CN106187693B - The cracking of butanol and octanol waste liquid collection and the separation method for adding hydrogen - Google Patents
The cracking of butanol and octanol waste liquid collection and the separation method for adding hydrogen Download PDFInfo
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Abstract
The technical field that butanol and octanol waste liquid collection disclosed by the invention cracks and the separation method of hydrogen is added to belong to octyl alconyl, in order to solve the problems, such as that butanol and octanol waste liquid raw material availability of the existing technology is not high or catalyst life is short, it proposes a kind of first by heavies removal in butanol and octanol waste liquid, the recombination cracking of weight-removing column bottom is further recycled, then it is alcohol that aldehyde therein, which carries out mixed hydrogenation, using distillation process, obtain the butanol and octanol products of high-purity, specific steps include de- weight, add hydrogen, dehydration, the processes such as separating butanol product and side take-off octanol products, the utilization rate of butanol and octanol waste liquid is not only significantly increased in this, increase economic benefit, also reduce the complicated composition degree of material, the difficulty of rectification cell can be reduced, reduce separation costs.In addition, the colloid by catalyst reactor bed is greatly reduced first by the heavies removal of C12 and C16 in butanol and octanol waste liquid in the present invention, helps to extend catalyst service life, improve the stability of hydrogenation plant.
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 discloses a kind of catalyst of the mixture liquid-phase hydrogenatin isooctanol of different octanal, the catalyst with
Ni is active component, and using alkaline-earth metal or/and aluminium oxide as promotor, 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, and nickel or its oxide be 8~
At least one of 35%, IA or Group IIA element or its oxide are at least one in (0.01~2.0) wt%, IIIA or IV group
Kind element or its oxide are (0.01~20.0) wt%, and rare earth element is (0.01~5) wt%, and aluminium oxide is carrier, this is urged
Agent low temperature active is high, but catalyst composition is complex.CN102059121A discloses a kind of modified ambrose alloy octanol of lanthanum and adds hydrogen
Catalyst for refining, with γ-Al2O3For carrier, ambrose alloy is active component, and lanthanum is auxiliary agent, 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
It is divided into Ni, rare earth metal is promotor, and aluminium oxide is carrier, and addition silicon makees auxiliary agent.CN1275439A discloses a kind of liquid phase and adds
Hydrogen catalyst is in unsaturated aldehyde liquid-phase hydrogenatin technique.The catalyst does carrier by silica, and nickel is the first active component,
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.
Existing butanol and octanol waste liquid hydrogen addition technology some has that raw material availability is not high, and there is energy consumption height for some
The problem of, it is some to there is a problem of that catalyst life is short.
Summary of the invention
It is of the existing technology in order to solve the problems, such as, it proposes a kind of first by heavies removal in butanol and octanol waste liquid, will weigh
Component further cracks recycling, and then aldehyde therein is hydrogenated to alcohol, using distillation process, obtain high-purity butanol and
Octanol products.
Butanol and octanol waste liquid collection cracking of the invention and the separation method for adding hydrogen, specifically include hydrogenation unit, cracking unit and
Rectification cell, comprising the following steps:
(1) it takes off weight: butanol and octanol waste liquid is passed through weight-removing column, by distillation process, steam water, hydro carbons, different from weight-removing column top
Butyraldehyde, n-butanal and butanol, octenal and octanol contain the weight containing 12 carbon atoms and 16 carbon atoms from tower bottom extraction
Component streams；
(2) crack: the heavy constituent logistics from weight-removing column bottom enters pyrolysis furnace cracking, and logistics after cracking is passed through flash distillation
Tank, the light component stream that flash distillation tank deck steams return to weight-removing column and carry out rectifying, and tank bottom is heavy oil discharge；
(3) add hydrogen: the logistics and hydrogen of autospasy in future weight tower top enter the hydrogenator equipped with hydrogenation catalyst, anti-
It answers under 50~200 DEG C of temperature, 0.4~5.0MPa of reaction pressure, butyraldehyde therein is hydrogenated to butanol, and octenal is hydrogenated to pungent
Alcohol obtains the reaction solution after adding hydrogen；
(4) 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 tower base stream from tower bottom；
(5) 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；
(6) separate miscellaneous oil: the logistics from butanol tower tower bottom enters miscellaneous oily tower, through distillation process, from miscellaneous oily overhead extraction
Containing butanol, butyl butyrate, enanthol and the logistics for adding the remaining octenal of hydrogen, as miscellaneous oil discharge, from tower side take-off octanol,
From the heavy constituent of tower bottom extraction lauryl alcohol and hexadecanol, it is discharged as heavy oil.
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 (3), 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 (3), 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 (3), 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 (3)
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.
To maximally utilize butanol and octanol waste liquid raw material, the heavy constituent logistics of weight-removing column bottom is passed through pyrolysis furnace and carried out by the present invention
Cracking, and the light component after cracked in logistics is flashed off by flash tank and is recycled.Preferably, described in step (2)
Pyrolysis furnace is cracked into containing water-splitting, and cracking mode is thermal cracking or catalytic pyrolysis, and cracking temperature is 200~800 DEG C.
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 weight-removing column is 30~50 DEG C, and tower top pressure is 0.04~0.08MPa, tower reactor
Temperature is 170~230 DEG C；Cracking furnace temperature is 300~600 DEG C；The tower top temperature of dehydrating tower is 40~70 DEG C, and tower top pressure is
0.1~0.2MPa, bottom temperature are 120~140 DEG C；The tower top temperature of the butanol tower is 80~100 DEG C, and tower top pressure is
0.02~0.04MPa, bottom temperature are 140~160 DEG C；The tower top temperature of the miscellaneous oily tower is 70~90 DEG C, and tower top pressure is
0.004~0.017MPa, bottom temperature are 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 co-precipitation, deposition-precipitation, steams in ammonia-sinking shallow lake, melting-suction filtration, ball milling and sol-gel
One or more combinations, it is mostly ripe for those skilled in the art as existing mature technology that these prepare catalyst method
Know 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 ammonia-sinking shallow lake side of the present invention
Method, briefly steps are as follows: (1) active component salt being dissolved in the water, it is also possible to contain other metals or non-metal salt；(2)
Ammonium hydroxide is gradually added in above-mentioned salting liquid, forms ammonium complex compound with ammonia；(3) other components are added；(4) heating gradually steams ammonia
Hair, active ingredient precipitation get off；(5) it washs, filter；(6) dry, roasting.The step of melting-suction method in the present invention essence
Refer to the preparation process of Raney catalyst: (1) by a furnace by with catalytic activity metal active constituent and aluminium (or
Person's silicon) fusion, obtained melt carries out quenching cooling, is then comminuted into as uniform fine grained, dissolves and be also possible to add in step
Add other auxiliary agents；(2) catalyst fines are formed, forming technique can using existing well known technology, such as beat piece,
Mediate 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
Cracking recycling is carried out at butanol, octanol, and by heavy constituent, the utilization rate of butanol and octanol waste liquid is not only significantly increased in this,
Economic benefit is increased, the complicated composition degree of material is also reduced, the difficulty of rectification cell can be reduced, reduces separation costs.
In addition, method of the invention first reduces the heavies removal of C12 and C16 in butanol and octanol waste liquid by urging in reactor
The colloid of agent bed is more advantageous to the progress of hydrogenation reaction, helps to extend catalyst service life, improves plus hydrogen fills
The stability set.
Specific embodiment
The method that butanol and octanol waste liquid front-end hydrogenation of the invention is explained further by way of examples below, but the present invention is not
It is confined to this.
Embodiment 1
Butanol and octanol waste liquid collection of the invention cracks and adds the separation method of hydrogen, specifically includes hydrogenation unit and rectification cell,
The following steps are included:
(1) it takes off weight: butanol and octanol waste liquid is passed through weight-removing column, by distillation process, steam water, hydro carbons, different from weight-removing column top
Butyraldehyde, n-butanal and butanol, octenal and octanol contain the weight containing 12 carbon atoms and 16 carbon atoms from tower bottom extraction
Component；The tower top temperature of the weight-removing column is 40 DEG C, tower top pressure 0.07MPa, and bottom temperature is 199 DEG C；
(2) crack: the heavy constituent logistics from weight-removing column bottom enters pyrolysis furnace cracking, and logistics after cracking is passed through flash distillation
Tank, the light component stream that flash distillation tank deck steams return to weight-removing column and carry out rectifying, and tank bottom is heavy oil discharge；Cracking temperature is 650 DEG C,
Cracking mode is that anaerobic contains hydrothermal cracking；
(3) add hydrogen: the logistics and hydrogen of autospasy in future weight tower top enter the hydrogenator equipped with hydrogenation catalyst, anti-
It answers under 50~130 DEG C of temperature, reaction pressure 4.0MPa, the butyraldehyde in butanol and octanol waste liquid is hydrogenated to butanol, and octenal adds hydrogen raw
At octanol, the reaction solution after adding hydrogen is obtained；It is hydrogenated to liquid phase reactor, hydrogenation catalyst is the nickel system of Beijing Chemical Research Institute's production
Catalyst BC-H-48, the liquid phase air speed of butanol and octanol waste liquid are 0.75h-1, hydrogen inlet amount is that butanol and octanol waste liquid adds hydrogen consumption amount
1.05 again；
(4) be dehydrated: the reaction solution after adding hydrogen enters dehydrating tower, through distillation process, steams water from dehydration tower top, hydro carbons, adds
The remaining isobutylaldehyde of hydrogen and n-butanal are condensate in quantizer and separate water phase discharge, oil phase part point extraction, partial reflux, from
Tower bottom produces tower base stream；The tower top temperature of the dehydrating tower is 48 DEG C, tower top pressure 0.13MPa, bottom temperature 132
℃；
(5) 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 85 DEG C, tower top pressure 0.03MPa, tower reactor
Temperature is 150 DEG C；
(6) separate miscellaneous oil: the logistics from butanol tower tower bottom enters miscellaneous oily tower, through distillation process, from miscellaneous oily overhead extraction
Bottoms is produced from tower bottom as miscellaneous oil discharge containing butyl butyrate, enanthol, butanol and the logistics for adding the remaining octenal of hydrogen
Stream；The tower top temperature of the miscellaneous oily tower is 86 DEG C, tower top pressure 0.007MPa, and bottom temperature is 203 DEG C.
Claims (8)
1. a kind of butanol and octanol waste liquid collection cracking and the separation method for adding hydrogen, which is characterized in that the method includes hydrogenation unit, split
Solve unit and rectification cell, comprising the following steps:
(1) take off weight: butanol and octanol waste liquid be passed through weight-removing column, by distillation process, from weight-removing column top steam water, hydro carbons, isobutylaldehyde,
N-butanal and butanol, octenal and octanol contain the heavy constituent containing 12 carbon atoms and 16 carbon atoms from tower bottom extraction
Logistics；
(2) crack: the heavy constituent logistics from weight-removing column bottom enters pyrolysis furnace cracking, and logistics after cracking is passed through flash tank, dodges
The light component stream that steaming pot top steams returns to weight-removing column and carries out rectifying, and tank bottom is heavy oil discharge；
(3) add hydrogen: the logistics and hydrogen of autospasy in future weight tower top enter the hydrogenator equipped with hydrogenation catalyst, are reacting temperature
Under 50~200 DEG C of degree, 0.4~5.0MPa of reaction pressure, butyraldehyde therein is hydrogenated to butanol, and octenal is hydrogenated to octanol,
Obtain the reaction solution after adding hydrogen；
(4) 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 tower base stream from tower bottom；
(5) 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；
(6) separate miscellaneous oil: the logistics from butanol tower tower bottom enters miscellaneous oily tower, through distillation process, contains from miscellaneous oily overhead extraction
Butanol, butyl butyrate, enanthol and the logistics for adding the remaining octenal of hydrogen, as miscellaneous oil discharge, from tower side take-off octanol, from tower
Bottom produces the heavy constituent of lauryl alcohol and hexadecanol, is discharged as heavy oil.
2. butanol and octanol waste liquid collection cracking as described in claim 1 and the separation method for adding hydrogen, which is characterized in that described plus hydrogen step
Suddenly liquid phase reactor is hydrogenated in (3), 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 liquid phase air speed of butanol and octanol waste liquid is 0.15~1.5h-1, hydrogen into
Doses is 1.05~20 times that butanol and octanol waste liquid adds hydrogen consumption amount.
3. butanol and octanol waste liquid collection cracking as described in claim 1 and the separation method for adding hydrogen, which is characterized in that described plus hydrogen step
Suddenly liquid phase reactor is hydrogenated in (3), 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, and the liquid phase air speed of butanol and octanol waste liquid is 0.15~1.2h-1, hydrogen into
Doses is 1.05~5 times that butanol and octanol waste liquid adds hydrogen consumption amount.
4. butanol and octanol waste liquid collection cracking as described in claim 1 and the separation method for adding hydrogen, which is characterized in that described plus hydrogen step
Suddenly gas phase reaction is hydrogenated in (3), 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, 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.
5. butanol and octanol waste liquid collection cracking as described in claim 1 and the separation method for adding hydrogen, which is characterized in that described plus hydrogen step
Suddenly it is hydrogenated to gas-liquid phase reaction in (3), is divided into gas phase in the middle part of butanol and octanol waste liquid, is partially liquid phase, hydrogenation catalyst is applicable
Cu-series catalyst in butyl octanol unit gas phase hydrogenation or the nickel catalyst suitable for butyl octanol unit liquid-phase hydrogenatin, reaction temperature
Degree 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. butanol and octanol waste liquid collection cracking as described in claim 1 and the separation method for adding hydrogen, which is characterized in that the octyl alconyl
Waste liquid be from butyl octanol unit containing hydrocarbon, butyraldehyde, butanol, butyl butyrate, enanthol, matsutake alcohol, octanal, octenal, octanol,
Lauryl alcohol, lauric aldehyde, hexadecanoyl and hexadecanol material.
7. butanol and octanol waste liquid collection cracking as described in claim 1 and the separation method for adding hydrogen, which is characterized in that in step (2)
The pyrolysis furnace is cracked into containing water-splitting, and cracking mode is thermal cracking or catalytic pyrolysis, and cracking temperature is 200~800 DEG C.
8. butanol and octanol waste liquid collection cracking as described in claim 1 and the separation method for adding hydrogen, which is characterized in that the weight-removing column
Tower top temperature be 30~50 DEG C, tower top pressure be 0.04~0.08MPa, bottom temperature be 170~230 DEG C；Crack furnace temperature
It is 300~600 DEG C；The tower top temperature of dehydrating tower be 40~70 DEG C, tower top pressure be 0.1~0.2MPa, bottom temperature be 120~
140℃；The tower top temperature of the butanol tower be 80~100 DEG C, tower top pressure be 0.02~0.04MPa, bottom temperature be 140~
160℃；The tower top temperature of the miscellaneous oily tower is 70~90 DEG C, and tower top pressure is 0.004~0.017MPa, bottom temperature 180
~220 DEG C.
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| CN108069824A (en) * | 2018-01-24 | 2018-05-25 | 德州德田化工有限公司 | The device and its technique that a kind of octyl alconyl raffinate recycles |
| CN112321386B (en) * | 2020-11-04 | 2023-05-09 | 吉林市道特化工科技有限责任公司 | Method for hydrotreating butanol-octanol raffinate |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101913991A (en) * | 2010-08-20 | 2010-12-15 | 南化集团研究院 | Recycling method of butanol and octanol waste liquid through hydrocracking and catalyst |
| 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 |
| CN103342625A (en) * | 2013-07-12 | 2013-10-09 | 上海东化环境工程有限公司 | Treatment process of 2-ethyl hexanol liquid waste |
| 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 |
| CN104447194A (en) * | 2014-11-11 | 2015-03-25 | 中国海洋石油总公司 | Method for processing butyl-octyl alcohol residual liquid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH061733A (en) * | 1992-06-16 | 1994-01-11 | Mitsubishi Kasei Corp | Production of alcohol |
-
2015
- 2015-04-29 CN CN201510211828.6A patent/CN106187693B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101913991A (en) * | 2010-08-20 | 2010-12-15 | 南化集团研究院 | Recycling method of butanol and octanol waste liquid through hydrocracking and catalyst |
| 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 |
| CN103342625A (en) * | 2013-07-12 | 2013-10-09 | 上海东化环境工程有限公司 | Treatment process of 2-ethyl hexanol liquid waste |
| 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 |
| CN104447194A (en) * | 2014-11-11 | 2015-03-25 | 中国海洋石油总公司 | Method for processing butyl-octyl alcohol residual liquid |
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