CN105924329A - Coupling production process for preparing alcohol through acetic acid - Google Patents
Coupling production process for preparing alcohol through acetic acid Download PDFInfo
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- CN105924329A CN105924329A CN201610353795.3A CN201610353795A CN105924329A CN 105924329 A CN105924329 A CN 105924329A CN 201610353795 A CN201610353795 A CN 201610353795A CN 105924329 A CN105924329 A CN 105924329A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a coupling production process for preparing alcohol through acetic acid. Acetic acid and/or acetate serve as reaction raw materials to prepare high-purity alcohol, and the coupling production process comprises three sections of acetic acid hydrogenation, acetate hydrogenation and crude product purification. In the section of acetic acid hydrogenation, acetic acid and hydrogen serve as raw materials to prepare alcohol; in the section of acetate hydrogenation, acetate and hydrogen-rich tail gas from the section of acetic acid hydrogenation serve as raw materials to prepare alcohol; crude alcohol is subjected to the section of crude product purification, and then high-purity alcohol is obtained. Continuous production is carried out, hydrogen is subjected to deep reaction, the raw materials have higher conversion rate and yield, operation continuity and stability are very high, and in the same scale capacity, investment is greatly reduced; moreover, the reaction tail gas and the reaction heat are reasonably recycled and used, high-quality steam can be by-produced, the additional value is increased for a factory, and the requirement of cleaner production is met well.
Description
Technical field
The present invention relates to acetic acid and prepare the coupling production technology of ethanol, belong to technical field of chemical synthesis.
Background technology
Ethanol be find the earliest, a kind of fatty alcohol that purposes is the widest, be also the main component of wine.Under room temperature, ethanol is colourless, volatile, inflammable liquid.Ethanol of many uses, such as can be used to produce the multiple industrial chemicals such as acetaldehyde, ether, ethyl acetate, ethamine, oxirane, be all widely used at multiple fields such as disinfectant, beverage, diluent, environmental protection coating material, pesticide, medicine, rubber, plastics, staple fibre, detergents.
At present the process route of alcohol fuel mainly has two kinds of forms: (one) is with grain and cellulose for raw material microbial fermentation technology ethanol；(2) acetic acid hydrogenation chemistry method prepares ethanol.
(1) fermentation method prepares ethanol
Being raw material with the grain such as Semen Maydis, Semen Tritici aestivi, the alcohol fuel using traditional fermentation method manufacture is first generation alcohol fuel.Being raw material with industrial crops such as Maninot esculenta crantz., Caulis Sacchari sinensis, sweet Sorghum vulgare Pers., Radix Ipomoeae, the alcohol fuel using traditional fermentation method manufacture is 1.5 Replacing fuel ethanol.
Owing to the production of grain alcohol and non-grain ethanol will take more land, exist and strive the problem of grain with people and animals, and national food security can be affected, the most gradually limited by national governments' relevant policies or forbid.
(2) chemical method prepares ethanol
Chemical method synthesizing alcohol is mainly with coal as raw material, and process route has two kinds: one is producing synthesis gas from coal CO, H2, it is directly synthesized ethanol；Another kind is CO, H2Synthesis acetic acid, acetic acid is the most directly or indirectly hydrogenated with and acetic acid is reduced to ethanol.CO、H2Synthesis gas is directly synthesized ethanol and is limited by technical conditions, and Technology is the most ripe.CO、H2Synthesis gas acetic acid is further converted to ethanol, by the more and more concern of the same industry, tends to ripe.Acetic acid hydrogenation produces ethanol and comprises two kinds of processes: one is that acetic acid direct hydrogenation is reduced to ethanol；Another kind is first esterified repeated hydrogenation for acetic acid and is converted into ethanol.
But, find through productive experiment, the hydracid proportion requirement of acetic acid direct hydrogenation is high, and hydrogen conversion per pass is relatively low, needs bigger circulating load, process cycles needs relatively systemic circulation machine, the power consumption of unit ethanol production significantly raises, and simultaneous reactions temperature requirement is high, and equipment material is harsh, coarse ethanol purity is low, separates costly.Acetic acid first carries out esterification and generates acetate, then acetate and hydrogen is sent into reaction unit and reacts generation ethanol under catalyst action, needs to circulate hydrogen amount and significantly reduce.But acetic acid esterified hydrogenation needs first to experience esterification technique, this technique ethanol is raw material and product, necessarily has the loss of ethanol during process cycles, and in turn resulting in unit ethanol production cost of material increases, Catalyst Conversion and selectivity are low simultaneously, and unit interval production capacity is low.
How to overcome acetic acid hydrogenation, acetate hydrogenation process these problems produced, it is thus achieved that higher conversion ratio and lower energy consumption, be current problem demanding prompt solution.
Summary of the invention
For solving the problems referred to above that prior art exists, it is an object of the invention to provide acetic acid and prepare the coupling production technology of ethanol, it is achieved that Dichlorodiphenyl Acetate hydrogenation, the coupling of acetate hydrogenation utilize, and improve feed stock conversion, reduce energy consumption.
For achieving the above object, the technical solution adopted in the present invention is:
The coupling production technology of ethanol prepared by a kind of acetic acid, with acetic acid and/or acetate as reaction raw materials, purifies three workshop sections including acetic acid hydrogenation, acetate hydrogenation and crude product.
Concretely comprising the following steps of described coupling production technology:
A, acetic acid are hydrogenated with
Acetic acid and hydrogen enter vaporization mixing in vapourizing unit I after preheating respectively, be then fed into the bottom of reactor I, and reaction mixture gas flows up, and through hydrogenation catalyst bed, the generation catalytic hydrogenation reaction of reactor I, generate ethanol；Product enter gas-liquid separator separate, liquid coarse ethanol be sent directly into crude product purify workshop section purify；Hydrogen rich off gas is sent into acetate as reaction raw materials and is hydrogenated with workshop section；
B, acetate are hydrogenated with
Acetate and the hydrogen rich off gas from workshop section A enter vaporization mixing in vapourizing unit II after preheating respectively, be then fed into the bottom of reactor II, and reaction mixture gas flows up, and through hydrogenation catalyst bed, the generation catalytic hydrogenation reaction of reactor II, generate ethanol；Product enter gas-liquid separator separate, liquid coarse ethanol be sent directly into crude product purify workshop section purify；Secondary tail gas through recycle compressor group compress after, all as raw material send back to acetic acid be hydrogenated with workshop section；
C, crude product purify
After the coarse ethanol mixing of workshop section A and workshop section B, after gas-liquid separation, rectification and purification, it is thus achieved that high purity ethanol.
In described workshop section A,
Vaporizing mixed reactor feed gas and initially enter heat-exchange unit I, using high-temperature reaction product as thermal source, realize further heating up reactor feed gas, the reaction raw materials temperature after heat exchange reaches the temperature requirement of catalytic hydrogenation reaction；
A hydrogen rich off gas part send into acetate hydrogenation workshop section as esterification hydrogenation raw material, another part through recycle compressor group compress after send hydrogen delivery tube road back to, in this workshop section in circulate；
Described reactor I is fixed bed isothermal reactor；Hydrogenation catalyst is Supported Pt Nanoparticles/silver catalyst, and reaction pressure is 2.5～4.5MPa, and reaction temperature is 280～350 DEG C.
In described workshop section B,
Vaporizing mixed reactor feed gas and initially enter heat-exchange unit II, using high-temperature reaction product as thermal source, realize further heating up reactor feed gas, the reaction raw materials temperature after heat exchange reaches the temperature requirement of catalytic hydrogenation reaction；
Described reactor II is isothermal reactor, is inside provided for reclaiming the cooling coil of reaction heat, and cooling coil connects drum；Deoxygenated water absorbs reaction heat, byproduct steam by cooling coil tube wall；
Described hydrogenation catalyst is loaded copper oxide catalyst, and reaction temperature is 220～280 DEG C, and reaction pressure is 2.0～3.0MPa；
Described recycle compressor group includes primary cycle compressor and secondary cycle compressor；The part hydrogen rich off gas of workshop section A, workshop section B whole secondary tail gas all through primary cycle compressor, secondary cycle compressor two stages of compression, pressure is sent back in workshop section A after reaching 3.0～4.0MPa again.
Described workshop section C concretely comprises the following steps: coarse ethanol first passes through the further solid-liquid separation of two-stage gas-liquid separator, then after lightness-removing column, weight-removing column rectification and purification, obtains high purity ethanol；The isolated tail gas of described two-stage gas-liquid separator institute returns workshop section A circulation after recycle compressor group is pressurizeed.
The invention has the beneficial effects as follows:
The invention provides a kind of acetic acid and prepare the coupling production technology of ethanol, purify three workshop sections by acetic acid hydrogenation, acetate hydrogenation, crude product, prepare high purity ethanol.This production technology produces continuously, makes hydrogen obtain deep reaction, and hydracid ratio can control within 60, and it is the highest that raw material has higher conversion ratio and yield, continuity of operation and stability, and the investment of same size production capacity is greatly lowered；And reaction end gas and reaction heat have all been carried out rational recycling, acetic acid is hydrogenated with the hydrogen rich off gas of workshop section's generation and is hydrogenated with the raw material use of workshop section directly as acetate, acetate hydrogenation workshop section produce secondary tail gas send back to after compression acetic acid hydrogenation workshop section reaction, whole tail gas are all recycled, outer row, in reaction unit, constantly circulation, conversion ratio significantly improve raw material, and discharge amount of exhaust gas is the least, and energy by-product high-quality steam simultaneously, increase factory's added value, meet very much the requirement that cleaning produces.Liang Ge workshop section is coupled by the present invention, makes reaction raw materials fully be reacted, and the conversion per pass of acetic acid is up to more than 99%, and it is high that ethanol selectivity is up to more than 97% hydrogen utilization ratio.The present invention uses thermal coupled process, effect by heat-exchange unit, compression Cycle Unit etc., the system heat of making is fully utilized, after stable operation heat of reaction reclaim to greatest extent, the heat of external demand the lowest, the consumption of cold is also preferably minimized, the energy consumption of whole reaction unit significantly reduces, and relatively common process energy consumption reduces by more than 25%.
Present invention process is reasonable, consersion unit is conventional, device is flexible and changeable.Acetic acid is hydrogenated with workshop section, acetate is hydrogenated with between workshop section and connects each other and independent of one another.The two workshop section purifies workshop section with crude product respectively and is connected, and can form the preparation system of complete set.When extensive high-volume produces ethanol continuously, acetic acid is hydrogenated with workshop section, the coupling of acetate hydrogenation workshop section uses, it is possible to significantly improve raw material availability, reduce energy consumption and cost.If alcohol production amount is little or only single batch reaction time, whole plant running can bring the biggest energy resource consumption, material can be lost through each equipment, and the cleaning amount of multiple consersion unit is the biggest, at this moment can only select acetic acid hydrogenation workshop section or acetate to be hydrogenated with workshop section, cooperation crude product purifies workshop section and carrys out synthesizing alcohol, reduces the energy consumption of single batch reaction.
A hydrogen rich off gas part for acetic acid hydrogenation workshop section enters acetate hydrogenation workshop section as raw material, and a part directly sends the hydrogen delivery tube road of acetic acid hydrogenation workshop section after compression back to, all realizes circulation hydrogenation reaction；Acetate hydrogenation workshop section secondary tail gas compressed Cycle Unit compression, return to acetic acid hydrogenation workshop section use as part material.Whole reaction system does not has outside waste gas to arrange, and reaction raw materials constantly circulates in device, deep reaction；Compression Cycle Unit makes the pressure of tail gas and heat obtain rational recycling, increases the unstripped gas temperature entering acetic acid hydrogenation unit, reduces the energy input of vapourizing unit, and gas circulating load is little, compresses the low in energy consumption of Cycle Unit, and service life is long.
Described reactor I is fixed bed isothermal reactor, it is possible to keeps the reaction bed temperature in reactor I, improve catalytic reaction efficiency.Described reactor II is provided with the coil pipe for reclaiming reaction heat, in one side beneficially holding reactor II, reaction bed temperature is constant, it is easy to technology controlling and process, ensure stablizing of course of reaction and product quality, on the other hand can simultaneously a large amount of pressure of by-product reach 2.1～13.1MPa high-grade steam, provide thermal source for other workshop section of factory.The reaction temperature of reactor I, reaction pressure are above the reaction temperature of reactor II, reaction pressure, reactor I coarse ethanol discharged still can reach the reaction requirement of reactor II after heat exchange, it is not necessary to the most additionally heats.
Acetic acid is hydrogenated with workshop section, acetate is hydrogenated with the coarse ethanol purity height obtained by workshop section, thus reducing the difficulty of purifying crude, purification step is few, equipment investment is low, and coarse ethanol has higher temperature, enter crude product to purify after workshop section without preheating again, reduce energy consumption.The two-stage gas-liquid separator of coarse ethanol process is the silk screen gas-liquid separator of isothermal and isobaric, and separating rate is fast, good separating effect；On the one hand improve the purity of coarse ethanol, reduce follow-up rectification difficulty, reduce separating-purifying cost；On the other hand, after the compressed pressurization of tail gas that gas-liquid separator separates goes out, return acetic acid hydrogenation workshop section recycles, the kinetic energy consumption circulated in reducing system, it is ensured that stablizing that hydrogen recycles is carried out.
Accompanying drawing explanation
Fig. 1 is reaction unit schematic diagram of the present invention；
Wherein, 11, acetic acid conveyance conduit, 12, preheating device I A, 13, hydrogen delivery tube road, 14, preheating device I B, 15, vapourizing unit I, 16, reactor I, 17, gas-liquid separator I, 18, heat-exchange unit I, 21, acetate conveyance conduit, 22, preheating device II A, 23, preheating device II B, 24, vapourizing unit II, 25, reactor II, 26, gas-liquid separator II, 27, heat-exchange unit II, 28, drum, 3, crude product purifies workshop section, and 4, primary cycle compressor, 5, secondary cycle compressor；
The traffic direction of direction of arrow instruction material in figure.
Detailed description of the invention
Below by specific embodiment, the present invention is described in further detail, but embodiment is not the restriction of scope.
The coupling production technology of ethanol prepared by a kind of acetic acid, with acetic acid and acetate as reaction raw materials, purifies three workshop sections including acetic acid hydrogenation, acetate hydrogenation and crude product.Reaction unit used in the present invention, as it is shown in figure 1, include acetic acid hydrogenation workshop section, acetate hydrogenation workshop section, rectification and purification workshop section and compression Cycle Unit.Wherein, acetic acid hydrogenation workshop section and acetate are hydrogenated with workshop section and are used for synthesizing coarse ethanol, and rectification and purification workshop section for carrying out refined purification to coarse ethanol, and compression Cycle Unit is used for reaction end gas carrying out pressurization coupling, re-using.
Described acetic acid is hydrogenated with workshop section and includes preheating device I A12, preheating device I B14, vapourizing unit I 15, heat-exchange unit I 18, reactor I 16 and gas-liquid separator I 17.Wherein, preheating device I A12, preheating device I B14 are for being arranged in parallel, for preheating two kinds of raw materials respectively；Vapourizing unit I 15 is used for making two bursts of feed vaporization mix homogeneously；Heat-exchange unit I 18 is for reclaiming reaction gas waste heat, heating up the material mixed gas entering reactor II；Reactor I 16 is for realizing the catalytic hydrogenation of acetic acid, generating ethanol；Gas-liquid separator I 17, for product is carried out gas-liquid separation, extracts coarse ethanol.The concrete annexation of each equipment of acetic acid hydrogenation workshop section is:
The entrance of described preheating device I A12 connects acetic acid conveyance conduit 11, the charging aperture of its outlet to vapourizing unit I 15.The entrance of described preheating device I B14 connects hydrogen delivery tube road 13, the charging aperture of its outlet to vapourizing unit I 15.The tube-side inlet of the outlet heat-exchange unit I 18 of vapourizing unit I 15, the bottom feed mouth of the tube side outlet coupled reaction device I 16 of heat-exchange unit I 18.The top discharge mouth of reactor I 16 is connected with the shell side inlet of heat-exchange unit I 18, and the shell-side outlet of heat-exchange unit I 18 is communicated to the top entry of gas-liquid separator I 17.The liquid outlet opening of gas-liquid separator is communicated to rectification and purification workshop section 3, its upper air vent institute's connecting leg road has Liang Ge branch, first lateral be directly communicated to preheating device II 23 hydrogen rich off gas is sent into acetate hydrogenation workshop section as unstripped gas, the second lateral is communicated to primary cycle compressor 4.
Described acetate is hydrogenated with workshop section and includes preheating device II A22, preheating device II B23, vapourizing unit II 24, heat-exchange unit II 27, reactor II 25 and gas-liquid separator II 26.Wherein, preheating device II A22, preheating device II B23 are for being arranged in parallel, for preheating two kinds of raw materials respectively；Vapourizing unit II 24 is used for making two bursts of feed vaporization mix homogeneously；Heat-exchange unit II 27 is for reclaiming reaction gas waste heat, heating up the material mixed gas entering reactor II；Reactor II 25 is for realizing the catalytic hydrogenation of acetate, generating ethanol；Gas-liquid separator II 26, for product is carried out gas-liquid separation, extracts coarse ethanol.The concrete annexation of each equipment of acetate hydrogenation workshop section is:
The entrance of described preheating device II A22 connects acetate conveyance conduit 21, the charging aperture of its outlet to vapourizing unit II 24.The entrance of described preheating device II B23 connects the air vent of gas-liquid separator I 17, the i.e. hydrogen rich off gas of acetic acid hydrogenation workshop section and is hydrogenated with the reaction raw materials of workshop section as acetate, and the outlet of preheating device II B23 is also communicated to the charging aperture of vapourizing unit II 24.The discharging opening of described vapourizing unit II 24 through heat-exchange unit II 27 tube side, be connected with the bottom feed mouth of reactor II 25.The top discharge mouth of reactor II 25 connects the shell side of heat-exchange unit II 27, and shell-side outlet is communicated to the entrance of gas-liquid separator II 26；Liquid outlet opening bottom gas-liquid separator II 26 is communicated to rectification and purification workshop section 3, and the air vent on its top is directly communicated to primary cycle compressor 4 through pipeline；The entrance of the outlet secondary cycle compressor 5 of primary cycle compressor 4, the outlet of secondary cycle compressor 5 is to hydrogen delivery tube road 13.
Described reactor I 16 is fixed bed isothermal reactor.Described reactor II 25 is isothermal reactor, is inside provided for reclaiming the cooling coil of reaction heat, and cooling coil connects drum 28, byproduct steam.
Embodiment 1
The coupling production technology of ethanol prepared by a kind of acetic acid, with acetic acid and acetate as reaction raw materials, purifies three workshop sections including acetic acid hydrogenation, acetate hydrogenation and crude product.Concretely comprise the following steps:
A, acetic acid are hydrogenated with
Acetic acid and hydrogen enter vaporization mixing in vapourizing unit I after preheating respectively, send into the bottom of reactor I after heat-exchange unit heats up, and reaction mixture gas flows up, through reactor I hydrogenation catalyst bed, there is catalytic hydrogenation reaction, generate ethanol；Described catalyst is Supported Pt Nanoparticles/silver catalyst, and reaction temperature is 300～320 DEG C, reaction pressure 3.0～4.0MPa.
Product enter gas-liquid separator I separate, liquid coarse ethanol be sent directly into crude product purify workshop section purify；Hydrogen rich off gas is a part of is hydrogenated with workshop section as reaction raw materials feeding acetate, and a part is sent acetic acid after recycle compressor group is compressed back to and is hydrogenated with the hydrogen delivery tube road of workshop section, and the part as hydrogen feed recycles；
B, acetate are hydrogenated with
Ethyl acetate and the hydrogen rich off gas from workshop section A enter vaporization mixing in vapourizing unit II after preheating respectively, it is then fed into the bottom of reactor II, reaction mixture gas flows up, and through hydrogenation catalyst bed, the generation catalytic hydrogenation reaction of reactor II, generates ethanol；Described catalyst is loaded copper oxide catalyst, and reaction temperature is 240～260 DEG C, and reaction pressure is 2.2～2.5MPa.
Product enter gas-liquid separator II separate, liquid coarse ethanol be sent directly into crude product purify workshop section purify；Secondary tail gas is compressed to 3.5～4.0MPa through recycle compressor group, all sends acetic acid back to as raw material and is hydrogenated with workshop section, and the part as hydrogen feed recycles；
C, crude product purify
From workshop section A and workshop section B coarse ethanol mix after, carry out further gas-liquid separation through two-stage gas-liquid separation device, the ethanol crude product that sub-argument goes out through lightness-removing column, weight-removing column rectification and purification after, i.e. obtain mass fraction 99.7～the alcohol fuel of 99.9%.Described lightness-removing column pressure is calculated as 0.08～0.12MPa with gauge pressure, and the tower top pressure of weight-removing column is calculated as 0.38～0.42MPa with gauge pressure.
Embodiment 2
The coupling production technology of ethanol prepared by a kind of acetic acid, with acetic acid and acetate as reaction raw materials, purifies three workshop sections including acetic acid hydrogenation, acetate hydrogenation and crude product.Concretely comprise the following steps:
A, acetic acid are hydrogenated with
Acetic acid and hydrogen enter vaporization mixing in vapourizing unit I after preheating respectively, send into the bottom of reactor I after heat-exchange unit heats up, and reaction mixture gas flows up, through reactor I hydrogenation catalyst bed, there is catalytic hydrogenation reaction, generate ethanol；Described catalyst is Supported Pt Nanoparticles/silver catalyst, and reaction temperature is 320～340 DEG C, reaction pressure 2.5～3.5MPa.
Product enter gas-liquid separator I separate, liquid coarse ethanol be sent directly into crude product purify workshop section purify；Hydrogen rich off gas is a part of is hydrogenated with workshop section as reaction raw materials feeding acetate, and a part is sent acetic acid after recycle compressor group is compressed back to and is hydrogenated with the hydrogen delivery tube road of workshop section, and the part as hydrogen feed recycles；
B, acetate are hydrogenated with
Ethyl acetate and the hydrogen rich off gas from workshop section A enter vaporization mixing in vapourizing unit II after preheating respectively, it is then fed into the bottom of reactor II, reaction mixture gas flows up, and through hydrogenation catalyst bed, the generation catalytic hydrogenation reaction of reactor II, generates ethanol；Described catalyst is loaded copper oxide catalyst, and reaction temperature is 220～250 DEG C, and reaction pressure is 2.0～2.3MPa.
Product enter gas-liquid separator II separate, liquid coarse ethanol be sent directly into crude product purify workshop section purify；Secondary tail gas is compressed to 3.0～3.5MPa through recycle compressor group, all sends acetic acid back to as raw material and is hydrogenated with workshop section, and the part as hydrogen feed recycles；
C, crude product purify
From workshop section A and workshop section B coarse ethanol mix after, carry out further gas-liquid separation through two-stage gas-liquid separation device, the ethanol crude product that sub-argument goes out through lightness-removing column, weight-removing column rectification and purification after, i.e. obtain mass fraction 99.7～the alcohol fuel of 99.9%.Described lightness-removing column pressure is calculated as 0.09～0.13MPa with gauge pressure, and the tower top pressure of weight-removing column is calculated as 0.40～0.43MPa with gauge pressure.
Embodiment 3
The present embodiment is comparative example 1.
The reaction condition of the present embodiment is substantially the same manner as Example 1, and its difference is: only carry out acetic acid hydrogenation workshop section and crude product purifies workshop section；The produced hydrogen rich off gas of acetic acid hydrogenation workshop section is directly entered exhaust treatment system, is not involved in circular response.The parameter that the acetic acid hydrogenation hydrogenation catalyst of workshop section, hydrogenation reaction parameter and crude product purify workshop section is the most same as in Example 1.
Embodiment 4
The present embodiment is comparative example 2.
The reaction condition of the present embodiment is substantially the same manner as Example 1, and its difference is: only carry out acetate hydrogenation workshop section and crude product purifies workshop section；Acetate is hydrogenated with workshop section and is directly entered exhaust treatment system using fresh hydrogen and ethyl acetate as raw material, produced tail gas, is not involved in circular response.The parameter that the acetate hydrogenation hydrogenation catalyst of workshop section, hydrogenation reaction parameter and crude product purify workshop section is the most same as in Example 1.
Embodiment 5
The present embodiment is comparative example 3.
The reaction condition of the present embodiment is substantially the same manner as Example 1, and its difference is: being not provided with compressing Cycle Unit, tail gas produced by reactor I, reactor II is directly entered exhaust treatment system, is not involved in circular response.
After producing after a while, acetic acid conversion per pass, the ethanol selectivity of embodiment 1～embodiment 5 is calculated, and adjust often production electricity spent by one ton of ethanol and 1.6MPa quantity of steam.Result of calculation see table.
Be can be seen that by data in upper table, embodiment 1, the acetic acid conversion per pass of embodiment 2, ethanol selectivity are all significantly higher than comparative example 1～comparative example 3, embodiment 1, the electric consumption of embodiment 2 and steam consumption reduce amplitude and reach more than 25%, energy conservation and consumption reduction effects clearly, highly industrialization promotion.
Above-described embodiment is used for illustrating the present invention rather than limiting the invention, within the scope of the invention as claimed, any modification, equivalent substitution and improvement that the present invention is made, both fall within protection scope of the present invention.
Claims (10)
1. the coupling production technology of ethanol prepared by an acetic acid, it is characterised in that: with acetic acid and/
Or acetate is reaction raw materials, purify three works including acetic acid hydrogenation, acetate hydrogenation and crude product
Section.
The coupling production technology of ethanol prepared by acetic acid the most according to claim 1, and it is special
Levy and concretely comprise the following steps described in being:
A, acetic acid are hydrogenated with
Acetic acid and hydrogen enter vaporization mixing in vapourizing unit I after preheating respectively, be then fed into anti-
Answering the bottom of device I, reaction mixture gas flows up, through the hydrogenation catalyst bed of reactor I
Layer, generation catalytic hydrogenation reaction, generate ethanol；Product enters gas-liquid separator and carries out point
It is sent directly into crude product from, liquid coarse ethanol to purify workshop section and purify；Hydrogen rich off gas is as reaction
Raw material is sent into acetate and is hydrogenated with workshop section；
B, acetate are hydrogenated with
Acetate and the hydrogen rich off gas from workshop section A enter in vapourizing unit II after preheating respectively
Vaporization mixing, is then fed into the bottom of reactor II, and reaction mixture gas flows up, through anti-
Answer the hydrogenation catalyst bed of device II, catalytic hydrogenation reaction occurs, generate ethanol；Product
Enter gas-liquid separator separate, liquid coarse ethanol be sent directly into crude product purify workshop section carry
Pure；Secondary tail gas sends acetic acid hydrogenation work back to after recycle compressor group is compressed, all as raw material
Section；
C, crude product purify
After the coarse ethanol mixing of workshop section A and workshop section B, through gas-liquid separation, rectification and purification
After, it is thus achieved that high purity ethanol.
3. acetic acid as claimed in claim 2 prepares the coupling production technology of ethanol, its feature
It is: in described workshop section A, vaporizes mixed reactor feed gas and initially enter heat-exchange unit I,
Using high-temperature reaction product as thermal source, realize reactor feed gas being further heated up, after heat exchange
Reaction raw materials temperature reach the temperature requirement of catalytic hydrogenation reaction.
4. acetic acid as claimed in claim 3 prepares the coupling production technology of ethanol, its feature
Being: in described workshop section A, a hydrogen rich off gas part is sent into acetate and is hydrogenated with workshop section as esterification
Hydrogenation raw material, another part through recycle compressor group compress after send back to hydrogen delivery tube road,
Circulation in this workshop section.
5. acetic acid as claimed in claim 4 prepares the coupling production technology of ethanol, its feature
It is: described reactor I is fixed bed isothermal reactor；Hydrogenation catalyst is Supported Pt Nanoparticles/silver
Catalyst, reaction pressure is 2.5～4.5MPa, and reaction temperature is 280～350 DEG C.
6. acetic acid as claimed in claim 2 prepares the coupling production technology of ethanol, its feature
It is: described workshop section | in B, vaporize mixed reactor feed gas and initially enter heat-exchange unit
II, using high-temperature reaction product as thermal source, realize reactor feed gas is further heated up, change
Reaction raw materials temperature after heat reaches the temperature requirement of catalytic hydrogenation reaction.
7. acetic acid as claimed in claim 6 prepares the coupling production technology of ethanol, its feature
It is: the reactor II that described workshop section B is used is isothermal reactor, is inside provided for reclaiming
The cooling coil of reaction heat, cooling coil connects drum；Deoxygenated water is inhaled by cooling coil tube wall
Receive reaction heat, byproduct steam.
8. acetic acid as claimed in claim 7 prepares the coupling production technology of ethanol, its feature
Being: in described workshop section B, hydrogenation catalyst is loaded copper oxide catalyst, and reaction temperature is
220～280 DEG C, reaction pressure is 2.0～3.0MPa.
9. acetic acid as claimed in claim 2 prepares the coupling production technology of ethanol, its feature
It is: described recycle compressor group includes primary cycle compressor and secondary cycle compressor；Work
Section the part hydrogen rich off gas of A, workshop section B whole secondary tail gas all through primary cycle compressor,
Secondary cycle compressor two stages of compression, pressure is sent back in workshop section A after reaching 3.0～4.0MPa again.
10. the coupling production technology of ethanol prepared by acetic acid as claimed in claim 9, it is characterised in that
Described workshop section C concretely comprises the following steps: coarse ethanol first passes through the further solid-liquid of two-stage gas-liquid separator
Separate, then after lightness-removing column, weight-removing column crude product purify, obtain high purity ethanol；Described two
The isolated tail gas of level gas-liquid separator institute returns workshop section A after recycle compressor group is pressurizeed and follows
Ring.
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| CN109422623A (en) * | 2017-08-20 | 2019-03-05 | 杭州林达化工技术工程有限公司 | A kind of energy-saving acetic acid adds the production technology and its device of hydrogen or ethyl acetate preparation of ethanol by hydrogenating |
| CN110498732A (en) * | 2018-05-18 | 2019-11-26 | 国家能源投资集团有限责任公司 | The method of acetic acid preparation of ethanol through hydrogenation |
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| CN105924329B (en) | 2018-07-13 |
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