CN105836949A - Treatment method for benzene extraction raffinate in caprolactam production - Google Patents
Treatment method for benzene extraction raffinate in caprolactam production Download PDFInfo
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- CN105836949A CN105836949A CN201610291909.6A CN201610291909A CN105836949A CN 105836949 A CN105836949 A CN 105836949A CN 201610291909 A CN201610291909 A CN 201610291909A CN 105836949 A CN105836949 A CN 105836949A
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- Prior art keywords
- benzene
- caprolactam
- layer
- ammonium sulfate
- raffinate
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/16—Separation or purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D223/08—Oxygen atoms
- C07D223/10—Oxygen atoms attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/041—Treatment of water, waste water, or sewage by heating by distillation or evaporation by means of vapour compression
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
Abstract
The invention discloses a treatment method for benzene extraction raffinate in caprolactam production .The method comprises the following steps that 1, the benzene extraction raffinate generated in caprolactam production is evaporated and concentrated to obtain concentrate; 2, the concentrate is cooled and then mixed with benzene, standing is conducted for layering, the upper layer is a benzene layer containing caprolactam, the middle layer is an organic waste liquid layer, and the lower layer is a water layer containing ammonium sulfate; 3, the upper layer, the middle layer and the lower layer are separated, debenzolization is conducted on the upper benzene layer containing caprolactam to obtain crude caprolactam, organic waste liquid is obtained from the middle layer, and the lower water layer containing ammonium sulfate is concentrated and crystallized to produce solid ammonium sulfate .The treatment method has the advantages of being simple in technology, low in cost, good in treatment effect, safe and environmentally friendly.
Description
Technical field
The present invention relates to a kind of method separating and recovering utility from the waste liquid that caprolactam production process produces, especially
It is to provide benzene raffinate recycling processing method in a kind of caprolactam production.
Background technology
Using ketoamine method to produce in caprolactam production, crude caprolactam is entered by the most usual benzene as extractant
Row abstraction impurity removal.After crude caprolactam is processed by benzene extraction process, caprolactam and benzene solubility impurity enter benzene phase, and
Water-solubility impurity enters aqueous phase, and this aqueous phase separated is benzene raffinate.For 50,000 tons/year of process units, benzene extracts
Residual liquid generation amount is 4m3/ h, basic composition is ammonium sulfate 3-5%, caprolactam 0.5-2.5%, COD 100,000 mg/L
Left and right, remaining is water.For processing benzene raffinate, part producing producer uses concentration-incinerating method to process, and generally does
Method is first to be neutralized to thickening after neutrality with alkali liquor, then concentrated solution is delivered to incinerator burning disposal.The method exists
More problems: (1) needs extra fuel in burning, and causes processing cost high；(2) residual liquid is containing in a large amount of sulfate Radix Chloranthi Serrati
Amide substance, makes to produce a large amount of sulfide and nitrogen oxides in burning, and equipment is produced deep-etching, equipment material requirement
Height, the gas simultaneously produced need to absorb process, and environmental protection pressure is big.Technique is simple, processing cost is low for therefore, exploitation one,
Benzene raffinate recycling processing method in the caprolactam production of safety and environmental protection, reclaims valuable in residual liquid processing procedure
Material, both made residual liquid be effectively addressed, had again good economic benefit, production and development to caprolactam have
Great facilitation.
China Patent Publication No. CN101049980A, denomination of invention: a kind of benzene extracting concentrated solution of residue wastewater comprehensive utilization
Method: first benzene extracting concentrated solution of residue wastewater is evaporated, add solvent and make sulfur ammonium separate out, obtain sulfur through solid-liquid separation
Ammonium crystal, the liquid phase after separation is through distillating recovering solvent and removes water, obtains the Organic substance knot containing caprolactam after cooling
Brilliant.Wherein solvent includes the organic alcohols of ethanol, methanol, propanol, the tert-butyl alcohol, and Isosorbide-5-Nitrae-dioxane.Due to
The method need to add solvent to realize the separation of sulfur ammonium, causes complex process, separation costs is high, and obtains by the method
Caprolactam purity is low, and in residual liquid, major part Organic substance enters in the caprolactam reclaimed, and brings difficulty to follow-up purification.
Summary of the invention
Instant invention overcomes the defect of prior art, it is provided that a kind of technique is simple, low cost, high treating effect, safety collar
The processing method of benzene raffinate in the caprolactam production protected.
For realizing object above, the technical solution used in the present invention is: the place of benzene raffinate in a kind of caprolactam production
Reason method, comprises the steps:
(1) the benzene raffinate evaporation and concentration produced in caprolactam production is obtained concentrated solution；
(2) mixing with benzene after being cooled down by concentrated solution, stratification, upper strata is the benzene layer containing caprolactam, and middle level is for having
Machine waste liquid layer, lower floor is the water layer of liquid containing ammonium sulfate；
(3) separating upper, middle and lower three layers, the upper strata benzene layer containing caprolactam obtains caprolactam crude product, middle level after de-benzene
Obtaining organic liquid waste, the concentrated crystallization of water layer of lower floor's liquid containing ammonium sulfate produces solid ammonium sulfate.
Under concentrated solution room temperature described in step (1), (25 DEG C) density is preferably 1180-1220g/l.
Benzene described in step (2) is preferably 1 with the volume ratio of concentrated solution: 0.5-2.
The time of described stratification is preferably greater than or equal to 10min.
Compared with prior art, the device have the advantages that into:
1, technique is simple, processing cost is low, and use that simple benzene extraction process reclaims in benzene raffinate is valuable
Material, had both made residual liquid be effectively addressed, and can produce again good economic benefit；
2, high treating effect, benzene raffinate is efficiently separated the benzene into being more than or equal to 3.3wt% containing caprolactam by the present invention
Layer, organic waste liquid layer, the sulfur-bearing ammonium ammonium sulfate solution layer more than or equal to 30.5wt%；And achieve recycling；
3, safety and environmental protection, produces without the three wastes, obtains caprolactam crude product, solid ammonium sulfate product and organic waste after treatment
Liquid, caprolactam crude product, solid ammonium sulfate product can sell outward, and the organic liquid waste of carbon containing hydrogen-oxygen nitrogen can be as fuel utilization.
Detailed description of the invention
By the following examples the present invention is carried out more specific description, but the present invention is not limited to described embodiment.
Embodiment 1
Taking 1500g benzene raffinate evaporation and concentration at ambient pressure to 210g, obtaining density after being cooled to 25 DEG C is 1220g/L
Concentrated solution, concentrated solution is added in separatory funnel, add 170ml benzene, fully shake, stand 30min layering obtain
Three layers of clear interface, upper strata is subdiaphanous benzene layer, and middle level is the organic waste liquid layer of brownish black, and lower floor is ruddy sulfur
Aqueous ammonium layer.Upper, middle and lower separates, and obtains the benzene liquid 155g containing caprolactam 6.2wt%, organic liquid waste 63.5g, sulfur-bearing
The sulfur aqueous ammonium 135.5g of ammonium 39.5wt%.Benzene layer containing caprolactam is obtained caprolactam crude product after de-benzene, receives
Concentrated for ammonium sulfate solution crystallization, as fuel utilization, is produced solid ammonium sulfate by collection organic waste liquid layer.
Implement 2
Taking 1500g benzene raffinate evaporation and concentration at ambient pressure to 230g, obtaining density after being cooled to 25 DEG C is 1200g/L
Concentrated solution, concentrated solution is added in separatory funnel, add 190ml benzene, fully shake, stand 40min layering obtain
Three layers of clear interface, upper strata is subdiaphanous benzene layer, and middle level is the organic waste liquid layer of brownish black, and lower floor is ruddy sulfur
Aqueous ammonium layer.Upper, middle and lower separates, and obtains benzene liquid 173.6g, the organic liquid waste 58.2g containing caprolactam 5.5wt%, contains
The ammonium sulfate solution 162.2g of sulfur ammonium 34.3wt%.Benzene layer containing caprolactam is obtained caprolactam crude product after de-benzene, receives
Concentrated for ammonium sulfate solution crystallization, as fuel utilization, is produced solid ammonium sulfate by collection organic waste liquid layer.
Embodiment 3
Taking 1500g benzene raffinate evaporation and concentration at ambient pressure to 245g, obtaining density after being cooled to 25 DEG C is 1180g/L
Concentrated solution, concentrated solution is added in separatory funnel, add 210ml benzene, fully shake, stand 20min layering obtain
Three layers of clear interface, upper strata is subdiaphanous benzene layer, and middle level is the organic waste liquid layer of brownish black, and lower floor is ruddy sulfur
Aqueous ammonium layer.Upper, middle and lower separates, and obtains benzene liquid 192g, the organic liquid waste 51.7g containing caprolactam 4.9wt%, contains
The ammonium sulfate solution 183.5g of sulfur ammonium 30.5wt%.The upper strata benzene layer containing caprolactam is obtained caprolactam after de-benzene thick
Product, concentrated for ammonium sulfate solution crystallization, as fuel utilization, is produced solid ammonium sulfate by collection organic waste liquid layer.
Embodiment 4
Taking 1500g benzene raffinate evaporation and concentration at ambient pressure to 210g, obtaining density after being cooled to 25 DEG C is 1210g/L
Concentrated solution, concentrated solution is added in separatory funnel, add 340ml benzene, fully shake, stand 50min layering obtain
Three layers of clear interface, upper strata is subdiaphanous benzene layer, and middle level is the organic waste liquid layer of brownish black, and lower floor is ruddy sulfur
Aqueous ammonium layer.Upper, middle and lower separates, and obtains benzene liquid 307g, the organic liquid waste 63.2g containing caprolactam 3.3wt%, contains
The ammonium sulfate solution 136.3g of sulfur ammonium 39.6wt%.Benzene layer containing caprolactam is obtained caprolactam crude product after de-benzene, receives
Concentrated for ammonium sulfate solution crystallization, as fuel utilization, is produced solid ammonium sulfate by collection organic waste liquid layer.
Embodiment 5
Taking 1500g benzene raffinate evaporation and concentration at ambient pressure to 210g, obtaining density after being cooled to 25 DEG C is 1190g/L
Concentrated solution, concentrated solution is added in separatory funnel, add 85ml benzene, fully shake, stand 10min layering obtain
Three layers of clear interface, upper strata is subdiaphanous benzene layer, and middle level is the organic waste liquid layer of brownish black, and lower floor is ruddy sulfur
Aqueous ammonium layer.Upper, middle and lower separates, and obtains benzene liquid 82g, the organic liquid waste 64.0g containing caprolactam 11.5wt%, contains
The ammonium sulfate solution 136.5g of sulfur ammonium 39.3wt%.Benzene layer containing caprolactam is obtained caprolactam crude product after de-benzene, receives
Concentrated for ammonium sulfate solution crystallization, as fuel utilization, is produced solid ammonium sulfate by collection organic waste liquid layer.
Claims (4)
1. the processing method of benzene raffinate in a caprolactam production, it is characterised in that comprise the steps:
(1) the benzene raffinate evaporation and concentration produced in caprolactam production is obtained concentrated solution；
(2) mixing with benzene after being cooled down by concentrated solution, stratification, upper strata is the benzene layer containing caprolactam, and middle level is for having
Machine waste liquid layer, lower floor is the water layer of liquid containing ammonium sulfate；
(3) separating upper, middle and lower three layers, the upper strata benzene layer containing caprolactam obtains caprolactam crude product, middle level after de-benzene
Obtaining organic liquid waste, the concentrated crystallization of water layer of lower floor's liquid containing ammonium sulfate produces solid ammonium sulfate.
The processing method of benzene raffinate in caprolactam production the most according to claim 1, it is characterised in that step
Suddenly the concentrated solution room temperature lower density described in (1) is 1180-1220g/l.
The processing method of benzene raffinate in caprolactam production the most according to claim 1, it is characterised in that step
Suddenly the benzene described in (2) is 1: 0.5-2 with the volume ratio of concentrated solution.
The processing method of benzene raffinate in caprolactam production the most according to claim 1, it is characterised in that step
Suddenly the time of the stratification described in (2) is more than or equal to 10min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610291909.6A CN105836949A (en) | 2016-05-05 | 2016-05-05 | Treatment method for benzene extraction raffinate in caprolactam production |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610291909.6A CN105836949A (en) | 2016-05-05 | 2016-05-05 | Treatment method for benzene extraction raffinate in caprolactam production |
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| CN105836949A true CN105836949A (en) | 2016-08-10 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201610291909.6A Pending CN105836949A (en) | 2016-05-05 | 2016-05-05 | Treatment method for benzene extraction raffinate in caprolactam production |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112174423A (en) * | 2019-10-11 | 2021-01-05 | 福建天辰耀隆新材料有限公司 | Method for treating caprolactam production wastewater |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1158998A (en) * | 1965-12-09 | 1969-07-23 | Stamicarbon | Process for the Recovery of Ammonium Sulfate from Aqueous Ammonium Sulfate Solutions Containing Organic Components. |
| CN1281826A (en) * | 1999-07-26 | 2001-01-31 | 巴陵石化鹰山石油化工厂 | Method for treating benzene extraction waste liquor in production of caprolactam |
| CN101049980A (en) * | 2007-05-23 | 2007-10-10 | 徐明光 | Method for comprehensive utilization for benzene extracting concentrated solution of residue wastewater |
| WO2009075608A9 (en) * | 2007-12-10 | 2009-07-30 | Joint Stock Company Kuibysheva | Method for controlling caprolactam production |
| CN101767860A (en) * | 2010-01-28 | 2010-07-07 | 河北瑞通美邦工程有限公司 | Recovery process of caprolactam refining raffinate |
| CN102642946A (en) * | 2012-04-13 | 2012-08-22 | 天津市富特斯科技发展有限公司 | Treatment method of waste water produced in process for producing caprolactam by utilizing toluene method |
-
2016
- 2016-05-05 CN CN201610291909.6A patent/CN105836949A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1158998A (en) * | 1965-12-09 | 1969-07-23 | Stamicarbon | Process for the Recovery of Ammonium Sulfate from Aqueous Ammonium Sulfate Solutions Containing Organic Components. |
| CN1281826A (en) * | 1999-07-26 | 2001-01-31 | 巴陵石化鹰山石油化工厂 | Method for treating benzene extraction waste liquor in production of caprolactam |
| CN101049980A (en) * | 2007-05-23 | 2007-10-10 | 徐明光 | Method for comprehensive utilization for benzene extracting concentrated solution of residue wastewater |
| WO2009075608A9 (en) * | 2007-12-10 | 2009-07-30 | Joint Stock Company Kuibysheva | Method for controlling caprolactam production |
| CN101767860A (en) * | 2010-01-28 | 2010-07-07 | 河北瑞通美邦工程有限公司 | Recovery process of caprolactam refining raffinate |
| CN102642946A (en) * | 2012-04-13 | 2012-08-22 | 天津市富特斯科技发展有限公司 | Treatment method of waste water produced in process for producing caprolactam by utilizing toluene method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112174423A (en) * | 2019-10-11 | 2021-01-05 | 福建天辰耀隆新材料有限公司 | Method for treating caprolactam production wastewater |
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Application publication date: 20160810 |