CN106187693A - The cracking of butanol and octanol waste liquid collection and the separation method of hydrogenation - Google Patents
The cracking of butanol and octanol waste liquid collection and the separation method of hydrogenation Download PDFInfo
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Abstract
The separation method of butanol and octanol waste liquid collection disclosed by the invention cracking and hydrogenation belongs to the technical field of octyl alconyl, in order to solve the problem that butanol and octanol waste liquid raw material availability is the highest or catalyst life is short that prior art exists, propose one first by heavies removal in butanol and octanol waste liquid, restructuring cracking at the bottom of weight-removing column is recycled further, it is alcohol that aldehyde the most therein carries out mixed hydrogenation, again through distillation process, obtain highly purified butanol and octanol products, concrete steps include de-weight, hydrogenation, dehydration, the processes such as separating butanol product and side take-off octanol products, this is not only significantly increased the utilization rate of butanol and octanol waste liquid, increase economic benefit, also reduce the composition complexity of material, the difficulty of rectification cell can be reduced, reduce separation costs.Additionally, the present invention is first by the heavies removal of C12 and C16 in butanol and octanol waste liquid, colloid through catalyst reactor bed is greatly reduced, contributes to extending catalyst service life, improve the stability of hydrogenation plant.
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 a kind of 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 phthalic acid two fourth vinegar (DBP).Along with the development of China's plastics industry, the requirement of octyl alconyl is also being increased year by year by market in cumulative year after year, the production capacity of domestic butyl octanol unit.The vaporizer of butyl octanol unit reactor, phase separator and weight-removing column etc. all have a small amount of ejection, the mixed liquor discharged is referred to as octyl alconyl residual liquid, is equivalent to about the 10% of octyl alconyl product quality, and wherein contains a large amount of valuable composition, but due to composition complexity, the past is many as fuel.The domestic device such as batch fractionating tower etc. recycling octyl alconyl residual liquid that oneself has, the technique of employing is unreasonable, reclaims the of poor quality of product, and yield is low, and 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 Meixia (the reclaiming clean technology of butanol and octanol waste liquid. Inner Mongol petrochemical industry, 2000,7:53～54) etc. all carried out the work of this respect, but being essentially all and directly fractionate out butyraldehyde, butanol, C8 solvent from waste liquid, remaining residual liquid is used as fuel oil again.
CN101973846A discloses a kind of waste liquid discharged with butyl octanol unit for raw material production mixed butyl alcohol and the method for thick capryl alcohol, the method is by raw material fractionation unit, hydrogenation synthesis unit and product rectification cell composition, mixed butyl alcohol purity >=the 95wt%, the thick capryl alcohol purity >=97wt% of production produced.But this technique adds raw material fractionation unit before the reaction, flow process is complex, and cost of investment is big.CN101892066A discloses and octyl alconyl residual liquid is cracked under a kind of akaline liquid decomposition agent carbon four and the production technology of carbon eight.Carbon four, carbon eight that this technique does not produce through hydrotreating are the mixture of aldehyde and alcohol, and value is low.
Aldehyde, unsaturated alcohol in octyl alconyl residual liquid hydrogenation process mainly residual liquid are hydrogenated to corresponding alcohol, and part Long carbon chain component is hydrogenated with, is cracked into the alcohol of short carbon chain, 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 is with Ni as active component, and with alkaline-earth metal or/and aluminium oxide is as accelerator, siliceous compound is carrier.After hydrogenation, different octanal has remnants, and hydrogenation rate is 96%.CN102309968A discloses a kind of aldehyde liquid phase hydrogenating catalyst, nickel or its oxide are 8～35%, at least one element or its oxide in IA or Group IIA is (0.01～2.0) wt%, in IIIA or IV group, at least one element or its oxide are (0.01～20.0) wt%, rare earth element is (0.01～5) wt%, aluminium oxide is carrier, and this catalyst low-temperature activity is high, but catalyst composition is complex.CN102059121A discloses a kind of lanthanum modified nickel-copper octanol hydrorefining catalyst, with γ-Al2O3For carrier, ambrose alloy is active component, and lanthanum is auxiliary agent, and octenal, disloyalty aldehyde, matsutake alcohol hydrogenation rate all reach 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 discloses a kind of liquid phase hydrogenating catalyst in unsaturated aldehyde liquid-phase hydrogenatin technique.This catalyst is done carrier by silicon dioxide, and nickel is the first active component, and other active component is cobalt, molybdenum, chromium, potassium.Active component is complicated.
CN101973845B discloses and a kind of extracts butyraldehyde and butanol mixture and octenal, the method for capryl alcohol mixture from butyl octanol unit waste liquid.First fractionating out butyraldehyde and butanol mixture from waste liquid, be hydrogenated with for butyraldehyde hydrogenation plant, more therefrom fractionate out octenal and capryl alcohol mixture, for octenal hydrogenation plant, both materials are also used as by-product sale.The method is simple, but brings again miscellaneous for the many in waste liquid component into octyl alconyl.
Butanol and octanol waste liquid disclosed in CN103342625A process technique basic with Wang Lei (butanol and the recycling of capryl alcohol residual liquid. petrochemical industry, 2006,35 (8): 782～784) disclosed in technology identical, use four column rectification systems separation.The first rectifying column stage casing it is passed through, under the effect of entrainment reagent, from the first rectifying column removed overhead moisture and light component after butanol and octanol waste liquid is heated to 60 DEG C-100 DEG C；First tower bottom of rectifying tower liquid enters Second distillation column stage casing, and 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 the 4th rectifying column stage casing, and the 4th rectifying column tower top obtains purity > octanol products of 98%.This process technique relies solely on rectification mode, therefrom reclaims butanol and capryl alcohol, but does not utilize unsaturated component such as butyraldehyde, octenal and matsutake alcohol and octanal etc., and 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.It is made up of raw material fractionation unit, hydrogenation synthesis unit and product rectification cell, described raw material branch library unit includes that butyraldehyde fractionating column, butanol separation column and carbon eight fractionating column three overlap fractionating device, described hydrogenation synthesis unit and product rectification cell are applicable to hydrogenation and the rectification of the C-4-fraction from raw material fractionation unit, be also applied for hydrogenation and the rectification of carbon eight fraction from raw material fractionation unit, 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, the butyraldehyde component wherein contained is fractionated from butyraldehyde tower top, then by butanol separation column device, the butanol component wherein contained is fractionated from butanol tower top, finally by carbon eight fractionating column device, the carbon eight component octenal wherein contained and capryl alcohol are fractionated from carbon eight tower top；The butyraldehyde being fractionated and butanol are stored in carbon four storage tank, and octenal and capryl alcohol are stored in carbon eight storage tank；B. hydrogenation synthesis: enter hydrogenation synthesis unit from the butyraldehyde of carbon four storage tank of step a and butanol or octenal and capryl alcohol fraction from carbon eight storage tank, in hydrogenation reactor, by hydrogenation synthesis mixed butyl alcohol or synthesize thick capryl alcohol；C. product purification: the mixed butyl alcohol of step b hydrogenation synthesis or thick capryl alcohol, through rectified purified, prepare mixed butyl 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 hydrogen addition technology had also exists the problem that raw material availability is the highest, and have also exists the problem that energy consumption is high, the problem that some existence catalyst lifes are short.
Summary of the invention
In order to solve the problem that prior art exists, it is proposed that heavy constituent, first by heavies removal in butanol and octanol waste liquid, is cracked recycling by one further, and aldehyde the most therein is hydrogenated to alcohol, then through distillation process, it is thus achieved that highly purified butanol and octanol products.
The butanol and octanol waste liquid collection cracking of the present invention and the separation method of hydrogenation, specifically include hydrogenation unit, cracking unit and rectification cell, comprise the following steps:
(1) de-weight: butanol and octanol waste liquid is passed through weight-removing column, through distillation process, steam water, hydro carbons, isobutylaldehyde, hutanal and butanol, octenal and capryl alcohol from weight-removing column top, contain the heavy constituent logistics containing 12 carbon atoms and ten six carbon atoms from extraction at the bottom of tower；
(2) cracking: enter pyrolysis furnace cracking from the heavy constituent logistics at the bottom of weight-removing column, logistics after cracking is passed through flash tank, the light component stream that flash distillation tank deck steams returns weight-removing column and carries out rectification, tank bottoms for heavy oil discharge；
(3) hydrogenation: the logistics of autospasy weight tower top in the future enters the hydrogenation reactor equipped with hydrogenation catalyst with hydrogen, under reaction temperature 50～200 DEG C, reaction pressure 0.4～5.0MPa, butyraldehyde therein is hydrogenated to butanol, and octenal is hydrogenated to capryl alcohol, it is thus achieved that the reactant liquor after hydrogenation；
(4) dehydration: enter dehydrating tower from the reactant liquor after the hydrogenation of hydrogenation unit, through distillation process, water, hydro carbons, the remaining isobutylaldehyde of hydrogenation and hutanal is steamed from dehydration tower top, the condensed aqueous phase that separates in quantizer is discharged, oil phase part extraction, partial reflux, from extraction tower base stream at the bottom of tower；
(5) separating butanol: enter butanol tower from the logistics at the bottom of dehydrating tower tower, through distillation process, from butanol overhead extraction butanol product, from extraction tower base stream at the bottom of tower；
(6) miscellaneous oil is separated: enter miscellaneous oil tower from the logistics at the bottom of butanol tower tower, through distillation process, the logistics of the remaining octenal of butanol, butyl butyrate, enanthol and hydrogenation is contained from miscellaneous oil overhead extraction, discharge as miscellaneous oil, from tower side take-off capryl alcohol, from extraction lauryl alcohol at the bottom of tower and the heavy constituent of hexadecanol, discharge 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 (3), and hydrogenation catalyst is the nickel catalyst being applicable to butyl octanol unit liquid-phase hydrogenatin, and reaction temperature is 50～130 DEG C, 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 of butanol and octanol waste liquid hydrogenation consumption.
More preferably, described hydrogenation step is hydrogenated to liquid phase reactor in (3), and hydrogenation catalyst is the nickel catalyst being applicable to butyl octanol unit liquid-phase hydrogenatin, and reaction temperature is 60～130 DEG C, 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 inlet amount is 1.05～5 times of butanol and octanol waste liquid hydrogenation consumption.
Method of hydrotreating described in the method for the present invention can freely select according to factory condition to use, preferably, described hydrogenation step (3) is hydrogenated to gas phase reaction, hydrogenation catalyst is the Cu-series catalyst being applicable to butyl octanol unit gas phase hydrogenation, reaction temperature is 120～200 DEG C, reaction pressure is 0.4～0.8MPa, and butanol and octanol waste liquid 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.
Because butanol and octanol waste liquid contains the relatively low butyraldehyde of performance degree and butanol system, also the of a relatively high octenal of volatility and capryl alcohol system are contained, the component of 12 carbon atoms and the component of ten six carbon atoms possibly together with more weight, thus material can a part be gas phase in hydrogenation process, a part is liquid phase, preferably, described hydrogenation step (3) is hydrogenated to gas-liquid phase reaction, gas phase it is divided in the middle part of butanol and octanol waste liquid, part is liquid phase, hydrogenation catalyst is to be applicable to the Cu-series catalyst of butyl octanol unit gas phase hydrogenation or be applicable to the nickel catalyst of butyl octanol unit liquid-phase hydrogenatin, reaction temperature is 120～200 DEG C, reaction pressure is 0.4～0.8MPa, butanol and octanol waste liquid 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, it can be one waste liquid, it can also be the mixture of multiply waste liquid, it can be the waste liquid of butanol unit, contain only butyraldehyde and the material of butanol system, can also be the waste liquid of capryl alcohol unit, contain only octenal and the material of capryl alcohol system, it is also possible to be the mixture of these materials.For more representative, it is preferable that described butanol and octanol waste liquid is the material containing hydrocarbon, butyraldehyde, butanol, butyl butyrate, enanthol, matsutake alcohol, octanal, octenal, capryl alcohol, lauryl alcohol, lauric aldehyde, hexadecanoyl and hexadecanol from butyl octanol unit.Described butanol and octanol 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, butyraldehyde includes isobutylaldehyde and hutanal, butanol includes isobutanol and n-butyl alcohol, matsutake alcohol is 2-ethyl hexyl-2-alkene-1-alcohol, octanal is 2-ethyl hexanal, octenal is 2-ethyl hexyl-2-alkene-1-aldehyde, capryl alcohol is 2-Ethylhexyl Alcohol, lauryl alcohol is isobutylaldehyde and/or the hutanal alcohols containing 12 carbon atoms through being condensed and be hydrogenated to, lauric aldehyde is isobutylaldehyde and/or the hutanal aldehydes containing 12 carbon atoms through being condensed and be hydrogenated to, hexadecanol is isobutylaldehyde and/or the hutanal alcohols containing ten six carbon atoms through being condensed and be hydrogenated to, hexadecanoyl is 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 cracked by the present invention, and the light component in logistics recycles after flashing off cracking by flash tank.Preferably, pyrolysis furnace described in step (2) 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 determine according to the composition of self material and character.Preferably, the tower top temperature of described weight-removing column is 30～50 DEG C, and tower top pressure is 0.04～0.08MPa, and bottom temperature is 170～230 DEG C；Pyrolysis 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, and bottom temperature is 120～140 DEG C；The tower top temperature of described butanol tower is 80～100 DEG C, and tower top pressure is 0.02～0.04MPa, and bottom temperature is 140～160 DEG C；The tower top temperature of described miscellaneous oil tower is 70～90 DEG C, and tower top pressure is 0.004～0.017MPa, and bottom temperature is 180～220 DEG C.
Nickel catalyst of the present invention can be the nickel catalyst being supported on aluminium oxide, silicon oxide, aluminium oxide-silicon oxide, activated carbon, kieselguhr, zirconium oxide or calcium oxide, in addition to nickeliferous active component, it is also possible to containing components such as other auxiliary agent such as magnesium, potassium, lanthanum, zinc, calcium.Described nickel catalyst can also be the nickel catalyst that the sedimentation method obtain, such as the nickel catalyst of sedimentation method alumina dispersion.The hydrogenation catalyst of the present invention can also be that cobalt series catalyst, carrier or disperse medium are similar to nickel catalyst.In terms of mass percentage content, Nickel Content In Catalyst is 10%～50%, such as alumina load 15～the catalyst of 20% nickel, the 40 of alumina dispersion～50% catalyst of nickel.Described nickel catalyst can also be Raney's nickel catalyst, and Raney's nickel catalyst has 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.Such as it is supported on the Cu-series catalyst on aluminium oxide, silicon oxide, aluminium oxide-silicon oxide, activated carbon, kieselguhr, zirconium oxide or calcium oxide, in addition to copper-containing active component, it is also possible to containing components such as other auxiliary agent such as nickel, cobalt, magnesium, potassium, lanthanum, zinc, calcium.Co-precipitated catalyst can be copper zinc catalyst, copper and zinc element, CuZnAl catalyst, it is also possible to adds other auxiliary agent in these basic recipe catalyst, such as the auxiliary agent such as manganese, lanthanum.The percent mass content of copper 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 methods such as infusion process, ion exchange, blending method, kneading method, co-precipitation, deposition-precipitation, steaming ammonium precipitation, melted-sucking filtration, ball milling and sol-gels.Preferred method includes the combination of one or more in co-precipitation, deposition-precipitation, steaming ammonium precipitation, melted-sucking filtration, ball milling and sol-gel, these are prepared catalyst method and are mostly well known to those skilled in the art as existing mature technology, detailed introduction is all had in the books of this area, such as written " Preparation of Solid Catalysts " such as yellow Zhong Tao written " industrial catalyst design and development ", Gerhard professors Ertl.Steaming ammonium intermediate processing the most of the present invention, brief step is as follows: active component salt is dissolved in the water by (1), it is also possible to containing other metals or non-metal salt；(2) ammonia is gradually added in above-mentioned saline solution, forms ammonium complex compound with ammonia；(3) other components are added；(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 fusing the metal active constituent and aluminum (or silicon) with catalysis activity in a furnace, the melt obtained carries out quenching cooling, it is then comminuted into for uniform fine grained, dissolving the auxiliary agent being also possible to add other in step；(2) by catalyst fines molding, forming technique can use existing well known technology, as beaten sheet, mediating extrusion, spin etc.；(3) by above-mentioned preformed catalyst sucking filtration in alkali liquor of gained, i.e. obtain obtaining catalyst.
Butyraldehyde in butanol and octanol waste liquid, matsutake alcohol, octanal and octenal can be correspondingly hydrogenated to butanol, capryl alcohol by the method for the present invention, and heavy constituent is carried out cracking recycling, this is not only significantly increased the utilization rate of butanol and octanol waste liquid, add economic benefit, also reduce the composition complexity of material, the difficulty of rectification cell can be reduced, reduce separation costs.In addition, first the heavies removal of C12 and C16 in butanol and octanol waste liquid is decreased the colloid through catalyst reactor bed by the method for the present invention, it is more beneficial for the carrying out of hydrogenation reaction, contributes to extending catalyst service life, improve the stability of hydrogenation plant.
Detailed description of the invention
The method that the butanol and octanol waste liquid front-end hydrogenation of the present invention is explained further the most by way of example, but the present invention is not limited to this.
Embodiment 1
The butanol and octanol waste liquid collection cracking of the present invention and the separation method of hydrogenation, specifically include hydrogenation unit and rectification cell, comprise the following steps:
(1) de-weight: butanol and octanol waste liquid is passed through weight-removing column, through distillation process, steam water, hydro carbons, isobutylaldehyde, hutanal and butanol, octenal and capryl alcohol from weight-removing column top, contain containing 12 carbon atoms and the heavy constituent of ten six carbon atoms from extraction at the bottom of tower；The tower top temperature of described weight-removing column is 40 DEG C, and tower top pressure is 0.07MPa, and bottom temperature is 199 DEG C；
(2) cracking: enter pyrolysis furnace cracking from the heavy constituent logistics at the bottom of weight-removing column, logistics after cracking is passed through flash tank, the light component stream that flash distillation tank deck steams returns weight-removing column and carries out rectification, tank bottoms for heavy oil discharge；Cracking temperature is 650 DEG C, and cracking mode is that anaerobic contains hydrothermal cracking；
(3) hydrogenation: the logistics of autospasy weight tower top in the future enters the hydrogenation reactor equipped with hydrogenation catalyst with hydrogen, under reaction temperature 50～130 DEG C, reaction pressure 4.0MPa, butyraldehyde in butanol and octanol waste liquid is hydrogenated to butanol, and octenal is hydrogenated to capryl alcohol, it is thus achieved that the reactant liquor after hydrogenation；Being hydrogenated to liquid phase reactor, hydrogenation catalyst is the nickel catalyst BC-H-48 that Beijing Chemical Research Institute produces, and the liquid phase air speed of butanol and octanol waste liquid is 0.75h-1, hydrogen inlet amount is 1.05 times of butanol and octanol waste liquid hydrogenation consumption；
(4) dehydration: the reactant liquor after hydrogenation enters dehydrating tower, through distillation process, steams water, hydro carbons, the remaining isobutylaldehyde of hydrogenation and hutanal from dehydration tower top, the condensed aqueous phase that separates in quantizer is discharged, oil phase part extraction, partial reflux, from extraction tower base stream at the bottom of tower；The tower top temperature of described dehydrating tower is 48 DEG C, and tower top pressure is 0.13MPa, and bottom temperature is 132 DEG C；
(5) separating butanol: enter butanol tower from the logistics at the bottom of dehydrating tower tower, through distillation process, from butanol overhead extraction butanol product, from extraction tower base stream at the bottom of tower；The tower top temperature of described butanol tower is 85 DEG C, and tower top pressure is 0.03MPa, and bottom temperature is 150 DEG C；
(6) separate miscellaneous oil: enter miscellaneous oil tower from the logistics at the bottom of butanol tower tower, through distillation process, contain the logistics of the remaining octenal of butyl butyrate, enanthol, butanol and hydrogenation from miscellaneous oil overhead extraction, discharge, from extraction tower base stream at the bottom of tower as miscellaneous oil；The tower top temperature of described miscellaneous oil tower is 86 DEG C, and tower top pressure is 0.007MPa, and bottom temperature is 203 DEG C.
Claims (8)
1. butanol and octanol waste liquid collection cracking and the separation method of hydrogenation, it is characterised in that described method include hydrogenation unit,
Cracking unit and rectification cell, comprise the following steps:
(1) de-weight: butanol and octanol waste liquid is passed through weight-removing column, through distillation process, steam from weight-removing column top water, hydro carbons,
Isobutylaldehyde, hutanal and butanol, octenal and capryl alcohol, contain containing 12 carbon atoms and 16 carbon former from extraction at the bottom of tower
The heavy constituent logistics of son；
(2) 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 weight-removing column and carries out rectification, tank bottoms for heavy oil discharge；
(3) hydrogenation: the logistics of autospasy weight tower top in the future enters the hydrogenation reactor equipped with hydrogenation catalyst with hydrogen,
Under reaction temperature 50～200 DEG C, reaction pressure 0.4～5.0MPa, butyraldehyde therein is hydrogenated to butanol, and octenal is hydrogenated with
Generate capryl alcohol, it is thus achieved that the reactant liquor after hydrogenation；
(4) dehydration: enter dehydrating tower from the reactant liquor after the hydrogenation of hydrogenation unit, through distillation process, from dehydrating tower
Top steams water, hydro carbons, the remaining isobutylaldehyde of hydrogenation and hutanal, and the condensed aqueous phase that separates in quantizer is discharged, oil phase
Part extraction, partial reflux, from extraction tower base stream at the bottom of tower；
(5) separating butanol: enter butanol tower from the logistics at the bottom of dehydrating tower tower, through distillation process, adopt from butanol tower top
Go out butanol product, from extraction tower base stream at the bottom of tower；
(6) separate miscellaneous oil: enter miscellaneous oil tower from the logistics at the bottom of butanol tower tower, through distillation process, adopt from miscellaneous oil tower top
Go out the logistics containing the remaining octenal of butanol, butyl butyrate, enanthol and hydrogenation, discharge as miscellaneous oil, adopt from tower side line
Go out capryl alcohol, from extraction lauryl alcohol at the bottom of tower and the heavy constituent of hexadecanol, discharge as heavy oil.
2. butanol and octanol waste liquid collection cracking as claimed in claim 1 and the separation method of hydrogenation, it is characterised in that described in add
Hydrogen step is hydrogenated to liquid phase reactor in (3), and hydrogenation catalyst is the nickel system catalysis being applicable to butyl octanol unit liquid-phase hydrogenatin
Agent, 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 0.15～1.5
h-1, hydrogen inlet amount is 1.05～20 times of butanol and octanol waste liquid hydrogenation consumption.
3. butanol and octanol waste liquid collection cracking as claimed in claim 1 and the separation method of hydrogenation, it is characterised in that described in add
Hydrogen step is hydrogenated to liquid phase reactor in (3), and hydrogenation catalyst is the nickel system catalysis being applicable to butyl octanol unit liquid-phase hydrogenatin
Agent, reaction 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 0.15～1.2
h-1, hydrogen inlet amount is 1.05～5 times of butanol and octanol waste liquid hydrogenation consumption.
4. butanol and octanol waste liquid collection cracking as claimed in claim 1 and the separation method of hydrogenation, it is characterised in that described in add
Being hydrogenated to gas phase reaction in hydrogen step (3), hydrogenation catalyst is the copper system catalysis being applicable to butyl octanol unit gas phase hydrogenation
Agent, reaction temperature is 120～200 DEG C, and reaction pressure is 0.4～0.8MPa, butanol and octanol waste liquid charging air speed in terms of liquid phase
It is 0.15～1.5h-1, hydrogen inlet amount is 10～40 times of butanol and octanol waste liquid hydrogenation consumption.
5. butanol and octanol waste liquid collection cracking as claimed in claim 1 and the separation method of hydrogenation, it is characterised in that described in add
Being hydrogenated to gas-liquid phase reaction in hydrogen step (3), be divided into gas phase in the middle part of butanol and octanol waste liquid, part is liquid phase, and hydrogenation is urged
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
Catalyst, reaction temperature is 120～200 DEG C, and reaction pressure is 0.4～0.8MPa, and butanol and octanol waste liquid feeds in terms of liquid phase
Air speed is 0.15～1.5h-1, hydrogen inlet amount is 10～40 times of butanol and octanol waste liquid hydrogenation consumption.
6. butanol and octanol waste liquid collection cracking as claimed in claim 1 and the separation method of hydrogenation, it is characterised in that described fourth
Capryl alcohol waste liquid be from butyl octanol unit containing hydrocarbon, butyraldehyde, butanol, butyl butyrate, enanthol, matsutake alcohol, octanal,
The material of octenal, capryl alcohol, lauryl alcohol, lauric aldehyde, hexadecanoyl and hexadecanol.
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 (2)
Described in pyrolysis furnace be cracked into containing water-splitting, cracking mode is thermal cracking or catalytic pyrolysis, cracking temperature be 200～
800℃。
8. butanol and octanol waste liquid collection cracking as claimed in claim 1 and the separation method of hydrogenation, it is characterised in that described de-
The tower top temperature of weight tower is 30～50 DEG C, and tower top pressure is 0.04～0.08MPa, and bottom temperature is 170～230 DEG C；Split
Solving 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 is 120～140 DEG C；The tower top temperature of described butanol tower is 80～100 DEG C, and tower top pressure is 0.02～0.04
MPa, bottom temperature is 140～160 DEG C；Described miscellaneous oil tower tower top temperature be 70～90 DEG C, tower top pressure be 0.004～
0.017MPa, bottom temperature is 180～220 DEG C.
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