CN105085167A - 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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- CN105085167A CN105085167A CN201510535737.8A CN201510535737A CN105085167A CN 105085167 A CN105085167 A CN 105085167A CN 201510535737 A CN201510535737 A CN 201510535737A CN 105085167 A CN105085167 A CN 105085167A
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- 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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- 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 the technique of a kind of two-stage method hydrogenation of oxalate for preparing for ethanol.
Background technology
Ethanol, is commonly called as alcohol, as a kind of important industrial chemicals, is widely used in the fields such as food, medicine, chemical industry, national defence.Because the oxygen level of ethanol is up to 34.7%, thus also can add in gasoline as methyl tertiary butyl ether (MTBE) substitute and obtain ethanol petrol, both can reduce petrol consumption, and gasoline combustion can also be made more abundant, thus reduce the discharge of the pollutents such as aflame CO.The route of traditional mode of production ethanol mainly comprises two.Article one, be petroleum path, by adopting petroleum cracking product ethene to be raw material, hydration obtains ethanol.Other one is biological fermentation route, by adopting various sugary agricultural-food, agroforestry by product and wild plant to be raw material, makes disaccharide, polysaccharide conversion be monose and be further converted to ethanol through hydrolysis, fermentation.
Along with the fast development of automobile industry, China's bio-ethanol is produced and is obtained swift and violent development, has risen to the large fuel ethanol production state in third place in the world and country of consumption at present.Due to the restriction of China's national situation, extensive sugarcane or the Maize Production alcohol fuel of using is limited to, and adopts Mierocrystalline cellulose to be that the alcohol production technology of raw material is not yet ripe.Based on the national conditions of coal in China relative abundance, received by synthetic gas ethanol and pay close attention to widely.The synthetic gas reported directly ethanol procedure processed is that first synthetic gas uses Rh/SiO
2catalyzer reacts and generates carbon two product that acetaldehyde, ethanol, ethyl acetate and acetic acid are master, then at Cu/SiO under 3-10MPa and 300 DEG C condition
2[JP6259632], Pd-Fe/SiO
2the further hydrocrackings of by product such as acetaldehyde, ethyl acetate and acetic acid are ethanol by the catalyzer such as [JP61178940, JP61178942] or Cu-Zn-Al-Mg-Mo [CN1122567].Due to the shortcoming such as this technical matters condition harshness, poor catalyst stability, selectivity be low, not yet obtain large-scale application up to now.
Chinese patent CN101934228A reports a kind of copper-based catalysts of acetic ester preparation of ethanol by hydrogenating, carrier is aluminum oxide or silicon oxide, auxiliary agent is the oxide compound of the elements such as zinc, manganese, chromium, calcium, barium, iron, nickel, magnesium, and the transformation efficiency of acetic ester is up to 88%, but reaction efficiency is lower.
CN102327774A reports a kind of copper-based catalysts and is applied to acetic ester preparation of ethanol by hydrogenating reaction system, its preparation method adds silicon sol or aluminum soluble salt in the soluble salt and promoter metal soluble salt mixing solutions of copper, after stirring, join in the solution of precipitation agent by mixed solution under 50-95 DEG C of condition, then aging, filtration, washing, drying, roasting, shaping and reduction obtain catalyzer.The peak rate of conversion of institute's controlling catalyst in acetic ester hydrogenation reaction is 85%, and ethanol selectivity is 91%.
CN101941887A adopts silicon oxide or aluminum oxide to be carrier, copper is the metal such as active ingredient, Zn, Mn, Cr, Ca, Ba or metal oxide is that auxiliary agent obtains copper-based catalysts, selectivity in acetic ester hydrogenation reaction is up to 99%, and transformation efficiency is up to 92%.
CN101411990A discloses a kind of preparation method of hydrogenation of oxalate for preparing ethylene glycol copper Si catalyst, and the method is that in cupric ammine complex, add specific surface area be 600-1200m
2in the mesoporous silica molecular sieve powder of/g, then after filtration, washing, drying, roasting, reduction, make catalyzer.
CN102350358B openly reports a kind of preparation method and application of copper-based catalysts of preparing ethanol by oxalate hydrogenation, it adopts zirconium white and silicon oxide as complex carrier, copper is as active ingredient, the metals such as Mg, Ca, Ba, Mn or metal oxide are that auxiliary agent prepares copper-based catalysts, in preparing ethanol by oxalate hydrogenation, the transformation efficiency of barkite reaches 100%, and ethanol selectivity reaches 85%.
It is that raw material contacts with copper containing catalyst in fluidized-bed reactor with barkite that CN102649745A with CN102649744A discloses a kind of, generates the technical scheme of the effluent containing ethyl glycolate, to improve the selectivity of ethyl glycolate.
Experiment proves, there is the stability problem of the catalyzer under highly selective condition itself of the low and target product ethanol of selectivity of by product three carbon, four carbon alcohols in above-mentioned copper-based catalysts technique.
Summary of the invention
The object of this invention is to provide a kind of operational path of two-stage method preparing ethanol by oxalate hydrogenation, the method is, by two reactor, reactant barkite is finally converted into ethanol.First make barkite transform at a lower temperature in first reactor, then product in the second reactor at a higher temperature further hydrogenation generate ethanol.This technique can effectively suppress main side reaction, reduces the selectivity of three carbon alcohol, four carbon alcohols, thus the effective selectivity improving ethanol.Adopting with silicon oxide is carrier, with copper as active ingredient, using aluminium as modified additive; The acid-basicity of auxiliary agent aluminium to catalyst surface regulates and controls, and makes this catalyzer not only have comparatively ideal surface acidic-basic property, also have good side reaction rejection ability simultaneously, thus obtains higher ethanol selectivity.With optimal conditions, when the transformation efficiency of barkite reaches 100%, the selectivity of ethanol reaches 85.0%, also significantly reduces the cost of later separation while reducing waste discharge.In addition, under these processing condition, catalyst stabilization runs 100 hours, and activity does not have considerable change, illustrates that novel process and this catalyzer have excellent stability.
The invention provides a kind of two-stage method preparing ethanol by oxalate hydrogenation technique and mainly by two tandem reactors, reactant barkite is finally converted into ethanol.First make barkite be converted into intermediate product stream stock at a lower temperature in the first reactor, generate product flow stock-traders' know-how and cross the further pre-heating temperature elevation of preheater and to enter in the second reactor at a higher temperature hydrogenation further and generate containing ethanol stream stock.
The first described reactor is isothermal reactor.
The second described reactor is adiabatic reactor.
Described from the second reactor stream stock out at least comprise in methyl alcohol or ethanol one or both.
Described from the first reactor stream stock out at least also comprise in ethylene glycol and methyl glycolate one or both.
Two-stage method technique provided by the invention is used for the step that preparing ethanol by oxalate hydrogenation comprises:
The catalyzer prepared is put into respectively the first reactor (first paragraph reactor) and the second reactor (second segment reactor), first in hydrogen atmosphere, catalyzer is reduced; After reduction terminates, after adjustment first paragraph, second segment temperature to predetermined temperature of reaction and pressure, after the stream stock-traders' know-how containing barkite crosses low temperature preheater preheats, enter the first reactor and hydrogen reaction; Generate product flow stock and supplementary hydrogen stream stock mixing after in high-temperature preheater with the product flow stock heat exchange of the second reactor after, make temperature reach set(ting)value through electric heater heating again, then enter the second reactor and the stream stock of further hydrogenation reaction generation containing ethanol occurs; Enter gas-liquid separator after this product flow stock-traders' know-how condensing heat exchanger condensation and carry out gas-liquid separation, obtain liquid-phase product stream stock and non-condensable gas stream stock, mix with fresh hydrogen air-flow stock after non-condensable gas stream stock-traders' know-how crosses supercharger supercharging, then be divided into two to flow stock and do not enter the first reactor and the second reactor, the flow of two stream stocks makes two reactors reach the hydrogen ester ratio of setting respectively by flow control valve regulation.
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 temperature of reaction of described two-stage method technique first paragraph is 180-220 DEG C.
The temperature of reaction of described two-stage method technique second segment is 240-300 DEG C.
In described two-stage method technique first reactor, mole hydrogen ester is than being 40-100.
In described two-stage method technique second reactor, mole hydrogen ester is than being 180-300.
The total mass air speed of described two-stage method technique barkite charging is 0.5-3h
-1.
Alternatively, the reaction conditions of two-stage method technique is: be 200 DEG C in first paragraph temperature of reaction, and second segment temperature of reaction is 280 DEG C, and reaction pressure is 2.5MPa, and a first paragraph mole hydrogen ester ratio is 80, and a second segment mole hydrogen ester ratio is 200, and barkite mass space velocity is 1.0h
-1.
Described barkite is one in dimethyl oxalate and oxalic acid diethyl ester or two kinds.
The catalyst components that the present invention adopts accounts for catalyst weight percent and is: silicon oxide accounts for the 70-90% of catalyst weight, active ingredient copper accounts for the 5-30% of catalyst weight, auxiliary agent accounts for the 0.5-1.5% of catalyst weight, and the sum of each composition weight of described catalyzer is 100%; Wherein, preparation method can select following steps:
1) cupric nitrate and aluminum nitrate is selected to be mixed with mixed aqueous solution by metering;
2) in the solution in step 1), drip ammoniacal liquor, and stir 10-30 minute;
3) to step 2) middle dropping silicon sol, stirred at ambient temperature 2-10 hour;
4) slurry in step 3) be warming up to 80-95 DEG C and vacuumize, when liquid phase PH valve lower than 7 time, stop heating;
5) by after the liquid cooling in step 4), by sedimentation and filtration, washing to neutral;
6) filter cake in step 5) is dry under 80-120 DEG C of condition;
7), after being pulverized by filter cake dried in step 6), at 400-450 DEG C, catalyzer of the present invention is formed after roasting.
Described containing including in ethanol and methyl alcohol one or both in the stream stock of barkite as solvent except barkite.
The present invention adopts novel two-stage method technique to carry out preparing ethanol by oxalate hydrogenation reaction, is 200 DEG C in first paragraph temperature of reaction, and second segment temperature of reaction is 280 DEG C, reaction pressure is 2.5MPa, a first paragraph mole hydrogen ester ratio is 80, and a second segment mole hydrogen ester ratio is 200, and barkite mass space velocity is 1.0h
-1time, barkite average conversion reaches 99, and more than 9%, ethanol average selectivity, up to more than 85.0%, shows high hydrogenation activity and selectivity.(see figure 2)
The present invention adopts brand-new two-stage method technique, is first transformed at a lower temperature by barkite, then carries out further hydrogenation at comparatively high temps to its product, obtains target product ethanol.In two-stage method technique, barkite reacts the generation that effectively can suppress side reaction at low temperatures, makes by product three carbon, the selectivity of four carbon alcohols obviously reduces, thus significantly improve the selectivity of ethanol.Will be in conjunction with by this catalyzer and novel process, carry out preparing ethanol by oxalate hydrogenation reaction, with optimal conditions, when the transformation efficiency of barkite reaches 100%, the selectivity of ethanol reaches 85.0%, also significantly reduces the cost of later separation while reducing waste discharge.In addition, under these processing condition, catalyst stabilization runs 100 hours, and activity does not have considerable change, illustrates that novel process and this catalyzer have excellent stability.
Accompanying drawing explanation
Fig. 1. two-stage method preparing ethanol by oxalate hydrogenation process flow sheet.
Fig. 2. the operation stability graphic representation of prepared by dimethyl oxalate plus hydrogen alcohol catalysis agent in two-stage method technique.
Embodiment
Below the present invention is described further by embodiment, but is not limited only to the present embodiment.The experimental technique of unreceipted actual conditions in embodiment, usually conveniently condition and the condition described in handbook, or according to the condition that manufacturer advises; General-purpose equipment used, material, reagent etc., if no special instructions, all can obtain from commercial channels.
Fig. 1 is two-stage method preparing ethanol by oxalate hydrogenation process flow sheet.1-fresh hydrogen air-flow stock, 2-barkite stream stock, 3-pre-hydrogenation hydrogen stream stock, 4-hydrogen make-up air-flow stock, 5-low-temperature pre-heater, 6-first reactor (or being first paragraph reactor), 7-first paragraph hydrogenated products stream stock, 8-high-temperature preheater, 9-electric heater, 10-second reactor (or being second segment reactor), 11-condensing heat exchanger, 12-gas-liquid separator, non-condensable gas stream stock after 13-reaction, liquid-phase product stream stock after 14-reaction, 15-supercharger, 16-flowrate control valve.
Two-stage method technique is used for the step that preparing ethanol by oxalate hydrogenation comprises:
The catalyzer prepared is put into respectively the first reactor 6(first paragraph reactor) and the second reactor 10(second segment reactor), first in hydrogen atmosphere, catalyzer is reduced; After reduction terminates, after adjustment first paragraph, second segment temperature to predetermined temperature of reaction and pressure, the stream stock-traders' know-how containing barkite enters the first reactor 6 and hydrogen reaction after crossing low-temperature pre-heater 5 preheating; Generate product flow stock 7 and supplement hydrogen stream stock 4 mix after in high-temperature preheater 8 with the product flow stock heat exchange of the second reactor 10 after, make temperature reach set(ting)value through electric heater 9 heating again, then enter the second reactor and the stream stock of further hydrogenation reaction generation containing ethanol occurs; Enter gas-liquid separator 12 after this product flow stock-traders' know-how condensing heat exchanger 11 condensation and carry out gas-liquid separation, obtain liquid-phase product stream stock 14 and non-condensable gas stream stock 13, mix with fresh hydrogen air-flow stock 1 after non-condensable gas stream stock-traders' know-how crosses supercharger 15 supercharging, then be divided into two to flow stock 3 and 4 and enter the first reactor and the second reactor respectively, the flow of two stream stocks is regulated by flowrate control valve 16 and makes two reactors reach the hydrogen ester ratio of setting respectively.
Embodiment 1
Catalyst preparing
Take 15.40g Gerhardite in there-necked flask, add 150ml deionized water, in water bath with thermostatic control, be stirred to cupric nitrate and dissolve completely.Slow dropping 52ml ammoniacal liquor, in solution, after stirring, then adds 50ml deionized water, and after sealing, modulation 4 grades is stirred 30 minutes.After stirring, in solution, drip 45ml silicon sol, under whipped state aging 4 hours.Then be warming up to 80 DEG C and be evacuated down to 0.04MPa, evaporating unnecessary ammoniacal liquor, copper, aluminium and silicon oxide precipitation are got off.Throw out is filtered, and with deionized water wash 3 times.By filtrate 100 DEG C of dryings after 10 hours, 450 DEG C of roastings 4 hours.Final formation copper content is the Cu/SiO of 20wt%
2catalyzer is stand-by.
The catalyzer compressing tablet of preparation is sieved into 40-60 order, and then weigh 0.1gCu/SiO
2in catalyzer first reactor, claim 0.4gCu/SiO
2in catalyst loading to the second reactor.At 350 DEG C, 2.5MPa, reduces in hydrogen atmosphere, and gas gross controls at 300ml/min, and the recovery time is 4 hours.After reduction terminates, adjust the first temperature of reactor to 200 DEG C, the second temperature of reactor to 280 DEG C, and adjust hydrogen flowing quantity with the hydrogen ester ratio adapting to each section.Hydrogen ester wherein in the first reactor is than being the mole of feed speed of hydrogen of first paragraph and the ratio of the mole of feed speed of raw material DMO; Hydrogen ester in second reactor is than the mole of feed speed sum of hydrogen of supplementing for first paragraph remaining hydrogen and second segment and the ratio of the mole of feed speed of raw material DMO.Hydrogen ester ratio in first reactor is adjusted to 80:1, and the hydrogen ester ratio in the second reactor is adjusted to 200:1.The liquid mass air speed of DMO is 1.0h
-1, adopt the charging of phase autoclave pump.Be separated by 1 hour and sample and adopt the gas chromatographic analysis product of fid detector to form, and calculate DMO transformation efficiency and ethanol selectivity.Reaction result is in table 1.
Embodiment 2
Except the liquid mass air speed of the DMO adopted is 2.0h
-1outward, other conditions are all identical with embodiment 1, and reaction result is in table 1.
Embodiment 3
Catalyst preparing
Take 15.40g Gerhardite and 12.03g six nitric hydrate aluminium in there-necked flask, add 150ml deionized water, in water bath with thermostatic control, be stirred to cupric nitrate and dissolve completely.Slow dropping 52ml ammoniacal liquor, in solution, after stirring, then adds 50ml deionized water, and after sealing, modulation 4 grades is stirred 30 minutes.After stirring, in solution, drip 45ml silicon sol, under whipped state aging 4 hours.Then be warming up to 80 DEG C and be evacuated down to 0.04MPa, evaporating unnecessary ammoniacal liquor, copper, aluminium and silicon oxide precipitation are got off.Throw out is filtered, and with deionized water wash 3 times.By filtrate 100 DEG C of dryings after 10 hours, 450 DEG C of roastings 4 hours.Final formation copper content is 20wt%, and aluminium content is the Cu/SiO of 0.5wt%
2-0.5Al catalyzer is stand-by.
The catalyzer compressing tablet of preparation is sieved into 40-60 order, and then weigh 0.1gCu/SiO
2in catalyzer first reactor, claim 0.4gCu/SiO
2in-0.5Al catalyst loading to the second reactor.At 350 DEG C, 2.5MPa, reduces in hydrogen atmosphere.After reduction terminates, adjust the first temperature of reactor to 200 DEG C, the second temperature of reactor to 280 DEG C, and adjust hydrogen flowing quantity with the hydrogen ester ratio adapting to each section.Hydrogen ester wherein in the first reactor is than being the mole of feed speed of hydrogen of first paragraph and the ratio of the mole of feed speed of raw material DMO; Hydrogen ester in second reactor is than the mole of feed speed sum of hydrogen of supplementing for first paragraph remaining hydrogen and second segment and the ratio of the mole of feed speed of raw material DMO.Hydrogen ester ratio in first reactor is adjusted to 80:1, and the hydrogen ester ratio in the second reactor is adjusted to 200:1.The liquid mass air speed of DMO is 1.0h
-1, adopt the charging of phase autoclave pump.Be separated by 1 hour and sample and adopt the gas chromatographic analysis product of fid detector to form, and calculate DMO transformation efficiency and ethanol selectivity.Reaction result is in table 1.
Embodiment 4
Except the liquid mass air speed of the DMO adopted is 2.0h
-1outward, other conditions are all identical with embodiment 3, and reaction result is in table 1.
Embodiment 5
Catalyst preparing
Take 15.40g Gerhardite and 24.06g six nitric hydrate aluminium in there-necked flask, add 150ml deionized water, in water bath with thermostatic control, be stirred to cupric nitrate and dissolve completely.Slow dropping 52ml ammoniacal liquor, in solution, after stirring, then adds 50ml deionized water, and after sealing, modulation 4 grades is stirred 30 minutes.After stirring, in solution, drip 45ml silicon sol, under whipped state aging 4 hours.Then be warming up to 80 DEG C and be evacuated down to 0.04MPa, evaporating unnecessary ammoniacal liquor, copper, aluminium and silicon oxide precipitation are got off.Throw out is filtered, and with deionized water wash 3 times.By filtrate 100 DEG C of dryings after 10 hours, 450 DEG C of roastings 4 hours.Final formation copper content is 20wt%, and aluminium content is the Cu/SiO of 1.0wt%
2-1.0Al catalyzer is stand-by.
The catalyzer compressing tablet of preparation is sieved into 40-60 order, and then weigh 0.1gCu/SiO
2in catalyzer first reactor, claim 0.4gCu/SiO
2in-1.0Al catalyst loading to the second reactor.At 350 DEG C, 2.5MPa, reduces in hydrogen atmosphere.After reduction terminates, adjust the first temperature of reactor to 200 DEG C, the second temperature of reactor to 280 DEG C, and adjust hydrogen flowing quantity with the hydrogen ester ratio adapting to each section.Hydrogen ester wherein in the first reactor is than being the mole of feed speed of hydrogen of first paragraph and the ratio of the mole of feed speed of raw material DMO; Hydrogen ester in second reactor is than the mole of feed speed sum of hydrogen of supplementing for first paragraph remaining hydrogen and second segment and the ratio of the mole of feed speed of raw material DMO.Hydrogen ester ratio in first reactor is adjusted to 80:1, and the hydrogen ester ratio in the second reactor is adjusted to 200:1.The liquid mass air speed of DMO is 1.0h
-1, adopt the charging of phase autoclave pump.Be separated by 1 hour and sample and adopt the gas chromatographic analysis product of fid detector to form, and calculate DMO transformation efficiency and ethanol selectivity.Reaction result is in table 1.
Embodiment 6
Except the liquid mass air speed of the DMO adopted is 2.0h
-1outward, other conditions are all identical with embodiment 5, and reaction result is in table 1.
Embodiment 7
Catalyst preparing
Take 15.40g Gerhardite and 36.09g six nitric hydrate aluminium in there-necked flask, add 150ml deionized water, in water bath with thermostatic control, be stirred to cupric nitrate and dissolve completely.Slow dropping 52ml ammoniacal liquor, in solution, after stirring, then adds 50ml deionized water, and after sealing, modulation 4 grades is stirred 30 minutes.After stirring, in solution, drip 45ml silicon sol, under whipped state aging 4 hours.Then be warming up to 80 DEG C and be evacuated down to 0.04MPa, evaporating unnecessary ammoniacal liquor, copper, aluminium and silicon oxide precipitation are got off.Throw out is filtered, and washs 3 times respectively with deionized water and ethanol.By filtrate 100 DEG C of dryings after 10 hours, 450 DEG C of roastings 4 hours.Final formation copper content is 20wt%, and aluminium content is the Cu/SiO of 1.5wt%
2-1.5Al catalyzer is stand-by.
The catalyzer compressing tablet of preparation is sieved into 40-60 order, and then weigh 0.1gCu/SiO
2in catalyzer first reactor, claim 0.4gCu/SiO
2in-1.5Al catalyst loading to the second reactor.At 300 DEG C, 2.5MPa, reduces in hydrogen atmosphere.After reduction terminates, adjust the first temperature of reactor to 180 DEG C, the second temperature of reactor to 280 DEG C, and adjust hydrogen flowing quantity with the hydrogen ester ratio adapting to each section.Hydrogen ester wherein in the first reactor is than being the mole of feed speed of hydrogen of first paragraph and the ratio of the mole of feed speed of raw material DMO; Hydrogen ester in second reactor is than the mole of feed speed sum of hydrogen of supplementing for first paragraph remaining hydrogen and second segment and the ratio of the mole of feed speed of raw material DMO.Hydrogen ester ratio in first reactor is adjusted to 60:1, and the hydrogen ester ratio in the second reactor is adjusted to 220:1.The liquid mass air speed of DMO is 1.0h
-1, adopt the charging of phase autoclave pump.Be separated by 1 hour and sample and adopt the gas chromatographic analysis product of fid detector to form, and calculate DMO transformation efficiency and ethanol selectivity.Reaction result is in table 1.
Embodiment 8
Catalyst preparing
Take 15.40g Gerhardite and 36.09g six nitric hydrate aluminium in there-necked flask, add 150ml deionized water, in water bath with thermostatic control, be stirred to cupric nitrate and dissolve completely.Slow dropping 52ml ammoniacal liquor, in solution, after stirring, then adds 50ml deionized water, and after sealing, modulation 4 grades is stirred 30 minutes.After stirring, in solution, drip 45ml silicon sol, under whipped state aging 4 hours.Then be warming up to 80 DEG C, evaporate unnecessary ammoniacal liquor, copper, aluminium and silicon oxide precipitation are got off.Throw out is filtered, and washs 3 times respectively with deionized water and ethanol.By filtrate 100 DEG C of dryings after 10 hours, 450 DEG C of roastings 4 hours.Final formation copper content is 20wt%, and aluminium content is the Cu/SiO of 1.5wt%
2-1.5Al catalyzer is stand-by.
The catalyzer compressing tablet of preparation is sieved into 40-60 order, and then weigh 0.1gCu/SiO
2in catalyzer first reactor, claim 0.4gCu/SiO
2in-1.5Al catalyst loading to the second reactor.At 350 DEG C, 2.5MPa, reduces in hydrogen atmosphere.After reduction terminates, adjust the first temperature of reactor to 200 DEG C, the second temperature of reactor to 280 DEG C, and adjust hydrogen flowing quantity with the hydrogen ester ratio adapting to each section.Hydrogen ester wherein in the first reactor is than being the mole of feed speed of hydrogen of first paragraph and the ratio of the mole of feed speed of raw material DMO; Hydrogen ester in second reactor is than the mole of feed speed sum of hydrogen of supplementing for first paragraph remaining hydrogen and second segment and the ratio of the mole of feed speed of raw material DMO.Hydrogen ester ratio in first reactor is adjusted to 50:1, and the hydrogen ester ratio in the second reactor is adjusted to 250:1.The liquid mass air speed of DMO is 2.0h
-1, adopt the charging of phase autoclave pump.Be separated by 1 hour and sample and adopt the gas chromatographic analysis product of fid detector to form, and calculate DMO transformation efficiency and ethanol selectivity.Reaction result is in table 1.
Comparing embodiment 1
Catalyst preparing
Take 15.40g Gerhardite in there-necked flask, add 150ml deionized water, in water bath with thermostatic control, be stirred to cupric nitrate and dissolve completely.Slow dropping 52ml ammoniacal liquor, in solution, after stirring, then adds 50ml deionized water, and after sealing, modulation 4 grades is stirred 30 minutes.After stirring, in solution, drip 45ml silicon sol, under whipped state aging 4 hours.Then be warming up to 80 DEG C, evaporate unnecessary ammoniacal liquor, copper, aluminium and silicon oxide precipitation are got off.Throw out is filtered, and washs 3 times respectively with deionized water and ethanol.By filtrate 100 DEG C of dryings after 10 hours, 450 DEG C of roastings 4 hours.Final formation copper content is the Cu/SiO of 20wt%
2catalyzer is stand-by.
The catalyzer compressing tablet of preparation is sieved into 40-60 order, and then weigh 0.5gCu/SiO
2catalyst loading is in reactor.At 350 DEG C, 2.5MPa, reduces in hydrogen atmosphere.After reduction terminates, adjustment temperature of reactor to 280 DEG C, and adjust hydrogen flowing quantity to hydrogen ester than being 200:1.The liquid mass air speed of DMO is 2.0h
-1, adopt the charging of phase autoclave pump.Be separated by 1 hour and sample and adopt the gas chromatographic analysis product of fid detector to form, and calculate DMO transformation efficiency and ethanol selectivity.Reaction result is in table 1.
Comparing embodiment 2
Catalyst preparing
Take 15.40g Gerhardite and 24.06g six nitric hydrate aluminium in there-necked flask, add 150ml deionized water, in water bath with thermostatic control, be stirred to cupric nitrate and dissolve completely.Slow dropping 52ml ammoniacal liquor, in solution, after stirring, then adds 50ml deionized water, and after sealing, modulation 4 grades is stirred 30 minutes.After stirring, in solution, drip 45ml silicon sol, under whipped state aging 4 hours.Then be warming up to 80 DEG C, evaporate unnecessary ammoniacal liquor, copper, aluminium and silicon oxide precipitation are got off.Throw out is filtered, and washs 3 times respectively with deionized water and ethanol.By filtrate 100 DEG C of dryings after 10 hours, 450 DEG C of roastings 4 hours.Final formation copper content is 20wt%, and aluminium content is the Cu/SiO of 1.0wt%
2-1.0Al catalyzer is stand-by.
The catalyzer compressing tablet of preparation is sieved into 40-60 order, and then weigh 0.1gCu/SiO
2in catalyzer first reactor, claim 0.4gCu/SiO
2in-1.0Al catalyst loading to the second reactor.At 350 DEG C, 2.5MPa, reduces in hydrogen atmosphere.After reduction terminates, adjust the first temperature of reactor to 200 DEG C, the second temperature of reactor to 260 DEG C, and adjust hydrogen flowing quantity with the hydrogen ester ratio adapting to each section.Hydrogen ester wherein in the first reactor is than being the mole of feed speed of hydrogen of first paragraph and the ratio of the mole of feed speed of raw material DMO; Hydrogen ester in second reactor is than the mole of feed speed sum of hydrogen of supplementing for first paragraph remaining hydrogen and second segment and the ratio of the mole of feed speed of raw material DMO.Hydrogen ester ratio in first reactor is adjusted to 80:1, and the hydrogen ester ratio in the second reactor is adjusted to 200:1.The liquid mass air speed of DMO is 2.0h
-1, adopt the charging of phase autoclave pump.Be separated by 1 hour and sample and adopt the gas chromatographic analysis product of fid detector to form, and calculate DMO transformation efficiency and ethanol selectivity.Reaction result is in table 1.
Comparing embodiment 3
Catalyst preparing
Take 15.40g Gerhardite and 24.06g six nitric hydrate aluminium in there-necked flask, add 150ml deionized water, in water bath with thermostatic control, be stirred to cupric nitrate and dissolve completely.Slow dropping 52ml ammoniacal liquor, in solution, after stirring, then adds 50ml deionized water, and after sealing, modulation 4 grades is stirred 30 minutes.After stirring, in solution, drip 45ml silicon sol, under whipped state aging 4 hours.Then be warming up to 80 DEG C, evaporate unnecessary ammoniacal liquor, copper, aluminium and silicon oxide precipitation are got off.Throw out is filtered, and washs 3 times respectively with deionized water and ethanol.By filtrate 100 DEG C of dryings after 10 hours, 450 DEG C of roastings 4 hours.Final formation copper content is 20wt%, and aluminium content is the Cu/SiO of 1.0wt%
2-1.0Al catalyzer is stand-by.
The catalyzer compressing tablet of preparation is sieved into 40-60 order, and then weigh 0.1gCu/SiO
2in catalyzer first reactor, claim 0.4gCu/SiO
2in-1.0Al catalyst loading to the second reactor.At 350 DEG C, 2.5MPa, reduces in hydrogen atmosphere.After reduction terminates, adjust the first temperature of reactor to 200 DEG C, the second temperature of reactor to 240 DEG C, and adjust hydrogen flowing quantity with the hydrogen ester ratio adapting to each section.Hydrogen ester wherein in the first reactor is than being the mole of feed speed of hydrogen of first paragraph and the ratio of the mole of feed speed of raw material DMO; Hydrogen ester in second reactor is than the mole of feed speed sum of hydrogen of supplementing for first paragraph remaining hydrogen and second segment and the ratio of the mole of feed speed of raw material DMO.Hydrogen ester ratio in first reactor is adjusted to 80:1, and the hydrogen ester ratio in the second reactor is adjusted to 200:1.The liquid mass air speed of DMO is 2.0h
-1, adopt the charging of phase autoclave pump.Be separated by 1 hour and sample and adopt the gas chromatographic analysis product of fid detector to form, and calculate DMO transformation efficiency and ethanol selectivity.Reaction result is in table 1.
Table 1 preparing ethanol by oxalate hydrogenation reaction result:
Claims (10)
1. a two-stage method preparing ethanol by oxalate hydrogenation technique, the catalyst components adopted accounts for catalyst weight percent and is: silicon oxide accounts for the 70-90% of catalyst weight, active ingredient copper accounts for the 5-30% of catalyst weight, auxiliary agent accounts for the 0.5-1.5% of catalyst weight, and each composition weight sum of catalyzer is 100%; It is characterized in that:
By two tandem reactors, reactant barkite is finally converted into ethanol; First make barkite be converted into intermediate product stream stock at a lower temperature in first reactor, generate product flow stock-traders' know-how and cross further pre-heating temperature elevation and to enter in second reactor at a higher temperature hydrogenation further and generate containing ethanol stream stock; Reaction conditions is as follows:
Reaction pressure is 1.0-4.0MPa; Catalyst reduction temperature is 250-400 DEG C; The temperature of reaction of first paragraph is 180-220 DEG C; The temperature of reaction of second segment is 240-300 DEG C; In first reactor, mole hydrogen ester is than being 40-100; In second reactor, mole hydrogen ester is than being 180-300; The total mass air speed of barkite charging is 0.5-3h
-1.
2., according to technique according to claim 1, it is characterized in that in first paragraph temperature of reaction be 200 DEG C, second segment temperature of reaction is 280 DEG C, reaction pressure is 2.5MPa, a first paragraph mole hydrogen ester ratio is 80, and a second segment mole hydrogen ester ratio is 200, and barkite mass space velocity is 1.0h
-1.
3., according to technique according to claim 1, it is characterized in that first described reactor is isothermal reactor; Second described reactor is adiabatic reactor.
4. according to technique according to claim 1, the stream stock that to it is characterized in that from the second reactor out at least comprise in methyl alcohol or ethanol one or both.
5. according to technique according to claim 1, the stream stock that to it is characterized in that from the first reactor out at least also comprise in ethylene glycol and ethyl glycolate one or both.
6. a two-stage method preparing ethanol by oxalate hydrogenation technique, is characterized in that the step comprised:
1) catalyzer prepared is put into the first reactor and the second reactor respectively, first in hydrogen atmosphere, catalyzer is reduced;
2), after reduction terminates, after adjusting first, second temperature of reactor to predetermined temperature of reaction and pressure, after the stream stock-traders' know-how containing barkite crosses low temperature preheater preheats, the first reactor and hydrogen reaction is entered;
3) the product flow stock generated and supplementary hydrogen stream stock mixing after in high-temperature preheater with the product flow stock heat exchange of the second reactor after, make temperature reach set(ting)value through electric heater heating again, then enter the second reactor and the stream stock of further hydrogenation reaction generation containing ethanol occurs;
4) enter gas-liquid separator after this product flow stock-traders' know-how condensing heat exchanger condensation and carry out gas-liquid separation, obtain liquid-phase product stream stock and non-condensable gas stream stock, mix with fresh hydrogen air-flow stock after non-condensable gas stream stock-traders' know-how crosses supercharger supercharging, then be divided into two to flow stock and do not enter the first reactor and the second reactor, the flow of two stream stocks makes by flow control valve regulation the hydrogen ester ratio reaching setting in two reactors respectively.
7., according to technique according to claim 6, it is characterized in that reaction conditions is:
Reaction pressure is 1.0-4.0MPa; Catalyst reduction temperature is 250-400 DEG C; The temperature of reaction of first paragraph is 180-220 DEG C; The temperature of reaction of second segment is 240-300 DEG C; In first reactor, mole hydrogen ester is than being 40-100; In second reactor, mole hydrogen ester is than being 180-300; The total mass air speed of barkite charging is 0.5-3h
-1.
8., according to technique according to claim 6, it is characterized in that in first paragraph temperature of reaction be 200 DEG C, second segment temperature of reaction is 280 DEG C, reaction pressure is 2.5MPa, a first paragraph mole hydrogen ester ratio is 80, and a second segment mole hydrogen ester ratio is 200, and barkite mass space velocity is 1.0h
-1.
9., according to technique according to claim 6, it is characterized in that described barkite is one in dimethyl oxalate and oxalic acid diethyl ester or two kinds.
10., according to technique according to claim 6, it is characterized in that described containing including in ethanol and methyl alcohol one or both in the stream stock of barkite as solvent except barkite.
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| CN105418365A (en) * | 2015-12-27 | 2016-03-23 | 安徽淮化股份有限公司 | Novel synthetic-gas-to-ethylene-glycol hydrogenation unit |
| CN115894170A (en) * | 2022-11-07 | 2023-04-04 | 中触媒新材料股份有限公司 | Method for synthesizing ethylene glycol by dimethyl oxalate hydrogenation |
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| CN101475442A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol from oxalic ester |
| CN101830776A (en) * | 2010-05-20 | 2010-09-15 | 浙江大学 | Method for synthesizing ethanol |
| CN102211978A (en) * | 2011-04-15 | 2011-10-12 | 上海浦景化工技术有限公司 | Method for synthesizing glycol by hydrogenation of dimethyl oxalate |
| US20130072728A1 (en) * | 2008-07-31 | 2013-03-21 | Celanese International Corporation | Process for Vapor Phase Hydrogenation |
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| US20130072728A1 (en) * | 2008-07-31 | 2013-03-21 | Celanese International Corporation | Process for Vapor Phase Hydrogenation |
| CN101475442A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol from oxalic ester |
| CN101830776A (en) * | 2010-05-20 | 2010-09-15 | 浙江大学 | Method for synthesizing ethanol |
| CN102211978A (en) * | 2011-04-15 | 2011-10-12 | 上海浦景化工技术有限公司 | Method for synthesizing glycol by hydrogenation of dimethyl oxalate |
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| CN105418365A (en) * | 2015-12-27 | 2016-03-23 | 安徽淮化股份有限公司 | Novel synthetic-gas-to-ethylene-glycol hydrogenation unit |
| CN115894170A (en) * | 2022-11-07 | 2023-04-04 | 中触媒新材料股份有限公司 | Method for synthesizing ethylene glycol by dimethyl oxalate hydrogenation |
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