CN106986743A - The technique that a kind of acetic acid direct hydrogenation prepares ethanol - Google Patents
The technique that a kind of acetic acid direct hydrogenation prepares ethanol Download PDFInfo
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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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Abstract
The invention discloses the technique that a kind of acetic acid direct hydrogenation prepares ethanol, including, acetic acid raw material is mixed and gasified by (1) with hydrogen obtains material mixed gas, removes dust and drop in material mixed gas；(2) in the presence of hydrogenation catalyst, reacted the material mixed gas of chalk dust removing and drop, controlling reaction temperature is 210 290 DEG C, reaction pressure is 2.0 5.0；(3) reactant of the step (2), and isolated coarse ethanol and hydrogeneous gas phase are cooled down.The hydrogenation catalyst of the present invention includes calcium carbonate and/or barium carbonate.The selectivity of ethanol is improved, the amount of accessory substance acetone, isopropanol, ethyl acetate is reduced.
Description
Technical field
The invention belongs to chemosynthesis technical field, and in particular to the technique that a kind of acetic acid direct hydrogenation prepares ethanol.
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.
The content of the invention
Therefore, the technical problem to be solved in the present invention is to improve the selectivity of acetic acid direct hydrogenation reaction in the prior art
And the stability of catalyst, so as to propose that one kind can either meet hydrogenation production ethanol demand, plant investment, energy consumption are made again significantly
The technique that the acetic acid direct hydrogenation of reduction prepares ethanol.
Therefore, the technical scheme that the application takes is,
A kind of acetic acid direct hydrogenation prepares the technique of ethanol, including,
(1) 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)；
(2) 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；
(3) reactant of the step (2), and isolated coarse ethanol and hydrogeneous gas phase are cooled down.
Preferably, above-mentioned acetic acid direct hydrogenation is prepared in the technique of ethanol, and the hydrogeneous gas phase is compressed to be used as cooling institute
State the cooling medium of the reactant of step (2).
Preferably, above-mentioned acetic acid direct hydrogenation is prepared in the technique of ethanol, and in the step (2), hydrogenation catalyst includes
Metal carbonate.
Preferably, above-mentioned acetic acid direct hydrogenation is prepared in the technique of ethanol, and the metal carbonate is calcium carbonate and/or carbon
Sour barium.
Preferably, above-mentioned acetic acid direct hydrogenation is prepared in the technique of ethanol, and the crystallite dimension of the metal carbonate is 2-
20nm。
Preferably, above-mentioned acetic acid direct hydrogenation is prepared in the technique of ethanol, and the quality of the metal carbonate accounts for the vinegar
The 0.5-8% of sour hydrogenation catalyst gross mass.
Preferably, above-mentioned acetic acid direct hydrogenation is prepared in the technique of ethanol, and the formula of the hydrogenation catalyst is ABC@S,
Wherein 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 is that carrier is selected from silica, zirconium oxide or activated carbon.
Preferably, above-mentioned acetic acid direct hydrogenation is prepared in the technique of ethanol, described A, B, C mol ratio are 1：(0.5-
1.1)：(0.05-0.2).
Preferably, above-mentioned acetic acid direct hydrogenation is prepared in the technique of ethanol, the preparation method of the hydrogenation catalyst, at least
It is included in carbon dioxide partial pressure more than 80kpa, temperature in 20-100 DEG C of environment, the step of carbonization 12-48h.
Preferably, above-mentioned acetic acid direct hydrogenation is prepared in the technique of ethanol, and the reaction in the step (2) is in hydrogenation reaction
Carried out in device, the hydrogenation reactor includes isothermal reaction area and adiabatic reaction area.
Preferably, above-mentioned acetic acid direct hydrogenation is prepared in the technique of ethanol, and the reaction in the step (2) is in hydrogenation reaction
Carried out in device, the hydrogenation reactor is selected from thermal insulation, shell and tube, the adiabatic reactor with cold shock, tubulation-adiabatic reactor combination type reactor
In one kind.
Preferably, above-mentioned acetic acid direct hydrogenation is prepared in the technique of ethanol, and the hydrogenation reactor at least includes two absolutely
Thermal reaction area.
Preferably, above-mentioned acetic acid direct hydrogenation is prepared in the technique of ethanol, in the step (1), removes material mixed gas
In dust and the reaction of drop carried out in heavy materials separator, the heavy materials separator includes housing, is arranged in housing
Filter and enter gas disturbance pipeline, it is described enter gas disturbance pipeline outlet side be located at the lower section of inlet end.
In acetic acid direct hydrogenation of the invention prepares the technique of ethanol, mixing and the gasification of acetic acid raw material and hydrogen belong to
Common process, is not exclusively produced to reduce the metal of acetic acid drop etching apparatus generation or the dust of metal oxide and gasification
Fine droplet, material mixer enter hydrogenation reactor before carry out chalk dust removing remove drop processing, the processing procedure can
To be 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
The heavy materials separator includes housing 1, and the inside of the housing 1 is divided into impurity Disengagement zone 13 and positioned at the bottom of impurity Disengagement zone 13
Impurity 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 sets impurity outlet 15.Set some along housing the first filter 2 of axially staggered setting in impurity Disengagement zone 13,
First filter 2 is sequentially arranged above the second filter 3 and gas outlet 11 in the impurity Disengagement zone 13, below
Air inlet 12 is set, and 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.
In acetic acid direct hydrogenation of the invention prepares the technique of ethanol, hydrogenation catalyst can be using conventional catalyst
Catalytic reaction is carried out, but conventional catalyst hydrothermal stability is poor, and the selectivity of ethanol is relatively low, is mainly shown as in side reaction
Acetone, isopropanol, ethyl acetate amount it is more, and catalyst service life is short, therefore, the applicant employs specific hydrogenation
Catalyst carries out hydrogenation reaction, and the catalyst is using alkali carbonate and/or alkaline earth metal carbonate regulation reduction catalyst
Acid amount without increasing surface alkalinty, improve the selectivity of ethanol, reduce accessory substance acetone, isopropanol, ethyl acetate
Amount.Meanwhile, acetic acid hydrogenation catalyst used in the present invention is to water and insensitive, the usable thick acetic acid raw material for not removing moisture
Direct 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
The carrier；Wherein, the active component A is selected from the oxide of cobalt and/or copper；The active component B be selected from tin, tungsten, molybdenum and
One or more in the oxide of iron；The regulation component is alkali metal and/or one kind or several in alkaline earth metal carbonate
Kind, 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
For：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.
In acetic acid direct hydrogenation of the invention prepares the technique of ethanol, hydrogenation catalyst reaction is entered in hydrogenation reactor
OK, it can be using conventional hydrogenation reactor, for example, thermal insulation, shell and tube, the adiabatic reactor with cold shock, tubulation-adiabatic reactor combination
One kind in formula reactor.To reduce the floor space of reactor, investment reduction cost reduces energy consumption, improves catalytic performance, this
Apply for the hydrogenation reactor used, as shown in Figures 3 and 4, including be provided with the reactor shell 21 of charging aperture 22 and discharging opening 23,
It is provided with adiabatic reaction bed 24, isothermal reaction bed 25 and lower thermal insulation from top to bottom inside the reactor shell 21 anti-
Bed 26 is answered, heat exchange structure is provided with the isothermal reaction bed 25, it is included axially through isothermal reaction bed
Some heat exchanging pipes 27 for loading catalyst of layer 25, axial direction of the heat exchanging pipe 27 along the isothermal reaction bed 25
It is uniformly arranged, 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 are connected with upper adiabatic reaction bed 24, lower adiabatic reaction bed 26 respectively, the two neighboring heat exchanging pipe 27 it
Between, the heat transfer space of cooling but flow of media is collectively forming between heat exchanging pipe 27 and housing 21；At the end of isothermal reaction bed 25
Setting cooling medium inlet 213 on the corresponding housing 21 is held, in the corresponding housing 21 in the top of isothermal reaction bed 25
Upper setting cooling medium exports 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 acetic acid direct hydrogenation that the present invention is provided prepares the technique of ethanol, acetic acid raw material is mixed with hydrogen first
And gasification obtains material mixed gas, dust and drop in material mixed gas are removed；Then in the presence of hydrogenation catalyst, make
The material mixed gas of chalk dust removing and drop are gone to be 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 acetic acid direct hydrogenation that the present invention is provided prepares the technique of ethanol, specific hydrogenation catalyst has been used,
Using 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 that the application is used is steady
It is qualitative good, it is adaptable to the acetic acid raw material of various qualities, without acetic acid is carried out to carry out the anti-of preparation of ethanol through hydrogenation again after refining
Should, acetic acid hydrogenation catalyst used in the present invention can be used the thick acetic acid raw material for not removing moisture direct in water and insensitive
Hydrogenation.
3. a kind of acetic acid direct hydrogenation for providing of the present invention is prepared and not only included in the technique of ethanol, hydrogenation reactor etc.
Warm 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.
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 the process chart that acetic acid direct hydrogenation prepares 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 acetic acid direct hydrogenation of the present embodiment prepares ethanol is,
(1) it is 1 by mol ratio：20 acetic acid raw material, by being mixed in blender, gaseous mixture is conveyed into hydrogen
In vaporizer gasify obtaining material mixed gas, the former batch mixing mixture is delivered in heavy materials separator (as shown in Figure 2)
Remove the dust and drop 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 alcohol product is that coarse ethanol enters
Subsequent treatment.
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 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 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 7nm.
Embodiment 2
The technique that the acetic acid direct hydrogenation of the present embodiment prepares ethanol is,
(1) it is 1 by mol ratio：30 acetic acid raw material, by being mixed in blender, gaseous mixture is conveyed into hydrogen
In vaporizer gasify obtaining material mixed gas, the former batch mixing mixture is delivered in heavy materials separator (as shown in Figure 2)
Remove the dust and drop 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 alcohol product is that coarse ethanol enters
Subsequent treatment.
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.
Embodiment 3
As shown in figure 1, the technique that the acetic acid direct hydrogenation of the present embodiment prepares ethanol is,
(1) it is 1 by mol ratio：40 acetic acid raw material, by being mixed in blender, gaseous mixture is conveyed into hydrogen
In vaporizer gasify obtaining material mixed gas, the former batch mixing mixture is delivered in heavy materials separator (as shown in Figure 2)
Remove the dust and drop 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 alcohol product is that coarse ethanol enters
Subsequent treatment.
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.
Embodiment 4
As shown in figure 1, the technique that the acetic acid direct hydrogenation of the present embodiment prepares ethanol is,
(1) it is 1 by mol ratio：45 acetic acid raw material, by being mixed in blender, gaseous mixture is conveyed into hydrogen
In vaporizer gasify obtaining material mixed gas, the former batch mixing mixture is delivered in heavy materials separator (as shown in Figure 2)
Remove the dust and drop 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 alcohol product is that coarse ethanol enters
Subsequent treatment.
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.
The pressure drop of the present embodiment hydrogenation reactor (embodies the index that dust gathers effect, if pressure drop increase, compresses function
Consumption increase, while reaction result can be caused to deteriorate) operation 2000 hours after with operation first 72 hours substantially close to coarse ethanol group
Into being basically unchanged.
Comparative example 1
According to embodiment 4, simply cancel heavy materials separator, it is basically identical in initial reaction stage result and embodiment 4, but
After operation 2000 hours, reactor pressure decrease increase by 50%, while it is as shown in the table for the change of Export Ethanol composition：
The de- stable operation of drop and dust to device of heavy materials separator is most important as can be seen from the table.
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 (12)
1. a kind of acetic acid direct hydrogenation prepares the technique of ethanol, including,
(1) acetic acid raw material is mixed and gasified with hydrogen and obtain material mixed gas, remove the dust and drop in material mixed gas,
The mol ratio of wherein described acetic acid raw material and hydrogen is 1：(20-45)；
(2) 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；
(3) reactant of the step (2), and isolated coarse ethanol and hydrogeneous gas phase are cooled down.
2. the technique that acetic acid direct hydrogenation according to claim 1 prepares ethanol, it is characterised in that the hydrogeneous gas phase warp
Compress the cooling medium as the reactant for cooling down the step (2).
3. the technique that ethanol is prepared according to any described acetic acid direct hydrogenations of claim 1-2, it is characterised in that the step
(2) in, hydrogenation catalyst includes metal carbonate.
4. the technique that acetic acid direct hydrogenation according to claim 3 prepares ethanol, it is characterised in that the metal carbonate
For calcium carbonate and/or barium carbonate.
5. the technique that the acetic acid direct hydrogenation according to claim 3 or 4 prepares ethanol, it is characterised in that the metal carbon
The crystallite dimension of hydrochlorate is 2-20nm.
6. the technique that ethanol is prepared according to any described acetic acid direct hydrogenations of claim 3-5, it is characterised in that the metal
The quality of carbonate accounts for the 0.5-8% of the acetic acid hydrogenation catalyst gross mass.
7. the technique that ethanol is prepared according to any described acetic acid direct hydrogenations of claim 3-6, it is characterised in that the hydrogenation
The formula of catalyst is ABC@S, and wherein A is the oxide of cobalt and/or copper, and B is one kind in the oxide of tin, tungsten, molybdenum and iron
Or it is several, C is metal carbonate, and S is that carrier is selected from silica, zirconium oxide or activated carbon.
8. the technique that acetic acid direct hydrogenation according to claim 7 prepares ethanol, it is characterised in that the hydrogenation catalyst
Preparation method, it is the 12-48h 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.
9. the technique that ethanol is prepared according to any described acetic acid direct hydrogenations of claim 1-2, it is characterised in that the step
(2) reaction in is carried out in hydrogenation reactor, and the hydrogenation reactor includes isothermal reaction area and adiabatic reaction area.
10. the technique that ethanol is prepared according to any described acetic acid direct hydrogenations of claim 1-2, it is characterised in that the step
Suddenly the reaction in (2) is carried out in hydrogenation reactor, the hydrogenation reactor be selected from thermal insulation, shell and tube, the adiabatic reactor with cold shock,
One kind in tubulation-adiabatic reactor combination type reactor.
11. the technique that acetic acid direct hydrogenation according to claim 8 prepares ethanol, it is characterised in that the hydrogenation reaction
Device at least includes Liang Ge adiabatic reactions area.
12. the technique that ethanol is prepared according to any described acetic acid direct hydrogenations of claim 1-2, it is characterised in that the step
Suddenly in (1), the reaction for removing dust and drop in material mixed gas is carried out in heavy materials separator, the heavy materials separator bag
Include housing, the filter being arranged in housing and enter gas disturbance pipeline, it is described enter gas disturbance pipeline outlet side be located at inlet end
Lower section.
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| CN102847544A (en) * | 2012-09-26 | 2013-01-02 | 厦门大学 | Catalytic agent for preparing ethanol by using acetic acid hydrogenation and preparation method thereof |
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