CN110075908A - A kind of catalyst and preparation method thereof for synthesis gas one-step synthesis aromatic hydrocarbons - Google Patents
A kind of catalyst and preparation method thereof for synthesis gas one-step synthesis aromatic hydrocarbons Download PDFInfo
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- CN110075908A CN110075908A CN201910415837.5A CN201910415837A CN110075908A CN 110075908 A CN110075908 A CN 110075908A CN 201910415837 A CN201910415837 A CN 201910415837A CN 110075908 A CN110075908 A CN 110075908A
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- 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
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Abstract
Catalyst technical field of the present invention, specially a kind of catalyst for synthesis gas one-step synthesis aromatic hydrocarbons and its preparation method.Catalyst of the present invention is made of Si-Al molecular sieve and metal composite oxide；The surface of Si-Al molecular sieve is handled by silicon oxide deposition and metal-modified, and modification is selected from least one of Zn, Ga, Ag, Mo, Cu, Fe, Ni, Co, Mn, La, Pr, Nd with metal；Metal composite oxide is at least one of Ceria-zirconia, zinc oxide-zirconium oxide, zinc oxide-chromium oxide；The preparation method comprises the following steps: carrying out silicon oxide deposition and metal-modified to Si-Al molecular sieve surface first, it is uniformly mixed with metal composite oxide then, the catalyst is made after granulation.The method for preparing catalyst is simple, low in cost, has high activity, high arenes selectivity and high stability in synthesis gas conversion process, has good prospects for commercial application.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of catalyst for synthesis gas one-step synthesis aromatic hydrocarbons and
Preparation method.
Background technique
Aromatic hydrocarbons is a kind of important Elementary Chemical Industry raw material, especially benzene, toluene and dimethylbenzene, is widely used in synthesis tree
The manufacture of the products such as rouge, staple fibre, synthetic rubber.Aromatic hydrocarbons annual consumption in China's is huge at this stage, and is in rise year by year trend,
But it is wherein more than half to depend on import.In addition, aroamtic hydrocarbon raw material production in China's is mainly obtained by petroleum refining, therefore, in stone
In the case that oily resource increasingly lacks, hair opens the Aromatics Production Technology of novel Non oil-based route, to realization aroamtic hydrocarbon raw material preparation side
Method diversification, while improving China and having aromatic hydrocarbons production capacity by oneself with own strategic significance.
Synthesis gas is a kind of widely used carbon resource platform, prepares hydrocarbon product development for a long time by raw material of synthesis gas,
Especially low-carbon alkene is synthetically prepared through Fischer-Tropsch to be widely studied；In addition, synthesis gas through methanol producing light olefins technology has developed
Maturation simultaneously realizes industrialization.However in the above process, the content of aromatic hydrocarbons target product is but restricted.Therefore, it designs and develops new
Type catalyst system, the aromatic product improved in synthesis gas conversion process are selectively of great significance.In recent years, with defect oxygen
Compound-molecular sieve (OX-ZEO) complex catalyst system achieves important breakthrough in one step conversion process of synthesis gas, with zinc chrome
16% CO conversion ratio and 74% aromatic hydrocarbons alkyl selectivity may be implemented in the catalyst of spinelle and ZSM-5 molecular sieve composition.So
And the carbon distribution inactivation of molecular sieve is one of the principal element for limiting the development of such catalyst.Therefore, in synthesis gas one-step synthesis virtue
During hydrocarbon reaction, design and develop the catalyst with efficient stable, at the same realize catalyst preparation process it is simple, economical,
Environmental protection is one of the Technology Difficulties in the field.
Summary of the invention
The purpose of the present invention is to provide it is a kind of with high catalytic activity, high stability for synthesis gas one-step synthesis virtue
Catalyst of hydrocarbon and preparation method thereof.
The present invention carries out machine using the Si-Al molecular sieve and metal composite oxide by showing siliceous deposits and metal-modified
Tool mixing can be prepared by, and preparation method is simple, and gained catalyst activity component is uniformly dispersed, anti-in the direct preparing aromatic hydrocarbon of synthesis gas
There should be high catalytic activity in the process, the feature that high aromatic hydrocarbons overall selectivity is high and stability is high has a good application prospect.
Provided by the present invention for the catalyst of synthesis gas one-step synthesis aromatic hydrocarbons, aoxidized by Si-Al molecular sieve and composition metal
Object composition；The Si-Al molecular sieve is Hydrogen, in silica alumina ratio 40-400, including ZSM-5, ZSM-48, ZSM-11 molecular sieve
At least one；Silicon oxide deposition and metal-modified are passed through in the surface of the Si-Al molecular sieve；Wherein, the metal of modification is selected from
At least one of Zn, Ga, Ag, Mo, Cu, Fe, Ni, Co, Mn, La, Pr, Nd；The metal composite oxide is cerium oxide-oxygen
Change at least one of zirconium, zinc oxide-zirconium oxide, zinc oxide-chromium oxide；Sial solid acid and composition metal in the catalyst
The mass ratio of oxide is 0.1-10.
Provided by the present invention for the preparation method of the catalyst of synthesis gas one-step synthesis aromatic hydrocarbons, the specific steps are as follows:
(1) it disperses Si-Al molecular sieve material (self-control or commercially available) in organic solvent, a certain amount of silicon source is added, is adding
Silicon oxide deposition processing is carried out to Si-Al molecular sieve surface under conditions of heat；Then exist to the Si-Al molecular sieve handled through siliceous deposits
It is roasted in 400-500 DEG C of air atmosphere；Wherein the mass ratio of Si-Al molecular sieve and solvent is 1:(50-100), silicon source and silicon
The mass ratio of aluminum molecular screen is 1:(0.01-0.3)；
(2) equi-volume process metal-modified is carried out to the Si-Al molecular sieve after above-mentioned siliceous deposits, wherein metal quality content is heavy for silicon
The 0.01%-5% of Si-Al molecular sieve after product, then roasts under 400-500 DEG C of air atmosphere；
(3) mechanical mixture will be carried out through treated step (1) and (2) Si-Al molecular sieve and metal composite oxide to uniform,
It is granulated to get the composite catalyst.
In step (1) of the present invention, the organic solvent is toluene, n-hexane, hexamethylene, ether, one in carbon tetrachloride
Kind；The silicon source is in tetraethyl orthosilicate, silicon tetrachloride, tetramethoxy-silicane, dichlorodimethylsilane；The heating temperature
Degree is 60-120 DEG C.
Catalyst provided by the invention is used for synthesis gas one-step synthesis aromatic hydrocarbons, specific steps are as follows:
The catalyst is fitted into reactor, hydrogen reducing 2-12h is used at 400-550 DEG C, is passed through CO/H2Molar ratio is
Synthesis gas 1:(0.5-4), reaction temperature are 350-500 DEG C, reaction pressure 1.0-4.0MPa, and reaction gas air speed is 200-
5000h-1。
Advantages of the present invention:
(1) method for preparing composite catalyst is simple, economical, environmentally friendly, easy to industrialized production；
(2) there is the composite catalyst catalytic activity height, aromatic hydrocarbons always to select in synthesis gas one-step synthesis aromatic hydrocarbons reaction process
Property high and high stability feature.Catalyst is prepared in aromatic hydrocarbons reaction in synthesis gas conversion, and the conversion ratio of CO is 10-45%, greatly
Up to 30% or more, content of the aromatic hydrocarbons in hydrocarbon product is 50-95% for part.
Specific embodiment
The present invention will be described in further detail by example, but therefore it not limited below.
Embodiment 1
It disperses the ZSM-11 molecular sieve that 3g silica alumina ratio is 40 in 300g hexamethylene, 0.03g dichloro-dimethyl is added thereto
Silane carries out heating stirring 12h under conditions of 60 DEG C, molecular sieve is recovered by filtration later, and roast under 500 DEG C of air atmospheres
4h obtains sample and is denoted as Z11-Si.Metal La modification is carried out by equi-volume impregnating to above-mentioned gained Z11-Si, wherein La
Load capacity is 5%(in terms of metal oxide), and 4h is roasted under 500 DEG C of air atmospheres, gained sample is denoted as La-Z11-Si.It will be upper
It states La-Z11-Si and zinc oxide-zirconium oxide and mechanical mixture is carried out with mass ratio 1:2, obtain composite catalyst after granulation, be denoted as
ZnZrOx/La-Z11-Si。
Above-mentioned composite catalyst is applied to synthesis gas conversion and prepares aromatic hydrocarbons reaction process.Catalyst is first packed into reactor
In, with after hydrogen reducing 2h at 550 DEG C, it is down to room temperature, is passed through CO/H later2The synthesis gas that molar ratio is 4.0, reaction temperature
It is 500 DEG C, reaction velocity 200h-1, reaction pressure 4.0MPa.It negates product after answering 6h to be analyzed, acquired results are listed in
In table 1.
Embodiment 2
It disperses the ZSM-5 molecular sieve that 3g silica alumina ratio is 120 in 150g toluene, 0.9g tetraethyl orthosilicate is added thereto,
120oHeating stirring 12h is carried out under conditions of C, molecular sieve is recovered by filtration later, and roast 4h under 400 DEG C of air atmospheres,
It obtains sample and is denoted as Z5-Si.Metal Zn modification, the wherein load of Zn are carried out by equi-volume impregnating to above-mentioned gained Z5-Si
Amount is 0.5%(in terms of metal oxide), and 4h is roasted under 400 DEG C of air atmospheres, gained sample is denoted as Zn-Z5-Si.It will be above-mentioned
Zn-Z5-Si and Ceria-zirconia are obtained composite catalyst after granulation, are denoted as with mass ratio 1:1 progress mechanical mixture
CeZrOx/Zn-Z5-Si。
Above-mentioned composite catalyst is applied to synthesis gas conversion and prepares aromatic hydrocarbons reaction process.Catalyst is first packed into reactor
In, with after hydrogen reducing 12h at 400 DEG C, it is down to room temperature, is passed through CO/H later2The synthesis gas that molar ratio is 1.0, reaction temperature
Degree is 450 DEG C, reaction velocity 600h-1, reaction pressure 2.0MPa.It negates product after answering 6h to be analyzed, acquired results column
In table 1.
Embodiment 3
It disperses the ZSM-5 molecular sieve that 3g silica alumina ratio is 120 in 150g toluene, 0.3g silicon tetrachloride is added thereto, 120
Heating stirring 12h is carried out under conditions of DEG C, molecular sieve is recovered by filtration later, and roast 4h under 500 DEG C of air atmospheres, is obtained sample
Product are denoted as Z5-SiCl.Ni metal modification is carried out by equi-volume impregnating to above-mentioned gained Z5-SiCl, wherein the load capacity of Cu
It is 0.5%(in terms of metal oxide), and 4h is roasted under 500 DEG C of air atmospheres, gained sample is denoted as Cu-Z5-SiCl.It will be above-mentioned
Cu-Z5-SiCl and Ceria-zirconia are obtained composite catalyst after granulation, are denoted as with mass ratio 1:1 progress mechanical mixture
CeZrOx/Cu-Z5-SiCl。
Above-mentioned composite catalyst is applied to synthesis gas conversion and prepares aromatic hydrocarbons reaction process.Catalyst is first packed into reactor
In, with after hydrogen reducing 2h at 550 DEG C, it is down to room temperature, is passed through CO/H later2The synthesis gas that molar ratio is 1.0, reaction temperature
It is 450 DEG C, reaction velocity 600h-1, reaction pressure 3.6MPa.It negates product after answering 6h to be analyzed, acquired results are listed in
In table 1.
Embodiment 4
It disperses the ZSM-48 molecular sieve that 3g silica alumina ratio is 400 in 200g carbon tetrachloride, tetra- methyl of 0.6g is added thereto
Silane carries out heating stirring 12h under conditions of 60 DEG C, molecular sieve is recovered by filtration later, and roast under 450 DEG C of air atmospheres
4h obtains sample and is denoted as Z48-Si.W metal modification is carried out by equi-volume impregnating to above-mentioned gained Z48-Si, wherein Ni
Load capacity is 0.01%(in terms of metal oxide), and 4h is roasted under 450 DEG C of air atmospheres, gained sample is denoted as Ni-Z48-Si.
Above-mentioned Ni-Z48-Si and zinc oxide-chromium oxide are subjected to mechanical mixture with mass ratio 1:0.1, obtain composite catalyst after granulation,
It is denoted as ZnCrOx/Ni-Z48-Si。
Above-mentioned composite catalyst is applied to synthesis gas conversion and prepares aromatic hydrocarbons reaction process.Catalyst is first packed into reactor
In, with after hydrogen reducing 2h at 550 DEG C, it is down to room temperature, is passed through CO/H later2The synthesis gas that molar ratio is 0.5, reaction temperature
It is 350 DEG C, reaction velocity 5000h-1, reaction pressure 1.0MPa.It negates product after answering 6h to be analyzed, acquired results are listed in
In table 1.
Comparative example 1
3g silica alumina ratio is subjected to mechanical mixture for 40 ZSM-5 and Ceria-zirconia with mass ratio 1:1, is answered after granulation
Catalyst is closed, CeZrO is denoted asx/Z5。
Above-mentioned composite catalyst is applied to synthesis gas conversion and prepares aromatic hydrocarbons reaction process.Catalyst is first packed into reactor
In, with after hydrogen reducing 2h at 550 DEG C, it is down to room temperature, is passed through CO/H later2The synthesis gas that molar ratio is 1.0, reaction temperature
It is 450 DEG C, reaction velocity 3000h-1, reaction pressure 2.0MPa.It negates product after answering 6h to be analyzed, acquired results are listed in
In table 1.
Table 1
。
Claims (4)
1. a kind of catalyst for synthesis gas one-step synthesis aromatic hydrocarbons, which is characterized in that by Si-Al molecular sieve and composition metal oxygen
Compound composition；The Si-Al molecular sieve is Hydrogen, and silica alumina ratio 40-400 is selected from ZSM-5, ZSM-48, ZSM-11 molecular sieve
At least one of；Silicon oxide deposition and metal-modified are passed through in the surface of the Si-Al molecular sieve, wherein modification is selected from metal
At least one of Zn, Ga, Ag, Mo, Cu, Fe, Ni, Co, Mn, La, Pr, Nd；The metal composite oxide is cerium oxide-oxygen
Change at least one of zirconium, zinc oxide-zirconium oxide, zinc oxide-chromium oxide；Sial solid acid and composition metal in the catalyst
The mass ratio of oxide is 0.1-10.
2. a kind of preparation method for the catalyst of synthesis gas one-step synthesis aromatic hydrocarbons as described in claim 1, which is characterized in that
Specific step is as follows:
(1) it disperses Si-Al molecular sieve material in organic solvent, silicon source is added, under heating conditions to Si-Al molecular sieve table
Face carries out silicon oxide deposition processing；Then the Si-Al molecular sieve handled through siliceous deposits is carried out in 400-500 DEG C of air atmosphere
Roasting；Wherein the mass ratio of Si-Al molecular sieve and solvent is 1:(50-100), the mass ratio of silicon source and Si-Al molecular sieve is 1:
(0.01-0.3)；
(2) equi-volume process metal-modified is carried out to the Si-Al molecular sieve after above-mentioned siliceous deposits, wherein metal quality content is heavy for silicon
The 0.01%-5% of Si-Al molecular sieve after product, then roasts under 400-500 DEG C of air atmosphere；
(3) mechanical mixture will be carried out through treated step (1) and (2) Si-Al molecular sieve and metal composite oxide to uniform,
It is granulated to get the composite catalyst.
3. preparation method according to claim 2, which is characterized in that organic solvent described in step (1) be toluene, just oneself
One of alkane, hexamethylene, ether, carbon tetrachloride；The silicon source is selected from tetraethyl orthosilicate, silicon tetrachloride, tetramethoxy-silicane
One of alkane, dichlorodimethylsilane；The heating temperature is 60-120 DEG C.
4. application of the catalyst as described in claim 1 in the reaction of synthesis gas one-step synthesis aromatic hydrocarbons, which is characterized in that specific
Step are as follows: the catalyst is fitted into reactor, hydrogen reducing 2-12h is used at 450-550 DEG C, is passed through CO/H2Molar ratio
Example is the synthesis gas of 1:(0.5-4), and reaction temperature is 350-500 DEG C, reaction pressure 1.0-4.0MPa, and reaction gas air speed is
200-5000h-1。
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Cited By (5)
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| CN110560155A (en) * | 2019-09-17 | 2019-12-13 | 大连理工大学 | Preparation method and application of composite catalyst for directly producing propylene by bioethanol one-step method |
| CN111229303A (en) * | 2020-03-13 | 2020-06-05 | 华东理工大学 | Composite catalyst for directly preparing high-value aromatic hydrocarbon from carbon dioxide, preparation method and application |
| CN112745189A (en) * | 2019-10-29 | 2021-05-04 | 中国科学院大连化学物理研究所 | Method for producing aromatic hydrocarbon by carbonylation of normal hexane |
| CN113289674A (en) * | 2021-05-27 | 2021-08-24 | 复旦大学 | Bifunctional catalyst for preparing light aromatic hydrocarbon from synthesis gas and preparation method thereof |
| CN113289677A (en) * | 2021-04-26 | 2021-08-24 | 复旦大学 | Complex phase metal catalyst for preparing aromatic hydrocarbon from synthetic gas and preparation method thereof |
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| CN113289674A (en) * | 2021-05-27 | 2021-08-24 | 复旦大学 | Bifunctional catalyst for preparing light aromatic hydrocarbon from synthesis gas and preparation method thereof |
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