CN105085167B - Two-section method process for preparing alcohol by oxalic ester hydrogenation - Google Patents
Two-section method process for preparing alcohol by oxalic ester hydrogenation Download PDFInfo
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- CN105085167B CN105085167B CN201510535737.8A CN201510535737A CN105085167B CN 105085167 B CN105085167 B CN 105085167B CN 201510535737 A CN201510535737 A CN 201510535737A CN 105085167 B CN105085167 B CN 105085167B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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Abstract
The invention relates to a two-section method process for preparing alcohol by oxalic ester hydrogenation. An original one-section type high-temperature reactor is split into two sections; and the two reactor are respectively used for realizing transformation of oxalic ester in the low-temperature reactor and realizing further deep hydrogenation of a product in a high-temperature reactor, thus inhibiting the generation of C3 and C4 alcohols and obtaining the alcohol with high selectivity. The two-section method process is used in oxalic ester hydrogenation alcohol preparing reaction, the reaction temperature in the first section is 200 DEG C, the reaction temperature in the second section is 280 DEG C, the reaction pressure is 2.5 MPa, a hydrogen-ester molar ratio in the first section is 80, a hydrogen-ester molar ratio in the second section is 200, the mass space velocity of the oxalic ester is 1.0 h＜-1＞, the conversion rate of the oxalic ester is 100 percent, and the selectivity of the alcohol reaches up to 85.0 percent, expressing extremely high hydrogenation activity and selectivity.
Description
Technical field
The present invention relates to a kind of technique of two-stage method hydrogenation of oxalate for preparing for ethanol.
Background technology
Ethanol, is commonly called as ethanol, as a kind of important industrial chemicals, is widely used in food, medicine, chemical industry, national defence
Deng field.Because the oxygen content of ethanol is up to 34.7%, thus can also be used as methyl tertiary butyl ether(MTBE)（MTBE）Succedaneum adds vapour
Ethanol petrol is obtained in oil, gasoline consumption can have both been reduced, additionally it is possible to make gasoline combustion more abundant, it is aflame so as to reduce
The discharge of the pollutant such as CO.The route of traditional mode of production ethanol mainly includes two.One is petroleum path, by being split using oil
Solution product ethylene is raw material, and hydration obtains ethanol.Other one is biofermentation route, by using the various agricultural productions containing sugar
Product, agriculture and forestry by-product and wild plant are raw material, make disaccharidase, polysaccharide conversion for monosaccharide and further turn through hydrolysis, fermentation
Turn to ethanol.
With the fast development of automobile industry, China's bio-ethanol production has obtained swift and violent development, has risen at present
The big fuel ethanol production state in third place in the world and country of consumption.Due to the restriction of China's national situation, large-scale use Caulis Sacchari sinensis or Maize Production
Alcohol fuel is limited to, and adopts cellulose not yet ripe for the alcohol production technology of raw material.It is relatively rich based on coal in China
Rich national conditions, it is of great interest by synthesis gas ethanol.Directly ethanol procedure processed is synthesis gas to the synthesis gas reported
First by Rh/SiO2Catalyst reacts generation acetaldehyde, ethanol, ethyl acetate and acetic acid under the conditions of 3-10MPa and 300 DEG C
The main product of carbon two, then in Cu/SiO2[JP6259632]、Pd-Fe/SiO2[JP61178940, JP61178942] or Cu-
By the further hydro-conversion of the by-products such as acetaldehyde, ethyl acetate and acetic acid on the catalyst such as Zn-Al-Mg-Mo [CN1122567]
For ethanol.Due to the technical matters condition harshness, poor catalyst stability, the low shortcoming of selectivity, not yet obtain up to now
Large-scale application.
Chinese patent CN101934228A reports a kind of copper-based catalysts of acetate preparation of ethanol by hydrogenating, and carrier is oxygen
Change aluminum or silicon oxide, auxiliary agent is the oxide of the elements such as zinc, manganese, chromium, calcium, barium, ferrum, nickel, magnesium, and the conversion ratio of acetate is up to
To 88%, but reaction efficiency is relatively low.
CN102327774A reports a kind of copper-based catalysts and is applied to acetate preparation of ethanol by hydrogenating reaction system, its preparation
Method is that Ludox or aluminum soluble salt are added in the solvable mixed salt solution of soluble salt and promoter metal of copper, is stirred
Afterwards, mixed liquor is added in the solution of precipitant under the conditions of 50-95 DEG C, then aging, filtration, washing, drying, roasting,
Molding and reduction obtain catalyst.Maximum conversion of the made catalyst in acetate hydrogenation reaction is 85%, ethanol selectivity
For 91%.
CN101941887A adopts silicon oxide or aluminium oxide for carrier, and copper is the gold such as active component, Zn, Mn, Cr, Ca, Ba
Category or metal-oxide are that auxiliary agent is obtained copper-based catalysts, and the selectivity in acetate hydrogenation reaction is up to 99%, and turns
Rate is up to 92%.
CN1014 11990A disclose a kind of preparation method of hydrogenation of oxalate for preparing ethylene glycol copper Si catalyst, the method
It is to add specific surface area to be 600-1200m in cupric ammine complex2In the mesoporous silica molecular sieve powder body of/g, then pass through
Filter, washing, drying, roasting, reduction, make catalyst.
CN102350358B discloses the preparation method that reports a kind of copper-based catalysts of preparing ethanol by oxalate hydrogenation and should
With it adopts zirconium oxide and silicon oxide as complex carrier, and copper is used as the metals such as active component, Mg, Ca, Ba, Mn or metal oxygen
Compound prepares copper-based catalysts for auxiliary agent, and in preparing ethanol by oxalate hydrogenation, the conversion ratio of oxalate reaches 100%, ethanol
Selectivity reaches 85%.
CN102649745A and CN102649744A disclose one kind and include with fluidized-bed reactor by raw material of oxalate
Copper catalyst is contacted, and the technical scheme of the effluent containing ethyl glycolate is generated, to improve the selectivity of ethyl glycolate.
It is demonstrated experimentally that exist in above-mentioned copper-based catalysts technique the carbon of by-product three, four carbon alcohols selectivity is low and target
The catalyst under the conditions of high selectivity of the product ethanol stability problem of itself.
The content of the invention
It is an object of the invention to provide a kind of process route of two-stage method preparing ethanol by oxalate hydrogenation, the method is by two
Reactant oxalate is eventually converted into ethanol by section reactor.Make first oxalate in first reactor at a lower temperature
Conversion, then product is further hydrogenated at a higher temperature ethanol in second reactor.This technique can be effective
The main side reaction of suppression, reduce by three carbon alcohol, the selectivity of four carbon alcohols, so as to effectively improve the selectivity of ethanol.Adopt with
Silicon oxide is carrier, with copper as active component, using aluminum as modified additive；Auxiliary agent aluminum is carried out to the Acidity of Aikalinity of catalyst surface
Regulation and control, make the catalyst not only have comparatively ideal surface acidic-basic property, while also have good side reaction rejection ability, so as to obtain
Obtain higher ethanol selectivity.With optimal conditions, the conversion ratio of oxalate is reached in the case of 100%, and the selectivity of ethanol reaches
To 85.0%, the cost of later separation is also significantly reduced while reducing waste discharge.Additionally, under the process conditions, catalyst
Stable operation 100 hours, activity illustrates that new technology and the catalyst have excellent stability without significant change.
The present invention provides a kind of two-stage method preparing ethanol by oxalate hydrogenation technique mainly will be anti-by two tandem reactors
Thing oxalate is answered to be eventually converted into ethanol.Oxalate is set to be converted into intermediate products at a lower temperature in first reactor first
Stream stock, generates product stream stock-traders' know-how and crosses the further pre-heating temperature elevation of preheater and enter one at a higher temperature in second reactor
Step is hydrogenated to stock containing ethanol stream.
Described first reactor is isothermal reactor.
Described second reactor is adiabatic reactor.
The described stream stock from second reactor out is including at least one or two in methanol or ethanol.
The described stream stock from first reactor out at least also comprising the one kind in ethylene glycol and methyl glycollate or
Two kinds.
The step of two-stage method technique that the present invention is provided includes for preparing ethanol by oxalate hydrogenation：
The catalyst for preparing is respectively put into into first reactor（First paragraph reactor）In and second reactor（Second segment
Reactor）In, first catalyst is reduced in hydrogen atmosphere；After reduction terminates, adjustment first paragraph, second segment temperature are extremely
After predetermined reaction temperature and pressure, the stream stock-traders' know-how containing oxalate is crossed after low-temperature pre-heater preheating and enters first reactor and hydrogen
Reaction；After the hydrogen stream stock mixing of the product stream stock of generation and supplement in high-temperature preheater with the product stream of second reactor
After stock heat exchange, then make temperature reach setting value through electric heater heating, further hydrogenation occurs subsequently into second reactor
Reaction generates the stream stock containing ethanol；Gas-liquid point is carried out after the product stream stock-traders' know-how condensing heat exchanger condensation into gas-liquid separator
From, liquid-phase product stream stock and fixed gas stream stock are obtained, fixed gas stream stock-traders' know-how is crossed and mixed with fresh hydrogen air-flow stock after supercharger supercharging,
Then it is divided into two stream stocks and respectively enters first reactor and second reactor, the flow of two stream stocks is by flow-control valve regulation
Two reactors are made to respectively reach the hydrogen ester ratio of setting.
In described two-stage method technique, reaction pressure is 1.0-4.0MPa.
Described two-stage method process catalyst reduction temperature is 250-400 DEG C.
The reaction temperature of described two-stage method technique first paragraph is 180-220 DEG C.
The reaction temperature of described two-stage method technique second segment is 240-300 DEG C.
Mole hydrogen ester ratio is 40-100 in described two-stage method technique first reactor.
Mole hydrogen ester ratio is 180-300 in described two-stage method technique second reactor.
The gross mass air speed of described two-stage method technique oxalate charging is 0.5-3 h-1。
Alternatively, the reaction condition of two-stage method technique is：It is 200 DEG C in first paragraph reaction temperature, second segment reaction temperature
For 280 DEG C, reaction pressure is 2.5MPa, and first paragraph mole hydrogen ester ratio is 80, and second segment mole hydrogen ester ratio is 200, oxalate matter
Amount air speed is 1.0h-1。
Described oxalate is the one or two kinds of in dimethyl oxalate. and ethyl oxalate.
The catalyst components that adopt of the present invention account for catalyst weight percent for：Silicon oxide accounts for the 70- of catalyst weight
90%, active ingredient copper accounts for the 5-30% of catalyst weight, and auxiliary agent accounts for the 0.5-1.5% of catalyst weight, each group of the catalyst
The sum for dividing weight is 100%；Wherein, preparation method may be selected following steps：
1）Mixed aqueous solution is configured to by metering from copper nitrate and aluminum nitrate；
2）To step 1）In solution in Deca ammonia, and stir 10-30 minutes；
3）To step 2）Middle Deca Ludox, stirs 2-10 hours under room temperature；
4）By step 3）In slurry be warming up to 80-95 DEG C and evacuation, when liquid phase PH valve is less than 7, stop heating；
5）By step 4）In liquid cooling after, will precipitation filter, wash to neutrality；
6）By step 5）In filter cake under the conditions of 80-120 DEG C be dried；
7）By step 6）In after dried filter cake pulverizes, catalyst of the present invention is formed after roasting at 400-450 DEG C.
One kind or two in ethanol and methanol can also be included in the described stream stock containing oxalate in addition to oxalate
Plant as solvent.
The present invention carries out preparing ethanol by oxalate hydrogenation reaction using new two-stage method technique, is in first paragraph reaction temperature
200 DEG C, second segment reaction temperature is 280 DEG C, and reaction pressure is 2.5MPa, and first paragraph mole hydrogen ester ratio is 80, second segment mole
Hydrogen ester ratio is 200, and oxalate mass space velocity is 1.0h-1When, oxalate average conversion reaches 99, more than 9%, and ethanol is averagely selected
Selecting property is up to more than 85.0%, shows high hydrogenation activity and selectivity.（See Fig. 2）
The present invention adopts brand-new two-stage method technique, first at a lower temperature converts oxalate, then in higher temperatures
Degree is further hydrogenated with to its product, obtains target product ethanol.In two-stage method technique, oxalate reacts at low temperature can
Effectively to suppress the generation of side reaction so that the carbon of by-product three, the selectivity of four carbon alcohols are substantially reduced, so as to greatly improved
The selectivity of ethanol.The catalyst and new technology will be combined, preparing ethanol by oxalate hydrogenation reaction will be carried out, with optimal conditions,
The conversion ratio of oxalate is reached in the case of 100%, and the selectivity of ethanol reaches 85.0%, while reduction waste discharge also significantly
Reduce the cost of later separation.Additionally, under the process conditions, catalyst stabilization runs 100 hours, activity is without substantially change
Change, illustrate that new technology and the catalyst have excellent stability.
Description of the drawings
Fig. 1. two-stage method preparing ethanol by oxalate hydrogenation process chart.
Fig. 2. operation stability curve chart of the prepared by dimethyl oxalate plus hydrogen alcohol catalysis agent in two-stage method technique.
Specific embodiment
The present invention is described further by embodiment below, but is not limited only to the present embodiment.It is unreceipted in embodiment
The experimental technique of actual conditions, generally according to the condition described in normal condition and handbook, or according to proposed by manufacturer
Condition；Common apparatus, material, reagent used etc., if no special instructions, commercially obtain.
Fig. 1 is two-stage method preparing ethanol by oxalate hydrogenation process chart.1- fresh hydrogen air-flow stocks, 2- oxalate stream stocks, 3-
Pre- hydrogenation hydrogen stream stock, 4- hydrogen make-up stream stocks, 5- low-temperature pre-heaters, 6- first reactors（Or it is first paragraph reactor）, 7-
First paragraph hydrogenated products stream stock, 8- high-temperature preheaters, 9- electric heaters, 10- second reactors（Or it is second segment reactor）,
11- condensing heat exchangers, 12- gas-liquid separators, fixed gas stream stock after 13- reactions, liquid-phase product stream stock after 14- reactions, 15- superchargings
Machine, 16- flow control valves.
The step of two-stage method technique includes for preparing ethanol by oxalate hydrogenation：
The catalyst for preparing is respectively put into into first reactor 6（First paragraph reactor）In and second reactor 10（The
Second stage reactor）In, first catalyst is reduced in hydrogen atmosphere；After reduction terminates, adjustment first paragraph, second segment temperature
Spend to predetermined reaction temperature and pressure, the stream stock-traders' know-how containing oxalate is crossed after low-temperature pre-heater 5 is preheated and enters first reactor 6
With hydrogen reaction；The product stream stock 7 of generation and the hydrogen stream stock 4 for supplementing react in high-temperature preheater 8 after mixing with second
After the product stream stock heat exchange of device 10, then make temperature reach setting value through the heating of electric heater 9, send out subsequently into second reactor
The further hydrogenation reaction of life generates the stream stock containing ethanol；The product stream stock-traders' know-how condensing heat exchanger 11 enters gas-liquid separation after condensing
Device 12 carries out gas-liquid separation, obtains liquid-phase product stream stock 14 and fixed gas stream stock 13, and fixed gas stream stock-traders' know-how is crossed supercharger 15 and is pressurized
Mix with fresh hydrogen air-flow stock 1 afterwards, be then divided into two stream stocks 3 and 4 and respectively enter first reactor and second reactor, two
The flow of stream stock is adjusted the hydrogen ester ratio for making two reactors respectively reach setting by flow control valve 16.
Embodiment 1
Catalyst preparation
15.40g Gerhardites are weighed into there-necked flask, 150ml deionized waters are added, in water bath with thermostatic control, is stirred
Mix to copper nitrate and be completely dissolved.52ml ammonia is slowly added dropwise into solution, after stirring, 50ml deionized waters is added, it is close
4 grades of modulation of being honored as a queen is stirred 30 minutes.After stirring, the Deca 45ml Ludox in solution, aging 4 is little under stirring
When.Then heat to 80 DEG C and be evacuated down to 0.04MPa, evaporate unnecessary ammonia, make copper, aluminum and silicon oxide precipitation get off.Will
Precipitate is filtered, and is washed with deionized 3 times.By filtrate after 100 DEG C of dryings 10 hours, in 450 DEG C of roastings 4 hours.
Ultimately form the Cu/SiO that copper content is 20wt%2Catalyst is stand-by.
The catalyst tabletting of preparation is sieved into into 40-60 mesh, then weigh 0.1gCu/SiO2Catalyst first reactor
In, claim 0.4gCu/SiO2Catalyst packing is into second reactor.At 350 DEG C, 2.5MPa is reduced in hydrogen atmosphere, gas
In 300ml/min, the recovery time is 4 hours for body overall control.After reduction terminates, first reactor temperature is adjusted to 200 DEG C, the
Two temperature of reactor adjust hydrogen flowing quantity to adapt to each section of hydrogen ester ratio to 280 DEG C.Hydrogen ester ratio wherein in first reactor
The ratio of the mole of feed speed of mole of feed speed and raw material DMO for the hydrogen of first paragraph；Hydrogen ester ratio in second reactor
The mole of feed speed sum of the hydrogen supplemented for first paragraph remaining hydrogen and second segment and the mole of feed speed of raw material DMO it
Than.Hydrogen ester ratio in first reactor is adjusted to 80:1, the hydrogen ester ratio in second reactor is adjusted to 200:1.The liquid of DMO
Mass space velocity is 1.0h- 1, fed using phase autoclave pump.It is separated by and samples within 1 hour and using the gas chromatogram point of fid detector
Division thing is constituted, and is calculated DMO conversion ratios and ethanol selectivity.Reaction result is shown in Table 1.
Embodiment 2
Except the liquid quality air speed of the DMO for adopting is for 2.0h- 1Outward, other conditions are same as Example 1, reaction result
It is shown in Table 1.
Embodiment 3
Catalyst preparation
15.40g Gerhardites and the nitric hydrate aluminum of 12.03g six are weighed into there-necked flask, add 150ml go from
Sub- water, in water bath with thermostatic control, stirs to copper nitrate and is completely dissolved.52ml ammonia is slowly added dropwise into solution, after stirring, then
50ml deionized waters are added, 4 grades is modulated after sealing and is stirred 30 minutes.After stirring, the Deca 45ml Ludox in solution,
Aging 4 hours under stirring.Then heat to 80 DEG C and be evacuated down to 0.04MPa, evaporate unnecessary ammonia, make copper, aluminum and
Silicon oxide precipitation gets off.Precipitate is filtered, and is washed with deionized 3 times.By filtrate after 100 DEG C of dryings 10 hours,
In 450 DEG C of roastings 4 hours.It is 20wt% to ultimately form copper content, and aluminium content is the Cu/SiO of 0.5wt%2- 0.5Al catalyst
It is stand-by.
The catalyst tabletting of preparation is sieved into into 40-60 mesh, then weigh 0.1gCu/SiO2Catalyst first reactor
In, claim 0.4gCu/SiO2- 0.5Al Catalyst packings are into second reactor.At 350 DEG C, 2.5MPa is carried out in hydrogen atmosphere
Reduction.After reduction terminates, to 200 DEG C, second reactor temperature adjusts hydrogen stream to adjustment first reactor temperature to 280 DEG C
Measure to adapt to each section of hydrogen ester ratio.Hydrogen ester ratio wherein in first reactor is the mole of feed speed and original of the hydrogen of first paragraph
The ratio of the mole of feed speed of material DMO；Hydrogen ester ratio in second reactor is the hydrogen that first paragraph remaining hydrogen and second segment are supplemented
The ratio of the mole of feed speed sum of gas and the mole of feed speed of raw material DMO.By the hydrogen ester ratio in first reactor adjust to
80:1, the hydrogen ester ratio in second reactor is adjusted to 200:1.The liquid quality air speed of DMO is 1.0h- 1, using phase autoclave pump
Charging.Be separated by sample within 1 hour and using fid detector gas chromatographic analysiss product constitute, and be calculated DMO conversion ratios and
Ethanol selectivity.Reaction result is shown in Table 1.
Embodiment 4
Except the liquid quality air speed of the DMO for adopting is for 2.0h- 1Outward, other conditions are same as Example 3, reaction result
It is shown in Table 1.
Embodiment 5
Catalyst preparation
15.40g Gerhardites and the nitric hydrate aluminum of 24.06g six are weighed into there-necked flask, add 150ml go from
Sub- water, in water bath with thermostatic control, stirs to copper nitrate and is completely dissolved.52ml ammonia is slowly added dropwise into solution, after stirring, then
50ml deionized waters are added, 4 grades is modulated after sealing and is stirred 30 minutes.After stirring, the Deca 45ml Ludox in solution,
Aging 4 hours under stirring.Then heat to 80 DEG C and be evacuated down to 0.04MPa, evaporate unnecessary ammonia, make copper, aluminum and
Silicon oxide precipitation gets off.Precipitate is filtered, and is washed with deionized 3 times.By filtrate after 100 DEG C of dryings 10 hours,
In 450 DEG C of roastings 4 hours.It is 20wt% to ultimately form copper content, and aluminium content is the Cu/SiO of 1.0wt%2- 1.0Al catalyst
It is stand-by.
The catalyst tabletting of preparation is sieved into into 40-60 mesh, then weigh 0.1gCu/SiO2Catalyst first reactor
In, claim 0.4gCu/SiO2- 1.0Al Catalyst packings are into second reactor.At 350 DEG C, 2.5MPa is carried out in hydrogen atmosphere
Reduction.After reduction terminates, to 200 DEG C, second reactor temperature adjusts hydrogen stream to adjustment first reactor temperature to 280 DEG C
Measure to adapt to each section of hydrogen ester ratio.Hydrogen ester ratio wherein in first reactor is the mole of feed speed and original of the hydrogen of first paragraph
The ratio of the mole of feed speed of material DMO；Hydrogen ester ratio in second reactor is the hydrogen that first paragraph remaining hydrogen and second segment are supplemented
The ratio of the mole of feed speed sum of gas and the mole of feed speed of raw material DMO.By the hydrogen ester ratio in first reactor adjust to
80:1, the hydrogen ester ratio in second reactor is adjusted to 200:1.The liquid quality air speed of DMO is 1.0h- 1, using phase autoclave pump
Charging.Be separated by sample within 1 hour and using fid detector gas chromatographic analysiss product constitute, and be calculated DMO conversion ratios and
Ethanol selectivity.Reaction result is shown in Table 1.
Embodiment 6
Except the liquid quality air speed of the DMO for adopting is for 2.0h- 1Outward, other conditions are same as Example 5, reaction result
It is shown in Table 1.
Embodiment 7
Catalyst preparation
15.40g Gerhardites and the nitric hydrate aluminum of 36.09g six are weighed into there-necked flask, add 150ml go from
Sub- water, in water bath with thermostatic control, stirs to copper nitrate and is completely dissolved.52ml ammonia is slowly added dropwise into solution, after stirring, then
50ml deionized waters are added, 4 grades is modulated after sealing and is stirred 30 minutes.After stirring, the Deca 45ml Ludox in solution,
Aging 4 hours under stirring.Then heat to 80 DEG C and be evacuated down to 0.04MPa, evaporate unnecessary ammonia, make copper, aluminum and
Silicon oxide precipitation gets off.Precipitate is filtered, and deionized water and ethanol wash respectively 3 times.By filtrate in 100 DEG C of dryings
After 10 hours, in 450 DEG C of roastings 4 hours.It is 20wt% to ultimately form copper content, and aluminium content is the Cu/SiO of 1.5wt%2-
1.5Al catalyst is stand-by.
The catalyst tabletting of preparation is sieved into into 40-60 mesh, then weigh 0.1gCu/SiO2Catalyst first reactor
In, claim 0.4gCu/SiO2- 1.5Al Catalyst packings are into second reactor.At 300 DEG C, 2.5MPa is carried out in hydrogen atmosphere
Reduction.After reduction terminates, to 180 DEG C, second reactor temperature adjusts hydrogen stream to adjustment first reactor temperature to 280 DEG C
Measure to adapt to each section of hydrogen ester ratio.Hydrogen ester ratio wherein in first reactor is the mole of feed speed and original of the hydrogen of first paragraph
The ratio of the mole of feed speed of material DMO；Hydrogen ester ratio in second reactor is the hydrogen that first paragraph remaining hydrogen and second segment are supplemented
The ratio of the mole of feed speed sum of gas and the mole of feed speed of raw material DMO.By the hydrogen ester ratio in first reactor adjust to
60:1, the hydrogen ester ratio in second reactor is adjusted to 220:1.The liquid quality air speed of DMO is 1.0h- 1, using phase autoclave pump
Charging.Be separated by sample within 1 hour and using fid detector gas chromatographic analysiss product constitute, and be calculated DMO conversion ratios and
Ethanol selectivity.Reaction result is shown in Table 1.
Embodiment 8
Catalyst preparation
15.40g Gerhardites and the nitric hydrate aluminum of 36.09g six are weighed into there-necked flask, add 150ml go from
Sub- water, in water bath with thermostatic control, stirs to copper nitrate and is completely dissolved.52ml ammonia is slowly added dropwise into solution, after stirring, then
50ml deionized waters are added, 4 grades is modulated after sealing and is stirred 30 minutes.After stirring, the Deca 45ml Ludox in solution,
Aging 4 hours under stirring.80 DEG C are then heated to, unnecessary ammonia is evaporated, makes copper, aluminum and silicon oxide precipitation get off.Will
Precipitate is filtered, and deionized water and ethanol wash respectively 3 times.By filtrate after 100 DEG C of dryings 10 hours, at 450 DEG C
Roasting 4 hours.It is 20wt% to ultimately form copper content, and aluminium content is the Cu/SiO of 1.5wt%2- 1.5Al catalyst is stand-by.
The catalyst tabletting of preparation is sieved into into 40-60 mesh, then weigh 0.1gCu/SiO2Catalyst first reactor
In, claim 0.4gCu/SiO2- 1.5Al Catalyst packings are into second reactor.At 350 DEG C, 2.5MPa is carried out in hydrogen atmosphere
Reduction.After reduction terminates, to 200 DEG C, second reactor temperature adjusts hydrogen stream to adjustment first reactor temperature to 280 DEG C
Measure to adapt to each section of hydrogen ester ratio.Hydrogen ester ratio wherein in first reactor is the mole of feed speed and original of the hydrogen of first paragraph
The ratio of the mole of feed speed of material DMO；Hydrogen ester ratio in second reactor is the hydrogen that first paragraph remaining hydrogen and second segment are supplemented
The ratio of the mole of feed speed sum of gas and the mole of feed speed of raw material DMO.By the hydrogen ester ratio in first reactor adjust to
50:1, the hydrogen ester ratio in second reactor is adjusted to 250:1.The liquid quality air speed of DMO is 2.0h- 1, using phase autoclave pump
Charging.Be separated by sample within 1 hour and using fid detector gas chromatographic analysiss product constitute, and be calculated DMO conversion ratios and
Ethanol selectivity.Reaction result is shown in Table 1.
Comparing embodiment 1
Catalyst preparation
15.40g Gerhardites are weighed into there-necked flask, 150ml deionized waters are added, in water bath with thermostatic control, is stirred
Mix to copper nitrate and be completely dissolved.52ml ammonia is slowly added dropwise into solution, after stirring, 50ml deionized waters is added, it is close
4 grades of modulation of being honored as a queen is stirred 30 minutes.After stirring, the Deca 45ml Ludox in solution, aging 4 is little under stirring
When.80 DEG C are then heated to, unnecessary ammonia is evaporated, makes copper, aluminum and silicon oxide precipitation get off.Precipitate is filtered, and is spent
Ionized water and ethanol wash respectively 3 times.By filtrate after 100 DEG C of dryings 10 hours, in 450 DEG C of roastings 4 hours.Ultimately form
Copper content is the Cu/SiO of 20wt%2Catalyst is stand-by.
The catalyst tabletting of preparation is sieved into into 40-60 mesh, then weigh 0.5gCu/SiO2Catalyst packing is to reactor
In.At 350 DEG C, 2.5MPa is reduced in hydrogen atmosphere.After reduction terminates, adjustment temperature of reactor is adjusted to 280 DEG C
Hydrogen flowing quantity to hydrogen ester ratio is 200:1.The liquid quality air speed of DMO is 2.0h- 1, fed using phase autoclave pump.It is separated by 1 little
When sample and the gas chromatographic analysiss product using fid detector is constituted, and be calculated DMO conversion ratios and ethanol selectivity.
Reaction result is shown in Table 1.
Comparing embodiment 2
Catalyst preparation
15.40g Gerhardites and the nitric hydrate aluminum of 24.06g six are weighed into there-necked flask, add 150ml go from
Sub- water, in water bath with thermostatic control, stirs to copper nitrate and is completely dissolved.52ml ammonia is slowly added dropwise into solution, after stirring, then
50ml deionized waters are added, 4 grades is modulated after sealing and is stirred 30 minutes.After stirring, the Deca 45ml Ludox in solution,
Aging 4 hours under stirring.80 DEG C are then heated to, unnecessary ammonia is evaporated, makes copper, aluminum and silicon oxide precipitation get off.Will
Precipitate is filtered, and deionized water and ethanol wash respectively 3 times.By filtrate after 100 DEG C of dryings 10 hours, at 450 DEG C
Roasting 4 hours.It is 20wt% to ultimately form copper content, and aluminium content is the Cu/SiO of 1.0wt%2- 1.0Al catalyst is stand-by.
The catalyst tabletting of preparation is sieved into into 40-60 mesh, then weigh 0.1gCu/SiO2Catalyst first reactor
In, claim 0.4gCu/SiO2- 1.0Al Catalyst packings are into second reactor.At 350 DEG C, 2.5MPa is carried out in hydrogen atmosphere
Reduction.After reduction terminates, to 200 DEG C, second reactor temperature adjusts hydrogen stream to adjustment first reactor temperature to 260 DEG C
Measure to adapt to each section of hydrogen ester ratio.Hydrogen ester ratio wherein in first reactor is the mole of feed speed and original of the hydrogen of first paragraph
The ratio of the mole of feed speed of material DMO；Hydrogen ester ratio in second reactor is the hydrogen that first paragraph remaining hydrogen and second segment are supplemented
The ratio of the mole of feed speed sum of gas and the mole of feed speed of raw material DMO.By the hydrogen ester ratio in first reactor adjust to
80:1, the hydrogen ester ratio in second reactor is adjusted to 200:1.The liquid quality air speed of DMO is 2.0h- 1, using phase autoclave pump
Charging.Be separated by sample within 1 hour and using fid detector gas chromatographic analysiss product constitute, and be calculated DMO conversion ratios and
Ethanol selectivity.Reaction result is shown in Table 1.
Comparing embodiment 3
Catalyst preparation
15.40g Gerhardites and the nitric hydrate aluminum of 24.06g six are weighed into there-necked flask, add 150ml go from
Sub- water, in water bath with thermostatic control, stirs to copper nitrate and is completely dissolved.52ml ammonia is slowly added dropwise into solution, after stirring, then
50ml deionized waters are added, 4 grades is modulated after sealing and is stirred 30 minutes.After stirring, the Deca 45ml Ludox in solution,
Aging 4 hours under stirring.80 DEG C are then heated to, unnecessary ammonia is evaporated, makes copper, aluminum and silicon oxide precipitation get off.Will
Precipitate is filtered, and deionized water and ethanol wash respectively 3 times.By filtrate after 100 DEG C of dryings 10 hours, at 450 DEG C
Roasting 4 hours.It is 20wt% to ultimately form copper content, and aluminium content is the Cu/SiO of 1.0wt%2- 1.0Al catalyst is stand-by.
The catalyst tabletting of preparation is sieved into into 40-60 mesh, then weigh 0.1gCu/SiO2Catalyst first reactor
In, claim 0.4gCu/SiO2- 1.0Al Catalyst packings are into second reactor.At 350 DEG C, 2.5MPa is carried out in hydrogen atmosphere
Reduction.After reduction terminates, to 200 DEG C, second reactor temperature adjusts hydrogen stream to adjustment first reactor temperature to 240 DEG C
Measure to adapt to each section of hydrogen ester ratio.Hydrogen ester ratio wherein in first reactor is the mole of feed speed and original of the hydrogen of first paragraph
The ratio of the mole of feed speed of material DMO；Hydrogen ester ratio in second reactor is the hydrogen that first paragraph remaining hydrogen and second segment are supplemented
The ratio of the mole of feed speed sum of gas and the mole of feed speed of raw material DMO.By the hydrogen ester ratio in first reactor adjust to
80:1, the hydrogen ester ratio in second reactor is adjusted to 200:1.The liquid quality air speed of DMO is 2.0h- 1, using phase autoclave pump
Charging.Be separated by sample within 1 hour and using fid detector gas chromatographic analysiss product constitute, and be calculated DMO conversion ratios and
Ethanol selectivity.Reaction result is shown in Table 1.
The preparing ethanol by oxalate hydrogenation reaction result of table 1：
Claims (8)
1. a kind of two-stage method preparing ethanol by oxalate hydrogenation technique, the catalyst components for adopting account for catalyst weight percent for：
Silicon oxide accounts for the 70-90% of catalyst weight, and active ingredient copper accounts for the 5-30% of catalyst weight, and auxiliary agent accounts for catalyst weight
0.5-1.5%, each component weight sum of catalyst is 100%；It is characterized in that：
Reactant oxalate is eventually converted into into ethanol by two tandem reactors；Oxalate is made first in first reactor
In be converted into intermediate product stream stock at a lower temperature, generate the excessively further pre-heating temperature elevation of product stream stock-traders' know-how anti-into second
Answer and be further hydrogenated at a higher temperature in device stock containing ethanol stream；Reaction condition is as follows：
Reaction pressure is 1.0-4.0MPa；Catalyst reduction temperature is 250-400 DEG C；The reaction temperature of first paragraph is 180-220
℃；The reaction temperature of second segment is 280 DEG C；Mole hydrogen ester ratio is 40-100 in first reactor；Moles of hydrogen in second reactor
Ester ratio is 180-300；The gross mass air speed of oxalate charging is 0.5-3 h-1;
First described reactor is isothermal reactor；Second described reactor is adiabatic reactor；
Stream stock from second reactor out is including at least one or two in methanol or ethanol.
2. according to the technique described in claim 1, it is characterised in that first paragraph reaction temperature be 200 DEG C, second segment reaction pressure
Power is 2.5MPa, and first paragraph mole hydrogen ester ratio is 80, and second segment mole hydrogen ester ratio is 200, and oxalate mass space velocity is 1.0h-1。
3. according to the technique described in claim 1, it is characterised in that the stream stock from first reactor out at least also includes second
One or two in glycol and ethyl glycolate.
4. a kind of two-stage method preparing ethanol by oxalate hydrogenation technique, it is characterised in that including the step of：
1）The catalyst for preparing is respectively put in first reactor and in second reactor, will be urged first in hydrogen atmosphere
Agent is reduced；
2）After reduction terminates, after first, second temperature of reactor of adjustment to predetermined reaction temperature and pressure, the stream containing oxalate
Stock-traders' know-how is crossed and first reactor is entered after low-temperature pre-heater preheating with hydrogen reaction；
3）After the hydrogen stream stock mixing of the product stream stock of generation and supplement in high-temperature preheater with the product of second reactor
After stream stock heat exchange, then make temperature reach setting value through electric heater heating, occur further to add subsequently into second reactor
Hydrogen reaction generates the stream stock containing ethanol；
4）Gas-liquid separation is carried out into gas-liquid separator after the product stream stock-traders' know-how condensing heat exchanger condensation, liquid-phase product stream stock is obtained
With fixed gas stream stock, fixed gas stream stock-traders' know-how cross supercharger supercharging after mix with fresh hydrogen air-flow stock, be then divided into two flow stocks
Not Jin Ru first reactor and second reactor, the flows of two stream stocks make in two reactors respectively by flow-control valve regulation
Reach the hydrogen ester ratio of setting.
5. according to the technique described in claim 4, it is characterised in that reaction condition is：
Reaction pressure is 1.0-4.0MPa；Catalyst reduction temperature is 250-400 DEG C；The reaction temperature of first paragraph is 180-220
℃；The reaction temperature of second segment is 280 DEG C；Mole hydrogen ester ratio is 40-100 in first reactor；Moles of hydrogen in second reactor
Ester ratio is 180-300；The gross mass air speed of oxalate charging is 0.5-3 h-1。
6. according to the technique described in claim 4, it is characterised in that first paragraph reaction temperature be 200 DEG C, second segment reaction pressure
Power is 2.5MPa, and first paragraph mole hydrogen ester ratio is 80, and second segment mole hydrogen ester ratio is 200, and oxalate mass space velocity is 1.0h-1。
7. according to the technique described in claim 4, it is characterised in that described oxalate is dimethyl oxalate. and ethyl oxalate
In one or two kinds of.
8. according to the technique described in claim 4, it is characterised in that in the described stream stock containing oxalate in addition to oxalate
One or two can also be included in ethanol and methanol as solvent.
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