CN1670139A - Method for reclaiming power from waste materials stream in production process of caprolactam - Google Patents
Method for reclaiming power from waste materials stream in production process of caprolactam Download PDFInfo
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- CN1670139A CN1670139A CN 200410045149 CN200410045149A CN1670139A CN 1670139 A CN1670139 A CN 1670139A CN 200410045149 CN200410045149 CN 200410045149 CN 200410045149 A CN200410045149 A CN 200410045149A CN 1670139 A CN1670139 A CN 1670139A
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- waste
- coal
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- hexanolactam
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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Abstract
The invention relates to a method for reclaiming energy from the waste material flow of processing hexanolactam. The waste material flow is used as fuel of the coal-burning boiler. The said waste material flow can be the basic waste material from the processing of cyclohexanone, the light and heavy distillate from the distilling of cyclohexanone, the water-containing discharge liquor from the reclaiming of hexanolactam, the light distillate from the purifying of hexanolactam, the produced organic material from the decanter of processing sodium sulfate, the hydrogen-containing waste gas from benzene hydrogenization processing, the waste gas generated in the hydroxylamine reactor of processing cyclohexanone oxime, the waste gas generated during the stripping and storing of benzene and/or toluene.
Description
Invention field
The present invention relates to a kind of from the resulting waste streams of caprolactam production process the method for recovered energy.
Background technology
Hexanolactam can prepare by the following method: cyclohexane oxidation is become pimelinketone, pimelinketone generates cyclohexanone-oxime with azanol reaction in toluene solvant, use oleum the cyclohexanone-oxime Beckmann rearrangement to be become to contain the neutralized rearrangement mixture of hexanolactam vitriol in excess sulfuric acid, with in the ammoniacal liquor and above-mentioned neutralized rearrangement mixture to generate ammonium sulfate and hexanolactam, from concentrated ammonium sulfate solution, isolate aqueous crude caprolactam, extract hexanolactam with benzene from crude caprolactam, this extraction process produces a kind of moisture liquid effluent.The purification of hexanolactam subsequently realizes by the distillation of weight component especially.Hexanaphthene can obtain by benzene hydrogenation, therefore obtains containing the waste gas (off-gas) of hydrogen.In the cyclohexane oxidation part of caprolactam production process, hexanaphthene can be oxidized into hexalin and pimelinketone under the situation that catalyzer exists, and generates simultaneously such as acetic acid, hexanodioic acid, CO, CO
2With the lower oxidation products of ester, use in the caustic soda and described acid and the described ester of saponification, thereby produce alkaline waste.As a displaced way, hexanaphthene can be oxidized to cyclohexyl hydroperoxide, more a spot of pimelinketone and hexalin under the situation that does not have catalyzer to exist, generate lower oxidation products simultaneously such as acetic acid and hexanodioic acid, then cyclohexyl hydroperoxide is resolved into pimelinketone and hexalin, and in the presence of caustic soda and catalyzer, neutralize described acid and the described ester of saponification, thereby produce alkaline waste.Alkaline waste can further be used vitriolization with preparation sodium sulfate.The recovery of the pimelinketone in the caprolactam production process/purification part, light constituent and heavy constituent (following finger distillation lighting end (lights) and last running (heavies)) are preferably separated from pimelinketone and hexalin by the distillatory method.Azanol can obtain in gas-liquid reactor, and hydrogen contacts with the circulation inorganic liquid that contains nitrate ion, buffering acid and noble metal catalyst in this gas-liquid reactor, thereby obtains comprising the exhaust flow of hydrogen.Cyclohexanone-oxime in the hexanolactam preparation process prepares part, can obtain containing the exhaust flow of toluene from the removing and store of toluene.Hexanolactam recovery part in the hexanolactam preparation process, benzene can cause producing waste gas containing benzene from the removing of benzene in the use of extraction in the hexanolactam from crude caprolactam and flow.
In the caprolactam production process, for example, in the caprolactam production process as previously discussed, some waste streams have also been obtained hexanolactam that obtains except hope and the ammonium sulfate.These waste streams in the caprolactam production process are solid, liquid or gas stream.In most of chemical plants, waste streams or burned (gas), quilt are incinerated (dense organic waste materials) or quilt biological treatment (dilute aqueous soln).Some waste streams comprise a lot of energy.For example, the pimelinketone in the caprolactam production process prepares part, and a large amount of benzene feedstock carbon ends in alkaline waste and light, the last running, in the caprolactam production process some ammoniacal nitrogen raw materials end at moisture liquid effluent and distillation is light, in the last running.These come from stream exhaust system, that contain just like benzene, toluene and hydrogen and also have steam all to comprise lot of energy.
Summary of the invention
The objective of the invention is to find the method for recovered energy in a kind of energy content waste streams that from the caprolactam production process, obtains.
The waste streams of this purpose by will obtaining from the caprolactam production process, the waste streams that particularly contains energy act as a fuel and are used for coal burning boiler and realize.
Have been found that by method energy of the present invention and can from the waste streams that contains energy that the caprolactam production process obtains, reclaim.By method of the present invention, the energy that is present in the above-mentioned waste streams can be recovered with the form of high-pressure spray, and this is very favorable from viewpoint of energy.Another advantage of the present invention is that the waste streams that is transported in the coal burning boiler room need not to handle in environment.An additional advantage is that the part coal can be substituted from the waste streams that contains energy that comes from the caprolactam production process, thereby has saved coal.
In the method for the present invention, the waste streams that contains energy that comes from the caprolactam production workshop acts as a fuel and is used in the coal charging boiler house to produce high-pressure spray.Have been found that the waste streams that contains energy that comes from the caprolactam production process also can be added in the existing coal burning boiler room of existing coal charging boiler house, preferably process transformation, these contain the exhaust flow of energy to burn.Under latter event, new pipeline preferably is installed, this pipeline has instrument, pump and valve to carry waste streams to coal firing boiler and waste streams is added in the coal firing boiler.By method of the present invention, the waste streams that contains energy can substitute the coal in the boiler house charging.Have been found that the waste streams that at least 10% coal can be contained energy substitutes.Preferably be no more than 20%, the waste streams that the coal more preferably no more than 15% can be contained energy substitutes.When having been found that surpassing waste streams that 20% coal contained energy substitutes, will cause needs to clear up reaction product on burner wall and/or fluid hose, that obtain by combustion residue stream.Alternatively, the waste streams that contains energy concentrates before being added to the coal burning boiler room.It is favourable being concentrated under the situation that contains a large amount of water in the waste streams that for example contains energy.A large amount of water may cause extinguishing of flame.Preferably, in order to burn fully, waste streams must be introduced in the burner by a kind of special method, for example cuts the inlet of grade air by coal.More preferably, waste streams is introduced in the coal burning boiler room together with coal and primary air.
In principle, all waste streams that contain energy can be dosed in the coal burning boiler room.The suitable example that contains the energy waste streams that comes from the caprolactam production workshop as mentioned above, more detailed explanation will provide below.
Be suitable for typically having composition given below as the liquid waste stream of coal burning boiler room charging.
The alkaline waste that obtains from the Cyclohexanone Production process comprises sodium salt and/or the organic acid of 25-35wt.% usually, 50-60wt.% water, and all the other are mainly NaOH and Na
2CO
3
Distillation lighting end that obtains from the pimelinketone purification process and last running comprise the organism of 100wt.% usually.
The water that in the hexanolactam removal process, comprises 50-60wt.% usually by the moisture liquid effluent that uses benzene extraction crude caprolactam to obtain, the ammonium sulfate of 10-20wt.%, other inorganics of the organism of 10-20wt.% and 5-15wt.%.
The top products of the lighting end rectifying tower lighting end that obtains in the hexanolactam purification process comprises the hexanolactam of 55-65wt.% and other organism of 35-45wt.% usually.
The organism part that obtains in the decantor in the sodium sulfate preparation process comprises sodium salt and/or the organic acid of 0.5-5wt.% usually, and all the other are organism.
Be suitable for typically having composition given below as the exhaust flow of coal burning boiler room raw material.
Prepare the H that the hydrogen offgas circulation that obtains in the hexanaphthene often contains 8-9wt.% at benzene hydrogenation
2, the CH of 30-35wt.%
4, all the other mainly are N
2
The exhaust flow that obtains in the hydroxylamine reactor in the cyclohexanone-oxime preparation process contains the H of 4-5wt.% usually
2, the CH of 15-20wt.%
4, the N of 65-75wt.%
2, the N of 6-8wt.%
2O, all the other are mainly water.
Come from the benzene that exhaust flow that benzene removes comprises 1-2wt.% usually, all the other are mainly N
2
Come from the toluene that exhaust flow that toluene removes and store comprises 20-22wt.% usually, the N of 65-75wt.%
2, all the other are mainly O
2
The coal burning boiler room can comprise one or more process furnace.
Embodiment
The present invention will illustrate by following examples, but the present invention is not limited in this embodiment.
Embodiment
The following waste streams that comes from the caprolactam production workshop be added to have two process furnace, total power is in the coal burning boiler room of 135MW:
Fluid 1:2700kg/ hour come from the corrodibility alkaline waste that partly obtains from the Cyclohexanone Production in caprolactam production workshop, it comprises the NaOH of 8wt.%, the H of 50wt.%
2O, the Na of the salt of 35wt.% sodium or organic acid and 7wt.%
2CO
3,
Fluid 2:947kg/ hour come from the waste material that from crude caprolactam, extracts hexanolactam with benzene, it comprises the H of 58wt.%
2O, the organism of 15wt.%, other inorganics of the ammonium sulfate of 16wt.% and 11wt.%,
Fluid 3:520kg/ hour the distillation lighting end and the last running that in the pimelinketone purification process, obtain, it comprises the organism of 100wt.%,
Fluid 4:106kg/ hour prepare the hydrogen offgas stream that obtains in the hexanaphthene at benzene hydrogenation, it comprises the H of 8wt.%
2, the CH of 34wt.%
4N with 58wt.%
2
Fluid 5:424kg/ hour come from exhaust flow in the hydroxylamine reactor in the cyclohexanone-oxime preparation process, it comprises the H of 4.6wt.%
2, the CH of 17wt.%
4, the N of 71wt.%
2, the N of 7wt.%
2The H of O and 0.4wt.%
2O,
Fluid 6:132kg/ hour the exhaust flow that benzene removes that comes from comprises the benzene of 1.5wt.% and the N of 98.5wt.%
2,
Fluid 7:122kg/ hour come from the exhaust flow that toluene removes and stores, it comprises 21wt.% toluene, the N of 72wt.%
2O with 7wt.%
2, and
By dosing above-mentioned fluid in the coal burning boiler room, can replace 11.43% coal, can produce the steam of 15.2MW, 30-35 crust simultaneously.
Claims (6)
1. the method for the waste streams recovered energy that obtains from the caprolactam production process is characterized in that the fuel of described waste streams as coal burning boiler.
2. according to the method for claim 1, wherein said waste streams is selected from: the alkaline waste that produces in the Cyclohexanone Production process, lighting end that produces in the still-process of pimelinketone purification process and last running, the moisture liquid effluent that produces in the hexanolactam removal process, the lighting end that produces in the still-process of hexanolactam purification process, the organism part that produces in the decantor in the sodium sulfate preparation process, the hydrogen waste gas that produces in the benzene hydrogenation reaction of preparation hexanaphthene, the waste gas that is produced by hydroxylamine reactor in the cyclohexanone-oxime preparation process, benzene removes the waste gas of generation and/or the waste gas that toluene removed and stored generation.
3. according to each method among the claim 1-2, wherein the content of water in waste streams makes and can prevent fray-out of flame.
4. according to each method among the claim 1-3, wherein at least 10% the coal waste streams that come from the caprolactam production process replaces.
5. according to each method among the claim 1-4, wherein at least 20% the coal waste material that come from the caprolactam production process replaces.
6. according to each method among the claim 1-5, wherein waste material enters coal burning boiler with coal and primary air.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410045149 CN1670139A (en) | 2004-03-20 | 2004-03-20 | Method for reclaiming power from waste materials stream in production process of caprolactam |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410045149 CN1670139A (en) | 2004-03-20 | 2004-03-20 | Method for reclaiming power from waste materials stream in production process of caprolactam |
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|---|---|
| CN1670139A true CN1670139A (en) | 2005-09-21 |
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| CN 200410045149 Pending CN1670139A (en) | 2004-03-20 | 2004-03-20 | Method for reclaiming power from waste materials stream in production process of caprolactam |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7897801B2 (en) | 2003-05-12 | 2011-03-01 | Invista North America S.A R.L. | Process for the preparation of dinitriles |
| US7919646B2 (en) | 2006-07-14 | 2011-04-05 | Invista North America S.A R.L. | Hydrocyanation of 2-pentenenitrile |
| US7973174B2 (en) | 2005-10-18 | 2011-07-05 | Invista North America S.A.R.L. | Process of making 3-aminopentanenitrile |
| US7977502B2 (en) | 2008-01-15 | 2011-07-12 | Invista North America S.A R.L. | Process for making and refining 3-pentenenitrile, and for refining 2-methyl-3-butenenitrile |
| US8088943B2 (en) | 2008-01-15 | 2012-01-03 | Invista North America S.A R.L. | Hydrocyanation of pentenenitriles |
| US8101790B2 (en) | 2007-06-13 | 2012-01-24 | Invista North America S.A.R.L. | Process for improving adiponitrile quality |
| US8178711B2 (en) | 2006-03-17 | 2012-05-15 | Invista North America S.A R.L. | Method for the purification of triorganophosphites by treatment with a basic additive |
| US8247621B2 (en) | 2008-10-14 | 2012-08-21 | Invista North America S.A.R.L. | Process for making 2-secondary-alkyl-4,5-di-(normal-alkyl)phenols |
| US8338636B2 (en) | 2009-08-07 | 2012-12-25 | Invista North America S.A R.L. | Hydrogenation and esterification to form diesters |
| US8373001B2 (en) | 2003-02-10 | 2013-02-12 | Invista North America S.A R.L. | Method of producing dinitrile compounds |
| US8906334B2 (en) | 2007-05-14 | 2014-12-09 | Invista North America S.A R.L. | High efficiency reactor and process |
| CN104624021A (en) * | 2015-01-29 | 2015-05-20 | 湖南百利工程科技股份有限公司 | Method for recovering extraction agent from discharge gas in caprolactam production process |
-
2004
- 2004-03-20 CN CN 200410045149 patent/CN1670139A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8373001B2 (en) | 2003-02-10 | 2013-02-12 | Invista North America S.A R.L. | Method of producing dinitrile compounds |
| US7897801B2 (en) | 2003-05-12 | 2011-03-01 | Invista North America S.A R.L. | Process for the preparation of dinitriles |
| US7973174B2 (en) | 2005-10-18 | 2011-07-05 | Invista North America S.A.R.L. | Process of making 3-aminopentanenitrile |
| US8178711B2 (en) | 2006-03-17 | 2012-05-15 | Invista North America S.A R.L. | Method for the purification of triorganophosphites by treatment with a basic additive |
| US7919646B2 (en) | 2006-07-14 | 2011-04-05 | Invista North America S.A R.L. | Hydrocyanation of 2-pentenenitrile |
| US8394981B2 (en) | 2006-07-14 | 2013-03-12 | Invista North America S.A R.L. | Hydrocyanation of 2-pentenenitrile |
| US8906334B2 (en) | 2007-05-14 | 2014-12-09 | Invista North America S.A R.L. | High efficiency reactor and process |
| US8101790B2 (en) | 2007-06-13 | 2012-01-24 | Invista North America S.A.R.L. | Process for improving adiponitrile quality |
| US8088943B2 (en) | 2008-01-15 | 2012-01-03 | Invista North America S.A R.L. | Hydrocyanation of pentenenitriles |
| US7977502B2 (en) | 2008-01-15 | 2011-07-12 | Invista North America S.A R.L. | Process for making and refining 3-pentenenitrile, and for refining 2-methyl-3-butenenitrile |
| US8247621B2 (en) | 2008-10-14 | 2012-08-21 | Invista North America S.A.R.L. | Process for making 2-secondary-alkyl-4,5-di-(normal-alkyl)phenols |
| US8338636B2 (en) | 2009-08-07 | 2012-12-25 | Invista North America S.A R.L. | Hydrogenation and esterification to form diesters |
| CN104624021A (en) * | 2015-01-29 | 2015-05-20 | 湖南百利工程科技股份有限公司 | Method for recovering extraction agent from discharge gas in caprolactam production process |
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