolysate is extracted and rectified to obtain the resorcinol product.
2. The resource utilization method according to claim 1, characterized in that: in the step (2), the acidity of the prepared diluted acid solution is 6-20%.
3. The resource utilization method according to claim 2, characterized in that: in the step (2), the acidity of the prepared diluted acid solution is 8-15%.
4. The resource utilization method according to claim 1, characterized in that: the amount of the m-phenylenediamine added is such that the ratio of the total mole number of the m-phenylenediamine and the m-phenylenediamine sulfonate to the mole number of the sulfuric acid in the raw material liquid is 1: 1.7-2.4.
5. The resource utilization method according to any one of claims 1 to 4, characterized in that: in the step (2), during the hydrolysis reaction of the raw material liquid, the temperature is controlled to be 180-260 ℃, and the hydrolysis reaction time is 120-300 min.
6. The resource utilization method according to claim 5, characterized in that: in the step (2), the temperature is controlled to be 200-250 ℃ during the hydrolysis reaction of the raw material liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710262398.XA CN107188785B (en) | 2017-04-20 | 2017-04-20 | Resource utilization method of 2, 4-diaminobenzene sulfonic acid and salt production wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710262398.XA CN107188785B (en) | 2017-04-20 | 2017-04-20 | Resource utilization method of 2, 4-diaminobenzene sulfonic acid and salt production wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107188785A CN107188785A (en) | 2017-09-22 |
| CN107188785B true CN107188785B (en) | 2021-12-21 |
Family
ID=59871052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710262398.XA Active CN107188785B (en) | 2017-04-20 | 2017-04-20 | Resource utilization method of 2, 4-diaminobenzene sulfonic acid and salt production wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107188785B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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 |
|---|
| "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;吴晓宇等;《化工进展》;20091231;第28卷(第2期);第236-353页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107188785A (en) | 2017-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104693009B (en) | Naphthalene sulfonated products direct alkali fusion coproduction 1-naphthols and the method for beta naphthal | |
| CN106083660B (en) | A kind of preparation process of 1- amino -4- bromo anthraquinone -2- sodium sulfonates | |
| CN109503410B (en) | Method for recovering DMF (dimethyl formamide) solvent in sucralose production | |
| CN110002649B (en) | Method for resource utilization of graphene waste acid | |
| CN102442888B (en) | Method for producing 1,5-dihydroxy naphthalene | |
| CN103539707A (en) | Preparation process of 2-naphthylamine-3,6,8-trisulfonic acid | |
| CN101492399B (en) | Method for preparing methylpropene sodium sulfonate | |
| CN102050716B (en) | Method for separating and purifying 2-ethyl anthraquinone from sulphuric acid | |
| CN104592064A (en) | Synthetic method of 2-aminophenol-4-sulfonamide | |
| CN101525309A (en) | Method for producing amino-phenyl-beta-hydroxyethyl sulfone sulfate | |
| CN108530271A (en) | A kind of naphthalene method of sulfonating of coproduction 1- naphthols and beta naphthal | |
| CN107188785B (en) | Resource utilization method of 2, 4-diaminobenzene sulfonic acid and salt production wastewater | |
| CN101671039A (en) | Method for comprehensively recycling salt-manufacturing waste liquor | |
| RU2708204C1 (en) | Method of producing potassium sulphate from potassium chloride and sulfuric acid | |
| CN104628609A (en) | Separation and extraction method of taurine | |
| CN106586990B (en) | With the method for Wet-process Phosphoric Acid Production potassium dihydrogen phosphate | |
| CN106916947B (en) | The method of sodium and potassium in quasi- fractional extraction separation lithium sulfate | |
| CN104262212A (en) | Method for continuously preparing 2,6-dinonyl naphthalene sulfonic acid | |
| CN109942377B (en) | Process for recycling mother liquor wastewater in naphthol production | |
| CN104150519A (en) | Method for preparing barium sulfate and sodium carbonate from waste sodium sulfate liquid | |
| CN109748310A (en) | A kind of separation method of barium sulfate and potassium carbonate mixed solution | |
| CN1310880C (en) | Improved process for preparing 2-sodium naphthalenesulfonate in production of beta-naphthol | |
| CN102391159B (en) | Process and system for recovering sulfonic acid mother liquor by dewatering | |
| CN106316990A (en) | Method for recycling epoxycyclohexane and n-pentanol from light oil | |
| CN106966901A (en) | A kind of preparation method of 6- hydroxyls -8- Lipase Catalyzed Resolution of Racemic Ethyl |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |