CN107011118A - The technique that a kind of methanol prepares and refines ethanol - Google Patents
The technique that a kind of methanol prepares and refines ethanol Download PDFInfo
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- CN107011118A CN107011118A CN201710373082.8A CN201710373082A CN107011118A CN 107011118 A CN107011118 A CN 107011118A CN 201710373082 A CN201710373082 A CN 201710373082A CN 107011118 A CN107011118 A CN 107011118A
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- 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
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- 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
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- 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
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- 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
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The technique that ethanol is prepared and refined the invention discloses a kind of methanol, including, acetic acid is mixed and gasified by (1) acetic acid synthesis from methanol carbonylation (2) with hydrogen obtains material mixed gas, removes dust and drop in material mixed gas；(3) in the presence of hydrogenation catalyst, reacted the material mixed gas of chalk dust removing and drop；(4) cool down the reactant of the step (3), and isolated coarse ethanol, (5) coarse ethanol first take off it is light, neutralize and then purify again and dehydration obtains refined ethanol.The hydrogenation catalyst of the present invention includes calcium carbonate and/or barium carbonate.Improve the selectivity of ethanol, reduce the amount of accessory substance acetone, isopropanol, ethyl acetate, the step of using first light rear neutralization is taken off, it is 0 to make acetaldehyde in obtained refined ethanol, in the step of carbonylation acetic acid, de- iodine is carried out using specific extraction position, the content of iodine in thick acetic acid is reduced, reduces the influence to catalyst.
Description
Technical field
The invention belongs to chemosynthesis technical field, and in particular to a kind of acetic acid direct hydrogenation prepares the work of the smart ethanol of simultaneously essence
Skill.
Background technology
Ethanol is a kind of important chemical industry, medicine, the energy and raw-food material.Alcohol at normal temperature is colourless, volatile, inflammable
Liquid.Ethanol can be used to produce the originals such as acetaldehyde, ether, ethyl acetate, ethamine, ethyl acrylate, oxirane, medicine, agricultural chemicals
Material, can be mixed in gasoline and diesel oil, can be with water, acetic acid, acetone, benzene, carbon tetrachloride, chloroform, ether, ethylene glycol, glycerine, nitro
Methane, pyridine and toluene equal solvent are miscible, also do disinfectant, beverage, diluent, environmental protection coating material, agricultural chemicals, medicine, rubber, modeling
Several broad aspects such as material, staple fibre, detergent.
The industrial process of ethanol mainly has fermentation method, ethylene hydration method and acetic acid hydrogenation method.Ethylene hydration method is companion
Develop with the rise of petrochemical industry, including indirect hydration method and direct hydration method.In recent years by production cost of ethylene
Improve, in China, ethylene process is substantially at end-of-life state.The primary raw material of fermentation method is crops (including corn, sugarcane, height
Fine strain of millet, cassava, paddy etc.), obtain ethanol by using the amylofermentation in crops.The main alcohol production enterprise of China makes
Raw material is corn, wheat and cassava (relying primarily on import).In fact grain cost sharp rises in recent years, while ethanol
The problem of in the presence of grain is striven with people.
To solve the above problems, research uses the technique that acetic acid produces ethanol as raw material always in recent years.One is vinegar
Acid is through esterification generation acetate, and then acetate is hydrogenated to ethanol, then carries out refined raw producing and ethanol product；Two be that acetic acid is direct
Ethanol is hydrogenated to, then alcohol product is produced through subtractive process.Esterification process relative energy consumption and material consumption are higher, therefore many tendencies at present
Ethanol is produced using acetic acid directed hydrogenation, but is due to the corrosive characteristics of acetic acid, stainless steel equipment is in acetic acid vaporescence
In can be corroded to form the metals such as iron, chromium, molybdenum or metal oxide, so as to form dust after vaporization, long-term cycle fortune
Turn to cause reactor pressure to continue to increase, will also result in the dirt inactivation of catalyst；Other drop acetic acid has pole to catalyst
Strong destructiveness, it is found by the applicant that in vaporescence, even if keeping more than 30 DEG C of overheat, however it remains with fine droplet shape
The liquid acetic that formula is present so that substantially there is certain liquid acetic in hydrogen and acetic acid mixing gas phase, cause the catalyst longevity
Life shortens.In addition, side reaction is more in the reaction of acetic acid direct hydrogenation, gas-phase product such as methane, ethane, carbon monoxide are least
It is ready obtained accessory substance, and acetaldehyde, ether, ethyl acetate and acetone are also to try to reduced accessory substance, therefore improve catalysis
The selectivity of agent is all that tool is marginal for the overall energy consumption of device, material consumption and plant investment.
As raw material-acetic acid of synthesizing alcohol, its main production process has acetaldehyde oxidation, alkene direct oxidation method and first
Alcohol carbonylation method.Wherein, methanol carbonylation has the advantages that methanol conversion height, accessory substance are small, is increasingly becoming production acetic acid
One of main method.Wherein, in the homogeneous catalytic reaction system of methanol carbonylation added with iodomethane, lithium iodide and its
Also the presence of iodine is had in the catalyst of use, so that inevitably contain iodine impurity in obtained product acetic acid, and
When producing downstream product using acetic acid as raw material, iodide often result in many catalyst poisonings inactivation, thus iodine control again
It is necessary, in summary, is controlled from the source of acetic synthesis, again can be effective while enterprise's production cost is reduced
The content of iodine in the acetate products of synthesis is controlled, there is far-reaching influence for the economic benefit for improving enterprise.
The content of the invention
Therefore, the technical problem to be solved in the present invention is to improve the technique that methanol prepares and refines ethanol in the prior art
In, follow-up acetic acid direct hydrogenation is prepared in the reaction of ethanol containing iodine in acetate products, ethanol selectivity is poor, and easily
Make the defect of catalyst inactivation, so as to propose that one kind can either meet hydrogenation production ethanol demand, make plant investment, energy consumption big again
The technique that the methanol of width reduction prepares and refines ethanol.
Therefore, the technical scheme that the application takes is,
A kind of methanol prepares and refines the technique of ethanol, including,
(1) acetic acid synthesis from methanol carbonylation；
(2) acetic acid raw material is mixed and gasified with hydrogen and obtain material mixed gas, remove material mixed gas in dust with
Drop, wherein the mol ratio of the acetic acid raw material and hydrogen is 1：(20-45)；
(3) in the presence of hydrogenation catalyst, reacted the material mixed gas of chalk dust removing and drop, control reaction
Temperature is 210-290 DEG C, and reaction pressure is 2.0-5.0；
(4) reactant of the step (3), and isolated coarse ethanol and hydrogeneous gas phase are cooled down.
(5) coarse ethanol is carried out being refining to obtain refined ethanol.
Preferably, above-mentioned methanol is prepared and refined in the technique of ethanol, and the hydrogeneous gas phase is compressed described as cooling
The cooling medium of the reactant of step (3).
Preferably, above-mentioned methanol is prepared and refined in the technique of ethanol, in the step (3), and hydrogenation catalyst includes gold
Belong to carbonate.
Preferably, above-mentioned methanol is prepared and refined in the technique of ethanol, and the metal carbonate is calcium carbonate and/or carbonic acid
Barium.
Preferably, above-mentioned methanol is prepared and refined in the technique of ethanol, and the crystallite dimension of the metal carbonate is 2-
20nm。
Preferably, above-mentioned methanol is prepared and refined in the technique of ethanol, and the quality of the metal carbonate accounts for the acetic acid
The 0.5-8% of hydrogenation catalyst gross mass.
Preferably, above-mentioned methanol is prepared and refined in the technique of ethanol, and the formula of the hydrogenation catalyst is ABC@S, its
Middle A is the oxide of cobalt and/or copper, and B is the one or more in the oxide of tin, tungsten, molybdenum and iron, and C is metal carbonate, S
Silica, zirconium oxide or activated carbon are selected from for carrier.
Preferably, above-mentioned methanol is prepared and refined in the technique of ethanol, and described A, B, C mol ratio are 1：(0.5-1.1)：
(0.05-0.2)。
Preferably, above-mentioned methanol is prepared and refined in the technique of ethanol, and the preparation method of the hydrogenation catalyst is at least wrapped
Include in carbon dioxide partial pressure is more than 80kpa, temperature for 20-100 DEG C of environment, the step of carbonization 12-48h.
Preferably, above-mentioned methanol prepares and refines the technique of ethanol, and the reaction in the step (3) is in hydrogenation reactor
Carry out, the hydrogenation reactor includes isothermal reaction area and adiabatic reaction area.
Preferably, above-mentioned methanol is prepared and refined in the technique of ethanol, and the reaction in the step (3) is in hydrogenation reactor
Middle to carry out, the hydrogenation reactor is in thermal insulation, shell and tube, the adiabatic reactor with cold shock, tubulation-adiabatic reactor combination type reactor
One kind.
Preferably, above-mentioned methanol is prepared and refined in the technique of ethanol, and the hydrogenation reactor at least includes two thermal insulation
Reaction zone.
Preferably, above-mentioned methanol is prepared and refined in the technique of ethanol, in the step (2), is removed in material mixed gas
Dust and the reaction of drop carried out in heavy materials separator, the heavy materials separator includes housing, the mistake being arranged in housing
Filter plate and enter gas disturbance pipeline, it is described enter gas disturbance pipeline outlet side be located at the lower section of inlet end.
The methanol of the application is prepared and refined in the technique of ethanol, and the technique for synthesizing acetic acid can be using existing any conjunction
Into the technique of acetic acid, it is preferred that its technique for synthesizing acetic acid includes, and (S1) in the presence of a catalyst, methanol and CO are passed through instead
Answer and carbonylation is carried out in kettle, the feeding flash column of the mixture containing acetic acid for reacting generation is flashed, it is isolated
Liquid phase component and gaseous component, gaseous component return to the reactor；(S2) by liquid phase component isolated in step (S1)
Progress rectifying separation in rectifying column is sent into the way of middle part is fed, overhead fraction, tower bottom distillate and de- iodine gas phase is respectively obtained,
The position of wherein described de- iodine gas phase 3-20 block plates above the feedboard of the rectifying column is produced, the rectifying column tower top temperature
For 100-130 DEG C；(S3) the de- iodine gas phase in step (S2) is sent into the way of middle part is fed in absorption tower and carries out de- iodine, obtained
To acetate products and tower reactor liquid phase ingredient, acetate products are by the overhead extraction on the absorption tower, the return rectifying of tower reactor liquid phase ingredient
The stripping section of tower, wherein the KOH aqueous solution is added at the absorption tower tower top 2-5 block towers is used as de- iodine absorbing liquid.It is further excellent
Selection of land, in the technique of synthesis acetic acid, in the step (S2), the extraction temperature of the de- iodine gas phase is 100-140 DEG C.Enter one
Preferably, in the technique of synthesis acetic acid, in the step (S2), the temperature at the rectifying tower bottom is 140-165 DEG C, tower to step
Interior pressure is 0.05-0.4MPa.It is further preferred that in the technique of synthesis acetic acid, in the step (S1), carbonylation is anti-
The temperature answered is 170-190 DEG C, pressure 2.0-3.5MPa；The condition of flash distillation is 50-160 DEG C of temperature, pressure 0.1-1.5MPa.Enter
Overhead fraction and tower bottom distillate preferably, in the technique of synthesis acetic acid, in the step (S2), in addition to are returned to institute by one step
The step of stating reactor.It is further preferred that synthesis acetic acid technique in, in the step (S3), in addition to it is described inhale
Receive and the step of methanol is as de- iodine absorbing liquid is added in tower, the mouth that adds of wherein methanol is located at KOH aqueous solution addition mouth
Lower section and the top of the absorption tower charging aperture.It is further preferred that in the technique of synthesis acetic acid, in the step (S3),
The mass ratio of methanol of the KOH aqueous solution added with adding is (10-40):(60-90).It is further preferred that in synthesis
In the technique of acetic acid, in the step (S3), the mass concentration of the KOH aqueous solution is 1-50wt%.It is further preferred that
In the technique for synthesizing acetic acid, in the step (S3), KOH amount described in the KOH aqueous solution and iodine in the de- iodine gas phase
The mol ratio of content is (80-120):100.It is further preferred that in the technique of synthesis acetic acid, in the step (S3), inhaling
It is 0.05-0.4MPa to receive tower tower pressure, and tower top temperature is 100-130 DEG C, and bottom temperature is 102-138 DEG C.It is further preferred that
In the technique for synthesizing acetic acid, in the step (S2), condensed before overhead fraction is returned into the reactor, condensation temperature is
40-55℃.It is further preferred that in the technique of synthesis acetic acid, in the step (S2), in addition to from rectifying column reboiler bottom
The step of reboiler residue is discharged in portion.
The methanol of the application is prepared and refined in the technique of ethanol, and obtaining can be using conventional purification step after coarse ethanol
It is many in the step of progress is refining to obtain refined ethanol, refined ethanol of the prior art to be directly added into alkali lye in de- light step
Neutralisation treatment is carried out, so operation can make to cause acetaldehyde to remain in lightness-removing column, and then can make the acetaldehyde and lightness-removing column of part
Bottom of towe residue is mixed into next step process, the ethanol of caused polishing and remains acetaldehyde.In addition, it is de- gently with neutralization
It is synchronous to carry out so that most ethyl acetate in lightness-removing column and alkali react generation acetate, not only bad for follow-up
The processing of discarded object, also result in the waste of ethyl acetate, it is preferred, therefore, that methanol prepares and refines the technique of ethanol, its essence
Step processed include first taking off it is light, the step of neutralize and then purify and be dehydrated again.Preferably, the de- light, neutralization procedure includes, with
Water is extractant, and ethanol raw material is passed through in rectifying column and carries out de- light processing, overhead and bottom of towe residue are obtained, to institute
State and be passed through aqueous slkali in bottom of towe residue and neutralized, and adjust pH value to 9-12, it is preferable that for the de- rectifying column gently handled
Its tower top gauge pressure is 10-40kPa.Preferably, the purification and dehydration include, and the bottom of towe residue after neutralization is passed through
Purified and be dehydrated in rectifying column, further dehydration obtains refined ethanol to the isolated overhead containing ethanol, its
In rectifying column its tower top gauge pressure for being used to purify be 30-200kPa.Further, it is preferable that the de- obtained tower top that gently handles is distillated
The bottom of towe production that thing and/or purification processes are obtained is reclaimed in step (1), the raw material for producing ethanol to be hydrogenated with as acetic acid.
Methanol in the present invention is prepared and refined in the technique of ethanol, and mixing and the gasification of acetic acid raw material and hydrogen belong to normal
Rule technique, in order to reduce the metal of acetic acid drop etching apparatus generation or the dust of metal oxide and gasify what is not exclusively produced
Fine droplet, carries out the processing that chalk dust removing removes drop, the processing procedure can be with before material mixer enters hydrogenation reactor
Handled using general deduster, but clearance is relatively low, it is preferred to use the heavy materials separator of the application, as shown in Fig. 2 should
Heavy materials separator includes housing 1, and the inside of the housing 1 is divided into impurity Disengagement zone 13 and positioned at the miscellaneous of the bottom of impurity Disengagement zone 13
Matter discharge area 14, the upper and lower part of impurity Disengagement zone 13 is respectively arranged with gas outlet 11 and air inlet 12, impurity discharge area 14
Bottom impurity outlet 15 is set.Setting is some in impurity Disengagement zone 13 sets the first filter 2 along housing is axially staggered,
First filter 2 is sequentially arranged above the second filter 3 and gas outlet 11 in the impurity Disengagement zone 13, sets below
Air inlet 12 is put, air inlet 12 is connected into gas disturbance pipeline 5, the outlet side for entering gas disturbance pipeline is located under the inlet end
Side.Wherein, the top of first filter is connected with the internal face of the housing 1, and radially extending along the housing 1,
It is provided with the internal perisporium connection of the periphery wall of second filter 3 and housing, first filter 2, second filter 3 logical
Hole, the length of first filter 2 is not less than the radius of the impurity Disengagement zone.It is preferred that, above-mentioned the first filter 2,
Second filter 3 is the woven wire with support, and the mesh number of the woven wire is not less than 100 mesh, and its porosity is
60%, it is described enter gas disturbance pipeline 5 center line be curve.
Methanol in the present invention is prepared and refined in the technique of ethanol, and hydrogenation catalyst can be entered using conventional catalyst
Row catalytic reaction, but conventional catalyst hydrothermal stability is poor, and the selectivity of ethanol is relatively low, is mainly shown as third in side reaction
Ketone, isopropanol, ethyl acetate amount it is more, and catalyst service life is short, is urged therefore, the applicant employs specific hydrogenation
Agent carries out hydrogenation reaction, and the catalyst reduces catalyst using alkali carbonate and/or alkaline earth metal carbonate regulation
Acid amount improves the selectivity of ethanol, reduces the amount of accessory substance acetone, isopropanol, ethyl acetate without increasing surface alkalinty.
Meanwhile, acetic acid hydrogenation catalyst used in the present invention can be used the thick acetic acid raw material for not removing moisture straight in water and insensitive
Connect hydrogenation.The hydrogenation catalyst formula of the present invention is ABC@S；A and B is the active component, and C is the regulation component, and S is institute
State carrier；Wherein, the active component A is selected from the oxide of cobalt and/or copper；The active component B is selected from tin, tungsten, molybdenum and iron
Oxide in one or more；The regulation component is the one or more in alkali metal and/or alkaline earth metal carbonate,
The carrier S is selected from silica, zirconium oxide or activated carbon.Preferably, it is described regulation component be calcium carbonate and/or barium carbonate, its
Crystallite dimension is 2-20nm.Preferably, the active component A, the active component B and the regulation component C mol ratio are：
1：(0.5-1.1)：(0.05-0.2), it is preferable that the regulation component accounts for the 0.5- of the acetic acid hydrogenation catalyst gross mass
8wt%.The preparation method of the application hydrogenation catalyst can use the existing method for preparing catalyst such as infusion process, the precipitation method,
Its difference is essentially consisted in, on supported on carriers after active component and modifying ingredients, and first roasting obtains catalyst precarsor, then in dioxy
It is the 12-48h that in 20-100 DEG C of environment, is carbonized to change carbon partial pressure to be more than 80kpa, temperature, with obtain containing alkali carbonate with/
Or the hydrogenation catalyst of alkaline earth metal carbonate.
Methanol in the present invention is prepared and refined in the technique of ethanol, and hydrogenation catalyst reaction is carried out in hydrogenation reactor,
It can be using conventional hydrogenation reactor, for example, thermal insulation, shell and tube, the adiabatic reactor with cold shock, tubulation-adiabatic reactor combined type
One kind in reactor.To reduce the floor space of reactor, investment reduction cost reduces energy consumption, improves catalytic performance, this Shen
The hydrogenation reactor that please be used, as shown in Figures 3 and 4, including is provided with the reactor shell 21 of charging aperture 22 and discharging opening 23,
Adiabatic reaction bed 24, isothermal reaction bed 25 and lower adiabatic reaction are provided with inside the reactor shell 21 from top to bottom
Bed 26, heat exchange structure is provided with the isothermal reaction bed 25, and it is included axially through the isothermal reaction bed
25 some heat exchanging pipes 27 for loading catalyst, axial direction of the heat exchanging pipe 27 along the isothermal reaction bed 25 is
It is even to set, and the upper and lower ends of the heat exchanging pipe 27 are respectively arranged with upper perforated plate 28 and lower perforated plate 29, the heat exchanging pipe 27
Two ends connected respectively with upper adiabatic reaction bed 24, lower adiabatic reaction bed 26, between the two neighboring heat exchanging pipe 27,
The heat transfer space of cooling but flow of media is collectively forming between heat exchanging pipe 27 and housing 21；In the end pair of isothermal reaction bed 25
Cooling medium inlet 213 is set on the housing 21 answered, set on the corresponding housing 21 in the top of isothermal reaction bed 25
Put cooling medium outlet 214.
As alternative hydrogenation reactor structure, cooling medium, catalyst dress can be passed through in the heat exchanging pipe 27
Fill in outside heat exchanging pipe.As alternative hydrogenation reactor structure, the inside of the reactor shell 21 is divided into from upper cloth
It is set to isothermal reaction bed and two adiabatic reaction beds, and the setting cold shock structure between two adiabatic reaction beds.Nothing
By using which kind of above-mentioned structure, the catalyst of upper adiabatic reaction bed 24, isothermal reaction bed 25 and lower adiabatic reaction bed 26
Admission space ratio is (25~55)：(10~35)：(20~40), and the actual size of its reactor can calculate according to treating capacity
It is determined that.
Technical solution of the present invention, has the following advantages that：
1. a kind of methanol that the present invention is provided prepares and refines the technique of ethanol, acetic acid raw material is mixed simultaneously with hydrogen first
Gasification obtains material mixed gas, removes dust and drop in material mixed gas；Then in the presence of hydrogenation catalyst, make
The material mixed gas of chalk dust removing and drop are reacted；Finally cool down the reactant of the step (2), and isolated thick second
Alcohol.In the art, before hydrogenation reaction is carried out, dedusting is carried out to raw material first and except drop, reduces liquid-phase acetic acid pair
The corrosion of equipment, promotes the progress of gas phase reaction, while extending the service life of catalyst.
2. a kind of methanol that the present invention is provided prepares and refines the technique of ethanol, specific hydrogenation catalyst is used, has been adopted
With the acid amount of alkali carbonate and/or alkaline earth metal carbonate regulation reduction catalyst without increasing surface alkalinty, improve
The selectivity of ethanol, reduces the amount of accessory substance acetone, isopropanol, ethyl acetate.Meanwhile, the catalyst stabilization that the application is used
Property it is good, it is adaptable to the acetic acid raw material of various qualities, without by acetic acid carry out it is refined after carry out the reaction of preparation of ethanol through hydrogenation again,
Acetic acid hydrogenation catalyst used in the present invention the thick acetic acid raw material for not removing moisture can be used directly to add in water and insensitive
Hydrogen.
3. a kind of methanol that the present invention is provided, which is prepared and refined, not only includes isothermal in the technique of ethanol, hydrogenation reactor
Reaction zone also includes adiabatic reaction area, and two kinds of reaction zones cooperate, hydrogenation reaction is completed jointly, the body of reactor is reduced
Product, improves reaction efficiency, reduces the cost of investment of equipment.
4. a kind of methanol that the present invention is provided prepares and refines the technique of ethanol, its ethanol process for refining step, using water as
Extractant, ethanol raw material is passed through in rectifying column and carried out in de- light processing, removing hydrogen, methane, acetaldehyde, ether, acetone and vinegar
After acetoacetic ester, then the residue of bottom of towe is neutralized, acetic acid in the ethanol raw material not only effectively removed, and effectively kept away
Exempt from the decomposition of ethyl acetate, reduce the content of sodium acetate in the bottom of towe production of product tower；The neutralization is arranged on de-
After light, effectively avoid and cause acetaldehyde the problem of lightness-removing column exists always after entering lightness-removing column due to alkaline salt.
5. a kind of methanol that the present invention is provided prepares and refines the technique of ethanol, its ethanol process for refining step, using two
Equipment investment and energy consumption, the creative discovery of inventor, by the voltage-controlled system of product tower tower in table can be greatly reduced in the mode of tower rectifying
Press as 30-90kpa, it is 10-40kpa that lightness-removing column, which is controlled in gauge pressure, and the heat that can produce product tower, which fully meets lightness-removing column, to be made
With so as to for the lightness-removing column provide heat using the overhead fraction of the product tower as heating medium, improving the profit of heat
With rate, the energy consumption of technique is reduced, effective energy-conservation more than 20%.
6. a kind of methanol that the present invention is provided prepares and refines the technique of ethanol, the technique that it synthesizes acetic acid is simple, passes through
Reactant in reactor is sent directly into flash column, and the liquid phase in flash column is sent directly into the de- light place of progress in rectifying column
Reason, is iodinated by controlling the tower top temperature of rectifying column and in specific position extraction gas phase take off, i.e., de- by rectifying column
Contain iodine compound except most of, then remaining iodine substance is removed by absorption tower, save investment, reduce KOH and methanol
Usage amount.Using rectifying column plus the structure on absorption tower, the absorption tower in the application is that absorbing reaction tower is not rectifying column, therefore
And reboiler and condenser need not be configured, so that the more former cost of investment reduction by 50% for preparing smart acetic acid, energy consumption reduces by 40%,
So that more obvious from methanol ethanol economy.Thick production of acetic acid energy consumption is low, and it is complete totally for methanol to prepare ethanol
For process, in the case of based on same acetic acid hydrogenation technique, relative to refined acetic acid hydrogenation, energy consumption drop-out value reaches 60-
90kg marks oil/ton alcohol product.In the step of carbonylation acetic acid, de- iodine is carried out using specific extraction position,
The content of iodine in thick acetic acid is reduced, it is directly used in the process that follow-up hydrogenation produces ethanol, reduces the shadow to catalyst
Ring.
Brief description of the drawings
, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical scheme of the prior art
The accompanying drawing used required in embodiment or description of the prior art is briefly described, it should be apparent that, in describing below
Accompanying drawing is some embodiments of the present invention, for those of ordinary skill in the art, before creative work is not paid
Put, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is that methanol prepares and refines the process chart of ethanol in the embodiment of the present invention 1；
Fig. 2 is a kind of structural representation of heavy materials separator of the invention；
Fig. 3 is a kind of structural representation of hydrogenation reactor of the invention；
Fig. 4 is the A-A profiles of hydrogenation reactor shown in Fig. 3 of the present invention.
Wherein reference is expressed as：
1- housings；The filters of 2- first；The filters of 3- second；
4- spray equipments；5- enters gas disturbance pipeline connection；11- gas outlets；
12- air inlets；13- impurity Disengagement zone；14- impurity discharge region；
15- impurity outlets；
21- reactor shells；22- charging apertures；23- discharging openings；The upper adiabatic reaction beds of 24-；25- isothermal reaction beds；
Adiabatic reaction bed under 26-；27- heat exchanging pipes；28- upper perforated plates；29- lower perforated plates；213- cooling medium inlets；214- coolings are situated between
Matter is exported.
Embodiment
Embodiment 1
As shown in figure 1, the technique that the methanol of the present embodiment prepared and refined ethanol is,
Methanol prepares thick acetic acid
(S1) in the presence of a catalyst, methanol and CO are passed through in reactor and carry out carbonylation, generation will be reacted
Mixture feeding flash column containing acetic acid is flashed, and the temperature of flash distillation is 140 DEG C in flash column, and the pressure of flash distillation is
1.2MPa, flash distillation obtains liquid phase component and gaseous component, and gas phase group returns to the reactor, liquid phase component bag comprising CH3I and CO
Aqueous, sour, CH3I and HI enter next step.
(S2) liquid phase component isolated in step (S1) is sent into the way of middle part is fed and essence is carried out in rectifying column
Cut from, respectively obtain overhead fraction, tower bottom distillate and de- iodine gas phase, rectifying column has 60 blocks of column plates wherein in this step, feed
Plate is the 30th block of column plate of number from top to bottom, and de- iodine gas phase position of the 12nd block of plate above the feedboard of the rectifying column is adopted
Go out, it is 125 DEG C that it, which produces temperature, the rectifying column tower top temperature is 110 DEG C, the temperature of bottom of towe is 150 DEG C, and the pressure in tower is
0.1MPa, reflux ratio 1.2；Overhead fraction includes water, methyl acetate and CH3I, and reactor is returned after being condensed at 40 DEG C, produces
Raw condenser fixed gas passes through deep cooling, and liquid phase returns to reaction Fu, and gas phase is discharged after washing process, and tower bottom distillate includes vinegar
Sour and a small amount of water, wherein 80% returns to reactor, 20% returns to flash column, and specific return method for example can be, in rectifying column
The liquid-phase collection disk of tower reactor arrangement above one, liquid phase is produced from described liquid-phase collection disk, adopts and described sudden strain of a muscle is returned after pumping up
Steam tower and reaction Fu.Also include process periodically from rectifying column reboiler bottom discharge liquid phase high-boiling components and salt.
(S3) the de- iodine gas phase in step (S2) is sent into the way of middle part is fed in absorption tower and carries out de- iodine, obtain vinegar
Acid product and tower reactor liquid phase ingredient, acetate products are returned by the overhead extraction on the absorption tower, i.e., thick acetic acid, tower reactor liquid phase ingredient
Absorption tower is that plate column has 40 blocks of column plates in the stripping section of rectifying column, wherein this step, and feedboard is number the 20 from top to bottom
Block column plate, absorbing tower pressure is 0.3MPa, and tower top temperature is 110 DEG C, and bottom temperature is 125 DEG C, wherein in the absorbing tower
Push up and the KOH aqueous solution is added at 2 blocks of plates as de- iodine absorbing liquid, the mass concentration of the KOH aqueous solution is 25wt%, the KOH
The mol ratio of content of iodine is 80 in the amount of KOH described in the aqueous solution and the de- iodine gas phase:100, in the absorption tower tower top 10
Methanol is additionally added at block plate as the second de- iodine absorbing liquid, the mass ratio of methanol of the KOH aqueous solution of addition with adding is
10:60。
Thick acetic acid prepares and refines ethanol
(1) it is 1 by mol ratio：20 thick acetic acid (aqueous 2wt%, but thick acetic acid consumption is with isometric pure acetometer) with
Gaseous mixture is conveyed into vaporizer by being mixed in blender and gasify obtaining material mixed gas by hydrogen, the original
Batch mixing mixture is delivered to the dust and drop removed in heavy materials separator (as shown in Figure 2) in material mixed gas.
(2) in the presence of hydrogenation catalyst, the material mixed gas of chalk dust removing and drop are made to be passed through hydrogenation reactor (such as
Shown in Fig. 3 and 4) in reacted, controlling reaction temperature be 280 DEG C, reaction pressure is 2.0MPa；
(3) reactant of the step (2), and isolated coarse ethanol and hydrogeneous gas phase are cooled down, to improve the profit of heat
With rate, reduction energy consumption, the reactant of the step (2) is first carried out preliminary heat exchange cooling using cooling medium, then used again
Cooler is cooled down, and the reactant feeding gas-liquid separator after final cooling is carried out into gas-liquid separation, what is obtained is described hydrogeneous
After gas phase is compressed through compressor, used as the cooling medium tentatively exchanged heat, isolated coarse ethanol.
(4) it is 0.1 in mass ratio by coarse ethanol and water:1 proportioning, which is each led into lightness-removing column, to be carried out taking off light, isolated
Overhead and bottom of towe residue；Wherein overhead includes hydrogen, methane, acetaldehyde, ether, acetone and ethyl acetate,
Bottom of towe residue includes ethanol, water, acetic acid, isopropanol and n-butanol；The tower top gauge pressure of lightness-removing column is 10kpa；
(5) the bottom of towe residue of sodium hydroxide solution and lightness-removing column is sent into neutralizing tank and neutralized, take off light after neutralization
The pH value of the bottom of towe residue of tower is 9, will carry out purification and first in the bottom of towe residue feeding product tower of the lightness-removing column after neutralization
Step dehydration, the isolated overhead containing ethanol and the bottom of towe production containing water, wherein bottom of towe production include water
And n-butanol, the tower top gauge pressure of product tower is 30kpa；
(6) overhead of the step (5) is sent to dehydrating tower be dehydrated and obtain refined ethanol.
In order to improve the utilization rate of heat, energy consumption is reduced, product tower 50wt% overhead is delivered into lightness-removing column again
Device is boiled as heating medium, is carried out being dehydrated again after recuperation of heat heat to be changed and is obtained refined ethanol.
The preparation method for the hydrogenation catalyst that the application is used, comprises the following steps：
(1) copper nitrate and calcium nitrate are added to the water, after stirring, add ferric nitrate and nitric acid molybdenum, after stirring,
Obtain soak；
(2) sodium carbonate is added into the soak, precipitated liquid is formed, silica is added into the precipitated liquid and is carried
Body, cures 5h in the case where temperature is 70 DEG C of hydrothermal condition, was filtrated to get filter solid；
(3) amount for cleaning filter solid to sodium carbonate thereon is less than the 2% of filtering solid masses, in the case where temperature is 80 DEG C
After drying, in 600 DEG C of roastings, the catalyst precursor is obtained；
(4) catalyst precursor is placed in closed reaction vessel, is passed through carbon dioxide, until its partial pressure
For 250kpa, the temperature in reaction vessel is controlled to be in 70 DEG C, carbonization treatment 30h obtains acetic acid hydrogenation catalyst.After measured,
In the acetic acid hydrogenation catalyst prepared using the above method, the oxide of copper, the oxide of molybdenum, ferriferous oxide, calcium carbonate and load
Body silica accounts for 35%, 2%, 12% and the 4% and 47% of acetic acid hydrogenation catalyst gross mass respectively.
The coarse ethanol and refined ethanol prepared in above-mentioned technique is measured, its component and proportion of composing such as following table
It is shown.
Further, the service life of the more traditional hydrogenation catalyst of the service life of the application catalyst extends 45%.
The crystallite dimension in the present embodiment on hydrogenation catalyst is determined with x-ray diffractometer to calculate according to ScheHer formula, obtains it
Crystallite dimension is acetic acid sodium content 0.05% in 7nm, product tower bottom of towe production.In the present embodiment life can be hydrogenated with to produce one ton
The acetometer of producing and ethanol, 0.10kg/ tons of acetic acid of KOH consumptions prepare the thick acetic acid section equipment investment cost reduction by 30% of essence, after measured
Content of iodine in thick acetic acid is 2ppm, can be directly used for hydrogenation production ethanol.
Embodiment 2
The technique that the methanol of the present embodiment prepared and refined ethanol is,
Methanol prepares thick acetic acid
(S1) in the presence of a catalyst, methanol and CO are passed through in reactor and carry out carbonylation, generation will be reacted
Mixture feeding flash column containing acetic acid is flashed, and the temperature of flash distillation is 160 DEG C in flash column, and the pressure of flash distillation is
0.5MPa, flash distillation obtains liquid phase component and gaseous component, and gas phase group returns to the reactor, liquid phase component bag comprising CH3I and CO
Aqueous, sour, CH3I and HI enter next step.
(S2) liquid phase component isolated in step (S1) is sent into the way of middle part is fed and essence is carried out in rectifying column
Cut from, respectively obtain overhead fraction, tower bottom distillate and de- iodine gas phase, rectifying column has 80 blocks of column plates wherein in this step, feed
Plate is the 40th block of column plate of number from top to bottom, and de- iodine gas phase position of the 20th block of plate above the feedboard of the rectifying column is adopted
Go out, it is 140 DEG C that it, which produces temperature, the rectifying column tower top temperature is 130 DEG C, the temperature of bottom of towe is 165 DEG C, and the pressure in tower is
0.3MPa, reflux ratio 2；Overhead fraction includes water, methyl acetate and CH3I, and reactor is returned after being condensed at 40 DEG C, produces
Condenser fixed gas pass through deep cooling, liquid phase returns to reaction Fu, and gas phase discharge after washing process, and tower bottom distillate includes acetic acid
With a small amount of water, wherein 60% returns to reactor, 40% returns to flash column, in addition to periodically from rectifying column reboiler bottom discharge liquid
The process of phase high-boiling components and salt.
(S3) the de- iodine gas phase in step (S2) is sent into the way of middle part is fed in absorption tower and carries out de- iodine, obtain vinegar
Acid product and tower reactor liquid phase ingredient, acetate products are returned by the overhead extraction on the absorption tower, i.e., thick acetic acid, tower reactor liquid phase ingredient
Absorption tower is that plate column has 30 blocks of column plates in the stripping section of rectifying column, wherein this step, and feedboard is number the 15 from top to bottom
Block column plate, absorbing tower pressure is 0.4MPa, and tower top temperature is 100 DEG C, and bottom temperature is 102 DEG C, wherein in the absorbing tower
Push up and the KOH aqueous solution is added at 5 blocks of plates as de- iodine absorbing liquid, the mass concentration of the KOH aqueous solution is 50wt%, the KOH
The mol ratio of content of iodine is 120 in the amount of KOH described in the aqueous solution and the de- iodine gas phase:100, in the absorption tower tower top 8
Methanol is additionally added at block plate as the second de- iodine absorbing liquid, the mass ratio of methanol of the KOH aqueous solution of addition with adding is
40:90。
Thick acetic acid prepares and refines ethanol
(1) it is 1 by mol ratio：30 thick acetic acid (aqueous 4wt%, but thick acetic acid consumption is with isometric pure acetometer) with
Gaseous mixture is conveyed into vaporizer by being mixed in blender and gasify obtaining material mixed gas by hydrogen, the original
Batch mixing mixture is delivered to the dust and drop removed in heavy materials separator (as shown in Figure 2) in material mixed gas.
(2) in the presence of hydrogenation catalyst, the material mixed gas of chalk dust removing and drop are made to be passed through hydrogenation reactor (such as
Shown in Fig. 3 and 4) in reacted, controlling reaction temperature be 210 DEG C, reaction pressure is 3.0MPa；
(3) reactant of the step (2), and isolated coarse ethanol and hydrogeneous gas phase are cooled down, to improve the profit of heat
With rate, reduction energy consumption, the reactant of the step (2) is first carried out preliminary heat exchange cooling using cooling medium, then used again
Cooler is cooled down, and the reactant feeding gas-liquid separator after final cooling is carried out into gas-liquid separation, what is obtained is described hydrogeneous
After gas phase is compressed through compressor, used as the cooling medium tentatively exchanged heat, isolated coarse ethanol.
(4) it is 1 in mass ratio by coarse ethanol and water:1 proportioning, which is each led into lightness-removing column, carries out de- light, isolated tower
Push up distillate and bottom of towe residue；Wherein overhead includes hydrogen, methane, acetaldehyde, ether, acetone and ethyl acetate, tower
Bottom residue includes ethanol, water, acetic acid, isopropanol and n-butanol；The tower top gauge pressure of lightness-removing column is 20kpa；
(5) the bottom of towe residue of sodium hydroxide solution and lightness-removing column is sent into neutralizing tank and neutralized, take off light after neutralization
The pH value of the bottom of towe residue of tower is 10, will carry out purification and first in the bottom of towe residue feeding product tower of the lightness-removing column after neutralization
Step dehydration, the isolated overhead containing ethanol and the bottom of towe production containing water, wherein bottom of towe production include water
And n-butanol, the tower top gauge pressure of product tower is 60kpa；
(6) overhead of the step (5) is sent to dehydrating tower be dehydrated and obtain refined ethanol.
In order to improve the utilization rate of heat, energy consumption is reduced, product tower 40wt% overhead is delivered into lightness-removing column again
Device is boiled as heating medium, is carried out being dehydrated again after recuperation of heat heat to be changed and is obtained refined ethanol.
The preparation method for the hydrogenation catalyst that the application is used, comprises the following steps：
(1) cobalt nitrate and calcium nitrate are added to the water, after stirring, add ferric nitrate and nitric acid tin, after stirring,
Obtain soak；
(2) sodium carbonate is added into the soak, precipitated liquid is formed, silica is added into the precipitated liquid and is carried
Body, cures 3h in the case where temperature is 80 DEG C of hydrothermal condition, was filtrated to get filter solid；
(3) amount for cleaning filter solid to sodium carbonate thereon is less than the 2% of filtering solid masses, is 100 DEG C in temperature
After lower drying, in 300 DEG C of roastings, the catalyst precursor is obtained；
(4) catalyst precursor is placed in closed reaction vessel, is passed through carbon dioxide, until its partial pressure
For 150kpa, the temperature in reaction vessel is controlled to be in 50 DEG C, carbonization treatment 20h obtains the acetic acid that formula is ABC S and be hydrogenated with
Catalyst.
Wherein, in the acetic acid hydrogenation catalyst prepared in the present embodiment, the oxide of cobalt, the oxide of tin, the oxidation of iron
Thing, calcium carbonate and carrier silicas account for 15%, 20%, 10%, 3% and the 52% of acetic acid hydrogenation catalyst gross mass respectively.
The coarse ethanol prepared in above-mentioned technique is measured, its component and proportion of composing are as shown in the table.
Further, the service life of the more traditional hydrogenation catalyst of the service life of the application catalyst extends 35%.
The crystallite dimension in the present embodiment on hydrogenation catalyst is determined with x-ray diffractometer to calculate according to ScheHer formula, obtains it
Crystallite dimension is 10nm., acetic acid sodium content 0.03% in product tower bottom of towe production.It can be used in the present embodiment with producing one ton
The acetometer of hydrogenation production ethanol, 0.15kg/ tons of acetic acid of KOH consumptions, thick acetic synthesis section equipment investment cost reduction by 35%, warp
It is 3ppm to determine the content of iodine in thick acetic acid.
Embodiment 3
As shown in figure 1, the technique that the methanol of the present embodiment prepared and refined ethanol is,
Methanol prepares thick acetic acid
(S1) in the presence of a catalyst, methanol and CO are passed through in reactor and carry out carbonylation, generation will be reacted
Mixture feeding flash column containing acetic acid is flashed, and the temperature of flash distillation is 100 DEG C in flash column, and the pressure of flash distillation is
1.5MPa, flash distillation obtains liquid phase component and gaseous component, and gas phase group returns to the reactor, liquid phase component bag comprising CH3I and CO
Aqueous, sour, CH3I and HI enter next step.
(S2) liquid phase component isolated in step (S1) is sent into the way of middle part is fed and essence is carried out in rectifying column
Cut from, respectively obtain overhead fraction, tower bottom distillate and de- iodine gas phase, rectifying column has 60 blocks of column plates wherein in this step, feed
Plate is the 30th block of column plate of number from top to bottom, and de- iodine gas phase position of the 3rd block of plate above the feedboard of the rectifying column is adopted
Go out, it is 100 DEG C that it, which produces temperature, the rectifying column tower top temperature is 100 DEG C, the temperature of bottom of towe is 140 DEG C, and the pressure in tower is
0.4MPa, reflux ratio 3；Overhead fraction includes water, methyl acetate and CH3I, and reactor is returned after being condensed at 40 DEG C, produces
Condenser fixed gas pass through deep cooling, liquid phase returns to reaction Fu, and gas phase discharge after washing process, and tower bottom distillate includes acetic acid
Reactor is all returned with a small amount of water.Also include mistake periodically from rectifying column reboiler bottom discharge liquid phase high-boiling components and salt
Journey.
(S3) the de- iodine gas phase in step (S2) is sent into the way of middle part is fed in absorption tower and carries out de- iodine, obtain vinegar
Acid product and tower reactor liquid phase ingredient, acetate products are returned by the overhead extraction on the absorption tower, i.e., thick acetic acid, tower reactor liquid phase ingredient
Absorption tower is that plate column has 50 blocks of column plates in the stripping section of rectifying column, wherein this step, and feedboard is number the 25 from top to bottom
Block column plate, absorbing tower pressure is 0.1MPa, and tower top temperature is 130 DEG C, and bottom temperature is 138 DEG C, wherein in the absorbing tower
Push up and the KOH aqueous solution is added at 4 blocks of plates as de- iodine absorbing liquid, the mass concentration of the KOH aqueous solution is 30wt%, the KOH
The mol ratio of content of iodine is 1 in the amount of KOH described in the aqueous solution and the de- iodine gas phase:1, in described 10 blocks of plates of absorption tower tower top
Place is additionally added methanol as the second de- iodine absorbing liquid, and the mass ratio of methanol of the KOH aqueous solution of addition with adding is 30:
70。
Thick acetic synthesis and refined ethanol
(1) it is 1 by mol ratio：40 thick acetic acid (aqueous 6wt%, but thick acetic acid consumption is with isometric pure acetometer) with
Gaseous mixture is conveyed into vaporizer by being mixed in blender and gasify obtaining material mixed gas by hydrogen, the original
Batch mixing mixture is delivered to the dust and drop removed in heavy materials separator (as shown in Figure 2) in material mixed gas.
(2) in the presence of hydrogenation catalyst, the material mixed gas of chalk dust removing and drop are made to be passed through hydrogenation reactor (such as
Shown in Fig. 3 and 4) in reacted, controlling reaction temperature be 290 DEG C, reaction pressure is 4.0MPa；
(3) reactant of the step (2), and isolated coarse ethanol and hydrogeneous gas phase are cooled down, to improve the profit of heat
With rate, reduction energy consumption, the reactant of the step (2) is first carried out preliminary heat exchange cooling using cooling medium, then used again
Cooler is cooled down, and the reactant feeding gas-liquid separator after final cooling is carried out into gas-liquid separation, what is obtained is described hydrogeneous
After gas phase is compressed through compressor, used as the cooling medium tentatively exchanged heat, isolated coarse ethanol.
(4) it is 0.5 in mass ratio by coarse ethanol and water:1 proportioning, which is each led into lightness-removing column, to be carried out taking off light, isolated
Overhead and bottom of towe residue；Wherein overhead includes hydrogen, methane, acetaldehyde, ether, acetone and ethyl acetate,
Bottom of towe residue includes ethanol, water, acetic acid, isopropanol and n-butanol；The tower top gauge pressure of lightness-removing column is 30kpa；
(5) the bottom of towe residue of sodium hydroxide solution and lightness-removing column is sent into neutralizing tank and neutralized, take off light after neutralization
The pH value of the bottom of towe residue of tower is 11, will carry out purification and first in the bottom of towe residue feeding product tower of the lightness-removing column after neutralization
Step dehydration, the isolated overhead containing ethanol and the bottom of towe production containing water, wherein bottom of towe production include water
And n-butanol, the tower top gauge pressure of product tower is 90kpa；
(6) overhead of the step (5) is sent to dehydrating tower be dehydrated and obtain refined ethanol.
In order to improve the utilization rate of heat, energy consumption is reduced, product tower 30wt% overhead is delivered into lightness-removing column again
Device is boiled as heating medium, is carried out being dehydrated again after recuperation of heat heat to be changed and is obtained refined ethanol.
The preparation method for the hydrogenation catalyst that the application is used, comprises the following steps：
(1) copper nitrate and calcium nitrate are added to the water, after stirring, add ferric nitrate and nitric acid molybdenum, after stirring,
Obtain soak；
(2) sodium carbonate is added into the soak, precipitated liquid is formed, silica is added into the precipitated liquid and is carried
Body, cures 5h in the case where temperature is 70 DEG C of hydrothermal condition, was filtrated to get filter solid；
(3) amount for cleaning filter solid to sodium carbonate thereon is less than the 2% of filtering solid masses, in the case where temperature is 80 DEG C
After drying, in 600 DEG C of roastings, the catalyst precursor is obtained；
(4) catalyst precursor is placed in closed reaction vessel, is passed through carbon dioxide, until its partial pressure
For 300kpa, the temperature in reaction vessel is controlled to be in 80 DEG C, carbonization treatment 13h obtains acetic acid hydrogenation catalyst.After measured,
In the acetic acid hydrogenation catalyst prepared using the above method, the oxide of copper, the oxide of molybdenum, ferriferous oxide, calcium carbonate and load
Body silica accounts for 36%, 3%, 13% and the 8% and 40% of acetic acid hydrogenation catalyst gross mass respectively.
The coarse ethanol prepared in above-mentioned technique is measured, its component and proportion of composing are as shown in the table.
Further, the service life of the more traditional hydrogenation catalyst of the service life of the application catalyst extends 38%.
The crystallite dimension in the present embodiment on hydrogenation catalyst is determined with x-ray diffractometer to calculate according to ScheHer formula, obtains it
Crystallite dimension is 15nm., acetic acid sodium content 0.02% in product tower bottom of towe production.It is used to add to produce one ton in the present embodiment
Hydrogen produces the acetometer of ethanol, and 0.13kg/ tons of acetic acid of KOH consumptions prepare thick acetic acid section equipment investment cost reduction by 40%, through surveying
Content of iodine in fixed thick acetic acid is 2ppm.
Embodiment 4
As shown in figure 1, the technique that the methanol of the present embodiment prepared and refined ethanol is,
Methanol prepares thick acetic acid
(S1) in the presence of a catalyst, methanol and CO are passed through in reactor and carry out carbonylation, generation will be reacted
Mixture feeding flash column containing acetic acid is flashed, and the temperature of flash distillation is 80 DEG C in flash column, and the pressure of flash distillation is
1.5MPa, flash distillation obtains liquid phase component and gaseous component, and gas phase group returns to the reactor, liquid phase component bag comprising CH3I and CO
Aqueous, sour, CH3I and HI enter next step.
(S2) liquid phase component isolated in step (S1) is sent into the way of middle part is fed and essence is carried out in rectifying column
Cut from, respectively obtain overhead fraction, tower bottom distillate and de- iodine gas phase, rectifying column has 70 blocks of column plates wherein in this step, feed
Plate is the 35th block of column plate of number from top to bottom, and de- iodine gas phase position of the 8th block of plate above the feedboard of the rectifying column is adopted
Go out, it is 110 DEG C that it, which produces temperature, the rectifying column tower top temperature is 120 DEG C, the temperature of bottom of towe is 160 DEG C, and the pressure in tower is
0.2MPa, reflux ratio 4；Overhead fraction includes water, methyl acetate and CH3I, and reactor is returned after being condensed at 40 DEG C, produces
Condenser fixed gas pass through deep cooling, liquid phase returns to reaction Fu, and gas phase discharge after washing process, and tower bottom distillate includes acetic acid
With a small amount of water, wherein 85% returns to reactor, 15% returns to flash column, and specific return method for example can be, in rectifying tower
The liquid-phase collection disk of kettle arrangement above one, liquid phase is produced from described liquid-phase collection disk, adopts and described flash distillation is returned after pumping up
Tower and reaction Fu.Also include process periodically from rectifying column reboiler bottom discharge liquid phase high-boiling components and salt.
(S3) the de- iodine gas phase in step (S2) is sent into the way of middle part is fed in absorption tower and carries out de- iodine, obtain vinegar
Acid product and tower reactor liquid phase ingredient, acetate products are returned by the overhead extraction on the absorption tower, i.e., thick acetic acid, tower reactor liquid phase ingredient
Absorption tower is that plate column has 50 blocks of column plates in the stripping section of rectifying column, wherein this step, and feedboard is number the 25 from top to bottom
Block column plate, absorbing tower pressure is 0.2MPa, and tower top temperature is 120 DEG C, and bottom temperature is 130 DEG C, wherein in the absorbing tower
Push up and the KOH aqueous solution is added at 3 blocks of plates as de- iodine absorbing liquid, the mass concentration of the KOH aqueous solution is 10wt%, the KOH
The mol ratio of content of iodine is 1.2 in the amount of KOH described in the aqueous solution and the de- iodine gas phase:1, in 7 pieces of the absorption tower tower top
Methanol is additionally added at plate as the second de- iodine absorbing liquid, the mass ratio of methanol of the KOH aqueous solution of addition with adding is 10:
60。
Thick acetic acid prepares and refines ethanol
(1) it is 1 by mol ratio：45 thick acetic acid (aqueous 5wt%, but thick acetic acid consumption is with isometric pure acetometer) with
Gaseous mixture is conveyed into vaporizer by being mixed in blender and gasify obtaining material mixed gas by hydrogen, the original
Batch mixing mixture is delivered to the dust and drop removed in heavy materials separator (as shown in Figure 2) in material mixed gas.
(2) in the presence of hydrogenation catalyst, the material mixed gas of chalk dust removing and drop are made to be passed through hydrogenation reactor (such as
Shown in Fig. 3 and 4) in reacted, controlling reaction temperature be 250 DEG C, reaction pressure is 5.0MPa；
(3) reactant of the step (2), and isolated coarse ethanol and hydrogeneous gas phase are cooled down, to improve the profit of heat
With rate, reduction energy consumption, the reactant of the step (2) is first carried out preliminary heat exchange cooling using cooling medium, then used again
Cooler is cooled down, and the reactant feeding gas-liquid separator after final cooling is carried out into gas-liquid separation, what is obtained is described hydrogeneous
After gas phase is compressed through compressor, used as the cooling medium tentatively exchanged heat, isolated coarse ethanol.
(4) it is 1.5 in mass ratio by coarse ethanol and water:1 proportioning, which is each led into lightness-removing column, to be carried out taking off light, isolated
Overhead and bottom of towe residue；Wherein overhead includes hydrogen, methane, acetaldehyde, ether, acetone and ethyl acetate,
Bottom of towe residue includes ethanol, water, acetic acid, isopropanol and n-butanol；The tower top gauge pressure of lightness-removing column is 40kpa；
(5) the bottom of towe residue of sodium hydroxide solution and lightness-removing column is sent into neutralizing tank and neutralized, take off light after neutralization
The pH value of the bottom of towe residue of tower is 12, will carry out purification and first in the bottom of towe residue feeding product tower of the lightness-removing column after neutralization
Step dehydration, the isolated overhead containing ethanol and the bottom of towe production containing water, wherein bottom of towe production include water
And n-butanol, the tower top gauge pressure of product tower is 200kpa；
(6) overhead of the step (5) is sent to dehydrating tower be dehydrated and obtain refined ethanol.
In order to improve the utilization rate of heat, energy consumption is reduced, product tower 50wt% overhead is delivered into lightness-removing column again
Device is boiled as heating medium, is carried out being dehydrated again after recuperation of heat heat to be changed and is obtained refined ethanol.
The preparation method for the hydrogenation catalyst that the application is used, comprises the following steps：
(1) copper nitrate and calcium nitrate are added to the water, after stirring, add ferric nitrate and nitric acid molybdenum, after stirring,
Obtain soak；
(2) sodium carbonate is added into the soak, precipitated liquid is formed, silica is added into the precipitated liquid and is carried
Body, cures 6h in the case where temperature is 80 DEG C of hydrothermal condition, was filtrated to get filter solid；
(3) amount for cleaning filter solid to sodium carbonate thereon is less than the 2% of filtering solid masses, in the case where temperature is 80 DEG C
After drying, in 600 DEG C of roastings, the catalyst precursor is obtained；
(4) catalyst precursor is placed in closed reaction vessel, is passed through carbon dioxide, until its partial pressure
For 500kpa, the temperature in reaction vessel is controlled to be in 20 DEG C, carbonization treatment 48h obtains acetic acid hydrogenation catalyst.After measured,
In the acetic acid hydrogenation catalyst prepared using the above method, the oxide of copper, the oxide of molybdenum, ferriferous oxide, calcium carbonate and load
Body silica accounts for 25%, 5%, 23% and the 6% and 41% of acetic acid hydrogenation catalyst gross mass respectively.
The coarse ethanol prepared in above-mentioned technique is measured, its component and proportion of composing are as shown in the table.
Further, the service life of the more traditional hydrogenation catalyst of the service life of the application catalyst extends 42%.
The crystallite dimension in the present embodiment on hydrogenation catalyst is determined with x-ray diffractometer to calculate according to ScheHer formula, obtains it
Crystallite dimension is 12nm., acetic acid sodium content 0.06% in product tower bottom of towe production.It is used to add to produce one ton in the present embodiment
Hydrogen produces the acetometer of ethanol, and 0.15kg/ tons of acetic acid of KOH consumptions, thick acetic acid equipment investment cost reduces by 50%, after measured thick vinegar
Content of iodine in acid is 3ppm.
In above-described embodiment in carbonylation, methanol and CO mol ratio are 1:1.1, the temperature of carbonylation is
190 DEG C, reaction pressure is 3.0MPa, and catalyst can be any carbonylating catalyst, the institute as disclosed in CN102294265B
The low water catalyst stated.For ease of comparing, the following embodiments of the application are prepared using embodiment 1 in CN102294265B
Catalyst.
Obviously, above-described embodiment is only intended to clearly illustrate example, and the not restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (17)
1. a kind of methanol prepares and refines the technique of ethanol, including,
(1) acetic acid synthesis from methanol carbonylation；
(2) acetic acid is mixed with hydrogen and gasified and obtain material mixed gas, remove the dust and drop in material mixed gas, wherein
The mol ratio of the acetic acid raw material and hydrogen is 1：(20-45)；
(3) in the presence of hydrogenation catalyst, reacted the material mixed gas of chalk dust removing and drop, controlling reaction temperature
For 210-290 DEG C, reaction pressure is 2.0-5.0；
(4) reactant of the step (2), and isolated coarse ethanol and hydrogeneous gas phase are cooled down.
(5) coarse ethanol is carried out being refining to obtain refined ethanol.
2. the technique that methanol according to claim 1 prepares and refines ethanol, it is characterised in that in the step (3), plus
Hydrogen catalyst includes calcium carbonate and/or barium carbonate.
3. the technique that methanol according to claim 2 prepares and refines ethanol, it is characterised in that the calcium carbonate, carbonic acid
The crystallite dimension of barium is 2-20nm.
4. the technique that the methanol according to Claims 2 or 3 prepares and refines ethanol, it is characterised in that the calcium carbonate and/
Or the quality of barium carbonate accounts for the 0.5-8% of the acetic acid hydrogenation catalyst gross mass.
5. the technique for preparing according to any described methanol of claim 3-4 and refining ethanol, it is characterised in that the hydrogenation is urged
The formula of agent is ABC@S, and wherein A is the oxide of cobalt and/or copper, B be one kind in the oxide of tin, tungsten, molybdenum and iron or
Several, C is calcium carbonate and/or barium carbonate, and S is that carrier is selected from silica, zirconium oxide or activated carbon.
6. the technique for preparing according to any described methanol of claim 2-5 and refining ethanol, it is characterised in that the hydrogenation is urged
The preparation method of agent, it is the 12- that in 20-100 DEG C of environment, is carbonized at least to be included in carbon dioxide partial pressure more than 80kpa, temperature
The step of 48h.
7. the technique that methanol according to claim 1 prepares and refines ethanol, it is characterised in that in the step (3)
Reaction is carried out in hydrogenation reactor, and the hydrogenation reactor includes isothermal reaction area and adiabatic reaction area.
8. the technique that methanol according to claim 7 prepares and refines ethanol, it is characterised in that the hydrogenation reactor is extremely
Include Liang Ge adiabatic reactions area less.
9. the technique that methanol according to claim 1 prepares and refines ethanol, it is characterised in that in the step (2), go
Except the reaction of dust and drop in material mixed gas is carried out in heavy materials separator, the heavy materials separator includes housing, set
The filter that is placed in housing and enter gas disturbance pipeline, it is described enter gas disturbance pipeline outlet side be located at the lower section of inlet end.
10. the technique that methanol according to claim 1 prepares and refines ethanol, it is characterised in that the step (5) includes
First take off it is light, the step of neutralize and then purify and be dehydrated again.
11. the technique that methanol according to claim 10 prepares and refines ethanol, it is characterised in that the de- light, neutralization
Step includes, using water as extractant, and ethanol raw material is passed through in rectifying column and carries out de- light processing, overhead and bottom of towe is obtained
Residue, into the bottom of towe residue being passed through aqueous slkali is neutralized, and adjusts pH value to 9-12.
12. the technique that methanol according to claim 11 prepares and refines ethanol, it is characterised in that the purification and dehydration
Step includes, the bottom of towe residue after neutralization, which is passed through in rectifying column, to be purified and be dehydrated, isolated containing ethanol
Further dehydration obtains refined ethanol to overhead, wherein its tower top gauge pressure is 30-200kPa for the rectifying column of purification.
13. the technique that methanol according to claim 12 prepares and refines ethanol, it is characterised in that for taking off what is gently handled
Its tower top gauge pressure of rectifying column is 10-40kPa.
14. the technique that methanol according to claim 13 prepares and refines ethanol, it is characterised in that what de- light processing was obtained
The bottom of towe production that overhead and/or purification processes are obtained is reclaimed in step (2), being used as acetic acid hydrogenation production ethanol
Raw material.
15. the technique that methanol according to claim 1 prepares and refines ethanol, it is characterised in that in the step (1),
Acetic acid synthesis from methanol carbonylation comprises the following steps：
(S1) in the presence of a catalyst, methanol and CO are passed through in reactor and carry out carbonylation, containing for generation will be reacted
The mixture feeding flash column of acetic acid is flashed, and isolated liquid phase component and gaseous component, gaseous component return described anti-
Answer kettle；
(S2) liquid phase component isolated in step (S1) is sent into the way of middle part is fed and rectifying point is carried out in rectifying column
From overhead fraction, tower bottom distillate and de- iodine gas phase being respectively obtained, wherein the de- iodine gas phase is on the feedboard of the rectifying column
The position extraction of square 3-20 blocks plate, the rectifying column tower top temperature is 100-130 DEG C；
(S3) the de- iodine gas phase in step (S2) is sent into the way of middle part is fed in absorption tower and carries out de- iodine, obtain acetic acid production
Product and tower reactor liquid phase ingredient, acetate products are by the overhead extraction on the absorption tower, the stripping of tower reactor liquid phase ingredient return rectifying column
Section, wherein the KOH aqueous solution is added at the absorption tower tower top 2-5 block towers is used as de- iodine absorbing liquid.
16. the technique that methanol according to claim 15 prepares and refines ethanol, it is characterised in that the step (S2)
In, the extraction temperature of the de- iodine gas phase is 100-140 DEG C, and the temperature at the rectifying tower bottom is the pressure in 140-165 DEG C, tower
Power is 0.05-0.4MPa.
17. the technique that methanol according to claim 16 prepares and refines ethanol, it is characterised in that the step (S3)
In, in addition into the absorption tower the step of methanol is as de- iodine absorbing liquid being added, the wherein addition mouthful of methanol is located at described
The KOH aqueous solution adds the lower section of mouth and the top of the absorption tower charging aperture.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023108799A1 (en) * | 2021-12-15 | 2023-06-22 | 江苏湖大化工科技有限公司 | Co-production process method for synthesizing methyl propionate and other polyesters and alcohols from methanol and co |
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| CN102294265A (en) * | 2011-06-30 | 2011-12-28 | 北京化工大学 | Catalyst for synthesis of acetic acid through carbonylation at low water concentration, preparation method and application thereof |
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| CN103785414A (en) * | 2012-10-31 | 2014-05-14 | 中国石油化工股份有限公司 | Carboxylic acid hydrogenation catalyst, preparation method and application thereof |
| CN104250208A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Production method for preparing acetic acid through carbonylation of methanol |
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| CN1085540A (en) * | 1992-06-02 | 1994-04-20 | 英国石油化学品有限公司 | The production method of acetate |
| CN102282117A (en) * | 2008-11-13 | 2011-12-14 | 英国石油有限公司 | Hydrogenation of ethanoic acid to produce ethanol |
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