CN106187696B - The separation method of butanol and octanol waste liquid back end hydrogenation low energy consumption - Google Patents
The separation method of butanol and octanol waste liquid back end hydrogenation low energy consumption Download PDFInfo
- Publication number
- CN106187696B CN106187696B CN201510211836.0A CN201510211836A CN106187696B CN 106187696 B CN106187696 B CN 106187696B CN 201510211836 A CN201510211836 A CN 201510211836A CN 106187696 B CN106187696 B CN 106187696B
- Authority
- CN
- China
- Prior art keywords
- octanol
- butanol
- tower
- hydrogen
- logistics
- 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
Abstract
The separation method of butanol and octanol waste liquid back end hydrogenation low energy consumption disclosed by the invention belongs to the technical field of octyl alconyl, in order to solve the problems, such as that utilization rate of the existing technology is not high or energy consumption is high, it proposes and a kind of the aldehyde in butanol and octanol waste liquid is first hydrogenated to alcohol, using distillation process, obtain butanol and octanol products, specific steps include dehydration, separating butanol, separate miscellaneous oil, separate octanol, de- octanol, the butyraldehyde that separates of tower top will be dehydrated to add hydrogen and the octenal that miscellaneous oily tower top separates is added hydrogen and first passes through each plus after hydrogen and takes off light process, it is returned to during separating butanol and separation octanol etc. respectively again, the utilization rate of butanol and octanol waste liquid can be significantly increased, greatly improve utility value, increase economic benefit.The present invention can reduce the difficulty of rectification cell, reduce separation costs by adding the process of hydrogen to reduce the complicated composition degree of material.
Description
Technical field
Invention is related to a kind of method that butanol and octanol are recycled from butanol and octanol waste liquid, it is more particularly related to
A method of by adding hydrogen and obtaining butanol and octanol products through subtractive process.
Background technique
Butanol and octanol (abbreviation octyl alconyl) are mainly for the production of two pungent vinegar (DOP) of plasticizer phthalic acid and adjacent benzene two
Two fourth vinegar (DBP) of formic acid.With the development of China's plastics industry, market is to the requirement of octyl alconyl in cumulative year after year, domestic fourth
The production capacity of octanol device is also increasing year by year.Evaporator, phase-splitter and the weight-removing column etc. of butyl octanol unit reactor have on a small quantity
Effluent, the mixed liquor of discharge is known as octyl alconyl raffinate, is equivalent to 10% or so of octyl alconyl product quality, and wherein contain
A large amount of valuable ingredients, but due to complicated composition, the past is mostly used to make fuel.Oneself domestic some recycles octyl alconyl raffinate
Device such as batch fractionating tower etc., the technique of use is unreasonable, recycles the of poor quality of product, and yield is low, and economic benefit is undesirable.
Such as CN101423455A, Wu Jinyuan (butanol and octanol waste liquid recovery technology improvement petrochemical industry, 1999,28:832~834), king
It is of heap of stone (the recycling petrochemical industry of butanol and octanol raffinate, 2006,35 (8): 782~784), Xing Meixia (butanol and octanol waste liquid
The Inner Mongol reclaiming clean technology petrochemical industry, 2000,7:53~54) etc. the work of this respect has been carried out, but has been essentially all
Butyraldehyde, butanol, C8 solvent are directly fractionated out from waste liquid, remaining raffinate is used as fuel oil again.
CN101973846A disclose it is a kind of using butyl octanol unit discharge waste liquid be raw material produce mixed butyl alcohol and slightly it is pungent
The method of alcohol, for this method by raw material fractionation unit, hydrogenation synthesis unit and product rectification cell composition, the mixed butyl alcohol of production are pure
Degree >=95wt%, thick octanol purity >=97wt% of production.But the technique increases raw material fractionation unit before the reaction, process compared with
For complexity, cost of investment is big.CN101892066A is disclosed and octyl alconyl raffinate is cracked into carbon under a kind of akaline liquid decomposition agent
Four and carbon eight production technology.The mixture that the technique does not pass through the carbon four of hydrotreating production, carbon eight is aldehyde and alcohol, utilizes
It is worth low.
Octyl alconyl raffinate hydrogenation process is mainly that aldehyde, the unsaturated alcohol in raffinate are hydrogenated to corresponding alcohol and part
Long carbon chain component occurs plus hydrogen, the alcohol for being cracked into short carbon chain, used catalyst belong to aldehyde hydrogenating catalyst scope aldehyde and hydrogen added to be divided into
Gas phase hydrogenation and liquid-phase hydrogenatin, liquid-phase hydrogenatin are widely adopted in recent years since low energy consumption plus hydrogen effect is good.CN1478596A
A kind of catalyst of the mixture liquid-phase hydrogenatin isooctanol of different octanal is disclosed, the catalyst is using Ni as active component, with alkali
Earth metal or/and aluminium oxide are promotor, and siliceous compound is carrier.Different octanal after hydrogen is added to have remnants, hydrogenation rate 96%.
CN102309968A discloses a kind of aldehyde liquid phase hydrogenating catalyst, nickel or its oxide be in 8~35%, IA or Group IIA extremely
A kind of few element or its oxide are at least one of (0.01~2.0) wt%, IIIA or IV group element or its oxide is
(0.01~20.0) wt%, rare earth element are (0.01~5) wt%, and aluminium oxide is carrier, and the catalyst low-temperature activity is high, but urges
Agent composition is complex.CN102059121A discloses a kind of lanthanum modified nickel-copper octanol hydrorefining catalyst, with γ-Al2O3
For carrier, ambrose alloy is active component, and lanthanum is auxiliary agent, and octenal, disloyalty aldehyde, matsutake alcohol hydrogenation rate reach 95% or more.
CN1730151 discloses a kind of catalyst of thick octanol liquid-phase hydrogenatin refining reaction.The clean property group of catalyst is divided into Ni, rare earth metal
For promotor, aluminium oxide is carrier, and addition silicon makees auxiliary agent.CN1275439A discloses a kind of liquid phase hydrogenating catalyst for insatiable hunger
In aldehyde liquid-phase hydrogenatin technique.The catalyst does carrier by silica, and nickel is the first active component, and other active components are
Cobalt, molybdenum, chromium, potassium.Active component is complicated.
CN101973845B discloses one kind and extracts butyraldehyde and butanol mixture and octene from butyl octanol unit waste liquid
The method of aldehyde, octanol mixture.Butyraldehyde and butanol mixture are fractionated out from waste liquid first, adds hydrogen for butyraldehyde hydrogenation plant,
Octenal and octanol mixture are therefrom fractionated out again, is used for octenal hydrogenation plant, both materials are also used as byproduct
Sale.This method is simple, but brings many miscellaneous components in waste liquid into octyl alconyl again.
(recycling of butanol and octanol raffinate is sharp with Wang Lei substantially for butanol and octanol waste liquid treatment process disclosed in CN103342625A
With petrochemical industry, 2006,35 (8): technology disclosed in 782~784) is identical, is separated using four tower rectifying system.By octyl alconyl
Waste liquid is passed through first rectifying column middle section after being heated to 60 DEG C -100 DEG C, de- from first rectifying column tower top under the action of entrainment reagent
Moisture removal and light component；First rectifying column tower reactor liquid enters Second distillation column middle section, Second distillation column tower top obtain purity >
98% butanol product；Second distillation column tower reactor liquid enters third distillation column middle section, from third distillation column removed overhead C5-C7
And octenal component；Third distillation column tower reactor liquid enter the 4th rectifying midsection, the 4th the top of the distillation column obtain purity >
98% octanol products.The treatment process relies solely on rectifying mode, therefrom recycles butanol and octanol, but without utilizing fourth
The unsaturation component such as aldehyde, octenal and matsutake alcohol and octanal, utilization rate are low.
CN101973846B discloses the method for a kind of production of butyl octanol unit waste liquid mixed butyl alcohol and thick octanol.By raw material
Fractionation unit, hydrogenation synthesis unit and product rectification cell composition, the raw material branch library unit include butyraldehyde fractionating column, butanol point
Tower and carbon eight fractionating columns, three sets of fractionating devices are evaporated, the hydrogenation synthesis unit and product rectification cell are suitable for being fractionated from raw material
The C-4-fraction of unit adds hydrogen and rectifying, and be also applied for eight fraction of carbon from raw material fractionation unit adds hydrogen and rectifying, supplies
The two asks use of having a rest；The product rectification cell includes de-light rectification column device and de- heavy distillation column device；Including operating as follows
Step: a. raw material branch library: the waste liquid of butyl octanol unit discharge passes through butyraldehyde fractionating device first, the butyraldehyde component that will wherein contain
It is fractionated from butyraldehyde tower top, then by butanol separation column device, the butanol component wherein contained is fractionated from butanol tower top
Out, it is fractionated tower apparatus finally by carbon eight, the eight component octenal of carbon and octanol that wherein contain is fractionated out from eight tower top of carbon
Come；The butyraldehyde and butanol being fractionated are stored in four storage tank of carbon, and octenal and octanol are stored in eight storage tank of carbon；B. hydrogenation synthesis:
The butyraldehyde and butanol of four storage tank of carbon from step a or the octenal from eight storage tank of carbon and octanol fraction enter plus hydrogen closes
At unit, in hydrogenator, pass through hydrogenation synthesis mixed butyl alcohol or the thick octanol of synthesis；C. product purification: step b adds hydrogen
The mixed butyl alcohol of synthesis or thick octanol are through rectified purified, obtained mixed butyl alcohol or thick octanol.That there is separation equipments is more for this method,
The problem that octanol is steamed from the top of the distillation column twice, energy consumption is high.
The prior art has that utilization rate is not high and energy consumption is high.
Summary of the invention
In order to solve the problems, such as that utilization rate of the existing technology is not high and energy consumption is high, proposes and a kind of first octyl alconyl gives up
Aldehyde in liquid is hydrogenated to alcohol, using distillation process, obtains butanol and octanol products.
The separation method of butanol and octanol waste liquid back end hydrogenation low energy consumption of the invention, specifically includes hydrogenation unit and rectification cell,
The following steps are included:
(1) be dehydrated: butanol and octanol waste liquid enters dehydrating tower, through distillation process, steams water, hydro carbons, isobutylaldehyde from dehydration tower top
And n-butanal, it is condensate in quantizer and separates water phase discharge, oil phase part point extraction, partial reflux produces bottoms from tower bottom
Stream；
(2) separating butanol: the logistics from dehydrating tower tower bottom enters butanol tower, through distillation process, from butanol overhead extraction
Butanol product produces tower base stream from tower bottom；
(3) separate miscellaneous oil: the logistics from butanol tower tower bottom enters miscellaneous oily tower, through distillation process, from miscellaneous oily overhead extraction
Logistics containing butyl butyrate, enanthol, 3- methyl -4- enanthol, matsutake alcohol, octanal and octenal, as miscellaneous oil discharge, from tower bottom
Produce tower base stream；
(4) separate octanol: the logistics from miscellaneous oily tower tower bottom enters octanol tower, through distillation process, uses from octanol tower top
Octanol products produce the logistics containing octanol, lauryl alcohol and hexadecanol from tower bottom；
(5) take off octanol: the logistics containing octanol, lauryl alcohol and hexadecanol produced from octanol tower bottom enters de- octanol
Tower, through distillation process, from logistics of the overhead extraction containing octanol as octanol products or being incorporated in the logistics of miscellaneous oily overhead extraction
Hydrogen dilution is added to act on or return to octanol tower；
(6) add hydrogen: the oil phase thing stream and hydrogen of the quantizer from dehydration tower top, which enter, adds hydrogen equipped with hydrogenation catalyst
Reactor, at 50~200 DEG C of reaction temperature, 0.4~5.0MPa of reaction pressure, butyraldehyde therein is hydrogenated to butanol, obtains
Butanol reaction solution after adding hydrogen；Alternatively, miscellaneous oily logistics and hydrogen from miscellaneous oily tower top enter equipped with hydrogenation catalyst plus hydrogen
Reactor, at 50~200 DEG C of reaction temperature, 0.4~5.0MPa of reaction pressure, matsutake alcohol, octanal and octenal therein add
Hydrogen generates octanol, obtains the octanol reaction solution after adding hydrogen；Described two logistics add hydrogen switching to carry out；
(7) take off light: the butanol reaction solution enters lightness-removing column, through distillation process, contains hydro carbons and not instead from overhead extraction
The logistics for the butyraldehyde answered is discharged as light component, enters the butanol tower from logistics of the tower bottom extraction containing butanol；Or institute
Octanol reaction solution is stated into the lightness-removing column, through distillation process, contains butyl butyrate, enanthol, 3- methyl -4- heptan from overhead extraction
The logistics of pure and mild unreacted octenal is discharged as miscellaneous oily waste liquid, enters from logistics of the tower bottom extraction containing octanol described
Octanol tower.
Hydrogenation process described in method of the invention can be liquid phase reactor, be also possible to gas phase reaction.Preferably, described
Liquid phase reactor is hydrogenated in hydrogenation step (1), hydrogenation catalyst is the nickel catalyst suitable for butyl octanol unit liquid-phase hydrogenatin,
Reaction temperature is 50~130 DEG C, and reaction pressure is 2.0~5.0MPa, and the liquid phase air speed of butanol and octanol waste liquid is 0.15~1.5h-1,
Hydrogen inlet amount is 1.05~20 times that butanol and octanol waste liquid adds hydrogen consumption amount.
It is highly preferred that being hydrogenated to liquid phase reactor in the hydrogenation step (1), hydrogenation catalyst is suitable for butyl octanol unit
The nickel catalyst of liquid-phase hydrogenatin, reaction temperature are 60~130 DEG C, and reaction pressure is 3.0~5.0MPa, the liquid of butanol and octanol waste liquid
Phase air speed is 0.15~1.2h-1, hydrogen inlet amount is 1.05~5 times that butanol and octanol waste liquid adds hydrogen consumption amount.
Method of hydrotreating described in method of the invention can freely select use according to factory condition, it is preferable that institute
It states and is hydrogenated to gas phase reaction in hydrogenation step (1), hydrogenation catalyst is the copper system catalysis suitable for butyl octanol unit gas phase hydrogenation
Agent, reaction temperature are 120~200 DEG C, and reaction pressure is 0.4~0.8MPa, and air speed of the butanol and octanol waste liquid charging in terms of liquid phase is
0.15~1.5h-1, hydrogen inlet amount is 10~40 times that butanol and octanol waste liquid adds hydrogen consumption amount.
It is also relatively high containing volatility because containing performance degree relatively low butyraldehyde and butanol object system in butanol and octanol waste liquid
Octenal and octanol object system, also containing more weight 12 carbon atoms component and 16 carbon atoms component, thus
Material can a part of be gas phase in hydrogenation process, and a part is liquid phase, it is preferable that is hydrogenated to gas in the hydrogenation step (1)
Phase-liquid phase reactor, butanol and octanol waste liquid middle part are divided into gas phase, are partially liquid phase, and hydrogenation catalyst is suitable for butyl octanol unit gas
It is added the Cu-series catalyst of hydrogen or the nickel catalyst suitable for butyl octanol unit liquid-phase hydrogenatin, reaction temperature is 120~200
DEG C, reaction pressure is 0.4~0.8MPa, and air speed of the butanol and octanol waste liquid charging in terms of liquid phase is 0.15~1.5h-1, hydrogen inlet amount
It is 10~40 times of butanol and octanol waste liquid plus hydrogen consumption amount.
The octyl alconyl can be waste liquid arbitrarily from butyl octanol unit, can be one waste liquid, is also possible to multiply
The mixture of waste liquid can be the waste liquid of butanol unit, and only the material containing butyraldehyde and butanol object system, is also possible to octanol unit
Waste liquid, only the material containing octenal and octanol object system, can also be the mixture of these materials.It is excellent to be more representative
Selection of land, the butanol and octanol waste liquid are to contain hydrocarbon, butyraldehyde, butanol, butyl butyrate, enanthol, matsutake alcohol, pungent from butyl octanol unit
Aldehyde, octenal, octanol, lauryl alcohol, lauric aldehyde, hexadecanoyl and hexadecanol material.The butanol and octanol waste liquid can also be containing perhaps
A small amount of qualitative or not qualitative component of more butyl octanol unit by-products.In the present invention, each component can be the same of them
Enantiomers, butyraldehyde include isobutylaldehyde and n-butanal, and butanol includes isobutanol and n-butanol, and matsutake alcohol is 2- ethyl hex- 2- alkene-
1- alcohol, octanal are 2- ethyl hexanal, and octenal is 2- ethyl hex- 2- alkene -1- aldehyde, and octanol is 2-Ethylhexyl Alcohol, and lauryl alcohol is different
The alcohols containing 12 carbon atoms that butyraldehyde and/or n-butanal are condensed and are hydrogenated to, lauric aldehyde are isobutylaldehyde and/or positive fourth
The aldehydes containing 12 carbon atoms that aldehyde is condensed and is hydrogenated to, hexadecanol are that isobutylaldehyde and/or n-butanal are condensed and are added
The alcohols containing 16 carbon atoms that hydrogen generates, hexadecanoyl be isobutylaldehyde and/or n-butanal be condensed and be hydrogenated to contain ten
The aldehydes of six carbon atoms.
In the method for the invention, the operating condition of each rectifying column of rectification cell can be according to the composition of itself material
It is determined with property.Preferably, the tower top temperature of the dehydrating tower is 40~70 DEG C, and tower top pressure is 0.1~0.2MPa, tower reactor
Temperature is 120~140 DEG C；The tower top temperature of the butanol tower is 70~90 DEG C, and tower top pressure is 0.02~0.04MPa, tower reactor
Temperature is 140~160 DEG C；The tower top temperature of the miscellaneous oily tower is 65~80 DEG C, and tower top pressure is 0.004~0.017MPa, tower
Kettle temperature degree is 130~155 DEG C；The tower top temperature of the octanol tower is 95~120 DEG C, and tower top pressure is 0.004~0.017MPa,
Bottom temperature is 180~220 DEG C.
Nickel catalyst of the present invention can be supported on aluminium oxide, silica, aluminium oxide-silicon oxide, active carbon,
Nickel catalyst on diatomite, zirconium oxide or calcium oxide, in addition to nickeliferous active component, can also containing other auxiliary agents such as magnesium,
The components such as potassium, lanthanum, zinc, calcium.The nickel catalyst is also possible to the nickel catalyst of precipitation method acquisition, such as precipitation method aluminium oxide
The nickel catalyst of dispersion.Hydrogenation catalyst of the invention is also possible to cobalt series catalyst, and carrier or decentralized medium are similar to nickel
Series catalysts.In terms of mass percentage content, Nickel Content In Catalyst is 10%~50%, such as alumina load 15~20%
The catalyst of the catalyst of nickel, 40~50% nickel of alumina dispersion.The nickel catalyst is also possible to Raney's nickel catalyst,
Raney's nickel catalyst has powdered, particle, strip or bulk, preferably blocky Raney's nickel catalyst.
Cu-series catalyst of the present invention can be loaded catalyst, be also possible to co-precipitated catalyst.Such as it is negative
The Cu-series catalyst being loaded on aluminium oxide, silica, aluminium oxide-silicon oxide, active carbon, diatomite, zirconium oxide or calcium oxide, is removed
Copper-containing active group exceptionally, can also contain the components such as other auxiliary agents such as nickel, cobalt, magnesium, potassium, lanthanum, zinc, calcium.Co-precipitated catalyst can
To be copper zinc catalyst, copper and zinc element, CuZnAl catalyst, can also be added into these basic recipe catalyst other
Auxiliary agent, such as manganese, lanthanum auxiliary agent.The percent mass content of copper is 25%~50%.Such as CuZnAl catalyst contain 28~
45% copper, 45~65% zinc and 1~10% aluminium.
Method for preparing catalyst of the present invention can be obtained by existing catalyst preparation technology, as infusion process, from
Sub- exchange process, blending method, kneading method, co-precipitation, deposition-precipitation, steaming ammonia-sinking shallow lake, melting-suction filtration, ball milling and sol-gel etc.
Method.Preferred method includes that infusion process, co-precipitation, deposition-precipitation, steaming ammonia-sinking shallow lake, melting-suction filtration, ball milling and colloidal sol-are solidifying
One of glue or a variety of combinations, it is mostly those skilled in the art as existing mature technology that these, which prepare catalyst method,
It is known, there is detailed introduction in the books of this field, such as Huang Zhong Tao written " industrial catalyst design and development ",
Gerhard professor Ertl etc. is written " Preparation of Solid Catalysts ".Wherein steaming ammonium of the present invention
Intermediate processing, briefly steps are as follows: (1) active component salt being dissolved in the water, it is also possible to contain other metals or nonmetallic
Salt；(2) ammonium hydroxide is gradually added in above-mentioned salting liquid, forms ammonium complex compound with ammonia；(3) other components are added；(4) it heats up gradually
Ammonia is evaporated, active ingredient precipitation gets off；(5) it washs, filter；(6) dry, roasting.Melting-suction method step in the present invention
Rapid essence refers to the preparation process of Raney catalyst: (1) by a furnace by with catalytic activity metal active constituent and
Aluminium (or silicon) fusion, obtained melt carries out quenching cooling, is then comminuted into as uniform fine grained, dissolves in step and may be used also
Other auxiliary agents can be added；(2) catalyst fines are formed, forming technique can such as be beaten using existing well known technology
Piece, kneading extrusion, spin etc.；(3) resulting above-mentioned preformed catalyst is filtered in lye to get acquisition catalyst is arrived.
Method of the invention can correspondingly add butyraldehyde, matsutake alcohol, octanal and the octenal in butanol and octanol waste liquid hydrogen raw
At butanol, octanol, the utilization rate of butanol and octanol waste liquid can be significantly increased, greatly improve utility value, increase economic benefit.
The present invention can reduce the difficulty of rectification cell by adding the process of hydrogen to reduce the complicated composition degree of material, and energy consumption reduces,
Separation costs reduce.
Specific embodiment
The separation method of butanol and octanol waste liquid back end hydrogenation low energy consumption of the invention is explained further by way of examples below,
But the present invention is not limited to this.
Embodiment 1
(1) be dehydrated: butanol and octanol waste liquid enters dehydrating tower, through distillation process, steams water, hydro carbons, isobutylaldehyde from dehydration tower top
And n-butanal, it is condensate in quantizer and separates water phase discharge, oil phase part point extraction, partial reflux produces bottoms from tower bottom
Stream；
(2) separating butanol: the logistics from dehydrating tower tower bottom enters butanol tower, through distillation process, from butanol overhead extraction
Butanol product produces tower base stream from tower bottom；
(3) separate miscellaneous oil: the logistics from butanol tower tower bottom enters miscellaneous oily tower, through distillation process, from miscellaneous oily overhead extraction
Logistics containing butyl butyrate, enanthol, 3- methyl -4- enanthol, matsutake alcohol, octanal and octenal, as miscellaneous oil discharge, from tower bottom
Produce tower base stream；
(4) separate octanol: the logistics from miscellaneous oily tower tower bottom enters octanol tower, through distillation process, uses from octanol tower top
Octanol products produce the logistics containing octanol, lauryl alcohol and hexadecanol from tower bottom；
(5) take off octanol: the logistics containing octanol, lauryl alcohol and hexadecanol produced from octanol tower bottom enters de- octanol
Tower, through distillation process, from logistics of the overhead extraction containing octanol as octanol products or being incorporated in the logistics of miscellaneous oily overhead extraction
Hydrogen dilution is added to act on or return to octanol tower；
(6) add hydrogen: the oil phase thing stream and hydrogen of the quantizer from dehydration tower top, which enter, adds hydrogen equipped with hydrogenation catalyst
Reactor, at 50~200 DEG C of reaction temperature, 0.4~5.0MPa of reaction pressure, butyraldehyde therein is hydrogenated to butanol, obtains
Butanol reaction solution after adding hydrogen；Alternatively, miscellaneous oily logistics and hydrogen from miscellaneous oily tower top enter equipped with hydrogenation catalyst plus hydrogen
Reactor, at 50~200 DEG C of reaction temperature, 0.4~5.0MPa of reaction pressure, matsutake alcohol, octanal and octenal therein add
Hydrogen generates octanol, obtains the octanol reaction solution after adding hydrogen；Described two logistics add hydrogen switching to carry out；
(7) take off light: the butanol reaction solution enters lightness-removing column, through distillation process, contains hydro carbons and not instead from overhead extraction
The logistics for the butyraldehyde answered is discharged as light component, enters the butanol tower from logistics of the tower bottom extraction containing butanol；Or institute
Octanol reaction solution is stated into the lightness-removing column, through distillation process, contains butyl butyrate, enanthol, 3- methyl -4- heptan from overhead extraction
The logistics of pure and mild unreacted octenal is discharged as miscellaneous oily waste liquid, enters from logistics of the tower bottom extraction containing octanol described
Octanol tower.
The analysis data of each key position are listed in Table 1 below.
Lightness-removing column I is the lightness-removing column that butanol reaction solution carries out rectifying, and lightness-removing column II is that octanol reaction solution carries out the de- of rectifying
Light tower.
Claims (7)
1. a kind of separation method of butanol and octanol waste liquid back end hydrogenation low energy consumption, which is characterized in that the method includes hydrogenation unit and
Rectification cell, comprising the following steps:
(1) be dehydrated: butanol and octanol waste liquid enters dehydrating tower, through distillation process, steams water, hydro carbons, isobutylaldehyde and just from dehydration tower top
Butyraldehyde, is condensate in quantizer and separates water phase discharge, oil phase part point extraction, and partial reflux produces tower base stream from tower bottom；
(2) separating butanol: the logistics from dehydrating tower tower bottom enters butanol tower, through distillation process, from butanol overhead extraction butanol
Product produces tower base stream from tower bottom；
(3) separate miscellaneous oil: the logistics from butanol tower tower bottom enters miscellaneous oily tower, through distillation process, contains from miscellaneous oily overhead extraction
The logistics of butyl butyrate, enanthol, butanol, matsutake alcohol, octanal and octenal produces tower base stream from tower bottom as miscellaneous oil discharge；
(4) separate octanol: the logistics from miscellaneous oily tower tower bottom enters octanol tower, through distillation process, uses octanol from octanol tower top
Product produces the logistics containing 3- methyl -4- enanthol, octanol, lauryl alcohol and hexadecanol from tower bottom；
(5) octanol is taken off: the logistics containing 3- methyl -4- enanthol, octanol, lauryl alcohol and hexadecanol produced from octanol tower bottom
Into de- octanol tower, through distillation process, logistics from overhead extraction containing octanol as octanol products extraction, be incorporated to miscellaneous oily tower top and adopt
Serve in logistics out plus hydrogen dilution or return to octanol tower；
(6) add hydrogen: the oil phase thing stream and hydrogen of the quantizer from dehydration tower top enter the hydrogenation reaction equipped with hydrogenation catalyst
Device, at 50~200 DEG C of reaction temperature, 0.4~5.0MPa of reaction pressure, butyraldehyde therein is hydrogenated to butanol, obtains and adds hydrogen
Butanol reaction solution afterwards；Alternatively, miscellaneous oily logistics and hydrogen from miscellaneous oily tower top enter the hydrogenation reaction equipped with hydrogenation catalyst
Device, at 50~200 DEG C of reaction temperature, 0.4~5.0MPa of reaction pressure, matsutake alcohol, octanal and octenal therein add hydrogen raw
At octanol, the octanol reaction solution after adding hydrogen is obtained；Described two logistics add hydrogen switching to carry out；
(7) take off light: the butanol reaction solution enters lightness-removing column, through distillation process, contains hydro carbons and unreacted from overhead extraction
The logistics of butyraldehyde is discharged as light component, enters the butanol tower from logistics of the tower bottom extraction containing butanol；Or it is described pungent
Alcohol reaction solution enters the lightness-removing column, through distillation process, contains butyl butyrate, enanthol, butanol and unreacted from overhead extraction
The logistics of octenal is discharged as miscellaneous oily waste liquid, enters the octanol tower from logistics of the tower bottom extraction containing octanol.
2. the separation method of butanol and octanol waste liquid back end hydrogenation low energy consumption as described in claim 1, which is characterized in that described plus hydrogen step
Suddenly liquid phase reactor is hydrogenated in (6), hydrogenation catalyst is the nickel catalyst suitable for butyl octanol unit liquid-phase hydrogenatin, reaction temperature
Degree is 50~130 DEG C, and reaction pressure is 2.0~5.0MPa, and the oil phase thing stream or miscellaneous oily logistics feed the air speed in terms of liquid phase
For 0.15~1.5h-1, hydrogen inlet amount is 1.05~16 times for adding hydrogen consumption amount.
3. the separation method of butanol and octanol waste liquid back end hydrogenation low energy consumption as described in claim 1, which is characterized in that described plus hydrogen step
Suddenly liquid phase reactor is hydrogenated in (6), hydrogenation catalyst is the nickel catalyst suitable for butyl octanol unit liquid-phase hydrogenatin, reaction temperature
Degree is 60~130 DEG C, and reaction pressure is 3.0~5.0MPa, the liquid phase air speed of the oil phase thing stream or miscellaneous oily logistics is 0.15~
1.2h-1, hydrogen inlet amount is 1.05~5 times for adding hydrogen consumption amount.
4. the separation method of butanol and octanol waste liquid back end hydrogenation low energy consumption as described in claim 1, which is characterized in that described plus hydrogen step
Suddenly gas phase reaction is hydrogenated in (6), hydrogenation catalyst is the Cu-series catalyst suitable for butyl octanol unit gas phase hydrogenation, reaction temperature
Degree is 120~200 DEG C, and reaction pressure is 0.4~0.8MPa, and the oil phase thing stream or miscellaneous oily logistics feed the air speed in terms of liquid phase
For 0.15~1.5h-1, hydrogen inlet amount is 10~40 times for adding hydrogen consumption amount.
5. the separation method of butanol and octanol waste liquid back end hydrogenation low energy consumption as described in claim 1, which is characterized in that described plus hydrogen step
Suddenly it is hydrogenated to gas-liquid phase in (6) to react, the part of the oil phase thing stream or miscellaneous oily logistics is gas phase, is partially liquid phase, adds hydrogen
Catalyst is the Cu-series catalyst suitable for butyl octanol unit gas phase hydrogenation or the nickel system suitable for butyl octanol unit liquid-phase hydrogenatin
Catalyst, reaction temperature are 120~200 DEG C, and reaction pressure is 0.4~0.8MPa, the oil phase thing stream or miscellaneous oily logistics charging
Air speed in terms of liquid phase is 0.15~1.5h-1, hydrogen inlet amount is 10~40 times that butanol and octanol waste liquid adds hydrogen consumption amount.
6. the separation method of butanol and octanol waste liquid back end hydrogenation low energy consumption as described in claim 1, which is characterized in that the octyl alconyl
Waste liquid is to contain alkane, butyraldehyde, butanol, butyl butyrate, enanthol, matsutake alcohol, octanal, octenal, pungent from butyl octanol unit
Alcohol, lauryl alcohol, lauric aldehyde, hexadecanoyl and hexadecanol material.
7. the separation method of butanol and octanol waste liquid back end hydrogenation low energy consumption as described in claim 1, which is characterized in that the dehydrating tower
Tower top temperature be 40~70 DEG C, tower top pressure be 0.1~0.2MPa, bottom temperature be 120~140 DEG C；The butanol tower
Tower top temperature is 70~90 DEG C, and tower top pressure is 0.02~0.04MPa, and bottom temperature is 140~160 DEG C；The miscellaneous oily tower
Tower top temperature is 65~80 DEG C, and tower top pressure is 0.004~0.017MPa, and bottom temperature is 130~155 DEG C；The octanol tower
Tower top temperature be 95~120 DEG C, tower top pressure be 0.004~0.017MPa, bottom temperature be 180~220 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510211836.0A CN106187696B (en) | 2015-04-29 | 2015-04-29 | The separation method of butanol and octanol waste liquid back end hydrogenation low energy consumption |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510211836.0A CN106187696B (en) | 2015-04-29 | 2015-04-29 | The separation method of butanol and octanol waste liquid back end hydrogenation low energy consumption |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106187696A CN106187696A (en) | 2016-12-07 |
| CN106187696B true CN106187696B (en) | 2019-02-19 |
Family
ID=57458224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510211836.0A Active CN106187696B (en) | 2015-04-29 | 2015-04-29 | The separation method of butanol and octanol waste liquid back end hydrogenation low energy consumption |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106187696B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973846A (en) * | 2010-11-03 | 2011-02-16 | 淄博诺奥化工有限公司 | Method for producing mixed butanol and coarse octanol by using waste liquid discharged from octanol device as raw material |
-
2015
- 2015-04-29 CN CN201510211836.0A patent/CN106187696B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973846A (en) * | 2010-11-03 | 2011-02-16 | 淄博诺奥化工有限公司 | Method for producing mixed butanol and coarse octanol by using waste liquid discharged from octanol device as raw material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106187696A (en) | 2016-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103553876B (en) | Liquid phase hydrogenation method for residual liquids of butanol and octanol | |
| Kreutzer | Manufacture of fatty alcohols based on natural fats and oils | |
| CN104370722B (en) | Preparation and the refining method of butanone | |
| CN105622337B (en) | Novel reactive distillation coupling process and device for separating liquid-phase product of ethylene glycol prepared from coal | |
| CN106187693B (en) | The cracking of butanol and octanol waste liquid collection and the separation method for adding hydrogen | |
| CN107915612B (en) | Method for preparing purified MIBK from industrial byproduct waste liquid acetone | |
| CN104478676A (en) | Butanone preparing and refining system | |
| CN106187700B (en) | The separation method of butanol and octanol waste liquid back end hydrogenation | |
| EP1053217B1 (en) | Process for the production of n-propanol | |
| CN106187698B (en) | The separation and refining method of butanol and octanol waste liquid back end hydrogenation | |
| CN101913991B (en) | Recycling method of butanol and octanol waste liquid through hydrocracking and catalyst | |
| CN106187701B (en) | The method of butanol and octanol waste liquid front-end hydrogenation recycling butanol and octanol | |
| CN109704906B (en) | Process for producing hexane by using raffinate oil | |
| CN106187680B (en) | By the refining methd of butanol and octanol waste liquid back end hydrogenation recycling butanol and octanol | |
| CN101492349B (en) | Production process for energy-saving environment-friendly methanol dehydration joint production of combustion extractive dimethyl ether | |
| CN106187694B (en) | Recycle the refining methd of butanol and octanol from butanol and octanol waste liquid with hydrogenation reaction by cracking | |
| CN106187696B (en) | The separation method of butanol and octanol waste liquid back end hydrogenation low energy consumption | |
| CN106187695B (en) | The method of butanol and octanol waste liquid back end hydrogenation recycling butanol and octanol | |
| CN106187681B (en) | The separation method of butanol and octanol waste liquid front-end hydrogenation low energy consumption | |
| CN109704908B (en) | Method for preparing hexane from aromatic raffinate oil | |
| CN105418372B (en) | A kind of method of acetic acid hydrogenation production ethanol | |
| CN106187697A (en) | The separation method of butanol and octanol waste liquid front-end hydrogenation | |
| CN106187699B (en) | Butanol-octanol waste liquid pre-hydrogenation separation refining method | |
| CN109796304A (en) | A kind of synthetic method of BED | |
| CN107778151B (en) | Method for preparing methyl ethyl ketone by sec-butyl alcohol dehydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |