CN116392834A - Byproduct heavy component treatment system and recovery method for butanol device - Google Patents

Byproduct heavy component treatment system and recovery method for butanol device Download PDF

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CN116392834A
CN116392834A CN202310351251.3A CN202310351251A CN116392834A CN 116392834 A CN116392834 A CN 116392834A CN 202310351251 A CN202310351251 A CN 202310351251A CN 116392834 A CN116392834 A CN 116392834A
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butanol
rectifying tower
gas phase
coalescer
phase
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李想
朱占山
刘志龙
周胜达
孙世奇
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Hailan Zhiyun Technology Co ltd
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Hailan Zhiyun Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/12—Monohydroxylic acyclic alcohols containing four carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/125—Monohydroxylic acyclic alcohols containing five to twenty-two carbon atoms

Abstract

A recycling method of a byproduct heavy component treatment system of a butanol device comprises the following steps: heavy components of the byproduct of the butanol device enter the middle lower part of a rectifying tower, the heavy components are separated by the rectifying tower, and a gas phase is extracted from the middle lower part of the rectifying tower; the gas phase extracted from the rectifying tower is mixed with fresh hydrogen and recycle gas and then enters a hydrogenation reactor, the flow is selectively hydrogenated into butanol and water, and a hydrogenation catalyst is filled in the fixed bed reactor; returning the reaction product after the reaction to a rectifying tower, and separating butanol and water to the top of the rectifying tower; the gas phase at the top of the rectifying tower enters a coalescer after first-stage condensation, the non-condensable gas phase in the coalescer is subjected to deep cooling, the liquid phase returns to the coalescer, the gas phase returns to the hydrogenation reactor after being compressed by a compressor, and a circulating gas is discharged outside; and the coalescer separates oil from water in the condensed liquid phase, one part of the oil phase returns to the rectifying tower for reflux, the other part enters the butanol product tower of the device for purifying butanol product, and the water phase is discharged to the wastewater system.

Description

Byproduct heavy component treatment system and recovery method for butanol device
Technical Field
The invention relates to the field of chemical industry, in particular to a butanol device byproduct heavy component treatment system and a recycling method.
Background
The existing industrialized butanol device mainly comprises two main flow process technologies, namely a homogeneous hydroformylation reaction technology and a water-based hydroformylation reaction technology. The homogeneous hydroformylation reaction technology has wider application range, and the technology takes rhodium metal complex as a catalyst to cause the synthesis gas and propylene to generate butyraldehyde through carbonylation reaction, and butyraldehyde is further hydrogenated to generate butanol.
The byproduct of butyraldehyde device is obtained from carbonylation reaction and butyraldehyde hydrogenation reaction, which contains butyraldehyde 5-15%, butyric acid 0.5-1%, butanol 5-8%, butyrates 40-60%, octacarbon alcohol and dodecacarbon and above 10-30%, because the recombination grouping is mixed, the recovery difficulty is great, most devices are mainly burnt, the atom economy is poor, the butyraldehyde unit consumption is high, and the carbon emission reduction is also unfavorable.
Patent CN101973846B discloses a method for producing mixed butanol and crude octanol by using butanol-octanol device waste liquid as raw material, which comprises the steps of separating butyraldehyde, butanol and carbon eight components through a fractionating device, hydrogenating aldehydes substances to produce butanol-octanol, and obtaining high-purity butanol-octanol through a complex rectifying system. The process flow is relatively longer, the number of rectifying towers used for raw material fractionation and product refining is relatively more, and the investment is huge.
Patent CN112321386A discloses a method for hydrotreating butanol-octanol waste liquid, which comprises the steps of using organic alkali as an alkaline auxiliary agent, then carrying out catalytic hydrogenation conversion at 230-280 ℃ and separating to obtain an alcohol product. The alkaline auxiliary agent is complex in the separation process, and heavy components influence the activity of the hydrogenation catalyst
Patent CN113735688A discloses a method for recycling waste liquid of butanol device, which comprises the steps of treating metal ions through ion exchange resin, mixing materials with hydrogen, then introducing the mixture into a hydrogenation reactor for reaction, degassing the reaction liquid, returning gas phase to the butanol device, and introducing liquid phase into a butanol product tower.
The prior art has the following problems in main,
1. the physical separation method is used for refining heavy components, so that the process flow is long, the equipment investment is large, the yield of the product is very low, and the economical efficiency is very poor;
2. although the catalyst enters a hydrogenation reactor after being treated by an alkaline auxiliary agent or resin adsorption and the like, the heavy components such as the octacosanol, the dodecanol and the like in the heavy components have high content, are easy to coke on the surface of the catalyst in the hydrogenation reactor, influence the service life of the catalyst conversion effect agent, and meanwhile, the residual hydrogen after hydrogenation is treated by the discharge treatment, so that the economy is poor;
3. heavy components in the CN113735688A are subjected to hydrogenation after being adsorbed, the heavy components contain a large amount of polymers which cover the surface of a catalyst, the catalyst is deactivated quickly, reaction liquid directly enters a butanol product tower, butanol products are separated, water generated by hydrogenation reaction is extracted along with the butanol products, the butanol quality is poor, and the process feasibility is low;
4. traditional hydrogenation feeding needs heating, and the reaction liquid needs cooling after hydrogenation, so that energy waste is caused.
Disclosure of Invention
The invention aims to provide a butanol device byproduct heavy component treatment system and a recycling method, which have the advantages of short process flow, convenience in operation, less equipment investment and less device occupation.
The invention aims to provide a butanol device byproduct heavy component treatment system and a recycling method, which are reasonable in process flow, heavy components are subjected to gas-phase hydrogenation treatment after rectification, the catalyst active sites are not covered by heavy components in the reactor feed, and the service life of the catalyst is long.
The invention aims to provide a butanol device byproduct heavy component treatment system and a recycling method, wherein a product after reaction returns to a rectifying tower, butanol and water are separated from the top of the rectifying tower, butanol product quality is high, heavy components are discharged outside a rectifying tower kettle, and heavy components are prevented from accumulating in the system.
The invention aims to provide a butanol device byproduct heavy component treatment system and a recovery method, wherein gas phase extraction of a rectifying tower is adopted to directly enter a reactor, the gas phase after hydrogenation is returned to the rectifying tower, heat is fully utilized in the rectifying tower, tower kettle steam can be saved, and the energy consumption of the whole system is low.
The invention aims to provide a byproduct heavy component treatment system of a butanol device and a recovery method, wherein the oil-water phase of the hydrogenated reaction liquid is separated by a coalescer at the top of the tower after rectification, so that the water phase is prevented from entering a butanol product tower to influence the quality of butanol products, and meanwhile, the gas phase at the top of the tower is circulated back to a reactor by a compressor, so that hydrogen is saved, and the economical efficiency is improved.
In order to achieve at least one of the objects of the present invention, the present invention provides a method for recovering a byproduct heavy component processing system of a butanol apparatus, comprising the steps of:
heavy components of the byproduct of the butanol device enter the middle lower part of a rectifying tower, the heavy components are separated by the rectifying tower, and a gas phase is extracted from the middle lower part of the rectifying tower;
the gas phase extracted from the rectifying tower is mixed with fresh hydrogen and recycle gas and then enters a hydrogenation reactor, the flow is selectively hydrogenated into butanol and water, and a hydrogenation catalyst is filled in the fixed bed reactor;
returning the reaction product after the reaction to a rectifying tower, and separating butanol and water to the top of the rectifying tower;
the gas phase at the top of the rectifying tower enters a coalescer after first-stage condensation, the non-condensable gas phase in the coalescer is subjected to deep cooling, the liquid phase returns to the coalescer, the gas phase returns to the hydrogenation reactor after being compressed by a compressor, and a circulating gas is discharged outside; and
the coalescer realizes oil-water separation of the condensed liquid phase, one part of the oil phase returns to the rectifying tower for reflux, the other part enters the butanol product tower of the device for purifying butanol product, and the water phase is discharged to the wastewater system.
In some embodiments, wherein the rectification column is operated at positive pressure, the pressure is from 0.1 to 2.0MPaG, and the number of rectification trays is from 35 to 80 theoretical plates.
In some embodiments, wherein the byproduct recombinant stream from the butanol plant enters the rectifying column at a position of 5-10 theoretical plates from bottom to top, the vapor phase hydrogenation reactor is withdrawn from the rectifying column at the 15 th-18 th theoretical plate side line.
In some embodiments, the fresh hydrogen, the recycle gas and the gas phase extracted from the side line of the rectifying tower are mixed and then enter a hydrogenation reactor, the molar ratio of the hydrogen to the gas phase extracted from the side line is 6-15, wherein the hydrogenation reactor adopts a fixed bed, the reaction temperature of the hydrogenation reactor is 160-250 ℃, the reaction pressure is 0.5-1 MpaG, and the space velocity of the hydrogenation reaction is 0.5-3 h < -1 >.
In some embodiments, the vapor phase at the outlet of the hydrogenation reactor is distilled off from 20 to 30 theoretical plates in a rectifying column to distill the butanol and water produced by the hydrogenation reaction to the overhead vapor phase.
In some embodiments, after the gas phase at the top of the rectifying tower is condensed by the circulating water cooler, the gas-liquid two phases enter the coalescer, the liquid phase returns to the front compartment of the coalescer after the non-condensable gas phase is deeply cooled by the chilled water, the gas phase returns to the hydrogenation reactor after being compressed by the compressor, one gas phase is discharged outside, and the external exhaust gas phase accounts for 0.01-1% of the mass ratio of the circulating gas.
In some embodiments, wherein the coalescer internals are wire mesh and/or metal flaps, the coalescer residence time is 30 to 60 minutes, the coalescer separates an oil phase and a water phase, and the water phase is sent to a wastewater system.
In some embodiments, wherein a portion of the oil phase in the coalescer is returned to the rectifying column and another portion butanol product is withdrawn, the reflux ratio of the rectifying column is between 0.5 and 5.
In some embodiments, the heavy components of the byproduct of the butyraldehyde unit are derived from carbonylation reactions and butyraldehyde hydrogenation processes, including butyraldehyde 5-15%, butyric acid 0.5-1%, butanol 5-8%, butyraldehyde dimer 1-5%, butyrates 40-60%, octacarbon alcohol and dodecacarbon and above 10-20%.
In some embodiments, wherein the heavy fraction separated by the rectification column comprises octacosanol, dodecanol, metal ions, wherein the metal ions comprise rhodium catalyst and corrosion metals, the gas phase withdrawn from the middle lower portion of the rectification column comprises butyl butyrate, butyraldehyde polymer, butyric acid; wherein the hydrogenation reactor is filled with one or more of nickel-based catalyst, copper-based catalyst and palladium-based catalyst.
According to another aspect of the invention, there is also provided a butanol device byproduct heavy component treatment system, which is recovered by the recovery method of the butanol device byproduct heavy component treatment system, the butanol device byproduct heavy component treatment system comprises a rectifying tower, a hydrogenation reactor, a hydrogen compressor, a cooler, a coalescer and a condenser, a heavy component pipeline of a byproduct from the butanol device enters the lower part of the rectifying tower, a side-draw gas phase of the rectifying tower enters the hydrogenation reactor, meanwhile, fresh hydrogen and compressed gas from the hydrogen compressor enter the hydrogenation reactor, an outlet pipeline of the hydrogenation reactor is connected with the rectifying tower, a gas phase pipeline at the top of the rectifying tower is connected with the cooler, condensed materials are connected with the coalescer, a non-condensable gas phase at the top of the coalescer is connected with the condenser, a deep-cooled stream returns to the coalescer, a part of an oil phase of the coalescer returns to the hydrogenation compressor, a part of the oil phase of the coalescer returns to the rectifying tower, a part of the oil phase of the coalescer returns to the butanol product, and a part of the water phase of the oil phase returns to the rectifying tower, and the water phase of the rectifying tower enters the wastewater system.
Drawings
FIG. 1 is a process flow diagram of a butanol plant byproduct heavies processing system in accordance with one embodiment of the invention.
Fig. 2 is a process flow diagram of a comparative example.
Detailed Description
The following description is presented to enable one of ordinary skill in the art to make and use the invention. The preferred embodiments in the following description are by way of example only and other obvious variations will occur to those skilled in the art. The basic principles of the invention defined in the following description may be applied to other embodiments, variations, modifications, equivalents, and other technical solutions without departing from the spirit and scope of the invention.
It will be understood that the terms "a" and "an" should be interpreted as referring to "at least one" or "one or more," i.e., in one embodiment, the number of elements may be one, while in another embodiment, the number of elements may be plural, and the term "a" should not be interpreted as limiting the number.
As shown in fig. 1, a process flow diagram of a butanol plant byproduct heavies processing system in accordance with a preferred embodiment of the invention is shown. The byproduct heavy component treatment system of the butanol device has the advantages of short process flow, less equipment investment, less investment and device occupation, reasonable process flow, gas phase hydrogenation treatment of heavy components after rectification, no heavy components in the feeding of a reactor, long service life of a catalyst, return of the reacted product to a rectifying tower, separation of butanol and water at the top of the tower, return of crude butanol to a butanol product tower, discharge of heavy components outside the rectifying tower kettle, avoiding accumulation of heavy components in the system, direct entry of the gas phase of the rectifying tower into the reactor, return of the gas phase after hydrogenation to the rectifying tower, full utilization of heat in the rectifying tower, saving of tower kettle steam, reduction of energy consumption of the whole system, oil-water phase separation of the hydrogenated reaction liquid after rectification by a coalescer, avoiding entry of water phase into the butanol product tower, influencing butanol product quality, recycling of the gas phase at the top of the tower back to the reactor by a compressor, saving hydrogen, and improving economy.
The gas phase analysis conditions of the byproduct heavy component treatment system of the butanol device are as follows: adopting an Agilent7890B, a chromatographic column HP-5ms, and a vaporization chamber at 290 ℃ and a detector at 280 ℃; heating to 50deg.C for 2min; maintaining at 40 deg.c/min to 100 deg.c for 1min; heating to 150 ℃ at 10 ℃/min, and keeping for 2min; heating to 230 ℃ at 40 ℃/min, and keeping for 6min. The temperature of the sample inlet is 250 ℃.
Specifically, in the butanol device byproduct heavy component treatment system, the butanol device byproduct heavy component treatment system comprises a rectifying tower, a hydrogenation reactor, a hydrogen compressor, a cooler, a coalescer and a condenser. The rectifying tower is connected with the cooler, the coalescer, the hydrogenation reactor and the hydrogen compressor, and the coalescer is connected with the cooler and the condenser. The condenser is connected with the hydrogen compressor.
Specifically, the heavy component pipeline from the byproduct of the butanol device enters the lower part of the rectifying tower, the side line of the rectifying tower is pumped out to remove the gas phase from the hydrogenation reactor, fresh hydrogen and compressed gas from the hydrogen compressor are simultaneously removed from the hydrogenation reactor, the outlet pipeline of the hydrogenation reactor is connected with the rectifying tower, the gas phase pipeline at the top of the rectifying tower is connected with the cooler, the condensed material is connected with the coalescer, the non-condensable gas phase at the top of the coalescer is connected with the condenser, the flow returns to the coalescer after deep cooling, the gas phase returns to the hydrogenation compressor, a part of the oil phase of the coalescer returns to the rectifying tower, a part of the oil phase of the rectifying tower is used for extracting butanol product, and the water phase at the top of the rectifying tower enters a wastewater system.
Specifically, (1) heavy components from a byproduct of a butanol device pass through the rectifying tower, and are separated by a tower kettle, wherein a gas-phase flow stream containing butyraldehyde, butyric acid, butyl butyrate and the like is adopted at the middle side of the rectifying tower, and the gas-phase flow stream is mixed with fresh hydrogen and recycle gas and then enters the hydrogenation reactor; (2) The mixed flow is subjected to gas phase hydrogenation reaction, the product returns to the rectifying tower, and the gas phase at the top of the rectifying tower is subjected to two-stage condensation to realize gas phase-oil phase-water phase three-phase separation in the coalescer; (3) A part of oil phase extracted by the coalescer is refluxed to the rectifying tower, and a part of butanol product is extracted; (4) The gas phase after deep cooling is compressed by the hydrogen compressor and then returns to the hydrogenation reactor, and a stream of exhaust gas is extracted to avoid accumulation of micromolecular impurities in the circulating gas.
In order to better embody the technical effect of the byproduct heavy component treatment system of the butanol device, the prior structure shown in figure 2 is adopted for comparison. As shown in FIG. 2, the heavy component byproduct from the butanol device is connected with a 01 buffer tank, an outlet pipeline of the buffer tank is connected with a 02 pump, an outlet pipeline of the pump is connected with a hydrogen pipeline and then goes to a 03 hydrogenation reactor, an outlet pipeline of the hydrogenation reactor is connected with a 04 degassing tank, a gas phase pipeline at the top of the degassing tank is connected with a gas phase pipeline at the top of a 05 rectifying tower to remove waste gas, a discharging pipeline at the bottom of the degassing tank is connected with a 05 butanol product tower, butanol product is pumped out from the side line of the butanol product tower, and a heavy component removing pipeline is arranged at the outlet pipeline of a tower kettle.
Specifically, the following examples 1 to 4 employ the butanol apparatus byproduct heavy component treatment system of the present invention, and comparative examples 1 to 4 employ the structure and process flow shown in fig. 2.
More specifically, examples 1 to 4 of the byproduct heavy component treatment system using the butanol apparatus of the present invention are as follows:
example 1
According to the process flow connection device shown in FIG. 1, the byproduct of the butyraldehyde unit is produced from the carbonylation reaction and butyraldehyde hydrogenation reaction, and contains 5-15% of butyraldehyde, 0.5-1% of butyric acid, 5-8% of butanol, 1-5% of butyraldehyde dimer, 40-60% of butyrates, and 10-20% of octacosanol and dodecanol.
The rectifying tower is operated at positive pressure, the pressure is 1.0MPaG, the number of rectifying tower plates is 50 theoretical plates, the byproduct recombinant stream from the butanol device enters 9 plates (from bottom to top) of the rectifying tower, and the gas phase is pumped out from the 16 th plate side line of the rectifying tower to the hydrogenation reactor. Fresh hydrogen, circulating hydrogen and gas phase extracted from the side line of the rectifying tower are mixed and then enter the hydrogenation reactor, and the molar ratio of the hydrogen to the gas phase extracted from the side extraction is 10. The hydrogenation reactor adopts a fixed bed, the reaction temperature of the hydrogenation reactor is 230 ℃, the reaction pressure is 0.8MpaG, the space velocity of the hydrogenation reaction is 1h < -1 >, and the hydrogenation reactor is filled with a palladium carbon catalyst. And removing 20 plates of the rectifying tower from the gas phase at the outlet of the hydrogenation reactor, and steaming butanol and water generated by hydrogenation reaction to the gas phase at the top of the tower. The gas phase at the top of the rectifying tower is condensed by a circulating water cooler, then gas-liquid two phases enter the coalescer, the liquid phase returns to a compartment before the coalescer after the non-condensable gas phase is deeply cooled by chilled water, the gas phase returns to the hydrogenation reactor after being compressed by the hydrogen compressor, and in order to avoid the accumulation of impurities in the circulating gas, one gas phase is discharged, and the external exhaust phasor accounts for 0.5% of the mass ratio of the circulating gas. The coalescer internals adopt silk screen internals, the dwell time is 30min, the coalescer separates oil phase and aqueous phase, and the aqueous phase is sent to wastewater system, the reflux ratio of rectifying column is 1.
Example 2
According to the process flow connection device shown in FIG. 1, the byproduct of the butyraldehyde unit is produced from the carbonylation reaction and butyraldehyde hydrogenation reaction, and contains 5-15% of butyraldehyde, 0.5-1% of butyric acid, 5-8% of butanol, 1-5% of butyraldehyde dimer, 40-60% of butyrates, and 10-20% of octacosanol and dodecanol.
The rectifying tower is operated at positive pressure, the pressure is 0.8MPaG, the number of rectifying tower plates is 60 theoretical plates, and a by-product recombinant stream from the butanol device enters the position of 5 plates (from bottom to top) of the rectifying tower, and gas phase is pumped out from the 18 th plate side line of the rectifying tower to the hydrogenation reactor. Fresh hydrogen, circulating hydrogen and gas phase extracted from the side line of the rectifying tower are mixed and then enter the hydrogenation reactor, and the molar ratio of the hydrogen to the gas phase extracted from the side extraction is 8. The hydrogenation reactor adopts a fixed bed, the reaction temperature of the hydrogenation reactor is 250 ℃, the reaction pressure is 0.6MpaG, the space velocity of the hydrogenation reaction is 3h < -1 >, and the hydrogenation reactor is filled with a palladium carbon catalyst. And removing 25 plates of the rectifying tower from the gas phase at the outlet of the hydrogenation reactor, and steaming butanol and water generated by hydrogenation reaction to the gas phase at the top of the tower. The gas phase at the top of the rectifying tower is condensed by a circulating water cooler, then gas-liquid two phases enter the coalescer, the liquid phase returns to a compartment before the coalescer after the non-condensable gas phase is deeply cooled by chilled water, the gas phase returns to the hydrogenation reactor after being compressed by the hydrogen compressor, and in order to avoid the accumulation of impurities in the circulating gas, one gas phase is discharged, and the mass ratio of the external exhaust phasor to the circulating gas is 0.1%. The coalescer internals adopt silk screen internals, the dwell time is 60min, the coalescer separates oil phase and aqueous phase, and the aqueous phase is sent to wastewater system, the reflux ratio of rectifying column is 3.
Example 3
According to the process flow connection device shown in FIG. 1, the byproduct of the butyraldehyde unit is produced from the carbonylation reaction and butyraldehyde hydrogenation reaction, and contains 5-15% of butyraldehyde, 0.5-1% of butyric acid, 5-8% of butanol, 1-5% of butyraldehyde dimer, 40-60% of butyrates, and 10-20% of octacosanol and dodecanol.
The rectifying tower is operated at positive pressure, the pressure is 0.9MPaG, the number of rectifying tower plates is 60 theoretical plates, the byproduct recombinant stream from the butanol device enters the position of 5 plates (from bottom to top) of the rectifying tower, and the gas phase is pumped out from the 15 th plate side line of the rectifying tower to the hydrogenation reactor. Fresh hydrogen, circulating hydrogen and gas phase extracted from the side line of the rectifying tower are mixed and then enter the hydrogenation reactor, and the molar ratio of the hydrogen to the gas phase extracted from the side extraction is 15. The hydrogenation reactor adopts a fixed bed, the reaction temperature of the hydrogenation reactor is 180 ℃, the reaction pressure is 0.6MpaG, the space velocity of the hydrogenation reaction is 3h < -1 >, and the hydrogenation reactor is filled with a palladium carbon catalyst. And removing 30 plates of the rectifying tower from the gas phase at the outlet of the hydrogenation reactor, and steaming butanol and water generated by hydrogenation reaction to the gas phase at the top of the tower. The gas phase at the top of the rectifying tower is condensed by a circulating water cooler, then gas-liquid two phases enter the coalescer, the liquid phase returns to a compartment before the coalescer after the non-condensable gas phase is deeply cooled by chilled water, the gas phase returns to the hydrogenation reactor after being compressed by the hydrogen compressor, and in order to avoid the accumulation of impurities in the circulating gas, one gas phase is discharged, and the external exhaust phasor accounts for 0.5% of the mass ratio of the circulating gas. The coalescer internals adopt silk screen internals, the dwell time is 45min, the coalescer separates oil phase and aqueous phase, and the aqueous phase is sent to wastewater system, the reflux ratio of rectifying column is 2.
Example 4
According to the process flow connection device shown in FIG. 1, the byproduct of the butyraldehyde unit is produced from the carbonylation reaction and butyraldehyde hydrogenation reaction, and contains 5-15% of butyraldehyde, 0.5-1% of butyric acid, 5-8% of butanol, 1-5% of butyraldehyde dimer, 40-60% of butyrates, and 10-20% of octacosanol and dodecanol.
The rectifying tower is operated at positive pressure, the pressure is 1.0MPaG, the number of rectifying tower plates is 60 theoretical plates, the byproduct recombinant stream from the butanol device enters 7 plates (from bottom to top) of the rectifying tower, and the gas phase is pumped out from the 18 th plate side line of the rectifying tower to the hydrogenation reactor. Fresh hydrogen, circulating hydrogen and gas phase extracted from the side line of the rectifying tower are mixed and then enter the hydrogenation reactor, and the molar ratio of the hydrogen to the gas phase extracted from the side extraction is 6. The hydrogenation reactor adopts a fixed bed, the reaction temperature of the hydrogenation reactor is 240 ℃, the reaction pressure is 0.7MpaG, the space velocity of the hydrogenation reaction is 0.5h < -1 >, and the hydrogenation reactor is filled with a palladium-carbon catalyst. And removing 30 plates of the rectifying tower from the gas phase at the outlet of the hydrogenation reactor, and steaming butanol and water generated by hydrogenation reaction to the gas phase at the top of the tower. The gas phase at the top of the rectifying tower is condensed by a circulating water cooler, then gas-liquid two phases enter the coalescer, the liquid phase returns to a compartment before the coalescer after the non-condensable gas phase is deeply cooled by chilled water, the gas phase returns to the hydrogenation reactor after being compressed by the hydrogen compressor, and in order to avoid the accumulation of impurities in the circulating gas, one gas phase is discharged, and the mass ratio of the external exhaust phasor to the circulating gas is 0.1%. The coalescer internals adopt silk screen internals, the dwell time is 60min, the coalescer separates oil phase and aqueous phase, and the aqueous phase is sent to wastewater system, the reflux ratio of rectifying column is 1.
In contrast, comparative examples 1 to 4, which employ the structure shown in fig. 2 and the process flow, are as follows:
comparative example 1
According to the process flow connection device shown in FIG. 1, the byproduct of the butyraldehyde unit is produced from the carbonylation reaction and butyraldehyde hydrogenation reaction, and contains 5-15% of butyraldehyde, 0.5-1% of butyric acid, 5-8% of butanol, 1-5% of butyraldehyde dimer, 40-60% of butyrates, and 10-20% of octacosanol and dodecanol.
The rectifying tower is operated under positive pressure, the pressure is 1.0MPaG, the number of rectifying tower plates is 50 theoretical plates, the by-product recombinant stream from the butanol device enters 9 plates (from bottom to top) of the rectifying tower, and the gas phase is pumped out of the 16 th plate side line of the rectifying tower to remove the hydrogenation reactor. Fresh hydrogen, circulating hydrogen and gas phase extracted from side line of rectifying tower are mixed and fed into hydrogenation reactor, and the mole ratio of hydrogen and gas phase extracted from side extraction is 10. The hydrogenation reactor adopts a fixed bed, the reaction temperature of the hydrogenation reactor is 230 ℃, the reaction pressure is 0.8MpaG, the space velocity of the hydrogenation reaction is 1h < -1 >, and the hydrogenation reactor is filled with a copper catalyst. And (3) removing 20 plates of the rectifying tower from the gas phase at the outlet of the hydrogenation reactor, and steaming butanol and water generated by hydrogenation reaction to the gas phase at the top of the tower. The gas phase at the top of the rectifying tower is condensed by a circulating water cooler, then the gas-liquid two phases enter a coalescer, the non-condensable gas phase is subjected to cryogenic cooling by chilled water, then the liquid phase returns to a compartment in front of the coalescer, the gas phase is compressed by a compressor and returns to a hydrogenation reactor, a gas phase is discharged outside to avoid the accumulation of impurities in the circulating gas, and the mass ratio of the discharged gas phase to the circulating gas is 4.3%. The coalescer internals are silk screen internals, the residence time is 30min, the coalescer separates oil phase and water phase, the water phase is sent to a wastewater system, and the reflux ratio of the rectifying tower is 1.
Comparative example 2
According to the process flow connection device shown in FIG. 1, the byproduct of the butyraldehyde unit is produced from the carbonylation reaction and butyraldehyde hydrogenation reaction, and contains 5-15% of butyraldehyde, 0.5-1% of butyric acid, 5-8% of butanol, 1-5% of butyraldehyde dimer, 40-60% of butyrates, and 10-20% of octacosanol and dodecanol.
The rectifying tower is operated at positive pressure, the pressure is 0.8MPaG, the number of rectifying tower plates is 50 theoretical plates, the by-product recombinant stream from the butanol device enters 7 plates (from bottom to top) of the rectifying tower, and the gas phase is pumped out of the 18 th plate side line of the rectifying tower to remove the hydrogenation reactor. Fresh hydrogen, circulating hydrogen and gas phase extracted from side line of rectifying tower are mixed and fed into hydrogenation reactor, and the mole ratio of hydrogen and gas phase extracted from side extraction is 12. The hydrogenation reactor adopts a fixed bed, the reaction temperature of the hydrogenation reactor is 250 ℃, the reaction pressure is 0.8MpaG, the space velocity of the hydrogenation reaction is 1h < -1 >, and the hydrogenation reactor is filled with a nickel catalyst. And (3) removing 20 plates of the rectifying tower from the gas phase at the outlet of the hydrogenation reactor, and steaming butanol and water generated by hydrogenation reaction to the gas phase at the top of the tower. The gas phase at the top of the rectifying tower is condensed by a circulating water cooler, then the gas-liquid two phases enter a coalescer, the non-condensable gas phase is subjected to cryogenic cooling by chilled water, then the liquid phase returns to a compartment in front of the coalescer, the gas phase is compressed by a compressor and returns to a hydrogenation reactor, a gas phase is discharged outside to avoid the accumulation of impurities in the circulating gas, and the mass ratio of the discharged gas phase to the circulating gas is 4.5%. The coalescer internals are silk screen internals, the residence time is 30min, the coalescer separates oil phase and water phase, the water phase is sent to a wastewater system, and the reflux ratio of the rectifying tower is 1.
Comparative example 3
According to the process flow connection device shown in FIG. 1, the byproduct of the butyraldehyde unit is produced from the carbonylation reaction and butyraldehyde hydrogenation reaction, and contains 5-15% of butyraldehyde, 0.5-1% of butyric acid, 5-8% of butanol, 1-5% of butyraldehyde dimer, 40-60% of butyrates, and 10-20% of octacosanol and dodecanol.
The rectifying tower is operated at positive pressure, the pressure is 0.6MPaG, the number of rectifying tower plates is 50 theoretical plates, the by-product recombinant stream from the butanol device enters 10 plates (from bottom to top) of the rectifying tower, and the gas phase is pumped out of the 18 th plate side line of the rectifying tower to remove the hydrogenation reactor. Fresh hydrogen, circulating hydrogen and gas phase extracted from side line of rectifying tower are mixed and fed into hydrogenation reactor, and the mole ratio of hydrogen and gas phase extracted from side extraction is 8. The hydrogenation reactor adopts a fixed bed, the reaction temperature of the hydrogenation reactor is 230 ℃, the reaction pressure is 0.7MpaG, the space velocity of the hydrogenation reaction is 1h < -1 >, and the hydrogenation reactor is filled with a copper-based catalyst. And (3) removing 20 plates of the rectifying tower from the gas phase at the outlet of the hydrogenation reactor, and steaming butanol and water generated by hydrogenation reaction to the gas phase at the top of the tower. The gas phase at the top of the rectifying tower is condensed by a circulating water cooler, then the gas-liquid two phases enter a coalescer, the non-condensable gas phase is subjected to cryogenic cooling by chilled water, then the liquid phase returns to a compartment in front of the coalescer, the gas phase is compressed by a compressor and then returns to a hydrogenation reactor, in order to avoid the accumulation of impurities in the circulating gas, one gas phase is discharged, and the quantity of the discharged gas phase accounts for 5% of the mass ratio of the circulating gas. The coalescer internals are silk screen internals, the residence time is 60min, the coalescer separates oil phase and water phase, the water phase is sent to a wastewater system, and the reflux ratio of a rectifying tower is 2.
Comparative example 4
According to the process flow connecting device shown in the figure 1, the byproduct of the butyraldehyde device is produced from the carbonylation reaction and butyraldehyde hydrogenation reaction process, and contains 5-15% of butyraldehyde, 0.5-1% of butyric acid, 5-8% of butanol, 1-5% of butyraldehyde dimer, 40-60% of butyrates, and 10-20% of octacosanol and dodecanol. The heavy component is sent to a buffer tank, is conveyed to a feeding pipeline through a pump, is mixed with hydrogen and then enters a hydrogenation reactor, the reaction temperature is 280 ℃, the molar ratio of the hydrogen to the heavy component is 8, the airspeed is 2h < -1 >, the material after hydrogenation is sent to a degassing tank, the pressure of the degassing tank is 50kpa G, the top gas phase returns to a butanol device to recycle the hydrogen, the bottom is collected to obtain a butanol product tower, the butanol product tower 35 theoretical plate has the pressure of 0.8MPaG, the liquid phase of the gas phase at the top of the tower is totally refluxed after being condensed, the reflux ratio is 3, and the noncondensable gas phase is sent to a waste gas pipe network. Butanol products are extracted from the 28 th tower plate of the rectifying tower, heavy components are extracted from the tower bottom, and the residual butanol content in the heavy components is 10%.
Further by way of comparison, the conversion of the hydrogenation reaction, as well as the butanol yield, the hydrogen consumption in the examples and comparative examples, were evaluated in comparison with the operating cycles of the examples and comparative examples (based on 80% reduction in butanol yield) as follows:
Figure BDA0004161611650000101
therefore, the byproduct heavy component treatment system of the butanol device has the following effects: the process flow is short, the equipment investment is low, and the investment and the occupied area of the device are small; the process flow is reasonable, the heavy component is subjected to gas phase hydrogenation treatment after rectification, the heavy component is not fed into the reactor, and the service life of the catalyst is long; returning the reacted product to the rectifying tower, separating butanol and water at the tower top, extracting butanol at the tower top, discharging heavy components outside the rectifying tower kettle, and avoiding accumulation of the heavy components in the system; the traditional hydrogenation reaction feeding needs heating, the reaction liquid needs cooling after hydrogenation to cause energy waste, and the byproduct recombination treatment system of the butanol device adopts gas phase extraction of a rectifying tower to directly enter a reactor, the gas phase after hydrogenation returns to the rectifying tower, and the heat is fully utilized in the rectifying tower, so that the steam in the tower kettle can be saved, and the energy consumption of the whole system is reduced; the oil-water phase of the reaction liquid after hydrogenation is separated by the coalescer at the top of the tower after rectification, so that the water phase is prevented from entering the butanol product to influence the quality of the butanol product, and meanwhile, the gas phase at the top of the tower is recycled to the reactor through the compressor, so that the hydrogen is saved, and the economy is improved.
According to another aspect of the invention, the embodiment of the byproduct heavy component treatment system of the butanol device is provided, wherein heavy components from the butanol device are fed into a rectifying tower, the carbon octal, the carbon dodecanol and heavy components containing metals are removed from the tower bottom, a gas phase stream containing butyl butyrate, butyric acid, butyraldehyde and butyraldehyde dimer is extracted from the middle lower part of the tower, mixed with fresh hydrogen and circulating gas and fed into a hydrogenation reactor, a gas phase stream at a reaction outlet is returned to the middle part of the rectifying tower, a gas phase at the top of the rectifying tower is condensed by a condenser and fed into a coalescer, a separated gas phase is condensed by a cryogenic condenser and fed back to the coalescer, and a gas phase is fed back to the hydrogenation reactor by a hydrogen compressor, so as to prevent light components in the circulating gas from accumulating a small amount, the condensed liquid phase is subjected to oil-water phase separation in the coalescer, a water phase is removed from the wastewater system, and a part of the oil phase is returned to the tower, and a part of the oil phase is fed out to produce butanol product.
Specifically, the recovery method of the byproduct heavy component treatment system of the butanol device comprises the following steps:
s100: the heavy components of the byproduct of the butanol device are fed into the middle lower part of a rectifying tower, the heavy components such as the octacosanol, the dodecandiol, the metal ions and the like are separated by the rectifying tower, and a gas phase is extracted from the middle lower part of the rectifying tower, wherein the gas phase mainly contains butyl butyrate, butyraldehyde polymer, butyric acid and the like;
s200: the gas phase extracted from the rectifying tower is mixed with fresh hydrogen and recycle gas and then enters a hydrogenation reactor, the flow is selectively hydrogenated into butanol and water, and a hydrogenation catalyst is filled in the fixed bed reactor;
s300: returning the reaction product after the reaction to a rectifying tower, and separating butanol and water to the top of the rectifying tower;
s400: the gas phase at the top of the rectifying tower enters a coalescer after first-stage condensation, the non-condensable gas phase in the coalescer is subjected to deep cooling, the liquid phase returns to the coalescer, the gas phase returns to the hydrogenation reactor after being compressed by a compressor, and a circulating gas is discharged outside to avoid impurity accumulation;
s500: the coalescer realizes oil-water separation of the condensed liquid phase, a part of the oil phase returns to the rectifying tower for reflux, a part of the oil phase is removed to the butanol product tower for purifying butanol product, and the water phase is discharged to the wastewater system.
In the step S100, the recombinant component separated by the rectifying tower includes octacosanol, dodecanol and metal ions, wherein the metal ions include rhodium catalyst and corrosion metal, and the gas phase extracted from the middle lower part of the rectifying tower includes butyl butyrate, butyraldehyde polymer and butyric acid.
It is worth mentioning that heavy components of the butanol device are separated through a rectifying tower, an outlet gas phase flow is extracted from the middle part of the rectifying tower, butanol is mainly generated by hydrogenation under palladium/carbon catalyst which is mainly enriched with aldehyde, acid and ester, butanol can be recovered with high selectivity by adopting gas phase hydrogenation, no heavy components are in hydrogenation gas phase feeding, the service life of the catalyst is long, the product quality is stable, long-period stable operation of the device is ensured, the discharged heavy components of the device are reduced, the unit consumption of butyraldehyde is reduced, and the economical efficiency of the device is greatly improved.
Corresponding to the embodiment of the byproduct heavy component treatment system of the butanol device, the recycling method of the byproduct heavy component treatment system of the butanol device has good technical effects on butyraldehyde conversion rate, butyric acid conversion rate, butyl butyrate conversion rate, butanol recovery rate, hydrogen loss and operation period.
In the recycling method of the byproduct heavy component treatment system of the butanol device, the byproduct heavy component of the butyraldehyde device is generated from the carbonylation reaction and butyraldehyde hydrogenation reaction process and contains 5-15% of butyraldehyde, 0.5-1% of butyric acid, 5-8% of butanol, 1-5% of butyraldehyde dimer, 40-60% of butyrates, and 10-20% of octacarbon alcohol and dodecacarbon or more.
Preferably, the rectifying tower is operated at positive pressure, the pressure is 0.1-2.0 MPaG, and the number of rectifying tower plates is 35-80 theoretical plates; preferably, the byproduct recombinant stream from the butanol device enters the position of 5-10 plates (from bottom to top) of the rectifying tower, and the gas phase hydrogenation reactor is extracted from the 15 th-18 th plate side line of the rectifying tower; preferably, the fresh hydrogen, the recycle gas and the gas phase extracted from the side line of the rectifying tower are mixed and then enter the hydrogenation reactor, wherein the molar ratio of the hydrogen to the gas phase extracted from the side extraction is 6-15, more preferably, the molar ratio is 8-10; preferably, the hydrogenation reactor adopts a fixed bed, the reaction temperature of the hydrogenation reactor is 160-250 ℃, more preferably, the reaction temperature is 180-230 ℃, the reaction pressure is 0.5-1 MpaG, and the space velocity of the hydrogenation reaction is 0.5-3 h -1 Preferably 1 to 1.5h -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, one or more of nickel-based catalyst, copper-based catalyst and palladium-based catalyst are filled in the hydrogenation reactor, preferably palladium-carbon catalyst is adopted, and the reaction temperature is low, the impurities are few, the selectivity is high, and the butyl alcohol and the water are generated by the reaction; preferably, the gas phase at the outlet of the hydrogenation reactor is distilled to the gas phase at the top of a rectifying tower by 20-30 plates; preferably, after the gas phase at the top of the rectifying tower is condensed by a circulating water cooler, the gas-liquid two phases enter a coalescer, the liquid phase returns to a compartment in front of the coalescer after the non-condensable gas phase is deeply cooled by chilled water, the gas phase returns to a hydrogenation reactor after being compressed by a compressor, and in order to avoid the accumulation of impurities in the circulating gas, one gas phase is discharged, and the mass ratio of the external exhaust phasor to the circulating gas is 0.01-1%, so that the hydrogen can be saved; preferably, the inner parts of the coalescers are made of silk screens and or metal folded plates, the retention time of the coalescers is 30-60 min, the coalescers separate oil phase and water phase, and the water phase is sent to a wastewater system; preferably, a portion of the oil phase in the coalescer is returned to the rectifying column and a portion of the butanol product is withdrawn, the reflux ratio of the rectifying column being in the range of 0.5 to 5, more preferably, the reflux ratio being in the range of 1 to 3.
Therefore, the recycling method of the byproduct heavy component treatment system of the butanol device can reduce the material consumption of the butanol device, has high butanol yield compared with other methods, has short process flow, saves equipment investment and occupied area of the device, and greatly improves the economy of the butanol device.
It will be appreciated by persons skilled in the art that the embodiments of the invention described above and shown in the drawings are by way of example only and are not limiting. The objects of the present invention have been fully and effectively achieved. The functional and structural principles of the present invention have been shown and described in the examples and embodiments of the invention may be modified or practiced without departing from such principles.

Claims (11)

1. The recovery method of the byproduct heavy component treatment system of the butanol device is characterized by comprising the following steps of:
heavy components of the byproduct of the butanol device enter the middle lower part of a rectifying tower, the heavy components are separated by the rectifying tower, and a gas phase is extracted from the middle lower part of the rectifying tower;
the gas phase extracted from the rectifying tower is mixed with fresh hydrogen and recycle gas and then enters a hydrogenation reactor, the flow is selectively hydrogenated into butanol and water, and a hydrogenation catalyst is filled in the fixed bed reactor;
returning the reaction product after the reaction to a rectifying tower, and separating butanol and water to the top of the rectifying tower;
the gas phase at the top of the rectifying tower enters a coalescer after first-stage condensation, the non-condensable gas phase in the coalescer is subjected to deep cooling, the liquid phase returns to the coalescer, the gas phase returns to the hydrogenation reactor after being compressed by a compressor, and a circulating gas is discharged outside; and
the coalescer realizes oil-water separation of the condensed liquid phase, one part of the oil phase returns to the rectifying tower for reflux, the other part enters the butanol product tower of the device for purifying butanol product, and the water phase is discharged to the wastewater system.
2. The method for recovering a byproduct heavy component processing system in a butanol apparatus according to claim 1, wherein the rectifying column is operated at a positive pressure of 0.1 to 2.0MPaG and the number of rectifying trays is 35 to 80 theoretical plates.
3. The method for recovering a byproduct heavy component processing system in a butanol plant according to claim 1, wherein the heavy component stream of the byproduct from the butanol plant enters a position of 5 to 10 theoretical plates from bottom to top in a rectifying column, and the vapor phase hydrogenation reactor is drawn out from the 15 th to 18 th theoretical plates side line of the rectifying column.
4. The recovery method of byproduct heavy component treatment system of butanol apparatus according to claim 1, wherein fresh hydrogen, recycle gas and gas phase extracted from side stream of rectifying tower are mixed and then fed into hydrogenation reactor, molar ratio of hydrogen to gas phase extracted from side stream is 6-15, wherein the hydrogenation reactor adopts fixed bed, reaction temperature of hydrogenation reactor is 160-250 ℃, reaction pressure is 0.5-1 MpaG, space velocity of hydrogenation reaction is 0.5-3 h -1 。
5. The method for recovering a byproduct heavy component processing system in a butanol plant according to claim 1, wherein the butanol and water produced by the hydrogenation reaction are distilled to the top gas phase by removing 20 to 30 theoretical plates from the gas phase at the outlet of the hydrogenation reactor.
6. The recovery method of byproduct heavy component treatment system of butanol device according to claim 1, wherein after the gas phase at the top of the rectifying tower is condensed by a circulating water cooler, the gas-liquid two phases enter a coalescer, the non-condensable gas phase is returned to a front compartment of the coalescer after the chilled water is deeply cooled, the gas phase is returned to the hydrogenation reactor after being compressed by a compressor, one gas phase is discharged outside, and the external exhaust phasor accounts for 0.01-1% of the mass ratio of the circulating gas.
7. The method for recovering a byproduct heavies processing system from a butanol plant as claimed in claim 1, wherein the coalescer internals are wire mesh and/or metal flaps, the coalescer residence time is 30-60 min, the coalescer separates oil phase and water phase, and the water phase is sent to a wastewater system.
8. The method for recovering a byproduct heavy component processing system in a butanol apparatus according to claim 1, wherein a part of the oil phase in the coalescer is returned to the rectifying tower, and the butanol product is produced from the other part, and the reflux ratio of the rectifying tower is 0.5 to 5.
9. The method for recovering a byproduct heavy component treatment system for a butanol plant according to any one of claims 1 to 8, wherein the heavy component by-produced by the butyraldehyde plant is produced during the carbonylation reaction and butyraldehyde hydrogenation reaction, and comprises 5 to 15% of butyraldehyde, 0.5 to 1% of butyric acid, 5 to 8% of butanol, 1 to 5% of butyraldehyde dimer, 40 to 60% of butyrates, 10 to 20% of octacosanol and dodecandiol and above.
10. The method for recovering a byproduct heavies processing system from a butanol plant according to any one of claims 1 to 8, wherein the heavies separated by the rectifying column comprise octacosanol, dodecanol, metal ions, wherein the metal ions comprise rhodium catalyst and corrosion metal, and the gas phase withdrawn from the middle lower part of the rectifying column comprises butyl butyrate, butyraldehyde polymer, butyric acid; wherein the hydrogenation reactor is filled with one or more of nickel-based catalyst, copper-based catalyst and palladium-based catalyst.
11. A butanol plant byproduct heavy component treatment system characterized by being recovered by the recovery method of the butanol plant byproduct heavy component treatment system according to any one of claims 1 to 10, wherein the butanol plant byproduct heavy component treatment system comprises a rectifying tower, a hydrogenation reactor, a hydrogen compressor, a cooler, a coalescer and a condenser, a heavy component pipeline from the butanol plant byproduct enters the lower part of the rectifying tower, a gas phase extracted from the side of the rectifying tower enters the hydrogenation reactor, meanwhile, fresh hydrogen and compressed gas from the hydrogen compressor enter the hydrogenation reactor, an outlet pipeline of the hydrogenation reactor is connected with the rectifying tower, a gas phase pipeline at the top of the rectifying tower is connected with the cooler, condensed material is connected with the coalescer, a non-condensable gas phase at the top of the coalescer is connected with the condenser, a deep-cooled stream returns to the coalescer, a gas phase returns to the hydrogenation compressor, a part of an oil phase of the coalescer returns to the rectifying tower, and a part of an aqueous phase of the butanol product enters the wastewater of the rectifying tower.
CN202310351251.3A 2023-04-03 2023-04-03 Byproduct heavy component treatment system and recovery method for butanol device Pending CN116392834A (en)

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