CN106187694A - From butanol and octanol waste liquid, the process for purification of butanol and capryl alcohol is reclaimed by cracking and hydrogenation reaction - Google Patents
From butanol and octanol waste liquid, the process for purification of butanol and capryl alcohol is reclaimed by cracking and hydrogenation reaction Download PDFInfo
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Abstract
nullDisclosed by the invention from butanol and octanol waste liquid, reclaim the process for purification of butanol and capryl alcohol by cracking and hydrogenation reaction and belong to the technical field of octyl alconyl，In order to solve the problem that raw material availability is the highest or energy consumption is high that prior art exists，Propose one first by n-butyl alcohol product extraction，Restructuring cracking at the bottom of weight-removing column is recycled further，It is alcohol by the aldehyde mixed hydrogenation in butanol and octanol waste liquid again，Again through distillation process，Obtain highly purified butanol and octanol products，Concrete steps include dehydration、Separating butanol、Removing heavy constituent、Heavy constituent cracks、Butyraldehyde and octanal mixed hydrogenation、Removing hydro carbons、Isolate the process such as butanol product and side take-off octanol products，This is not only significantly increased the utilization rate of butanol and octanol waste liquid，Value is greatly improved，Increase economic benefit，Also reduce the composition complexity of material，Reduce the difficulty of rectification cell，Reduce separation costs.
Description
Technical field
Invention relates to a kind of recovery butanol and method of capryl alcohol from butanol and octanol waste liquid, it is more particularly related to one
Plant butanol and octanol waste liquid by hydrogenation and through subtractive process acquisition butanol and the method for octanol products.
Background technology
Butanol and capryl alcohol (abbreviation octyl alconyl) are mainly for the production of the pungent vinegar of plasticizer phthalic acid two (DOP) and O-phthalic
Acid two fourth vinegar (DBP).Along with the development of China's plastics industry, market to the requirement of octyl alconyl in cumulative year after year, domestic
The production capacity of butyl octanol unit is also increasing year by year.The vaporizer of butyl octanol unit reactor, phase separator and weight-removing column etc. all have
A small amount of ejection, the mixed liquor of discharge is referred to as octyl alconyl residual liquid, is equivalent to about the 10% of octyl alconyl product quality, and
Wherein contain a large amount of valuable composition, but due to composition complexity, the past is many as fuel.The domestic recycling that oneself has
The device of octyl alconyl residual liquid such as batch fractionating tower etc., the technique of employing is unreasonable, reclaims the of poor quality of product, and yield is low,
Economic benefit is undesirable.As CN101423455A, Wu Jinyuan etc. (butanol and octanol waste liquid recovery technology improve. petrochemical industry, 1999,
28:832～834), Wang Lei (butanol and the recycling of capryl alcohol residual liquid. petrochemical industry, 2006,35 (8): 782～784), Xing
Mei Xia (the reclaiming clean technology of butanol and octanol waste liquid. Inner Mongol petrochemical industry, 2000,7:53～54) etc. all carried out this respect
Work, but be essentially all and directly from waste liquid, fractionate out butyraldehyde, butanol, C8 solvent, remaining residual liquid is used as combustion again
Material oil.
CN101973846A discloses a kind of waste liquid discharged with butyl octanol unit for raw material production mixed butyl alcohol and thick capryl alcohol
Method, the method by raw material fractionation unit, hydrogenation synthesis unit and product rectification cell composition, the mixed butyl alcohol of production
Purity >=95wt%, the thick capryl alcohol purity >=97wt% of production.But this technique adds raw material fractionation unit before the reaction,
Flow process is complex, and cost of investment is big.CN101892066A discloses under a kind of akaline liquid decomposition agent octyl alconyl is residual
Liquid is cracked into carbon four and the production technology of carbon eight.This technique not through hydrotreating produce carbon four, carbon eight be aldehyde and alcohol
Mixture, value is low.
Aldehyde in octyl alconyl residual liquid hydrogenation process mainly residual liquid, unsaturated alcohol are hydrogenated to corresponding alcohol, and part is long
Carbochain component is hydrogenated with, is cracked into the alcohol of short carbon chain, and used catalyst belongs to aldehyde hydrogenating catalyst category aldehyde hydrogenation and is divided into
Gas phase hydrogenation and liquid-phase hydrogenatin, liquid-phase hydrogenatin, owing to energy consumption is low, it is effective to be hydrogenated with, is widely adopted in recent years.
CN1478596A discloses the catalyst of the mixture liquid-phase hydrogenatin isooctanol of a kind of different octanal, and this catalyst with Ni is
Active component, with alkaline-earth metal or/and aluminium oxide is as accelerator, siliceous compound is carrier.After hydrogenation, different octanal has residual
Remaining, hydrogenation rate is 96%.CN102309968A discloses a kind of aldehyde liquid phase hydrogenating catalyst, nickel or its oxide be 8～
At least one element or its oxide in 35%, IA or Group IIA are at least one in (0.01～2.0) wt%, IIIA or IV group
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 catalysis
Agent low temperature active is high, but catalyst composition is complex.CN102059121A discloses a kind of lanthanum modification ambrose alloy capryl alcohol and adds
Hydrogen catalyst for refining, with γ-A1203For carrier, ambrose alloy is active component, and lanthanum is auxiliary agent, octenal, disloyalty aldehyde, octene
Alcohol hydrogenation rate all reaches more than 95%.CN1730151 discloses the catalyst of a kind of thick capryl alcohol liquid-phase hydrogenatin refining reaction.
Catalyst clean property component is Ni, and rare earth metal is accelerator, and aluminium oxide is carrier, adds silicon and makees auxiliary agent.CN1275439A
Disclose a kind of liquid phase hydrogenating catalyst in unsaturated aldehyde liquid-phase hydrogenatin technique.This catalyst is done carrier by silicon dioxide,
Nickel is the first active component, and other active component is cobalt, molybdenum, chromium, potassium.Active component is complicated.
CN101973845B disclose a kind of extract from butyl octanol unit waste liquid butyraldehyde and butanol mixture and
Octenal, the method for capryl alcohol mixture.First from waste liquid, butyraldehyde and butanol mixture are fractionated out, for butyraldehyde
Hydrogenation plant is hydrogenated with, more therefrom fractionates out octenal and capryl alcohol mixture, and for octenal hydrogenation plant, these are two years old
Plant material and be also used as by-product sale.The method is simple, but brings again miscellaneous for the many in waste liquid component into fourth
Capryl alcohol.
Butanol and octanol waste liquid disclosed in CN103342625A process technique basic with Wang Lei (butanol and capryl alcohol residual liquid time
Receive utilize. petrochemical industry, 2006,35 (8): 782～784) disclosed in technology identical, use four column rectification systems to divide
From.The first rectifying column stage casing it is passed through after butanol and octanol waste liquid is heated to 60 DEG C-100 DEG C, under the effect of entrainment reagent,
From the first rectifying column removed overhead moisture and light component；First tower bottom of rectifying tower liquid enters Second distillation column stage casing,
Second distillation column tower top obtains purity > the butanol product of 98%；Second distillation column tower reactor liquid enters the 3rd rectifying column
Stage casing, from the 3rd rectifying column removed overhead C5-C7 and octenal component；3rd tower bottom of rectifying tower liquid enters
4th rectifying column stage casing, the 4th rectifying column tower top obtains purity > octanol products of 98%.This process technique only depends on
By rectification mode, therefrom reclaim butanol and capryl alcohol, but do not utilize butyraldehyde, octenal and matsutake alcohol and pungent
The unsaturated component such as aldehyde, utilization rate is low.
CN101973846B discloses a kind of butyl octanol unit waste liquid and produces mixed butyl alcohol and the method for thick capryl alcohol.By
Raw material fractionation unit, hydrogenation synthesis unit and product rectification cell composition, described raw material branch library unit include butyraldehyde fractionating column,
Butanol separation column and carbon eight fractionating column three overlap fractionating device, described hydrogenation synthesis unit and product rectification cell be applicable to from
The hydrogenation of the C-4-fraction of raw material fractionation unit and rectification, be also applied for the hydrogenation of carbon eight fraction from raw material fractionation unit
And rectification, for both ask and have a rest；Described product rectification cell includes de-light device of spiral-screen column and de-weight device of spiral-screen column；
Including following operating procedure: a. raw material branch library: the waste liquid of butyl octanol unit discharge first passes through butyraldehyde fractionating device, by it
In the butyraldehyde component that contains be fractionated from butyraldehyde tower top, then by butanol separation column device, the butanol that will wherein contain
Component is fractionated from butanol tower top, finally by carbon eight fractionating column device, by the carbon eight component octenal wherein contained and
Capryl alcohol is fractionated from carbon eight tower top；The butyraldehyde being fractionated and butanol are stored in carbon four storage tank, octenal and capryl alcohol and store
In carbon eight storage tank；B. hydrogenation synthesis: from the butyraldehyde of carbon four storage tank of step a and butanol or from carbon eight storage tank
Octenal and capryl alcohol fraction enter hydrogenation synthesis unit, in hydrogenation reactor, by hydrogenation synthesis mixed butyl alcohol or conjunction
Become thick capryl alcohol；C. product purification: the mixed butyl alcohol of step b hydrogenation synthesis or thick capryl alcohol, through rectified purified, prepare mixing fourth
Alcohol or thick capryl alcohol.The method also exists the problem that separation equipment is many, capryl alcohol steams for twice, energy consumption is high from rectifying column tower top.
What existing butanol and octanol waste liquid hydrogenation recovery technology had also exists the problem that raw material availability is the highest, and have also exists
The problem that energy consumption is high.
Summary of the invention
In order to solve the problem that raw material availability is the highest or energy consumption is high that prior art exists, it is proposed that one is first by n-butyl alcohol
Product extraction, recycles heavy constituent cracking at the bottom of weight-removing column further, then by the aldehyde mixed hydrogenation in butanol and octanol waste liquid is
Alcohol, then through distillation process, it is thus achieved that highly purified butanol and octanol products.
The process for purification being reclaimed butanol and capryl alcohol by cracking and hydrogenation reaction from butanol and octanol waste liquid of the present invention, is specifically wrapped
Include hydrogenation unit, cracking unit and rectification cell, comprise the following steps:
(1) dehydration: butanol and octanol waste liquid enters dehydrating tower, through distillation process, steams water, hydro carbons, different from dehydration tower top
Butyraldehyde and hutanal, condensed separate in quantizer aqueous phase discharge, oil phase part extraction, partial reflux, adopt from the bottom of tower
Go out tower base stream；
(2) separating butanol a: enter butanol tower a from the logistics at the bottom of dehydrating tower tower, through distillation process, from butanol tower a
Top extraction butanol product, from extraction tower base stream at the bottom of tower；
(3) de-weight: enter weight-removing column from the logistics at the bottom of butanol tower a tower, through distillation process, from the extraction of weight-removing column top
Miscellaneous oil logistics containing butyl butyrate, enanthol, butanol, matsutake alcohol, octanal, octenal and capryl alcohol, contains from extraction at the bottom of tower
There are 3-methyl-4-enanthol, lauryl alcohol and the heavy constituent of hexadecanol, discharge as heavy oil；
(4) cracking: enter pyrolysis furnace cracking from the heavy constituent logistics at the bottom of weight-removing column, logistics after cracking is passed through flash distillation
Tank, the light component stream that flash distillation tank deck steams returns dehydrating tower and carries out rectification, tank bottoms as heavy oil discharge；
(5) hydrogenation: the oil phase logistics of the quantizer from dehydrating tower top is mixed with the miscellaneous oil logistics from weight-removing column top,
The hydrogenation reactor equipped with hydrogenation catalyst it is passed through again, in reaction temperature 50～200 DEG C, reaction pressure together with hydrogen
Under 0.4～5.0MPa, butyraldehyde therein is hydrogenated to butanol, and matsutake alcohol, octanal and octenal are hydrogenated to capryl alcohol, obtain
Butanol after must being hydrogenated with and capryl alcohol reactant liquor；
(6) de-light: described butanol and capryl alcohol reactant liquor enter lightness-removing column, through distillation process, contain hydrocarbon from overhead extraction
Class and the logistics of unreacted butyraldehyde, discharge as light component, contains the logistics of butanol and capryl alcohol from extraction at the bottom of tower；
(7) separating butanol b: enter butanol tower b from lightness-removing column bottoms stream, through distillation process, from overhead extraction butanol
Product, contains the logistics of capryl alcohol from extraction at the bottom of tower；
(8) capryl alcohol is separated: enter capryl alcohol tower from the logistics containing capryl alcohol at the bottom of butanol tower b tower, contain from overhead extraction
There are butyl butyrate, enanthol, 3-methyl-4-enanthol and the logistics of unreacted octenal, discharge, from tower as miscellaneous oil waste liquid
Body side take-off octanol products, contains the heavy constituent containing 12 carbon atoms from extraction at the bottom of tower, discharges as heavy oil.
Hydrogenation process described in the method for the present invention can be liquid phase reactor, it is also possible to is gas phase reaction.Preferably, described
Hydrogenation step is hydrogenated to liquid phase reactor in (5), and hydrogenation catalyst is that the nickel system being applicable to butyl octanol unit liquid-phase hydrogenatin urges
Agent, reaction temperature is 50～130 DEG C, and reaction pressure is 2.0～5.0MPa, and described oil phase logistics is mixed with the logistics of miscellaneous oil
It is 0.15～1.5h that compound flows to material air speed in terms of liquid phase-1, hydrogen inlet amount is 1.05～16 times of hydrogenation consumption.
It is highly preferred that be hydrogenated to liquid phase reactor in described hydrogenation step (4), hydrogenation catalyst is for being applicable to octyl alconyl dress
Putting the nickel catalyst of liquid-phase hydrogenatin, reaction temperature is 60～130 DEG C, and reaction pressure is 3.0～5.0MPa, described oil phase
Logistics is 0.15～1.2h with the mixture flow liquid phase air speed of miscellaneous oil logistics-1, hydrogen inlet amount is the 1.05～5 of hydrogenation consumption
Times.
Method of hydrotreating described in the method for the present invention can freely select according to factory condition to use, it is preferable that described
Being hydrogenated to gas phase reaction in hydrogenation step (5), hydrogenation catalyst is that the copper system being applicable to butyl octanol unit gas phase hydrogenation urges
Agent, reaction temperature is 120～200 DEG C, and reaction pressure is 0.4～0.8MPa, and described oil phase logistics is mixed with the logistics of miscellaneous oil
It is 0.15～1.5h that compound flows to material air speed in terms of liquid phase-1, hydrogen inlet amount is 10～40 times of hydrogenation consumption.
Because butanol and octanol waste liquid contains the relatively low butyraldehyde of performance degree and butanol system, also contain volatility of a relatively high
Octenal and capryl alcohol system, possibly together with the component of 12 carbon atoms and the component of ten six carbon atoms of more weight, thus
In hydrogenation process, material can a part be gas phase, and a part is liquid phase, it is preferable that described hydrogenation step adds in (5)
Hydrogen is gas-liquid phase reaction, and the part of described oil phase logistics or the logistics of miscellaneous oil is gas phase, and part is liquid phase, hydrogenation catalyst
Agent is to be applicable to the Cu-series catalyst of butyl octanol unit gas phase hydrogenation or be applicable to the nickel system of butyl octanol unit liquid-phase hydrogenatin and urge
Agent, reaction temperature is 120～200 DEG C, and reaction pressure is 0.4～0.8MPa, described oil phase logistics or miscellaneous oil logistics charging
Air speed in terms of liquid phase is 0.15～1.5h-1, hydrogen inlet amount is 10～40 times of butanol and octanol waste liquid hydrogenation consumption.
Described octyl alconyl can be arbitrarily from the waste liquid of butyl octanol unit, can be one waste liquid, it is also possible to is that multiply is given up
The mixture of liquid, can be the waste liquid of butanol unit, contains only butyraldehyde and the material of butanol system, it is also possible to be capryl alcohol list
The waste liquid of unit, contains only octenal and the material of capryl alcohol system, it is also possible to be the mixture of these materials.For more representing
Property, it is preferable that described butanol and octanol waste liquid be from butyl octanol unit containing hydrocarbon, butyraldehyde, butanol, butyl butyrate, heptan
The material of alcohol, matsutake alcohol, octanal, octenal, capryl alcohol, lauryl alcohol, lauric aldehyde, hexadecanoyl and hexadecanol.Described fourth
Capryl alcohol waste liquid can also be containing a small amount of qualitative or not qualitative component of many butyl octanol unit by-products.In the present invention,
Each component can be their isomers, and butyraldehyde includes isobutylaldehyde and hutanal, and butanol includes isobutanol and positive fourth
Alcohol, matsutake alcohol is 2-ethyl hexyl-2-alkene-1-alcohol, and octanal is 2-ethyl hexanal, and octenal is 2-ethyl hexyl-2-alkene-1-aldehyde,
Capryl alcohol is 2-Ethylhexyl Alcohol, lauryl alcohol be isobutylaldehyde and/or hutanal through condensation and be hydrogenated to containing 12 carbon atoms
Alcohols, lauric aldehyde is isobutylaldehyde and/or hutanal through condensation and the aldehydes containing 12 carbon atoms that is hydrogenated to, 16
Alcohol is isobutylaldehyde and/or hutanal through condensation and the alcohols containing ten six carbon atoms that is hydrogenated to, hexadecanoyl be isobutylaldehyde and
/ or the hutanal aldehydes containing ten six carbon atoms through being condensed and be hydrogenated to.
For maximally utilizing butanol and octanol waste liquid raw material, heavy constituent logistics at the bottom of weight-removing column is passed through pyrolysis furnace and is split by the present invention
Solve, and the light component in logistics recycles after flashing off cracking by flash tank.Preferably, in step (4)
Described 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 according to the composition of self material and
Character determines.Preferably, the tower top temperature of described dehydrating tower is 40～70 DEG C, and tower top pressure is 0.1～0.2MPa, tower
Still temperature is 120～140 DEG C；The tower top temperature of described butanol tower a is 70～90 DEG C, and tower top pressure is 0.02～0.04MPa,
Bottom temperature is 140～160 DEG C；The tower top temperature of described weight-removing column is 80～100 DEG C, and tower top pressure is 0.007～0.017
MPa, bottom temperature is 190～215 DEG C；Described pyrolysis furnace temperature is 300～600 DEG C；The tower top temperature of described lightness-removing column
Degree is 40～60 DEG C, and tower top pressure is 0.1～0.2MPa, and bottom temperature is 130～150 DEG C；Described butanol tower b's
Tower top temperature is 50～70 DEG C, and tower top pressure is 0.02～0.04MPa, and bottom temperature is 120～140 DEG C；Described pungent
The tower top temperature of alcohol tower is 80～100 DEG C, and tower top pressure is 0.004～0.017MPa, and bottom temperature is 135～160 DEG C.
Nickel catalyst of the present invention can be to be supported on aluminium oxide, silicon oxide, aluminium oxide-silicon oxide, work
Nickel catalyst on property charcoal, kieselguhr, zirconium oxide or calcium oxide, in addition to nickeliferous active component, it is also possible to contain
There are the components such as other auxiliary agent such as magnesium, potassium, lanthanum, zinc, calcium.Described nickel catalyst can also be that the sedimentation method obtain
Nickel catalyst, such as the nickel catalyst of sedimentation method alumina dispersion.The hydrogenation catalyst of the present invention can also
Being cobalt series catalyst, carrier or disperse medium are similar to nickel catalyst.In terms of mass percentage content, catalysis
In agent, nickel content is 10%～50%, such as alumina load 15～the catalyst of 20% nickel, the 40 of alumina dispersion～50%
The catalyst of nickel.Described nickel catalyst can also be Raney's nickel catalyst, Raney's nickel catalyst have powder,
Granule, strip or bulk, preferably block Raney's nickel catalyst.
Cu-series catalyst of the present invention can be loaded catalyst, it is also possible to be co-precipitated catalyst.Example
As being supported on aluminium oxide, silicon oxide, aluminium oxide-silicon oxide, activated carbon, kieselguhr, zirconium oxide or calcium oxide
Cu-series catalyst, in addition to copper-containing active component, it is also possible to containing other auxiliary agent such as nickel, cobalt, magnesium, potassium, lanthanum,
The component such as zinc, calcium.Co-precipitated catalyst can be copper zinc catalyst, copper and zinc element, CuZnAl catalyst,
Other auxiliary agent can also be added, such as the auxiliary agent such as manganese, lanthanum in these basic recipe catalyst.The percentage ratio matter of copper
Amount content is 25%～50%.Such as CuZnAl catalyst contains 28～the copper of 45%, 45～65% zinc and 1～10% aluminum.
Method for preparing catalyst of the present invention can be obtained by existing catalyst preparation technology, such as infusion process, ion
Exchange process, blending method, kneading method, co-precipitation, deposition-precipitation, steaming ammonium precipitation, melted-sucking filtration, ball milling and colloidal sol-
The methods such as gel.Preferred method includes co-precipitation, deposition-precipitation, steaming ammonium precipitation, melted-sucking filtration, ball milling and molten
The combination of one or more in glue-gel, these prepare catalyst method is this area as existing mature technology mostly
Known to technical staff, all having detailed introduction in the books of this area, as written in yellow Zhong Tao " industrial catalyst designs
With exploitation ", Gerhard professor Ertl etc. written " Preparation of Solid Catalysts ".The most of the present invention
Steaming ammonium intermediate processing, brief step is as follows: active component salt is dissolved in the water by (1), it is also possible to containing other metals or
Person's non-metal salt；(2) ammonia is gradually added in above-mentioned saline solution, forms ammonium complex compound with ammonia；(3) other groups are added
Point；(4) heating up and progressively evaporated by ammonia, active ingredient precipitation gets off；(5) wash, filter；(6) dry, roasting.
The step essence of the melted-suction method in the present invention refers to the preparation process of Raney catalyst: (1) is by a furnace
To have metal active constituent and aluminum (or silicon) fusion of catalysis activity, the melt obtained carries out quenching cooling, then
It is crushed into uniform fine grained, dissolves the auxiliary agent being also possible to add other in step；(2) catalyst fines is become
Type, forming technique can use existing well known technology, as beaten sheet, mediating extrusion, spin etc.；(3) by gained
Above-mentioned preformed catalyst sucking filtration in alkali liquor, i.e. obtain obtain catalyst.
Butyraldehyde in butanol and octanol waste liquid, matsutake alcohol, octanal and octenal can correspondingly be added by the method for the present invention
Hydrogen generates butanol, capryl alcohol, the utilization rate of butanol and octanol waste liquid can be significantly increased, value is greatly improved,
Increase economic benefit.The present invention decreases the composition complexity of material by the process of hydrogenation, can reduce essence
Evaporate the difficulty of unit, reduce separation costs.
Detailed description of the invention
By cracking and hydrogenation reaction from butanol and octanol waste liquid being returned of the present invention is explained further the most by way of example
Receive butanol and the process for purification of capryl alcohol, but the present invention is not limited to this.
Embodiment 1
(1) dehydration: butanol and octanol waste liquid enters dehydrating tower, through distillation process, steams water, hydro carbons, different from dehydration tower top
Butyraldehyde and hutanal, condensed separate in quantizer aqueous phase discharge, oil phase part extraction, partial reflux, adopt from the bottom of tower
Go out tower base stream；Tower top temperature is 50 DEG C, and tower top pressure is 0.12MPa, and bottom temperature is 136 DEG C；
(2) separating butanol a: enter butanol tower a from the logistics at the bottom of dehydrating tower tower, through distillation process, from butanol tower a
Top extraction butanol product, from extraction tower base stream at the bottom of tower；Tower top temperature is 88 DEG C, and tower top pressure is 0.03MPa, tower reactor
Temperature is 150 DEG C；
(3) de-weight: enter weight-removing column from the logistics at the bottom of butanol tower a tower, through distillation process, from the extraction of weight-removing column top
Miscellaneous oil logistics containing butyl butyrate, enanthol, butanol, matsutake alcohol, octanal, octenal and capryl alcohol, contains from extraction at the bottom of tower
There are 3-methyl-4-enanthol, lauryl alcohol and the heavy constituent of hexadecanol, discharge as heavy oil；Tower top temperature is 92 DEG C, tower top
Pressure is 0.007MPa, and bottom temperature is 207 DEG C；
(4) cracking: enter pyrolysis furnace cracking from the heavy constituent logistics at the bottom of weight-removing column, logistics after cracking is passed through flash distillation
Tank, the light component stream that flash distillation tank deck steams returns dehydrating tower and carries out rectification, tank bottoms for heavy oil discharge；Cracking temperature is
700 DEG C, cracking mode is anaerobic thermal cracking；
(5) hydrogenation: the oil phase logistics of the quantizer from dehydrating tower top is mixed with the miscellaneous oil logistics from weight-removing column top,
The hydrogenation reactor equipped with hydrogenation catalyst it is passed through again, in reaction temperature 50～200 DEG C, reaction pressure together with hydrogen
Under 4.0MPa, butyraldehyde therein is hydrogenated to butanol, and matsutake alcohol, octanal and octenal are hydrogenated to capryl alcohol, it is thus achieved that add
Butanol after hydrogen and capryl alcohol reactant liquor；Being hydrogenated to liquid phase reactor, hydrogenation catalyst is the nickel system that Beijing Chemical Research Institute produces
Catalyst BC-H-48, the liquid phase air speed of butanol and octanol waste liquid is 0.8h-1, hydrogen inlet amount is that butanol and octanol waste liquid hydrogenation consumes
1.05 times of amount；
(6) de-light: described butanol and capryl alcohol reactant liquor enter lightness-removing column, through distillation process, contain hydrocarbon from overhead extraction
Class and the logistics of unreacted butyraldehyde, discharge as light component, contains the logistics of butanol and capryl alcohol from extraction at the bottom of tower；Tower top
Temperature is 45 DEG C, and tower top pressure is 0.12MPa, and bottom temperature is 145 DEG C；
(7) separating butanol b: enter butanol tower b from lightness-removing column bottoms stream, through distillation process, from overhead extraction butanol
Product, contains the logistics of capryl alcohol from extraction at the bottom of tower；Tower top temperature is 58 DEG C, and tower top pressure is 0.007MPa, tower reactor temperature
Degree is 126 DEG C；
(8) capryl alcohol is separated: enter capryl alcohol tower from the logistics containing capryl alcohol at the bottom of butanol tower b tower, contain from overhead extraction
There are butyl butyrate, enanthol, 3-methyl-4-enanthol and the logistics of unreacted octenal, discharge, from tower as miscellaneous oil waste liquid
Body side take-off octanol products, contains the heavy constituent containing 12 carbon atoms from extraction at the bottom of tower, discharges as heavy oil；Tower top
Temperature is 88 DEG C, and tower top pressure is 0.008MPa, and bottom temperature is 143 DEG C.
Claims (8)
1. reclaimed a process for purification for butanol and capryl alcohol from butanol and octanol waste liquid by cracking and hydrogenation reaction, its feature exists
In, described method includes hydrogenation unit, cracking unit and rectification cell, comprises the following steps:
(1) dehydration: butanol and octanol waste liquid enters dehydrating tower, through distillation process, steams water, hydro carbons, different from dehydration tower top
Butyraldehyde and hutanal, condensed separate in quantizer aqueous phase discharge, oil phase part extraction, partial reflux, adopt from the bottom of tower
Go out tower base stream；
(2) separating butanol a: enter butanol tower a from the logistics at the bottom of dehydrating tower tower, through distillation process, from butanol tower a
Top extraction butanol product, from extraction tower base stream at the bottom of tower；
(3) de-weight: enter weight-removing column from the logistics at the bottom of butanol tower a tower, through distillation process, from the extraction of weight-removing column top
Miscellaneous oil logistics containing butyl butyrate, enanthol, butanol, matsutake alcohol, octanal, octenal and capryl alcohol, contains from extraction at the bottom of tower
There are 3-methyl-4-enanthol, lauryl alcohol and the heavy constituent logistics of hexadecanol；
(4) cracking: enter pyrolysis furnace cracking from the heavy constituent logistics at the bottom of weight-removing column, logistics after cracking is passed through flash distillation
Tank, the light component stream that flash distillation tank deck steams returns dehydrating tower and carries out rectification, tank bottoms as heavy oil discharge；
(5) hydrogenation: the oil phase logistics of the quantizer from dehydrating tower top is mixed with the miscellaneous oil logistics from weight-removing column top,
The hydrogenation reactor equipped with hydrogenation catalyst it is passed through again, in reaction temperature 50～200 DEG C, reaction pressure together with hydrogen
Under 0.4～5.0MPa, butyraldehyde therein is hydrogenated to butanol, and matsutake alcohol, octanal and octenal are hydrogenated to capryl alcohol, obtain
Butanol after must being hydrogenated with and capryl alcohol reactant liquor；
(6) de-light: described butanol and capryl alcohol reactant liquor enter lightness-removing column, through distillation process, contain hydrocarbon from overhead extraction
Class and the logistics of unreacted butyraldehyde, discharge as light component, contains the logistics of butanol and capryl alcohol from extraction at the bottom of tower；
(7) separating butanol b: enter butanol tower b from lightness-removing column bottoms stream, through distillation process, from overhead extraction butanol
Product, contains the logistics of capryl alcohol from extraction at the bottom of tower；
(8) capryl alcohol is separated: enter capryl alcohol tower from the logistics containing capryl alcohol at the bottom of butanol tower b tower, contain from overhead extraction
There are butyl butyrate, enanthol, 3-methyl-4-enanthol and the logistics of unreacted octenal, discharge, from tower as miscellaneous oil waste liquid
Body side take-off octanol products, contains the heavy constituent containing 12 carbon atoms from extraction at the bottom of tower, discharges as heavy oil.
2. the essence being reclaimed butanol and capryl alcohol by cracking and hydrogenation reaction from butanol and octanol waste liquid as claimed in claim 1
Method processed, it is characterised in that described hydrogenation step is hydrogenated to liquid phase reactor in (5), and hydrogenation catalyst is for being applicable to fourth
The nickel catalyst of capryl alcohol device liquid-phase hydrogenatin, reaction temperature is 50～130 DEG C, and reaction pressure is 2.0～5.0MPa, institute
The mixture stating oil phase logistics and the logistics of miscellaneous oil flows to expect that the air speed in terms of liquid phase is 0.15～1.5h-1, hydrogen inlet amount is for adding
1.05～16 times of hydrogen consumption.
3. the essence being reclaimed butanol and capryl alcohol by cracking and hydrogenation reaction from butanol and octanol waste liquid as claimed in claim 1
Method processed, it is characterised in that described hydrogenation step is hydrogenated to liquid phase reactor in (5), and hydrogenation catalyst is for being applicable to fourth
The nickel catalyst of capryl alcohol device liquid-phase hydrogenatin, reaction temperature is 60～130 DEG C, and reaction pressure is 3.0～5.0MPa, institute
The liquid phase air speed of the mixing logistics stating oil phase logistics and the logistics of miscellaneous oil is 0.15～1.2h-1, hydrogen inlet amount is hydrogenation consumption
1.05～5 times.
4. the essence being reclaimed butanol and capryl alcohol by cracking and hydrogenation reaction from butanol and octanol waste liquid as claimed in claim 1
Method processed, it is characterised in that being hydrogenated to gas phase reaction in described hydrogenation step (5), hydrogenation catalyst is for being applicable to fourth
The Cu-series catalyst of capryl alcohol device gas phase hydrogenation, reaction temperature is 120～200 DEG C, and reaction pressure is 0.4～0.8MPa, institute
The mixture stating oil phase logistics and the logistics of miscellaneous oil flows to expect that the air speed in terms of liquid phase is 0.15～1.5h-1, hydrogen inlet amount is for adding
10～40 times of hydrogen consumption.
5. the essence being reclaimed butanol and capryl alcohol by cracking and hydrogenation reaction from butanol and octanol waste liquid as claimed in claim 1
Method processed, it is characterised in that being hydrogenated to gas-liquid phase reaction in described hydrogenation step (5), described oil phase logistics is with miscellaneous
The mixing stream portions of oil logistics is gas phase, and part is liquid phase, and hydrogenation catalyst is for being applicable to butyl octanol unit gas phase hydrogenation
Cu-series catalyst or be applicable to the nickel catalyst of butyl octanol unit liquid-phase hydrogenatin, reaction temperature is 120～200 DEG C, instead
Answering pressure is 0.4～0.8MPa, and described oil phase logistics flows to expect that the air speed in terms of liquid phase is with the mixture of miscellaneous oil logistics
0.15～1.5h-1, hydrogen inlet amount is 10～40 times of butanol and octanol waste liquid hydrogenation consumption.
6. the essence being reclaimed butanol and capryl alcohol by cracking and hydrogenation reaction from butanol and octanol waste liquid as claimed in claim 1
Method processed, it is characterised in that described butanol and octanol waste liquid be from butyl octanol unit containing alkane, butyraldehyde, butanol, fourth
The thing of acid butyl ester, enanthol, matsutake alcohol, octanal, octenal, capryl alcohol, lauryl alcohol, lauric aldehyde, hexadecanoyl and hexadecanol
Material.
7. butanol and octanol waste liquid collection cracking as claimed in claim 1 and the separation method of hydrogenation, it is characterised in that step (4)
Described in pyrolysis furnace be cracked into containing water-splitting, cracking mode is thermal cracking or catalytic pyrolysis, cracking temperature be 200～
800℃。
8. the essence being reclaimed butanol and capryl alcohol by cracking and hydrogenation reaction from butanol and octanol waste liquid as claimed in claim 1
Method processed, it is characterised in that the tower top temperature of described dehydrating tower is 40～70 DEG C, tower top pressure is 0.1～0.2MPa,
Bottom temperature is 120～140 DEG C；The tower top temperature of described butanol tower a is 70～90 DEG C, and tower top pressure is 0.02～0.04
MPa, bottom temperature is 140～160 DEG C；The tower top temperature of described weight-removing column is 80～100 DEG C, tower top pressure be 0.007～
0.017MPa, bottom temperature is 190～215 DEG C；Described pyrolysis furnace temperature is 300～600 DEG C；The tower of described lightness-removing column
Top temperature is 40～60 DEG C, and tower top pressure is 0.1～0.2MPa, and bottom temperature is 130～150 DEG C；Described butanol tower b
Tower top temperature be 50～70 DEG C, tower top pressure is 0.02～0.04MPa, and bottom temperature is 120～140 DEG C；Described
The tower top temperature of capryl alcohol tower is 80～100 DEG C, and tower top pressure is 0.004～0.017MPa, and bottom temperature is 135～160 DEG C.
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| CN113929558A (en) * | 2021-10-13 | 2022-01-14 | 中国海洋石油集团有限公司 | Method and device system for purifying and recycling waste alcohol in high-carbon alcohol production |
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