CN104909984B - A kind of method reclaiming Hexalin from pimelinketone device waste liquid - Google Patents
A kind of method reclaiming Hexalin from pimelinketone device waste liquid Download PDFInfo
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- CN104909984B CN104909984B CN201510316686.XA CN201510316686A CN104909984B CN 104909984 B CN104909984 B CN 104909984B CN 201510316686 A CN201510316686 A CN 201510316686A CN 104909984 B CN104909984 B CN 104909984B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/86—Separation; Purification; 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
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
Abstract
The invention belongs to technical field of organic chemistry, relate to a kind of method separating and recovering Hexalin from pimelinketone device waste liquid.It is characterized in that sequentially passing through waste liquid washing, be dried, a series of process such as de-light and refined, the isolated mass concentration cyclohexanol product more than 90%, in waste liquid, the yield of Hexalin reaches more than 90%.The process of the present invention is effectively increased the utilization rate of Hexalin, reduces the discharge capacity of waste liquid simultaneously.
Description
Technical field
The invention belongs to technical field of organic chemistry, relate to a kind of side separating and recovering Hexalin from pimelinketone device waste liquid
Method.
Background technology
Hexalin is a kind of broad-spectrum raw material of industry, is commonly used for the molten of resin, paint, ethyl cellulose, rubber etc.
Agent, also serves as cleaning agent, rubber reinforcing agent etc..Hexalin is the primary raw material preparing adipic acid and Ketohexamethylene, and it produces
Method mainly has phenol hydrogenation method, cyclohexane oxidation process and cyclohexene hydration method.Hexalin dehydrogenation under catalyst action is raw
Becoming product Ketohexamethylene, Ketohexamethylene is the primary raw material producing caprolactam.
The cyclohexene method prepares Ketohexamethylene process mainly following step: first, and benzene is hydrogenated with in catalyst action lower part
Cyclohexene, then through cyclohexene hydration Hexalin, and by-product hexamethylene, refined Hexalin is prepared through catalytic dehydrogenation
Ketohexamethylene product.In the process, sampling waste oil and technology waste gas condensed fluid, technique oily waste water are through chemical sewage tank receipts
Send into pimelinketone device waste water tank after collection, tank carries out oil-water separation.Waste oil is by being pumped to sump tank；Additionally, device
A small amount of technique relief liquor, the discharge opeing such as maintenance also collects in sump tank.The component of effluent collected in sump tank is complex,
But calorific value is higher, can use as fuel oil.But burn as fuel, not only lose useful component, also can cause one
Fixed environmental pollution.
Through analyze test, waste liquid mainly contains Hexalin, hexamethylene, cyclohexene, benzene, N,N-dimethylacetamide,
Dicyclo hexyl ether and cyclohexylcyclohexanol etc., wherein Hexalin content is higher.If its key component can be recycled, can
Produce economic benefit, also can reduce environmental pollution.
Key component Hexalin in waste liquid by a series of process such as washing, be dried, be de-light and refined, is divided by the present invention
From being met the cyclohexanol product for preparing Ketohexamethylene of purity requirement, it is effectively increased the utilization rate of Hexalin, with
Time reduce the discharge capacity of waste liquid.
Summary of the invention
It is an object of the invention to provide a kind of process separating and recovering Hexalin from pimelinketone device waste liquid, the party
Method includes following step: A waste liquid removes water-solubility impurity through water elution in extraction tower, and after extraction, oil phase enters and is dried
Tower；In B drying tower, removing residual moisture and a small amount of light composition impurity, enter lightness-removing column containing Hexalin heavy constituent；C is de-light
In tower, rectification removes light composition impurity, enters product tower containing Hexalin heavy constituent；Removing heavy constituent impurity in D product tower,
It is refining to obtain to meet and requires cyclohexanol product.
Further, in drying tower, residual moisture and a small amount of light composition impurity of removing make oil-water separation through sedimentation in decant tank.
Further, described extraction tower extractant is desalted water, and desalted water is 0.1～10 with the ratio of the feed volume flow of waste liquid:
1。
Further, described drying tower operates in atmospheric conditions, and feed entrance point is positioned at tower top, and tower top temperature is 60～70 DEG C,
Bottom temperature is 75～95 DEG C.
Further, described lightness-removing column under reduced pressure operates, and operating reflux ratio is 3～20, and tower top temperature is 50～90 DEG C, tower
Still temperature is 100～160 DEG C.
Further, described product tower under reduced pressure operates, and operating reflux ratio is 1～3, and tower top temperature is 80～90 DEG C, tower reactor
Temperature is 105～115 DEG C.
Further, described extraction tower theoretical cam curve >=10, drying tower theoretical cam curve >=10, lightness-removing column theoretical cam curve
>=40, product tower theoretical cam curve >=45.
The technological process of said process is as it is shown in figure 1, following be described further this technological process: outside waste liquid is by battery limit (BL)
Extraction tower T-101 sent into by delivery pump, is entered by bottom extraction tower T-101, carries out liquid-liquid extraction with the desalted water of tower top charging,
Washing removes the water-solubility impurity in raw material；The T-101 overhead extraction oil phase containing Hexalin sends into drying tower T-102, tower reactor
The waste water of extraction is delivered to sewage-treatment plant by pump P-101；The remaining moisture in material is removed on drying tower T-102 top
Composition impurity light with part, water and light composition impurity stand in decant tank S-101 through drying tower condenser E-102 and divide
Layer, oil phase and aqueous phase send battery limit (BL) respectively；Heavy constituent material containing major part Hexalin is sent by being dried tower reactor pump P-102
To lightness-removing column T-103, according to the reflux ratio set carry out rectification separation (during rectification, dehydrogenation tower reboiler E-103
Thermal source needed for rectification is provided), remove light composition impurity therein and successively return through condenser of light component removal column E-104 and lightness-removing column
Stream tank V-101, eventually passes a light oil pump P-104 part and is back to lightness-removing column T-103 as backflow, and another part send
Go out battery limit (BL)；The heavy constituent of lightness-removing column is sent into product tower T-104 by lightness-removing column still pump P-103；Carry out according to the reflux ratio set
Rectification separates (during rectification, product tower reboiler E-105 provides thermal source needed for rectification), product tower tower reactor
Heavy constituent impurity is sent battery limit (BL) as waste oil disposal by product tower reactor pump P-105, and product tower T-104 tower top is met pure
The cyclohexanol product that degree requires, gained Hexalin successively through product tower condenser E-106 and product tower return tank V-102,
And finally it being back to product tower T-104 by a Hexalin pump P-106 part as backflow, another part is as target product
Send battery limit (BL) stand-by.
In waste liquid, each constituent mass percent and atmospheric boiling point are as shown in the table:
The atmospheric boiling point of other the light composition impurities in said components less than the atmospheric boiling point of Hexalin, mainly include pentane,
Hexahydrotoluene, cyclohexene oxide, toluene, n-amyl alcohol etc.；The atmospheric boiling point of other heavy constituent impurity is higher than Hexalin
Atmospheric boiling point, mainly includes phenol, cyclohexyl benzene, cyclohexylidene hexamethylene etc..
The waste liquid of said components obtains target product Hexalin via following steps.
A waste liquid removes the water-solubility impurities such as N,N-dimethylacetamide in extraction tower through water elution, and after extraction, oil phase enters dry
Dry tower；
Removing residual moisture and a small amount of light composition impurity in B drying tower, including normal hexane and methyl cyclopentane etc., containing hexamethylene
Alcohol heavy constituent enters lightness-removing column；
In C lightness-removing column, rectification removes light composition impurity, and including benzene, cyclohexene, hexamethylene etc., the heavy constituent containing Hexalin is entered
Enter product tower；
Removing heavy constituent impurity in D product tower, including 1-cyclohexyl ring hexene, 2-cyclohexylcyclohxanone and hexamethylene ether etc.,
It is refining to obtain to meet and requires cyclohexanol product.
It is an advantage of the invention that and remove the water-solubility impurity in waste liquid by washing, be possible not only to reduce Hexalin and other group
Point-such as the separating difficulty of N,N-dimethylacetamide, reduce the load of follow-up rectification section, and N, N-can be reduced
The impurity such as dimethyl acetylamide hydrolyze the corrosion to equipment caused；It is more than 90% by rectification isolated mass concentration
Cyclohexanol product, the waste oil after process may continue as fuel oil and uses, will not cause new environmental pollution.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention.
In figure: T-101 extraction tower；T-102 drying tower；T-103 lightness-removing column；T-104 product tower；E-101—
Drying tower reboiler；E-102 drying tower condenser；E-103 lightness-removing column reboiler；E-104 condenser of light component removal column；
E-105 product tower reboiler；E-106 product tower condenser；S-101 drying tower decant tank；V-101 lightness-removing column
Return tank；V-102 product tower return tank；P-101 waste water pump；P-102 is dried tower reactor pump；P-103 lightness-removing column still
Pump；P-104 light oil pump；P-105 product tower reactor pump；P-106 Hexalin pump.
Detailed description of the invention
Embodiment 1
A kind of method technological process reclaiming Hexalin from pimelinketone device waste liquid is as it is shown in figure 1, the matter of each component of waste liquid
Amount percent is:
Take this waste liquid enter extraction tower T-101, extraction tower T-101 theoretical cam curve is 20, desalted water and waste liquid respectively by
Feeding at the bottom of tower top and tower, inlet amount is 0.5m3/ h, wherein, the density of waste liquid is 967kg/m3；Drying tower T-102
Theoretical cam curve is 20, and tower top feeds, and operates at ambient pressure, and tower top and tower reactor operation temperature are respectively 67 DEG C and 90 DEG C；
Lightness-removing column T-103 theoretical cam curve is 50, feeds at the 20th piece of theoretical plate, and tower top operation pressure is 50kPa, controls back
Flow ratio is 20, and tower top and bottom temperature are respectively 58 DEG C and 142 DEG C；Product tower T-104 theoretical cam curve is 60,
25 pieces of theoretical plate chargings, tower top operation pressure is 5kPa, and controlling reflux ratio is 2, and tower top and bottom temperature are respectively 85 DEG C
With 110 DEG C；Product overhead product obtains, through analyzing, the cyclohexanol product that mass fraction is 99.7%, and yield is 254.1kg/h,
Hexalin total recovery is 90.9%.
Embodiment 2
A kind of method technological process reclaiming Hexalin from pimelinketone device waste liquid is as it is shown in figure 1, the matter of each component of waste liquid
Amount percent is:
Take this waste liquid enter extraction tower T-101, extraction tower T-101 theoretical cam curve is 20, desalted water and waste liquid respectively by
Feeding at the bottom of tower top and tower, inlet amount is respectively 0.2m3/ h and 0.5m3/ h, wherein, the density of waste liquid is 967kg/m3；
Drying tower T-102 theoretical cam curve is 20, and tower top feeds, and operates at ambient pressure, and tower top and tower reactor operation temperature are respectively
65 DEG C and 87 DEG C；Lightness-removing column T-103 theoretical cam curve is 50, feeds at the 20th piece of theoretical plate, and tower top operation pressure is
50kPa, controlling reflux ratio is 5, and tower top and bottom temperature are respectively 57 DEG C and 140 DEG C；Product tower T-104 theoretical tray
Number is 60, feeds at the 25th piece of theoretical plate, and tower top operation pressure is 5kPa, and controlling reflux ratio is 1, tower top and tower reactor temperature
Degree is respectively 84 DEG C and 112 DEG C；Product overhead product obtains, through analyzing, the cyclohexanol product that mass fraction is 90.2%, produces
Amount is 183.7kg/h, and Hexalin total recovery is 95.2%.
Embodiment 3
A kind of method technological process reclaiming Hexalin from pimelinketone device waste liquid is as it is shown in figure 1, the matter of each component of waste liquid
Amount percent is:
Take this waste liquid enter extraction tower T-101, extraction tower T-101 theoretical cam curve is 20, desalted water and waste liquid respectively by
Feeding at the bottom of tower top and tower, inlet amount is respectively 1.0m3/ h and 0.5m3/ h, wherein, the density of waste liquid is 967kg/m3；
Drying tower T-102 theoretical cam curve is 20, and tower top feeds, and operates at ambient pressure, and tower top and tower reactor operation temperature are respectively
68 DEG C and 92 DEG C；Lightness-removing column T-103 theoretical cam curve is 50, feeds at the 20th piece of theoretical plate, and tower top operation pressure is
50kPa, controlling reflux ratio is 10, and tower top and bottom temperature are respectively 58 DEG C and 142 DEG C；Product tower T-104 theoretical tray
Number is 60, feeds at the 25th piece of theoretical plate, and tower top operation pressure is 5kPa, and controlling reflux ratio is 1, tower top and tower reactor temperature
Degree is respectively 85 DEG C and 111 DEG C；Product overhead product obtains, through analyzing, the cyclohexanol product that mass fraction is 95.5%, produces
Amount is 98.2kg/h, and Hexalin total recovery is 92.4%.
Above an embodiment of the invention is described in detail, but described content has been only the invention relatively
Good embodiment, it is impossible to be considered the practical range for limiting the invention.All made according to the invention application range
Impartial change and improvement etc., within all should still belonging to the patent covering scope of the invention.
Claims (2)
1. the method separating and recovering Hexalin from pimelinketone device waste liquid, it is characterised in that comprise the following steps:
A waste liquid removes water-solubility impurity through water elution in extraction tower, and after extraction, oil phase enters drying tower；
In B drying tower, removing residual moisture and a small amount of light composition impurity, enter lightness-removing column containing Hexalin heavy constituent；
In C lightness-removing column, rectification removes light composition impurity, enters product tower containing Hexalin heavy constituent；
Removing heavy constituent impurity in D product tower, is refining to obtain to meet and requires cyclohexanol product；
Wherein, described extraction tower extractant is desalted water, and desalted water is 0.1～10:1 with the ratio of the feed volume flow of waste liquid；
Described drying tower operates in atmospheric conditions, and feed entrance point is positioned at tower top, and tower top temperature is 60～70 DEG C, tower reactor temperature
Degree is 75～95 DEG C；
Described lightness-removing column under reduced pressure operates, and operating reflux ratio is 3～20, and tower top temperature is 50～90 DEG C, and bottom temperature is
100～160 DEG C；
Described product tower under reduced pressure operates, and operating reflux ratio is 1～3, and tower top temperature is 80～90 DEG C, and bottom temperature is
105～115 DEG C；
Described extraction tower theoretical cam curve >=10, drying tower theoretical cam curve >=10, lightness-removing column theoretical cam curve >=40, produce
Product tower theoretical cam curve >=45.
A kind of method separating and recovering Hexalin from pimelinketone device waste liquid, its feature exists
In, in drying tower, residual moisture and a small amount of light composition impurity of removing make oil-water separation through sedimentation in decant tank.
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| CN105669346B (en) * | 2016-03-03 | 2018-11-27 | 中国天辰工程有限公司 | A kind of method of pimelinketone device waste oil recycling comprehensive utilization |
| CN108299139B (en) * | 2018-01-30 | 2020-10-20 | 岳阳昌德环境科技有限公司 | Preparation method of cyclohexene |
| CN108358808B (en) * | 2018-02-28 | 2020-09-08 | 中国天辰工程有限公司 | Method for recovering dimethylacetamide in waste oil of cyclohexanone device |
| CN108484379A (en) * | 2018-05-02 | 2018-09-04 | 山东亚科环保科技有限公司 | A kind of Processes and apparatus detaching cyclohexanone, cyclohexanol, DMAC N,N' dimethyl acetamide mixture |
| CN111018214B (en) * | 2018-10-10 | 2023-02-03 | 中国石油化工股份有限公司 | Method for reducing COD content in waste water discharged from cyclohexanone device |
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| CH648542A5 (en) * | 1982-06-04 | 1985-03-29 | Inventa Ag | Process for the purification of cyclohexanone/cyclohexanol mixtures |
| JPH06104637B2 (en) * | 1990-04-06 | 1994-12-21 | 三菱化成株式会社 | Method for removing impurities from a mixture of cyclohexanone and cyclohexanol |
| CN104086371B (en) * | 2014-07-07 | 2015-12-30 | 湖南百利工程科技股份有限公司 | The processing method that in the cyclohexene method preparing cyclohexanone production process, hexalin is separated |
| CN105130754B (en) * | 2014-08-25 | 2017-02-01 | 泰山医学院 | Method for extracting cyclohexanol from cyclohexanone waste liquid by using composite extractant |
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