CN102294260B - Method for preparing low-carbon oxygen-containing compound from synthesis gas - Google Patents
Method for preparing low-carbon oxygen-containing compound from synthesis gas Download PDFInfo
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- CN102294260B CN102294260B CN2010102081217A CN201010208121A CN102294260B CN 102294260 B CN102294260 B CN 102294260B CN 2010102081217 A CN2010102081217 A CN 2010102081217A CN 201010208121 A CN201010208121 A CN 201010208121A CN 102294260 B CN102294260 B CN 102294260B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a method for preparing a low-carbon oxygen-containing compound from synthesis gas, which is mainly used for solving the problem of low product yield existing in the prior art. In the method, synthesis gas consisting of H2 and CO in the molar ratio 1:4 and serving as raw material gas undergoes a contact reaction with a catalyst under the condition that the reaction temperature is 200-400 DEG C, the reaction pressure 1.0-8.0 MPa and the volume per hour is 2,000-20,000 h<-1> to generate an oxygen-containing compound of over C2, wherein the catalyst comprises the following components in parts by weight: 0.5-10 parts of Rh, 0.05-10 parts of at least one of Mn, Ti and V, 0.05-10 parts of at least one of I and A, 0-10 parts of at least one of Fe, Co and Ni and 60-99.4 parts of MCM-28 molecular sieve carrier. By adopting the technical scheme, the problem is well solved; and the method can be applied to industrial production of a low-carbon oxygen-containing compound prepared from synthesis gas.
Description
Technical field
The present invention relates to a kind of method by the synthesis of gas produced low-carbon oxygenatedchemicals.
Background technology
Energy development and utilization are the strategic topic of human survival and development always.China is a petroleum resources scarcity, coal abundant country relative to natural gas resource, from resource effectively utilize angle, produce synthesis gas by coal gasification or natural gas and produce the low-carbon oxygen-containing compound, have broad application prospects.The low-carbon oxygen-containing compound (mainly comprises C
2～C
5the alcohols mixture) be based on derived energy chemical diversification of feedstock and clean coal utilization and chemistry of fuel product with strategic importance, high-octane rating, oligosaprobic vehicle fuel additive have been proved to be, can mix with gasoline and be made into alcohol-oil hybrid fuel, also can be used as the desirable cosolvent of Methanol-gasoline hybrid power fuel.
1975, the people such as Wilson of U.S.'s union carbide corporation reported on a kind of loaded catalyst of making active component with metal rhodium, can obtain from the CO hydrogenation reaction C of high yield
2the products such as alcohols and aldehydes.From that time, rhodium base catalyst has attracted numerous researchers' interest.According to the result of forefathers' research, the selection of carrier on the catalytic activity impact significantly, is carried on weakly acidic SiO
2rhodium base catalyst on carrier can be converted into oxygenatedchemicals efficiently by synthesis gas.For this reason, people improve on the one hand the decentralization of Rh and reduce its loading, and used additives (as the transition metal oxide of strong oxytropism) improves catalytic performance on the other hand, has obtained certain effect.
Yet, due to the SiO of different researchers' uses
2source and preparation method's difference are larger, and controllability prepared by corresponding catalyst and the repeatability of catalytic effect are all good not.In patent CN1225852A, adopt Rh-Sm-V-Co/SiO
2catalyst is reacted, and when reaction temperature is 310 ℃, reaction pressure is 3.0Mpa, and volume space velocity is 13000h
-1the time, c_2-oxygen compound selectively reach 69.2%, but the CO conversion ratio only has 5.3%, corresponding product yield is 3.67%.In patent CN1280116A, the metals such as Ir, Mn, Zr, Cu, Li, Fe, K are introduced by SiO
2the rhodium base catalyst supported, when reaction temperature is 300 ℃, reaction pressure is 3.0Mpa, volume space velocity is 15000h
-1the time, c_2-oxygen compound selectively reach 78.5%, but the conversion ratio of CO is only 3.9%, corresponding product yield is 3.06%, and the preparation process of catalyst is also comparatively loaded down with trivial details.In patent CN1354043A, adopt a kind of suitable aperture that has, than the MCM-41 molecular sieve of high silica alumina ratio as catalyst carrier, take Rh, Mn, Li is active component, and when reaction temperature is 320 ℃, reaction pressure is 3.0Mpa, when volume space velocity is 40000m/ (Kgh), C
2the conversion ratio that selectively reaches 47.5%, CO of oxygenatedchemicals is 11.6%, and corresponding product yield is 5.51%.
All there is the problem that product yield is lower in the rhodium base catalyst of above-mentioned bibliographical information.
Summary of the invention
Technical problem to be solved by this invention is all to have the lower problem of the above oxygenatedchemicals yield of C2 in prior art, and a kind of new method by synthesis gas reaction low-carbon oxygen-containing compound processed is provided.The method has advantages of that the above oxygenatedchemicals yield of C2 is higher.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method by the synthesis of gas produced low-carbon oxygenatedchemicals, and with molar ratio computing H
2the synthesis gas of/CO=1～4 is raw material, in reaction temperature, is 200～400 ℃, and reaction pressure is 1.0～8.0Mpa, and volume space velocity is 2000～20000h
-1condition under, unstripped gas and catalyst haptoreaction generate C
2and above oxygenatedchemicals.Wherein catalyst used comprises following composition in parts by weight:
A) metal of the Rh of 0.5～10 part or oxide;
B) 0.05～10 part be selected from least one metal or its oxide in Mn, Ti, V;
C) 0.05～10 part be selected from least one metal or its oxide in periodic table of elements I A;
D) 0～10 part be selected from least one metal or its oxide in Fe, Co, Ni;
E) the MCM-48 molecular sieve carrier of 60～99.4 parts.
In technique scheme, the parts by weight preferable range of the metal of Rh or oxide is 1.0～5.0 parts, being selected from least one metal in Mn, Ti, V or the parts by weight preferable range of its oxide is 0.1～5.0 part, being selected from least one metal in periodic table of elements I A or the parts by weight preferable range of its oxide is 0.05～5.0 part, being selected from least one metal in Fe, Co, Ni or the parts by weight preferable range of its oxide is 0.02～2.0 part, and the parts by weight preferable range of MCM-48 carrier is 83～98.73 parts.
In technique scheme by the method for synthesis gas reaction low-carbon oxygen-containing compound processed, 280～350 ℃ of reaction temperature preferable range, reaction pressure preferable range 2.0～5.0Mpa, reaction volume air speed preferable range 6000～15000h
-1.
Existing by synthesis of gas produced low-carbon oxygenatedchemicals reaction technology, catalyst used generally adopts Normal silica as carrier, and its specific area is many at 200～300m
2/ g, can not disperse and catalyst-loaded active component well, and surface contains the plurality of impurities such as Fe, Al, Na, Ca, Ti, Zr, the activity and selectivity of catalyst is caused to interference, so that the yield of product is lower, and the repeatability of reaction is also poor.In the present invention, owing to adopting high-ratio surface MCM-48 as catalyst carrier, specific area reaches 1200m
2/ g, have aperture and the pore volume of suitable this reaction and SiO
2purity to 99.95% more than, greatly reduced the interference of impurity to catalytic performance, improved the activity of catalyst.In addition due to metal Rh, at least one in Mn, Ti, V, at least one in periodic table of elements I A, at least one in Fe, Co, Ni is active component, what make the above oxygenatedchemicals of C2 in this course of reaction has selectively obtained larger raising, thereby has improved the yield of the above oxygenatedchemicals of C2.
Adopting method of the present invention, is 200～400 ℃ in reaction temperature, and reaction pressure is 1.0～8.0Mpa, and volume space velocity is 2000～20000h
-1condition under, what the conversion ratio of CO can reach 15.5%, C2 and above oxygenatedchemicals selectively can reach 53.7%, corresponding product yield can reach 8.32%.Obtained technique effect preferably.
Below by embodiment, the present invention is further elaborated.
The specific embodiment
[embodiment 1]
Support active component Kaolinite Preparation of Catalyst A on the MCM-48 molecular sieve, in catalyst A, the percetage by weight of Rh is 2%.Concrete preparation method and examination step are as follows:
1) prepare the MCM-48 molecular sieve
Under 70 ℃ of water bath with thermostatic control conditions, add surfactant softex kw (CTAB) and solid sodium hydroxide (NaOH) in beaker, after fully dissolving by appropriate amount of deionized water, add tetraethyl orthosilicate (TEOS) solution aging 2 hours.Wherein, Na
2o/TEOS, CTAB/TEOS, H
2the O/TEOS mol ratio respectively is 0.25,0.56, and 60.After ageing process finishes, mixed liquor is proceeded to and take in the stainless steel cauldron that polytetrafluoroethylene (PTFE) is liner, in 100 ℃ of thermostatic crystallizations 48 hours.Crystallization is filtered product after finishing successively, washing, and dried overnight, 550 ℃ of roastings, obtain high-purity MCM-48 white powder.
2) moulding of molecular sieve carrier
By gained MCM-48 pressed powder moulding in (1), pulverize and sieve, get that wherein 20～40 order particles are standby.
3) preparation method of catalyst
Prepare and contain 2.00 * 10
-2g gram Rh, 1.34 * 10
-2gram Mn, 1.35 * 10
-3gram Li, 1.09 * 10
-3the RhCl of gram Fe
3, Mn (NO
3)
2, Fe (NO
3)
3, LiNO
3mixed solution, take MCM-48 carrier 1.00 grams that obtain in (2) and carry out incipient impregnation.Sample standing 6 hours at ambient temperature, proceed to 100 ℃ of oven dryings 16 hours.Dried sample is proceeded in Muffle furnace to 450 ℃ of roastings 4 hours, obtain fresh catalyst A after cooling, be kept in drier.
4) the examination step of catalyst
The evaluation of catalyst is carried out on the flowable state fixed-bed micro-reactor.Reactor adopts 316 stainless steel tubes that internal diameter is 6mm, loaded catalyst 0.75ml.Catalyst first reduces 3 hours in 350 ℃ of normal pressures with pure hydrogen in reactor, then is down to reaction temperature, switches to synthesis gas (60%H
2, 30%CO, 10%N
2, more than be volume content) reacted.Reaction is at 315 ℃, 3.0Mpa, GHSV=9000h
-1carry out under condition, directly send into gas-chromatography Agilent4890 after the product insulation and carry out on-line analysis.Inorganic component, as CO, H
2, CO
2detected N Deng with TCD
2as interior mark, adopt Porapark Q packed column to separate.Organic component is detected with FID, determines the relative selectivity of each component by normalization method, adopts Plot Q capillary column separation.The evaluation result of catalyst A is listed in table 1.
[comparative example 1]
The catalyst performance of different silica supports relatively
According to step preparation and the examination catalyst of embodiment 1, the catalyst carrier of selecting while just changing the dipping active component.Take chromatographic silica gel as carrier, make catalyst B; With the SiO through extruded moulding
2for carrier, make catalyst C; Take SBA-15 as carrier, make catalyst D.The evaluation result of each catalyst is listed in table 1.
The catalyst performance of the different silica supports of table 1 relatively
| The catalyst title | The CO conversion ratio, % | Paraffin selectivity, % | C 2+Oxygenatedchemicals is selective, % | C 2+The oxygenatedchemicals yield, % |
| A | 14.4 | 44.5 | 49.3 | 7.01 |
| B | 9.1 | 57.7 | 34.1 | 3.10 |
| C | 4.4 | 64.1 | 26.8 | 1.18 |
| D | 9.6 | 54.9 | 37.0 | 3.56 |
[embodiment 2]
The impact of different auxiliary agent types on catalyst performance
Step preparation and examination catalyst according to embodiment 1, just change the active component of flooding in catalyst preparation process, and concrete component and the evaluation result of catalyst are listed in table 2.
The impact of the different auxiliary agent types of table 2 on catalyst performance
| The catalyst activity component | The CO conversion ratio, % | Paraffin selectivity, % | C 2+Oxygenatedchemicals is selective, % | C 2+The oxygenatedchemicals yield, % |
| Rh-Mn-Li | 13.5 | 55.7 | 39.9 | 5.39 |
| Rh-V-Li | 11.2 | 53.9 | 40.3 | 4.51 |
| Rh-Ti-K | 10.3 | 52.8 | 41.1 | 4.23 |
| Rh-Mn-Na-Fe | 16.1 | 60.5 | 35.2 | 5.67 |
| Rh-Mn-Li-Ni | 15.3 | 49.8 | 44.1 | 6.75 |
| Rh-Mn-K-Co | 14.2 | 48.6 | 45.5 | 6.46 |
| Rh-Mn-Li-Fe | 14.4 | 44.5 | 49.3 | 7.01 |
[embodiment 3]
The impact of active component parts by weight ratio on catalytic performance
According to step preparation and the examination catalyst of embodiment 1, just change the parts by weight ratio of Rh in catalyst preparation process, Mn, Li, Fe, corresponding evaluating catalyst the results are shown in table 3.
The impact of table 3 active component parts by weight ratio on catalytic performance
| Active component ratio of weight and number Rh: Mn: Li: Fe | The CO conversion ratio, % | Paraffin selectivity, % | C 2+Oxygenatedchemicals is selective, % | C 2+The oxygenatedchemicals yield, % |
| 1∶0.27∶0.068∶0.055 | 5.6 | 37.2 | 52.8 | 2.96 |
| 1∶0.80∶0.068∶0.055 | 12.4 | 45.1 | 45.7 | 5.67 |
| 1∶1.35∶0.068∶0.055 | 17.2 | 58.1 | 34.8 | 5.99 |
| 1∶0.53∶0.034∶0.055 | 11.0 | 61.8 | 32.2 | 3.54 |
| 1∶0.53∶0.10∶0.055 | 15.1 | 48.6 | 42.9 | 6.48 |
| 1∶0.53∶0.17∶0.055 | 16.3 | 43.9 | 46.3 | 7.55 |
| 1∶0.67∶0.084∶0.055 | 15.5 | 41.8 | 53.7 | 8.32 |
| 1∶0.53∶0.068∶0.11 | 12.9 | 42.6 | 53.1 | 6.85 |
| 1∶0.67∶0.084∶0.11 | 14.2 | 40.1 | 54.6 | 7.75 |
| 1∶0.67∶0.084∶0.28 | 11.3 | 38.4 | 57.1 | 6.45 |
| 1∶0.67∶0.084∶0.55 | 6.9 | 43.8 | 46.7 | 3.22 |
[embodiment 4]
The impact of reaction temperature on catalytic performance
According to step preparation and the examination catalyst of embodiment 1, just change the temperature of beds in course of reaction, corresponding evaluating catalyst the results are shown in table 4.
The impact of table 4 reaction temperature on catalytic performance
| Reaction temperature, ℃ | The CO conversion ratio, % | Paraffin selectivity, % | C 2+Oxygenatedchemicals is selective, % | C 2+The oxygenatedchemicals yield, % |
| 220 | 1.9 | 32.6 | 61.0 | 1.16 |
| 290 | 7.6 | 37.8 | 55.3 | 4.20 |
| 300 | 10.9 | 39.3 | 53.1 | 5.78 |
| 310 | 13.7 | 42.8 | 50.9 | 6.97 |
| 320 | 15.8 | 47.2 | 44.4 | 7.02 |
| 330 | 19.7 | 54.8 | 34.9 | 6.87 |
| 390 | 28.8 | 69.4 | 18.7 | 5.39 |
[embodiment 5]
The impact of reaction pressure on catalytic performance
According to step preparation and the examination catalyst of embodiment 1, just change the pressure of reaction system, corresponding evaluating catalyst the results are shown in table 5.
The impact of table 5 reaction pressure on catalytic performance
| Reaction pressure, MPa | The CO conversion ratio, % | Paraffin selectivity, % | C 2+Oxygenatedchemicals is selective, % | C 2+The oxygenatedchemicals yield, % |
| 1.0 | 7.9 | 54.2 | 38.1 | 3.01 |
| 2.0 | 11.7 | 50.1 | 42.5 | 4.97 |
| 3.0 | 14.4 | 44.5 | 49.3 | 7.01 |
| 4.0 | 16.2 | 39.9 | 53.7 | 8.70 |
| 5.0 | 18.4 | 35.5 | 56.1 | 10.32 |
| 8.0 | 23.6 | 30.4 | 62.7 | 14.80 |
[embodiment 6]
The impact of reaction velocity on catalytic performance
Step preparation and examination catalyst according to embodiment 1, just change the volume space velocity in course of reaction, and corresponding evaluating catalyst the results are shown in table 6.
The impact of table 6 reaction velocity on catalytic performance
| Reaction velocity, h -1 | The CO conversion ratio, % | Paraffin selectivity, % | C 2+Oxygenatedchemicals is selective, % | C 2+The oxygenatedchemicals yield, % |
| 2000 | 22.4 | 55.2 | 36.1 | 8.09 |
| 6000 | 17.9 | 48.7 | 41.2 | 7.37 |
| 9000 | 14.4 | 44.5 | 49.3 | 7.01 |
| 12000 | 12.5 | 42.8 | 51.1 | 6.38 |
| 15000 | 9.7 | 40.9 | 53.2 | 5.16 |
| 20000 | 4.3 | 37.9 | 57.0 | 2.45 |
Claims (1)
1. the method by the synthesis of gas produced low-carbon oxygenatedchemicals, prepare and contain 2.00 * 10
-2gram Rh, 1.34 * 10
-2gram Mn, 1.35 * 10
-3gram Li, 1.09 * 10
-3the RhCl of gram Fe
3, Mn (NO
3)
2, Fe (NO
3)
3, LiNO
3mixed solution, take MCM-48 carrier 1.00 grams and carry out incipient impregnation; Sample standing 6 hours at ambient temperature, proceed to 100 ℃ of oven dryings 16 hours; Dried sample is proceeded in Muffle furnace to 450 ℃ of roastings 4 hours, obtain fresh catalyst after cooling, be kept in drier;
The preparation method of described MCM-48 carrier is as follows: under 70 ℃ of water bath with thermostatic control conditions, add surfactant softex kw (CTAB) and solid sodium hydroxide (NaOH) in beaker, after fully dissolving by appropriate amount of deionized water, add tetraethyl orthosilicate (TEOS) solution aging 2 hours; Wherein, Na
2o/TEOS, CTAB/TEOS, H
2the O/TEOS mol ratio respectively is 0.25,0.56, and 60; After ageing process finishes, mixed liquor is proceeded to and take in the stainless steel cauldron that polytetrafluoroethylene (PTFE) is liner, in 100 ℃ of thermostatic crystallizations 48 hours; Crystallization is filtered product after finishing successively, washing, and dried overnight, 550 ℃ of roastings, obtain high-purity MCM-48 white powder; By the moulding of MCM-48 pressed powder, pulverize and sieve, get that wherein 20～40 order particles are standby;
The evaluation of catalyst is carried out on the flowable state fixed-bed micro-reactor; Reactor adopts 316 stainless steel tubes that internal diameter is 6mm, loaded catalyst 0.75ml; Catalyst in reactor first with pure hydrogen in 350 ℃ of normal pressures reduction 3 hours, then be down to reaction temperature, switch to synthesis gas and reacted, synthesis gas consist of 60%H
2, 30%CO and 10%N
2, more than be volume content; Reaction is at 315 ℃, 3.0Mpa, GHSV=9000h
-1carry out under condition, directly send into gas-chromatography Agilent4890 after the product insulation and carry out on-line analysis; Inorganic component CO, H
2, CO
2detected N with TCD
2as interior mark, adopt Porapark Q packed column to separate; Organic component is detected with FID, determines the relative selectivity of each component by normalization method, adopts Plot Q capillary column separation; The evaluation result of catalyst shows; The CO conversion ratio is 14.4%, C
2+selective and the yield of oxygenatedchemicals is respectively 49.3% and 7.01%.
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|---|---|---|---|
| CN2010102081217A CN102294260B (en) | 2010-06-24 | 2010-06-24 | Method for preparing low-carbon oxygen-containing compound from synthesis gas |
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| CN102294260B true CN102294260B (en) | 2013-12-18 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1179993A (en) * | 1996-10-16 | 1998-04-29 | 厦门大学 | Rhodium base catalyst for preparation of low carbon alcohol by synthetic gas and its preparing method |
| CN1717278A (en) * | 2002-11-20 | 2006-01-04 | 埃克森美孚研究工程公司 | Methods for preparing catalysts |
-
2010
- 2010-06-24 CN CN2010102081217A patent/CN102294260B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1179993A (en) * | 1996-10-16 | 1998-04-29 | 厦门大学 | Rhodium base catalyst for preparation of low carbon alcohol by synthetic gas and its preparing method |
| CN1717278A (en) * | 2002-11-20 | 2006-01-04 | 埃克森美孚研究工程公司 | Methods for preparing catalysts |
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