CN106187701B - The method of butanol and octanol waste liquid front-end hydrogenation recycling butanol and octanol - Google Patents
The method of butanol and octanol waste liquid front-end hydrogenation recycling butanol and octanol Download PDFInfo
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Abstract
The separation method of butanol and octanol waste liquid front-end hydrogenation recycling butanol and octanol 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 adding hydrogen, dehydration, separating butanol, separating butanol, de- butanol, separate miscellaneous oil, separate octanol, recycle the processes such as butanol and recycling 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, 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-A1203
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 method of butanol and octanol waste liquid front-end hydrogenation recycling butanol and octanol of the invention, specifically includes hydrogenation unit and rectifying list
Member, comprising the following steps:
(1) plus hydrogen: butanol and octanol waste liquid and hydrogen enter the hydrogenator equipped with hydrogenation catalyst, reaction temperature 50~
200 DEG C, under 0.4~5.0MPa of reaction pressure, the butyraldehyde in butanol and octanol waste liquid is hydrogenated to butanol, and octenal is hydrogenated to pungent
Alcohol obtains the reaction solution after adding hydrogen；
(2) be dehydrated: the reaction solution after from hydrogenation unit plus hydrogen enters dehydrating tower, through distillation process, from dehydration tower top
Water, hydro carbons plus the remaining isobutylaldehyde of hydrogen and n-butanal are steamed, is condensate in quantizer and separates water phase discharge, oil phase part point is adopted
Out, partial reflux produces the tower base stream containing n-butanol from tower bottom；
(3) 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；
(4) take off butanol: the logistics from butanol tower bottom enters de- butanol tower, through distillation process, from de- butanol overhead extraction
Logistics containing butanol as butanol product or returns to head tank, produces tower base stream from tower bottom；
(5) separate miscellaneous oil: the logistics for carrying out autospasy butanol tower tower bottom enters miscellaneous oily tower, through distillation process, adopts from miscellaneous oily tower top
Tower bottom is produced from tower bottom as miscellaneous oil discharge containing butyl butyrate, enanthol, butanol and the logistics for adding the remaining octenal of hydrogen out
Logistics；
(6) 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 heavy constituent logistics containing 3- methyl -4- enanthol, lauryl alcohol and hexadecanol from tower bottom, are discharged as heavy oil.
Preferably, the method also includes following steps:
(7) recycle octanol: the heavy constituent logistics produced from octanol tower bottom enters weight-removing column, through distillation process, adopts from tower top
Octanol as product or returns to head tank out, produces the heavy oil object containing 3- methyl -4- enanthol, lauryl alcohol and hexadecanol from tower bottom
Stream discharge.
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 select to use according to factory condition, it is preferable that described plus hydrogen
Gas phase reaction is hydrogenated in step (1), hydrogenation catalyst is the Cu-series catalyst suitable for butyl octanol unit gas phase hydrogenation, reaction
Temperature is 120~200 DEG C, and reaction pressure is 0.4~0.8MPa, air speed of the butanol and octanol waste liquid charging in terms of liquid phase be 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
Degree 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
Degree is 130~160 DEG C；The tower top temperature of the de- 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
Butanol and octanol waste liquid front-end hydrogenation recycling butanol and octanol of the invention is explained further by way of examples below
Method, but the present invention is not limited to this.
Embodiment 1
(1) plus hydrogen: butanol and octanol waste liquid and hydrogen enter the hydrogenator equipped with hydrogenation catalyst, reaction temperature 50~
130 DEG C, under 0.4~5.0MPa of reaction pressure, the butyraldehyde in butanol and octanol waste liquid is hydrogenated to butanol, and octenal is hydrogenated to pungent
Alcohol obtains the reaction solution after adding hydrogen；It is hydrogenated to liquid phase reactor, hydrogenation catalyst is the nickel system catalysis of Beijing Chemical Research Institute's production
Agent BC-H-48, the liquid phase air speed of butanol and octanol waste liquid are 0.7h-1, hydrogen inlet amount is that butanol and octanol waste liquid adds the 1.05 of hydrogen consumption amount
Times；
(2) be dehydrated: the reaction solution after from hydrogenation unit plus hydrogen enters dehydrating tower, through distillation process, from dehydration tower top
Water, hydro carbons plus the remaining isobutylaldehyde of hydrogen and n-butanal are steamed, is condensate in quantizer and separates water phase discharge, oil phase part point is adopted
Out, partial reflux produces the tower base stream containing n-butanol from tower bottom；The tower top temperature of the dehydrating tower is 45 DEG C, tower top pressure
Power is 0.12MPa, and bottom temperature is 130 DEG C；
(3) 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；The tower top temperature of the butanol tower is 82 DEG C, tower top pressure 0.03MPa, tower reactor
Temperature is 144 DEG C；
(4) take off butanol: the logistics from butanol tower bottom enters de- butanol tower, through distillation process, from de- butanol overhead extraction
Logistics containing butanol as butanol product or returns to head tank, produces tower base stream from tower bottom；The tower top temperature of the butanol tower
Degree is 82 DEG C, tower top pressure 0.03MPa, and bottom temperature is 154 DEG C；
(5) separate miscellaneous oil: the logistics for carrying out autospasy butanol tower tower bottom enters miscellaneous oily tower, through distillation process, adopts from miscellaneous oily tower top
Tower bottom is produced from tower bottom as miscellaneous oil discharge containing butyl butyrate, enanthol, butanol and the logistics for adding the remaining octenal of hydrogen out
Logistics；The tower top temperature of the miscellaneous oily tower is 75 DEG C, tower top pressure 0.007MPa, and bottom temperature is 143 DEG C；
(6) 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 heavy constituent logistics containing 3- methyl -4- enanthol, lauryl alcohol and hexadecanol from tower bottom, are discharged as heavy oil.
(7) recycle butanol: the oil produced from the quantizer of dehydration column overhead mutually enters lightness-removing column, through distillation process, from de-
Light overhead extraction contains the logistics of hydro carbons plus hydrogen remaining isobutylaldehyde and n-butanal, produces the logistics containing butanol from tower bottom, returns
Return head tank；
(8) recycle octanol: the heavy constituent logistics produced from octanol tower bottom enters weight-removing column, through distillation process, adopts from tower top
Octanol as product or returns to head tank out, produces the heavy oil object containing 3- methyl -4- enanthol, lauryl alcohol and hexadecanol from tower bottom
Stream discharge.
The analysis data of each key position are listed in Table 1 below.
Claims (8)
1. a kind of method of the recycling of butanol and octanol waste liquid front-end hydrogenation butanol and octanol, which is characterized in that the method includes adding hydrogen list
Member and rectification cell, comprising the following steps:
(1) add hydrogen: butanol and octanol waste liquid and hydrogen enter the hydrogenator equipped with hydrogenation catalyst, in reaction temperature 50~200
DEG C, under 0.4~5.0MPa of reaction pressure, the butyraldehyde in butanol and octanol waste liquid is hydrogenated to butanol, and octenal is hydrogenated to octanol, obtains
Reaction solution after hydrogen must be added；
(2) be dehydrated: the reaction solution after from hydrogenation unit plus hydrogen enters dehydrating tower, through distillation process, steams from dehydration tower top
Water, hydro carbons plus the remaining isobutylaldehyde of hydrogen and n-butanal are condensate in quantizer and separate water phase discharge, oil phase part point extraction, portion
Divide reflux, produces the tower base stream containing n-butanol from tower bottom；
(3) 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；
(4) take off butanol: the logistics from butanol tower bottom enters de- butanol tower and contains through distillation process from de- butanol overhead extraction
The logistics of butanol as butanol product or returns to head tank, produces tower base stream from tower bottom；
(5) separate miscellaneous oil: the logistics for carrying out autospasy butanol tower tower bottom enters miscellaneous oily tower, through distillation process, contains from miscellaneous oily overhead extraction
There are butyl butyrate, enanthol, butanol and the logistics for adding the remaining octenal of hydrogen, as miscellaneous oil discharge, produces tower base stream from tower bottom；
(6) 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 heavy constituent logistics containing 3- methyl -4- enanthol, lauryl alcohol and hexadecanol from tower bottom, is discharged as heavy oil.
2. the method for the recycling of butanol and octanol waste liquid front-end hydrogenation butanol and octanol as described in claim 1, which is characterized in that the side
Method also following steps:
(7) recycle octanol: the heavy constituent logistics produced from octanol tower bottom enters weight-removing column, pungent from overhead extraction through distillation process
Alcohol is as product or returns to head tank, and the heavy oil streams row containing 3- methyl -4- enanthol, lauryl alcohol and hexadecanol is produced from tower bottom
Out.
3. the method for the recycling of butanol and octanol waste liquid front-end hydrogenation butanol and octanol as described in claim 1, which is characterized in that described to add
Liquid phase reactor is hydrogenated in hydrogen step (1), hydrogenation catalyst is the nickel catalyst suitable for butyl octanol unit liquid-phase hydrogenatin, instead
Answering 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
Gas inlet amount is 1.05~16 times that butanol and octanol waste liquid adds hydrogen consumption amount.
4. the method for the recycling of butanol and octanol waste liquid front-end hydrogenation butanol and octanol as described in claim 1, which is characterized in that described to add
Liquid phase reactor is hydrogenated in hydrogen step (1), hydrogenation catalyst is the nickel catalyst suitable for butyl octanol unit liquid-phase hydrogenatin, instead
Answering temperature is 60~130 DEG C, and reaction pressure is 3.0~5.0MPa, and the liquid phase air speed of butanol and octanol waste liquid is 0.15~1.2h-1, hydrogen
Gas inlet amount is 1.05~5 times that butanol and octanol waste liquid adds hydrogen consumption amount.
5. the method for the recycling of butanol and octanol waste liquid front-end hydrogenation butanol and octanol as described in claim 1, which is characterized in that described to add
Gas phase reaction is hydrogenated in hydrogen step (1), hydrogenation catalyst is the Cu-series catalyst suitable for butyl octanol unit gas phase hydrogenation, instead
Answering temperature is 120~200 DEG C, and reaction pressure is 0.4~0.8MPa, air speed of the butanol and octanol waste liquid charging in terms of liquid phase be 0.15~
1.5h-1, hydrogen inlet amount is 10~40 times that butanol and octanol waste liquid adds hydrogen consumption amount.
6. the method for the recycling of butanol and octanol waste liquid front-end hydrogenation butanol and octanol as described in claim 1, which is characterized in that described to add
It is hydrogenated to gas-liquid phase reaction in hydrogen step (1), is divided into gas phase in the middle part of butanol and octanol waste liquid, is partially liquid phase, hydrogenation catalyst is
Cu-series catalyst suitable for butyl octanol unit gas phase hydrogenation or the nickel catalyst suitable for butyl octanol unit liquid-phase hydrogenatin, instead
Answering temperature is 120~200 DEG C, and reaction pressure is 0.4~0.8MPa, air speed of the butanol and octanol waste liquid charging in terms of liquid phase be 0.15~
1.5h-1, hydrogen inlet amount is 10~40 times that butanol and octanol waste liquid adds hydrogen consumption amount.
7. the method for the recycling of butanol and octanol waste liquid front-end hydrogenation butanol and octanol as described in claim 1, which is characterized in that the fourth
Octanol waste liquid is to contain alkane, butyraldehyde, butanol, butyl butyrate, enanthol, matsutake alcohol, octanal, octene from butyl octanol unit
Aldehyde, octanol, lauryl alcohol, lauric aldehyde, hexadecanoyl and hexadecanol material.
8. the method for the recycling of butanol and octanol waste liquid front-end hydrogenation butanol and octanol as described in claim 1, which is characterized in that described de-
The tower top temperature of water tower is 40~70 DEG C, and tower top pressure is 0.1~0.2MPa, and bottom temperature is 120~140 DEG C；The butanol
The tower top temperature of tower is 70~90 DEG C, and tower top pressure is 0.02~0.04MPa, and bottom temperature is 130~160 DEG C；The de- fourth
The tower top temperature of alcohol tower is 70~90 DEG C, and tower top pressure is 0.02~0.04MPa, and bottom temperature is 140~160 DEG C；It is described miscellaneous
The tower top temperature of oily tower is 65~80 DEG C, and tower top pressure is 0.004~0.017MPa, and bottom temperature is 130~155 DEG C；It is described
The tower top temperature of octanol tower is 95~120 DEG C, and tower top pressure is 0.004~0.017MPa, and bottom temperature is 180~220 DEG C.
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| CN101121638A (en) * | 2007-07-27 | 2008-02-13 | 淄博元齐化工科技有限公司 | Method for producing mixed butanol and octanol by butanol and octanol residual liquid |
| 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 |
| CN103553876A (en) * | 2013-10-23 | 2014-02-05 | 中国海洋石油总公司 | Liquid phase hydrogenation method for residual liquids of butanol and octanol |
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| CN101121638A (en) * | 2007-07-27 | 2008-02-13 | 淄博元齐化工科技有限公司 | Method for producing mixed butanol and octanol by butanol and octanol residual liquid |
| 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 |
| CN103553876A (en) * | 2013-10-23 | 2014-02-05 | 中国海洋石油总公司 | Liquid phase hydrogenation method for residual liquids of butanol and octanol |
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