CN102008963B - Method for preparing low-carbon mixed alcohol catalyst from synthesis gas - Google Patents

Method for preparing low-carbon mixed alcohol catalyst from synthesis gas Download PDF

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CN102008963B
CN102008963B CN2010105233669A CN201010523366A CN102008963B CN 102008963 B CN102008963 B CN 102008963B CN 2010105233669 A CN2010105233669 A CN 2010105233669A CN 201010523366 A CN201010523366 A CN 201010523366A CN 102008963 B CN102008963 B CN 102008963B
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cuo
mgo
surfactant
catalyst
ceo
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CN102008963A (en
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贺德华
张荣俊
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Tsinghua University
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention relates to a method for preparing low-carbon mixed alcohol catalyst from a synthesis gas and belongs to the technical field of chemicals. The method is characterized in that: a Cuo-MgO-CeO2 catalyst is prepared by using surfactant as an auxiliary material and inorganic salts of copper, magnesium and cerium as the raw materials; and C1 to C5 mixed alcohols are prepared by using the synthesis gas as a raw material gas under heating and pressurizing conditions in the presence of the Cuo-MgO-CeO2 catalyst. The Cuo-MgO-CeO2 catalyst prepared by adding the surfactant has higher activity and time space yield in the formation of the C1 to C5, than the catalyst without the surfactant, particularly the time space yield in the formation of C2 to C5 mixed alcohols is improved greatly.

Description

A kind of Preparation of catalysts method that is used for the synthesis gas preparation MAS
Technical field
The present invention relates to a kind of from synthesis gas (gaseous mixture of hydrogen and carbon monoxide) manufacturing C 1~C 5The Catalysts and its preparation method of MAS, a kind of preparation CuO-MgO-CeO more specifically says so 2The method of catalyst belongs to chemical technology field.
Background technology
In recent years, along with growing to even greater heights of environmental requirement, from preparing low-carbon mixed alcohol by synthetic gas (C 1~C 5Alcohol) research receives special concern.C wherein 2~C 5Mixed alcohol is eco-friendly liquid fuel additive (not sulfur-bearing, nitrogen, an aromatic compound etc.), and its surcharge is high, can directly substitute the gasoline additive that the methyl tertiary butyl ether(MTBE) (MTBE) with potentially contaminated property becomes the high-quality cleaning.Produce synthesis gas by coal, act as a fuel or gasoline additive from preparing low-carbon mixed alcohol by synthetic gas again, application promise in clinical practice is arranged.
Mainly contain two big types from the catalyst of preparing low-carbon mixed alcohol by synthetic gas.One type is the composite oxide catalysts of transition metal, and another kind of is sulfide catalyst.It is the Octamix technology (U.S. Pat-No. 4031123 with US-2327066 number) of catalyst principal component with Cu-Zn that Germany Lurgi company has developed; It is the IFP technology (U.S. US-4122110 number) of catalyst principal component with Cu-Co that France Petroleum Institute has developed; The Dow Chemical Co. (US) 2030 Dow Center, Abbott Road, Midland, Michigan 48640, and union carbide corporation have been developed cooperatively with MoS 2Be the Sygmol technology of catalyst main component (U.S. Pat-No. 4675344 and European patent EP-0235886).These patented technologies differ from one another, wherein C in the product of Sygmol and IFP technology 2+Alcohol content is higher; Octamix process using low-pressure process has higher space-time yield, water content low, and its products distribution is expected further improvement.But the composition of the catalyst that uses in these patented technologies is comparatively complicated, and preparation technology is comparatively loaded down with trivial details.On the other hand, Chinese patent CN1428192, CN1481934 and CN1179993 have reported also that from the method for synthesis gas preparation low-carbon alcohols wherein Preparation of catalysts needs the multistep dipping, complicated process of preparation, and the selectivity of low-carbon alcohols and yield are also lower.
It is that the method for auxiliary material prepares CuO-MgO-CeO with the surfactant that the present invention has adopted 2Catalyst has improved activity of such catalysts and has generated C 1~C 5The space-time yield of mixed alcohol, especially C 2~C 5The space-time yield of mixed alcohol improves a lot.
Summary of the invention
The purpose of this invention is to provide a kind of being used for from synthesis gas system C 1~C 5The Catalysts and its preparation method of mixed alcohol.Use the CuO-MgO-CeO that this method makes 2The catalyst that catalyst makes than traditional intermediate processing has higher activity and generates C 1~C 5The space-time yield of mixed alcohol, especially C 2~C 5The space-time yield of mixed alcohol improves a lot.
The present invention proposes is used for synthesis gas system C 1~C 5The CuO-MgO-CeO of mixed alcohol 2Catalysts and its preparation method; It is characterized in that: to adopt surfactant softex kw or polyethylene glycol-propane diols-polyethylene glycol blocked copolymer be auxiliary material, be raw material with the inorganic salts of copper, magnesium, cerium; Paste mixture through cupric, magnesium, cerium and surfactant that post precipitation obtains is aging under 80 ℃; Through filtration, washing, drying and roasting, obtain CuO-MgO-CeO then 2Use the CuO-MgO-CeO of the inventive method preparation 2As catalyst, with the synthesis gas is raw material, under the condition of warming and pressurizing, can make C efficiently 1~C 5Mixed alcohol.
Preparation CuO-MgO-CeO 2The detailed process of catalyst comprises;
(1) preparation raw material salting liquid
Join in the deionized water sonicated in ultrasonic instrument to surfactant softex kw or polyethylene glycol-propane diols-polyethylene glycol blocked copolymer; Take by weighing Cu (NO according to certain ratio 3) 23H 2O, Mg (NO 3) 23H 2O and Ce (NO 3) 36H 2O joins in the above-mentioned solution, stirs half an hour.
(2) deposition, aging and last handling process
Be added to raw material salt solution to the NaOH drips of solution, generate deposition; Paste mixture 80 ℃ down aging, filter then, wash, drying, place powder Muffle furnace 400 ℃ of following roastings at last.
The present invention is unstripped gas with the synthesis gas, at warming and pressurizing and CuO-MgO-CeO 2Prepare C under the condition that catalyst exists 1~C 5Mixed alcohol.The synthesis gas that the present invention uses is the gaseous mixture of carbon monoxide and hydrogen ratio=1: 1.Carry out above-mentioned reaction by method of the present invention, under heating, carry out.Reaction temperature is generally 250~350 ℃.Carry out above-mentioned reaction by the inventive method, carry out adding to depress.The pressure of synthesis gas is generally 6MPa.
The specific embodiment
Below in conjunction with embodiment technical scheme of the present invention is done further explanation.
Embodiment 1
(1) 10wt%CuO-MgO-CeO 2(CTAB, 0.188) Preparation of catalysts (mol ratio of CTAB and metal=0.188):
Take by weighing 2.73g (7.5mmol) softex kw (being called for short CTAB) and join in the 250ml deionized water, sonicated is 15 minutes in ultrasonic instrument.According to Cu: Mg: Ce=0.5: the ratio of 5: 1 (mol ratio) takes by weighing 0.77gCu (NO respectively 3) 23H 2O, 7.87g Mg (NO 3) 23H 2O, 2.67g Ce (NO 3) 36H 2O pours in the above-mentioned solution, stirs half an hour.Dropwise be added drop-wise to 0.2mol/L NaOH solution in the above-mentioned mixed liquor, and regulate pH value to 9, stir half an hour again after dropwising.Placed 80 ℃ of baking ovens to paste mixture aging 3 hours, take out the back and filter, wash 5 times with deionized water (500mL).Placed 110 ℃ of dryings of baking oven to filter cake 12 hours, dried powder places Muffle furnace to be warming up to 400 ℃ with 2 ℃/min, and roasting 4 hours promptly gets the CuO mass fraction and be 10% CuO-MgO-CeO 2(CTAB, 0.188) catalyst.
(2) synthesis gas system C 1~C 5The reaction of mixed alcohol:
Synthesis gas system C 1~C 5Carry out in the miniature fixed bed movable reactor that is reflected at stainless steel tube liner quartz ampoule (internal diameter 10mm) of mixed alcohol.Take by weighing 10wt%CuO-MgO-CeO 2(CTAB, 0.188) catalyst 0.5g is loaded on the quartz ampoule middle part, and beds is all filled out silica wool in two ends up and down.Before the reaction, catalyst is at H 2/ N 2Gaseous mixture (V N2/ V H2=4/1) rises to 270 ℃ from room temperature with 1 ℃/min in, reduced 4 hours down at 270 ℃.Be adjusted to 250 ℃ of reaction temperatures then, switch to unstripped gas (V again H2/ V CO=1/1), under 6MPa pressure, react, (air speed is 6000h to raw gas flow by mass flowmenter control -1), reaction pressure is by pressure maintaining valve and counterbalance valve control, and reaction bed temperature is measured and control by thermocouple and temperature controller.The reaction tube exit gas carries out online detection and assay products with online gas-chromatography down in insulation (150 ℃) after reducing pressure.The sample analysis of 250 ℃ of reactions is warming up to 300 ℃ to beds and reacts after finishing, and the reaction tube exit gas carries out online detection and assay products with online gas-chromatography equally.The sample analysis of 300 ℃ of reactions is warming up to 350 ℃ to beds and reacts after finishing, and the reaction tube exit gas carries out online detection and assay products with online gas-chromatography equally.Reaction result is listed in table 1.
Embodiment 2
(1) 10wt%CuO-MgO-CeO 2(CTAB, 0.125) Preparation of catalysts (mol ratio of CTAB and metal=0.125):
Take by weighing 1.82g (5.0mmol) softex kw (being called for short CTAB) and join in the 250ml deionized water, sonicated is 15 minutes in ultrasonic instrument.According to Cu: Mg: Ce=0.5: the ratio of 5: 1 (mol ratio) takes by weighing 0.77gCu (NO respectively 3) 23H 2O, 7.87g Mg (NO 3) 23H 2O, 2.67g Ce (NO 3) 36H 2O pours in the above-mentioned solution, stirs half an hour.Other follow-up step is with embodiment 1, promptly gets the CuO mass fraction and be 10% CuO-MgO-CeO 2(CTAB, 0.125) catalyst.
(2) synthesis gas system C 1~C 5The reaction of mixed alcohol:
Operation is with embodiment 1 (2).Reaction result is listed in table 2.
Embodiment 3
(1) 10wt%CuO-MgO-CeO 2(CTAB, 0.25) Preparation of catalysts (mol ratio of CTAB and metal=0.25):
Take by weighing 3.64g (10.0mmol) softex kw (being called for short CTAB) and join in the 250ml deionized water, sonicated is 15 minutes in ultrasonic instrument.According to Cu: Mg: Ce=0.5: the ratio of 5: 1 (mol ratio) takes by weighing 0.77gCu (NO respectively 3) 23H 2O, 7.87g Mg (NO 3) 23H 2O, 2.67g Ce (NO 3) 36H 2O pours in the above-mentioned solution, stirs half an hour.Other follow-up step is with embodiment 1, promptly gets the CuO mass fraction and be 10% CuO-MgO-CeO 2(CTAB, 0.25) catalyst.
(2) synthesis gas system C 1~C 5The reaction of mixed alcohol:
Operation is with embodiment 1 (2).Reaction result is listed in table 3.
Embodiment 4
(1) 10wt%CuO-MgO-CeO 2(P123,0.188) Preparation of catalysts (mol ratio of P123 and metal=0.188):
Take by weighing 4.35g (0.75mmol) polyethylene glycol-propane diols-polyethylene glycol blocked copolymer (being called for short P123) and join in the 250ml deionized water, sonicated is 15 minutes in ultrasonic instrument.According to Cu: Mg: Ce=0.5: the ratio of 5: 1 (mol ratio) takes by weighing 0.77g Cu (NO respectively 3) 23H 2O, 7.87g Mg (NO 3) 23H 2O, 2.67g Ce (NO 3) 36H 2O pours in the above-mentioned solution, stirs half an hour.Other follow-up step is with embodiment 1, promptly gets the CuO mass fraction and be 10% CuO-MgO-CeO 2(P123,0.188) catalyst.
(2) synthesis gas system C 1~C 5The reaction of mixed alcohol:
Operation is with embodiment 1 (2).Reaction result is listed in table 4.
Comparative example 1
(1) 10wt%CuO-MgO-CeO 2The preparation of (surfactant-free):
According to Cu: Mg: Ce=0.5: the ratio of 5: 1 (mol ratio) takes by weighing 0.77g Cu (NO respectively 3) 23H 2O, 7.87gMg (NO 3) 23H 2O, 2.67g Ce (NO 3) 36H 2O pours in the 250ml deionization, stirs half an hour.Other follow-up step is with embodiment 1, promptly gets the CuO mass fraction and be the catalyst of 10% Cu-Mg-Ce (surfactant-free).
(2) synthesis gas system C 1~C 5The reaction of mixed alcohol:
Operation is with embodiment 1 (2).Reaction result is listed in table 5.
Table 1 embodiment 1 (10wt%CuO-MgO-CeO 2(CTAB, 0.188)) reaction result
Figure BSA00000322892800041
Annotate: total alcohol product refers to: dimethyl ether+methyl alcohol+C 2~C 5The summation of alcohol (down together).
Table 2 embodiment 2 (10wt%CuO-MgO-CeO 2(CTAB, 0.125)) reaction result
Figure BSA00000322892800042
Figure BSA00000322892800051
Table 3 embodiment 3 (10wt%CuO-MgO-CeO 2(CTAB, 0.25)) reaction result
Figure BSA00000322892800052
Table 4 embodiment 4 (10wt%CuO-MgO-CeO 2(P123,0.188)) reaction result
Figure BSA00000322892800053
Table 5 comparative example 1 (10wt%CuO-MgO-CeO 2(surfactant-free)) reaction result
Figure BSA00000322892800054

Claims (1)

1. Preparation of catalysts method that is used for the synthesis gas preparation MAS, it is characterized in that: the employing surfactant is an auxiliary material, is feedstock production CuO-MgO-CeO with the inorganic salts of copper, magnesium, cerium 2Catalyst; Described surfactant is softex kw or polyethylene glycol-propane diols-polyethylene glycol blocked copolymer; The consumption of described copper, magnesium, cerium is Cu: Mg: Ce=0.5: 5: 1 (mol ratio), CuO accounts for CuO-MgO-CeO 2Mass percent (wt%) be 10%; Said amount of surfactant is: the surfactant molal quantity is 0.125~0.25 with the ratio of total mole of copper, magnesium, ce metal; The paste mixture of the cupric that obtains during preparation, magnesium, cerium and surfactant wore out 3 hours down at 80 ℃; The CuO-MgO-CeO that obtains during preparation 2Presoma 400 ℃ of following roastings 4 hours in air.
CN2010105233669A 2010-10-22 2010-10-22 Method for preparing low-carbon mixed alcohol catalyst from synthesis gas Expired - Fee Related CN102008963B (en)

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