CN1160155C - Catalyst for synthesizing arylhydrocarbon with mathane and its application in synthesizing reaction - Google Patents
Catalyst for synthesizing arylhydrocarbon with mathane and its application in synthesizing reaction Download PDFInfo
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- CN1160155C CN1160155C CNB991128842A CN99112884A CN1160155C CN 1160155 C CN1160155 C CN 1160155C CN B991128842 A CNB991128842 A CN B991128842A CN 99112884 A CN99112884 A CN 99112884A CN 1160155 C CN1160155 C CN 1160155C
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Abstract
The present invention relates to a catalyst for directly synthesizing arene with methane. The present invention is characterized in that the catalyst is MCM-22 zeolite modified by ZnO, Ca2O3, Cr2O3, In2O3, WO3 or MoO3, wherein the ratio of SiO2 to Al2O3 of the MCM-22 is 30 to 100, and the weight percentage content of active components is from 2 to 30%. The reaction of synthesizing arene with methane is carried out in a fixed bed type reactor system with continuous feed, the reaction airflow is diluted by pure methane or inert gas, the reaction temperature is between 650 and 800 DEG C, and the reaction space velocity is from 750 to 5000 ml/g. h. The catalyst of the present invention can prepare benzene with methane with high selectivity and high stability.
Description
The methane system of the present invention relates to aromatic hydrocarbons technology has specifically just provided the raw catelyst of a kind of high selectivity and high stability ground from direct synthesis of arene with methane, and the application of this catalyst in the reaction of methane system aromatic hydrocarbons.
The minimum response temperature that methane thermal changes into benzene is 1173K, is 1480～1580K and obtain 6～10% the needed reaction temperature of benzene.Science in 1966 have reported the result of methyl hydride catalyzed synthetic aromatic hydrocarbons on silica-gel catalyst, obtain 4.2～7.2% aromatics yield at 1273K.In addition, reported that from the eighties methane is at boron nitride (BN).Multi-functional composite metal oxide, silica-rich zeolite support the result of the synthetic aromatic hydrocarbons of catalysis on Pt-Cr and Ga catalyst and the carbon fibre material.Reported the patent (patent publication No. is CN1102359A) of the aromatization of methane on Mo/HZSM-5 and Zn/HZSM-5 catalyst system and catalyzing in 1993.1996, the inventor applied for the patent (number of patent application is 96115364.4) of the HZRP-1 zeolite catalyst system aromatic hydrocarbons that the patent (number of patent application is 96115372.5) of the aromatization of methane on the bimetallic-modified zeolite catalyst and methane support at Mo.
The object of the present invention is to provide the catalyst of the synthetic aromatic hydrocarbons of a kind of methane, use this catalyst methane can high selectivity and high stability system benzene.
The invention provides a kind of catalyst of direct synthesis of arene with methane, it is characterized in that: this catalyst is for using ZnO, Ga
2O
3, Cr
2O
3, In
2O
3, WO
3Or MoO
3The MCM-22 zeolite of modification, the wherein SiO of MCM-22
2/ Al
2O
3Than being 30～100, the active component weight percentage is 2～30%.
Be MoO with the active component among the present invention
3Best results, the MoO that it is best
3Content is 2～10%.
The present invention can also improve activity of such catalysts and stability as auxiliary agent by adding other transition metal.
In addition, the invention provides the application of above-mentioned catalyst in the directly synthetic aromatic hydrocarbons of low-carbon alkanes such as methane, reaction is to carry out in the fixed bed type reactor system of continuous feed, reaction gas flow dilutes with pure methane or with inert gas, reaction temperature is between 650～800 ℃, and reaction velocity is 750～5000ml/g.h.
The present invention reported pure methane or with the methane feed gas of inert gas dilution in 650～800 ℃ temperature range, can high selectivity on the MCM-22 catalyst that metal component supports under oxygen free condition and high stability transform aromatic hydrocarbons.The Mo/MCM-22 catalyst is when 700 ℃ of reactions, and methane conversion can reach more than 10%, and arenes selectivity is greater than 80%.
What compared with prior art, the present invention adopted is that the MCM-22 molecular sieve is as carrier.Compare with HZSM-5 equimolecular sieve, reaction has better catalytic performance to Mo/MCM-22 for oxygen-free dehydrogenating aromatization of methane, and catalyst shows better benzene selective and reaction stability.
Below by drawings and Examples in detail the present invention is described in detail.
Fig. 1 is a methane in the reactivity worth of the 6Mo/MCM-22 situation of change with the reaction time.
Fig. 2 is that the anaerobic dehydrogenation and aromatization performance of methane on 6Mo/MCM-22 and two kinds of catalyst of 6Mo/HZSM-5 compares.
Example 1: Preparation of Catalyst
HMCM-22 after ion-exchange or without the NaMCM-22 molecular sieve of low Na content of exchange, dry with roasting after be used for Preparation of Catalyst.Mo/MCM-22 is with MCM-22 molecular sieve dipping ammonium molybdate aqueous solution method or carry out ion-exchange or the preparation of mechanical mixture method.Prepared catalyst sample is 110 ℃ of oven dry, 500～550 ℃ of roastings 2～8 hours.
Example 2: catalytic reaction experiment 1
The Mo/MCM-22 catalyst of different Mo loading adopts traditional dipping method preparation.Methyl hydride catalyzed being reflected in the quartz tube reactor that continuous feed fixed bed internal diameter is 7～8mm carried out, and the each loading amount of catalyst is 0.2g, handles 30 minutes with He at 700 ℃, switches CH then
4-N
2Unstripped gas reacts.The methane gas air speed is 1500 a milliliters/gram. hour, pressure is 1atm.Product on-line analysis on OV-101 and the Shimadzu GC-9AM gas chromatograph that enters hydrogen flame and thermal conductivity cell detector after HayeSep D post separates provides area by C-R 3A and C-R 6A, adopts N
2Interior mark provides the carbon number EQUILIBRIUM CALCULATION FOR PROCESS result who comprises coking.
The Mo/HMCM-22 catalyst anaerobic dehydrogenation and aromatization performance of table 1 different metal content
Mo content reaction time methane change the line of production thing yield (%) (%) (hour) change rate (%)
One oxidative ethane benzene, naphthalene carbon species
Change the carbon vinyl toluene
2 1 6.32 0.28 0.27 3.62 0.46 1.69
2 6.75 0.063?0.28 3.91 0.48 2.02
4 5.25 0.028?0.30 3.65 0.43 0.87
6 4.59 0.020?0.29 3.12 0.32 0.84
6 1 11.43 0.20 0.28 5.69 0.57 4.69
2 10.87 0.077 0.30 6.98 0.59 2.92
4 10.38 0.037 0.31 7.22 0.49 2.32
6 9.17 0.020 0.32 7.04 0.41 1.38
10 1 6.81 0.35 0.26 4.20 0.28 1.71
2 7.09 0.086 0.25 4.03 0.84 2.48
4 4.68 0.044 0.26 3.25 0.16 0.96
6 3.61 0.033 0.20 2.38 0.12 0.87
Example 3: catalytic reaction experiment 2
Dress 0.2g 6Mo/MCM-22 catalyst in the fixed bed reactors of continuous feed carries out catalytic reaction by the reaction condition of example 2, and the reactivity worth of catalyst is listed among Fig. 1 with the situation of change in reaction time.As can be seen, in about 24 hours reaction time, the total recovery of aromatic hydrocarbons remains between 6～8% always.This shows that the Mo/MCM-22 catalyst has aromatization performance and reaction stability preferably.
Example 4: catalytic reaction experiment 3
Dress 0.2g 6Mo/HMCM-22 catalyst in the fixed bed reactors of continuous feed, reaction condition is undertaken by example 2, and the reactivity worth of catalyst is listed in the table 2 with the variation of reaction temperature.As can be seen along with the raising of reaction temperature, the time that catalyst reaches optimum activity to be needed shortens, and activity of such catalysts and aromatics yield all be improved to some extent, but the reaction stability of being not difficult to find out catalyst is downward trend along with the raising of reaction temperature.In the temperature range of being investigated, 690～720 ℃ is best.
The anaerobic dehydrogenation and aromatization result of table 2 6Mo/HMCM-22 catalyst under the differential responses temperature
The reaction response time methane thing yield (%) of changing the line of production
Temperature (hour) the change rate
(℃) (%) an oxidative ethane benzene, naphthalene carbon species
Change the carbon vinyl toluene
690 0.5 9.31 0.69 0.23 3.90 0.39 4.10
1 9.45 0.36 0.26 5.33 0.52 2.97
2 10.10 0.086 0.27 6.24 0.55 2.97
4 8.57 0.035 0.32 6.55 0.44 1.22
6 8.35 0.026 0.28 6.39 0.38 1.27
8 7.85 0 0.30 6.16 0.33 1.06
700 0.5 10.41 0.74 0.26 4.03 0.45 4.93
1 11.43 0.20 0.28 5.69 0.57 4.69
2 10.87 0.077 0.30 6.98 0.59 2.92
4 10.38 0.037 0.31 7.22 0.49 2.32
6 9.17 0.020 0.32 7.04 0.41 1.38
8 8.83 0 0.31 6.73 0.36 1.43
720 0.5 12.33 0.68 0.31 5.01 0.58 5.74
1 12.54 0.36 0.35 7.31 0.75 3.78
2 13.44 0.097 0.36 8.47 0.67 3.84
4 12.23 0.050 0.36 8.49 0.46 2.87
6 11.20 0.035 0.37 8.12 0.36 2.31
8 9.82 0.026 0.40 7.71 0.30 1.40
740 0.5 13.73 0.62 0.36 5.81 0.65 6.19
1 13.58 0.30 0.40 8.54 0.78 3.56
2 13.54 0.078 0.43 9.18 0.60 3.26
4 11.86 0.033 0.45 8.60 0.36 2.41
6 10.37 0.030 0.46 7.64 0.27 1.97
8 8.62 0.021 0.49 6.31 0.21 1.59
760 0.5 15.96 0.60 0.40 6.58 0.72 7.66
1 14.71 0.30 0.44 9.46 0.72 3.79
2 14.64 0.065 0.46 9.68 0.46 3.97
4 11.55 0.035 0.52 7.94 0.27 2.78
6 9.18 0.034 0.58 5.60 0.19 2.78
8 6.16 0.025 0.60 3.24 0.10 2.20
Example 5: catalytic reaction experiment 4
Dress 0.2g 6Mo/MCM-22 catalyst in the fixed bed reactors of continuous feed, reaction condition is undertaken by example 2, and the reactivity worth of catalyst is listed in the table 3 with the variation of air speed.Along with the raising of air speed, the time that catalyst reaches optimum activity to be needed shortens.Increase owing to air speed simultaneously makes methane feed gas reduce in the time of staying of catalyst surface, thereby makes the generation of aromatic hydrocarbons and carbon deposit be downward trend.This illustrates that also further generating species such as aromatic hydrocarbons and carbon deposit by middle species needs certain time of staying.Its best air speed is 900～1500ml/g.h.
The anaerobic dehydrogenation and aromatization performance of table 3 6Mo/HMCM-22 catalyst under different air speed conditions
The reaction response time methane thing yield (%) of changing the line of production
Air speed (hour) the change rate
(milliliter/(%) an oxidative ethane benzene, naphthalene carbon species
Gram. hour) change carbon vinyl toluene
900 0.5 11.09 1.26 0.24 2.37 0.25 6.97
1 11.14 0.59 0.28 4.60 0.54 5.03
2 11.86 0.14 0.29 6.40 0.67 4.35
4 10.75 0.069?0.31 7.01 0.64 2.52
6 10.88 0.041?0.33 7.33 0.53 2.64
8 10.70 0.036?0.33 7.31 0.47 2.57
1500 0.5 10.41 0.74 0.26 4.03 0.45 4.93
1 11.43 0.20 0.28 5.69 0.57 4.69
2 10.87 0.077?0.30 6.98 0.59 2.92
4 10.38 0.037?0.31 7.22 0.49 2.32
6 9.17 0.020?0.32 7.04 0.41 1.38
8 8.83 0 0.31 6.73 0.36 1.43
2400 0.5 9.42 0.38 0.27 5.77 0.52 2.48
1 9.53 0.094 0.29 6.48 0.53 2.14
2 9.26 0.040 0.30 6.65 0.50 1.77
4 8.01 0.017 0.31 5.88 0.36 1.43
6 7.16 0 0.31 5.77 0.31 0.77
8 6.37 0 0.31 5.01 0.26 0.79
3000 0.5 11.20 0.17 0.31 6.08 0.52 4.12
1 9.55 0.063 0.29 6.60 0.50 2.09
2 8.70 0.029 0.31 6.50 0.42 1.45
4 7.92 0 0.29 5.66 0.32 1.65
6 6.95 0 0.32 4.96 0.26 1.41
8 5.94 0 0.29 4.23 0.21 1.21
Comparative example: the performance of Mo/HZSM-5 catalyst
Method by example 1 replaces the MCM-22 molecular sieve to prepare the Mo/HZSM-5 catalyst with HZSM-5, and reacts by the condition of example 2.Mo/HZSM-5 reactivity worth and Mo/MCM-22 relatively see Fig. 2.As can be seen, the 6Mo/MCM-22 catalyst is compared with 6Mo/HZSM-5 and is shown good reaction activity and reaction stability.Mo/MCM-22 still has good benzene yield in reaction time of 24 hours reaching; And the 6Mo/HZSM-5 catalyst just is tangible downward trend after reaction is carried out 6 hours.
Claims (4)
1. the catalyst of a direct synthesis of arene with methane, it is characterized in that: this catalyst is for using MoO
3The MCM-22 zeolite of modification, the wherein SiO of MCM-22
2/ Al
2O
3Than being 30～100, the active component weight percentage is 2～30%.
2. according to the described catalyst of claim 1, it is characterized in that: MoO
3Content be 2～10%.
3. according to claim 1 or 2 described catalyst, it is characterized in that: add other transition metal as auxiliary agent.
4. application in the directly synthetic aromatic hydrocarbons of low-carbon alkanes such as methane according to claim 1 or 2 described catalyst, it is characterized in that: reaction is to carry out in the fixed bed type reactor system of continuous feed, reaction gas flow dilutes with pure methane or with inert gas, reaction temperature is between 650～800 ℃, and reaction velocity is 750～5000ml/g.h.
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|---|---|---|---|
| CNB991128842A CN1160155C (en) | 1999-04-28 | 1999-04-28 | Catalyst for synthesizing arylhydrocarbon with mathane and its application in synthesizing reaction |
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|---|---|---|---|
| CNB991128842A CN1160155C (en) | 1999-04-28 | 1999-04-28 | Catalyst for synthesizing arylhydrocarbon with mathane and its application in synthesizing reaction |
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| CN1160155C true CN1160155C (en) | 2004-08-04 |
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|---|---|---|---|---|
| CZ297691B6 (en) * | 2003-05-05 | 2007-03-07 | Ústav fyzikální chemie J. Heyrovského AV CR, v.v.i. | Mesoporous catalyst of olefin metathesis and process for preparing thereof |
| CN101733146B (en) * | 2008-11-21 | 2012-09-05 | 中国石油化工股份有限公司 | Catalyst for synthesizing propylene by using ethylene and butylene |
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