CN107649146B - Acetylene ring trimerization benzene catalyst and its preparation method and application - Google Patents
Acetylene ring trimerization benzene catalyst and its preparation method and application Download PDFInfo
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- CN107649146B CN107649146B CN201710843263.2A CN201710843263A CN107649146B CN 107649146 B CN107649146 B CN 107649146B CN 201710843263 A CN201710843263 A CN 201710843263A CN 107649146 B CN107649146 B CN 107649146B
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- palladium
- cobalt
- acetylene
- benzene
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 321
- 239000003054 catalyst Substances 0.000 title claims abstract description 184
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 117
- 238000005829 trimerization reaction Methods 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 218
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 126
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 126
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 126
- 238000006243 chemical reaction Methods 0.000 claims abstract description 122
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 104
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000011651 chromium Substances 0.000 claims abstract description 70
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000010941 cobalt Substances 0.000 claims abstract description 55
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 44
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 30
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- 239000008246 gaseous mixture Substances 0.000 claims description 34
- 239000012266 salt solution Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 31
- 150000002940 palladium Chemical class 0.000 claims description 27
- 239000003426 co-catalyst Substances 0.000 claims description 26
- 150000001868 cobalt Chemical class 0.000 claims description 26
- 238000007598 dipping method Methods 0.000 claims description 25
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 21
- 229960000359 chromic chloride Drugs 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 15
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 14
- 230000004913 activation Effects 0.000 claims description 10
- 150000001844 chromium Chemical class 0.000 claims description 10
- 238000011065 in-situ storage Methods 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 230000008901 benefit Effects 0.000 claims description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 description 32
- 239000007864 aqueous solution Substances 0.000 description 14
- 238000005660 chlorination reaction Methods 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 12
- KHKWHTCWOCAWME-UHFFFAOYSA-N acetylene benzene Chemical compound C#C.C1=CC=CC=C1.C#C KHKWHTCWOCAWME-UHFFFAOYSA-N 0.000 description 11
- 239000010935 stainless steel Substances 0.000 description 11
- 229910001220 stainless steel Inorganic materials 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 229910000684 Cobalt-chrome Inorganic materials 0.000 description 6
- 239000010952 cobalt-chrome Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 150000001345 alkine derivatives Chemical class 0.000 description 5
- 150000001555 benzenes Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- -1 chromium transition-metal Chemical class 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000006006 cyclotrimerization reaction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- FDTGUDJKAXJXLL-UHFFFAOYSA-N acetylene Chemical group C#C.C#C FDTGUDJKAXJXLL-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/42—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion
- C07C2/48—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion of only hydrocarbons containing a carbon-to-carbon triple bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of acetylene ring trimerization benzene catalyst and its preparation method and application, which includes: cobalt, palladium, chromium and ɑ-Al2O3Carrier, wherein be based on the ɑ-Al2O3The quality of carrier, the load capacity of the cobalt are 0.1~3wt%, and the load capacity of the palladium is 0.03~2wt%, and the load capacity of the chromium is 0.05~3wt%.The catalyst component simply easily obtains, and lasts a long time, and is remarkably improved the conversion ratio of acetylene and the selectivity of benzene, has a good application prospect.
Description
Technical field
The invention belongs to chemical technology fields, specifically, the present invention relates to acetylene ring trimerization benzene catalyst and its
Preparation method and application.
Background technique
The light aromatics such as benzene, toluene and dimethylbenzene (three is referred to as BTX) are answered extensively as most basic Organic Chemicals
For producing the chemical products such as rubber, fiber, plastics, dyestuff.Currently, aromatic hydrocarbons is mainly derived from the catalytic reforming in petrochemical industry
Coal chemical industry is derived from hydrocarbon cracking (about 90%), only about 10%.In recent years, one side petroleum resources gradually decrease, separately
One side synthetic material and the growing of other fine chemicals demands form higher demand to aromatics production, therefore develop virtue
The new technology of hydrocarbon production is imperative.If acyclic simple molecules, such as methane, methanol, acetylene can be utilized, bring it about
Aromatization is directly translated into the light aromatics of high added value, will be with important strategic importance.
Acetylene has high reactivity, and cyclotrimerization is thermodynamically strongly exothermic.It was reacting simultaneously
Tetramer, pentamer, polymer etc. are likely to form in journey.And the existing reaction that benzene is generated using catalyst acetylene, it deposits
Severe reaction conditions, reaction feed complicated components or the catalyst easy in inactivation the problems such as, and the choosing of the conversion ratio and benzene of acetylene
Selecting property is lower.Therefore, the existing technology for preparing benzene by acetylene is still further improved.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is to propose a kind of acetylene ring trimerization benzene catalyst and its preparation method and application.The catalyst component is simple
It easily obtains, lasts a long time, and be remarkably improved the conversion ratio of acetylene and the selectivity of benzene, have a good application prospect.
In one aspect of the invention, the invention proposes a kind of acetylene ring trimerization benzene catalyst, according to the present invention
Embodiment, which includes: cobalt, palladium, chromium and ɑ-Al2O3Carrier, wherein be based on the ɑ-Al2O3The quality of carrier, institute
The load capacity for stating cobalt is 0.1~3wt%, and the load capacity of the palladium is 0.03~2wt%, the load capacity of the chromium is 0.05~
3wt%.
Acetylene ring trimerization benzene catalyst according to an embodiment of the present invention, acetylene are adsorbed on metal surface, pass through acetylene bond
Fracture carries out cyclotrimerization and obtains benzene, and since the s track of Metal Palladium does not have electronics, and the d track of cobalt fills up electronics, the s of chromium
Track and d track do not fill up electronics, therefore palladium, cobalt, chromium can form metallic bond by mutual hydridization, and three kinds of metals is made to form one
A catalyst integrally carrys out catalyzing acetylene trimerization.And and intensity higher ɑ-Al larger by selection specific surface area2O3For carrier system
Standby composite load type cobalt/palladium/chromium transition-metal catalyst, that is, acetylene ring trimerization benzene catalyst.On the one hand, bigger serface
Carrier preferable dispersion can be formed to active component；On the other hand, this feature is conducive to the diffusion of product benzene molecular, thus effectively
Reduce the generation of the heavy aromatics such as Multi substituted benzenes.The catalyst component simply easily obtains, and lasts a long time, and is remarkably improved acetylene
The selectivity (up to 80% or more) of conversion ratio (can reach 70% or more) and benzene, has a good application prospect.
In addition, acetylene ring trimerization benzene catalyst according to the above embodiment of the present invention can also have it is following additional
Technical characteristic:
In some embodiments of the invention, it is based on ɑ-the Al2O3The quality of carrier, the load capacity of the cobalt is 0.1~
1.5wt%, the load capacity of the palladium are 0.03~1.8wt%, and the load capacity of the chromium is 0.05~1.5wt%.Thus, it is possible to
Acetylene conversion ratio with higher during guarantee acetylene ring trimerization benzene, benzene selectivity with higher.
In some embodiments of the invention, it is based on ɑ-the Al2O3The quality of carrier, the load capacity of the cobalt is 0.1~
1.0wt%, the load capacity of the palladium are 0.05~1.5wt%, and the load capacity of the chromium is 0.08~1.0wt%.Thus, it is possible to
Acetylene conversion ratio with higher during guarantee acetylene ring trimerization benzene, benzene selectivity with higher.
In another aspect of the invention, above-mentioned acetylene ring trimerization benzene catalyst is prepared the invention proposes a kind of
Method, according to an embodiment of the invention, this method comprises:
(1) palladium salt is mixed with water, to obtain palladium salt solution；
(2) cobalt salt is mixed with water, to obtain cobalt salt solution；
(3) chromic salts is mixed with water, to obtain chromium salt solution；
(4) by ɑ-Al2O3Carrier and the palladium salt solution are mixed with dipping, crushed after being dried, to obtain ɑ-Al2O3Load
Palladium catalyst；
(5) by the ɑ-Al2O3Loaded palladium catalyst and the cobalt salt solution are mixed with dipping, crushed after being dried, to obtain
ɑ-Al2O3Supported palladium Co catalysts；
(6) by the ɑ-Al2O3Supported palladium Co catalysts and the chromium salt solution are mixed with dipping, and crushed after being dried simultaneously roasts,
To obtain acetylene ring trimerization benzene catalyst.
The method according to an embodiment of the present invention for preparing acetylene ring trimerization benzene catalyst, by by ɑ-Al2O3Carrier according to
It is secondary to be impregnated with palladium salt solution, cobalt salt solution and chromium salt solution, palladium, cobalt and chromium can all be loaded to ɑ-Al2O3On carrier, obtain
To the acetylene ring trimerization benzene catalyst containing palladium, cobalt and chromium.And because of ɑ-Al2O3The specific surface area of carrier is larger, intensity compared with
It is high, on the one hand, preferable dispersion can be formed to active component；On the other hand, be conducive to the diffusion of product benzene molecular, to effectively drop
The generation of the heavy aromatics such as low Multi substituted benzenes.Entire simple process, reaction condition are mild, and resulting catalyst is in acetylene ring trimerization system
The conversion ratio of acetylene may make to reach 70% or more in the technique of benzene, the selectivity of benzene is up to 90% or more.
In addition, the method according to the above embodiment of the present invention for preparing acetylene ring trimerization benzene catalyst can also have
Following additional technical characteristic:
In some embodiments of the invention, in step (1), the palladium salt be in palladium chloride, palladium nitrate extremely
It is one of few.Be conducive to improve the quality of acetylene ring trimerization benzene catalyst as a result,.
In some embodiments of the invention, in step (2), the cobalt salt be in cobalt chloride, cobalt nitrate extremely
It is one of few.It can further improve the quality of acetylene ring trimerization benzene catalyst as a result,.
In some embodiments of the invention, in step (3), the chromic salts is in chromium trichloride, chromic nitrate
At least one.It can further improve the quality of acetylene ring trimerization benzene catalyst as a result,.
In some embodiments of the invention, in step (6), the temperature of the roasting is 350~500 degrees Celsius, when
Between be 3~6h.It can further improve the quality of acetylene ring trimerization benzene catalyst as a result,.
In an additional aspect of the present invention, the invention proposes a kind of methods of acetylene ring trimerization benzene, according to the present invention
Embodiment, this method comprises:
(a) under anhydrous, anaerobic state, catalyst is subjected to in-situ activation processing in hydrogen atmosphere, to obtain gold
Belong to state catalyst；
(b) the metallic state catalyst is contacted with the gaseous mixture containing acetylene and nitrogen, control gaseous mixture flow and
Reaction temperature, to obtain benzene,
Wherein, the catalyst is above-mentioned acetylene ring trimerization benzene catalyst.
The method of acetylene ring trimerization benzene according to an embodiment of the present invention, under conditions of only acetylene and nitrogen participate in,
By using above-mentioned acetylene ring trimerization benzene catalyst, benzene can be converted the acetylene to, and the conversion ratio of acetylene up to 70% with
On, for the selectivity of benzene up to 80% or more, unreacted acetylene is reusable, while entire reaction condition is more mild, behaviour
Make simply, to be suitable for industrialized production.
In addition, the method for acetylene ring trimerization benzene according to the above embodiment of the present invention can also have following additional skill
Art feature:
In some embodiments of the invention, in step (a), the temperature of the in-situ activation processing is taken the photograph for 600~800
Family name's degree, time are 1~3h.Be conducive to improve the conversion ratio of acetylene as a result,.
In some embodiments of the invention, in step (b), the body of acetylene described in the gaseous mixture and the nitrogen
Product is than being (20~50): (50~80).It can further improve the conversion ratio of acetylene as a result,.
In some embodiments of the invention, the volume space velocity of the gaseous mixture is 200-2000h-1.It as a result, can be further
Improve the conversion ratio of acetylene.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Above-mentioned and/or additional aspect of the invention and advantage will become from the description of the embodiment in conjunction with the following figures
Obviously and it is readily appreciated that, in which:
Fig. 1 is the method flow signal according to an embodiment of the invention for preparing acetylene ring trimerization benzene catalyst
Figure；
Fig. 2 is the method flow schematic diagram of acetylene ring trimerization benzene according to an embodiment of the invention.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to is used to explain the present invention, and is not considered as limiting the invention.
In one aspect of the invention, the invention proposes a kind of acetylene ring trimerization benzene catalyst, according to the present invention
Embodiment, which includes: cobalt, palladium, chromium and ɑ-Al2O3Carrier, wherein be based on ɑ-Al2O3The quality of carrier, cobalt are born
Carrying capacity is 0.1~3wt%, and the load capacity of palladium is 0.03~2wt%, and the load capacity of chromium is 0.05~3wt%.Inventors have found that
Since the s track of Metal Palladium does not have electronics, and the d track of cobalt fills up electronics, and the s track and d track of chromium do not fill up electronics,
Therefore palladium, cobalt, chromium can form metallic bond by mutual hydridization, so that three kinds of metals is formed a catalyst and integrally carry out catalyzing acetylene three
It is poly-.Inventor has been surprisingly found that by many experiments, if the load capacity of cobalt, palladium and chromium is too low, the active site of catalyst is on the low side, urges
Agent activity reduces；And if the load capacity of cobalt, palladium and chromium is excessively high, not only results in metal accumulation, or even can block carrier
Duct reduces the activity of catalyst instead.And and intensity higher ɑ-Al larger by selection specific surface area2O3For carrier system
Standby composite load type cobalt/palladium/chromium transition-metal catalyst, that is, acetylene ring trimerization benzene catalyst, on the one hand, bigger serface
Carrier preferable dispersion can be formed to active component；On the other hand, this feature is conducive to the diffusion of product benzene molecular, thus effectively
Reduce the generation of the heavy aromatics such as Multi substituted benzenes.The catalyst component simply easily obtains, and lasts a long time, and is remarkably improved acetylene
The selectivity (up to 90% or more) of conversion ratio (can reach 70% or more) and benzene, has a good application prospect.
According to one embodiment of present invention, it is based on ɑ-Al2O3The quality of carrier, the load capacity of cobalt are 0.1~1.5wt%,
The load capacity of palladium is 0.03~1.8wt%, and the load capacity of chromium is 0.05~1.5wt%.Thus, it is possible to guarantee acetylene ring trimerization system
Acetylene conversion ratio with higher during benzene, benzene selectivity with higher.
Still another embodiment in accordance with the present invention is based on ɑ-Al2O3The quality of carrier, the load capacity of cobalt is 0.1~
1.0wt%, the load capacity of palladium are 0.05~1.5wt%, and the load capacity of chromium is 0.08~1.0wt%.Thus, it is possible to guarantee acetylene
Acetylene conversion ratio with higher during ring trimerization benzene, benzene selectivity with higher.
Acetylene ring trimerization benzene catalyst according to an embodiment of the present invention, since the s track of Metal Palladium does not have electronics, and
The d track of cobalt fills up electronics, and the s track and d track of chromium do not fill up electronics, therefore palladium, cobalt, chromium can be formed by mutual hydridization
Metallic bond makes three kinds of metals form a catalyst and integrally carrys out catalyzing acetylene trimerization.And by choose specific surface area it is larger and
Higher ɑ-the Al of intensity2O3Composite load type cobalt/palladium/chromium transition-metal catalyst i.e. acetylene ring trimerization benzene is prepared for carrier to use
Catalyst.On the one hand, the carrier of bigger serface can form preferable dispersion to active component；On the other hand, this feature is advantageous
It is spread in product benzene molecular, so that the generation of the heavy aromatics such as Multi substituted benzenes be effectively reduced.The catalyst component simply easily obtains, the longevity
Life is longer, and is remarkably improved the conversion ratio (up to 70% or more) of acetylene and the selectivity (up to 80% or more) of benzene, has
Good application prospect.
In another aspect of the invention, above-mentioned acetylene ring trimerization benzene catalyst is prepared the invention proposes a kind of
Method, according to an embodiment of the invention, with reference to Fig. 1, this method comprises:
S100: palladium salt is mixed with water
In the step, palladium salt is dissolved in aqueous solution, so that it is uniformly dispersed after shaking, to obtain palladium salt solution.
According to one embodiment of present invention, palladium salt is selected from least one of palladium chloride, palladium nitrate.Invention human hair
Existing, palladium chloride and palladium nitrate relative low price are easy wiring solution-forming, and other palladium salts are expensive, and are difficult to find conjunction
Suitable solvent dissolution.
According to one embodiment of present invention, the liquid-solid ratio of water and palladium salt is (10-50): 1, preferably (10-20): 1.Hair
Bright people's discovery, if the liquid-solid ratio of water and palladium salt is too low, palladium salt is poorly soluble completely；And if the liquid-solid ratio of water and palladium salt is excessively high,
Then palladium salt solution concentration is too low, and required concentration is not achieved.
S200: cobalt salt is mixed with water
In the step, cobalt salt is dissolved in aqueous solution, so that it is uniformly dispersed after shaking, to obtain cobalt salt solution.
According to one embodiment of present invention, cobalt salt is selected from least one of cobalt chloride, cobalt nitrate.Invention human hair
Existing, cobalt chloride, cobalt nitrate relative low price are easy wiring solution-forming, and other cobalt salts are expensive, and are difficult to find properly
Solvent dissolution.
According to one embodiment of present invention, the liquid-solid ratio of water and cobalt salt is (10-50): 1, preferably (10-20): 1.Hair
Bright people's discovery, if the liquid-solid ratio of water and cobalt salt is too low, cobalt salt is poorly soluble completely；And if the liquid-solid ratio of water and cobalt salt is excessively high,
Then cobalt salt solution concentration is too low, and required concentration is not achieved.
S300: chromic salts is mixed with water
In the step, chromic salts is dissolved in aqueous solution, so that it is uniformly dispersed after shaking, to obtain chromium salt solution.
According to one embodiment of present invention, chromic salts is selected from least one of chromium trichloride, chromic nitrate.Invention human hair
Existing, the relative low price of chromium trichloride and chromic nitrate is easy wiring solution-forming, and other chromic salts are expensive, and are difficult
Find suitable solvent dissolution.
The liquid-solid ratio of still another embodiment in accordance with the present invention, water and chromic salts is (10-50): 1, preferably (10-20): 1.Hair
Bright people's discovery, if the liquid-solid ratio of water and chromic salts is too low, chromic salts is poorly soluble completely；And if the liquid-solid ratio of water and chromic salts is excessively high,
Concentration of salt solution is too low, and required concentration is not achieved.
S400: by ɑ-Al2O3Carrier and palladium salt solution are mixed with dipping, crushed after being dried
In the step, by ɑ-Al2O3Carrier and palladium salt solution obtained above are mixed with dipping, crushed after being dried, to obtain
ɑ-Al2O3Loaded palladium catalyst.Specifically, by ɑ-Al2O3Carrier, which is added in equal volume in palladium salt solution, to be impregnated, then in air
It is dry in atmosphere, it finally crushes, obtains ɑ-Al2O3Loaded palladium catalyst.Inventors have found that by by palladium salt solution and in equal volume
ɑ-Al2O3Dipping can make palladium salt be dispersed in ɑ-Al2O3On carrier.
According to one embodiment of present invention, the time of dipping is 6-12h.Inventors have found that if dipping time it is too short,
Then load to ɑ-Al2O3In palladium salt amount reduce, resulting ɑ-Al2O3Loaded palladium catalyst quality reduces；And if the time impregnated
It is too long, ɑ-Al in the unit time2O3The yield of loaded palladium catalyst declines.Use dip time proposed by the present invention can be with as a result,
Significantly improve ɑ-Al2O3The quality and yield of loaded palladium catalyst.
Still another embodiment in accordance with the present invention, drying temperature are 100-120 degrees Celsius, time 6-12h.Invention human hair
Existing, if drying temperature is too low, the time is too short, moisture can not be removed, and temperature is excessively high, can destroy ɑ-Al2O3The structure of carrier.
S500: by ɑ-Al2O3Loaded palladium catalyst and cobalt salt solution are mixed with dipping, crushed after being dried
In the step, by ɑ-Al2O3Loaded palladium catalyst and cobalt salt solution are mixed with dipping, crushed after being dried, to obtain ɑ-
Al2O3Supported palladium Co catalysts.Specifically, by ɑ-Al2O3Loaded palladium catalyst is added in cobalt salt solution in equal volume to be impregnated, so
It is dry in air atmosphere afterwards, it finally crushes, obtains ɑ-Al2O3Supported palladium Co catalysts.Inventors have found that by the way that cobalt salt is molten
Liquid and isometric ɑ-Al2O3Supported palladium Co catalysts dipping, which may make, makes cobalt salt be dispersed in ɑ-Al2O3The catalysis of supported palladium cobalt
In agent.
According to one embodiment of present invention, the time of dipping is 6-12h.Inventors have found that if dipping time it is too short,
Then load to ɑ-Al2O3Cobalt salt amount in loaded palladium catalyst is reduced, resulting ɑ-Al2O3Supported palladium Co catalysts quality reduces；
And if the overlong time impregnated, ɑ-Al in the unit time2O3The yield of supported palladium Co catalysts declines.It is mentioned as a result, using the present invention
Dip time out can significantly improve ɑ-Al2O3The quality and yield of supported palladium Co catalysts.
Still another embodiment in accordance with the present invention, drying temperature are 100-120 degrees Celsius, time 6-12h.Invention human hair
Existing, if drying temperature is too low, the time is too short, moisture can not be removed, and carrier structure can be destroyed if drying temperature is excessively high.
S600: by ɑ-Al2O3Supported palladium Co catalysts and chromium salt solution are mixed with dipping, and crushed after being dried simultaneously roasts
In the step, by ɑ-Al2O3Supported palladium Co catalysts and chromium salt solution are mixed with dipping, and crushed after being dried simultaneously roasts, with
Just acetylene ring trimerization benzene catalyst is obtained.Specifically, by ɑ-Al2O3It is molten that supported palladium Co catalysts are added to chromic salts in equal volume
It is impregnated in liquid, the then dry, crushing in air atmosphere is finally roasted, obtains ɑ-Al2O3Supported palladium cobalt chrome catalysts.Hair
Bright people discovery, by by chromium salt solution and isometric ɑ-Al2O3Supported palladium Co catalysts dipping may make chromic salts to be dispersed in
ɑ-Al2O3On supported palladium Co catalysts, then palladium salt, cobalt salt and chromic salts can be made to become metal oxide supported in ɑ-by roasting
Al2O3On carrier.
According to one embodiment of present invention, the time of dipping is 6-12h.Inventors have found that if dipping time it is too short,
Then load to ɑ-Al2O3Chromic salts amount in supported palladium Co catalysts is reduced, resulting ɑ-Al2O3Supported palladium cobalt chrome catalysts quality
It reduces；And if the overlong time impregnated, ɑ-Al in the unit time2O3The yield of supported palladium cobalt chrome catalysts declines.It uses as a result,
Dip time proposed by the present invention can significantly improve ɑ-Al2O3The quality and yield of supported palladium cobalt chrome catalysts.
Still another embodiment in accordance with the present invention, drying temperature are 100-120 degrees Celsius, time 6-12h.Invention human hair
Existing, if drying temperature is too low, the time is too short, moisture can not be removed, and carrier structure can be destroyed if drying temperature is excessively high.
According to still another embodiment of the invention, the temperature of roasting is 350~500 degrees Celsius, and the time is 3~6h.Invention
People's discovery, if the temperature of roasting is too low, various metal salts, which can not decompose, becomes oxidation state, and can if the temperature of roasting is excessively high
Destroy carrier structure.
The method according to an embodiment of the present invention for preparing acetylene ring trimerization benzene catalyst, by by ɑ-Al2O3Carrier according to
It is secondary to be impregnated with palladium salt solution, cobalt salt solution and chromium salt solution, palladium, cobalt and chromium can all be loaded to ɑ-Al2O3On carrier, obtain
To the acetylene ring trimerization benzene catalyst containing palladium, cobalt and chromium.And because of ɑ-Al2O3The specific surface area of carrier is larger, intensity compared with
It is high, on the one hand, preferable dispersion can be formed to active component；On the other hand, be conducive to the diffusion of product benzene molecular, to effectively drop
The generation of the heavy aromatics such as low Multi substituted benzenes.Entire simple process, reaction condition are mild, and resulting catalyst is in acetylene ring trimerization system
The conversion ratio of acetylene may make to can reach 70% or more in the technique of benzene, the selectivity of benzene is up to 80% or more.
In an additional aspect of the present invention, the invention proposes a kind of methods of acetylene ring trimerization benzene, according to the present invention
Embodiment, with reference to Fig. 2, this method comprises:
Sa: under anhydrous, anaerobic state, catalyst is subjected to in-situ activation processing in hydrogen atmosphere
In the step, under anhydrous, anaerobic state, catalyst is subjected to in-situ activation processing in hydrogen atmosphere, so as to
Obtain metallic state catalyst, wherein the catalyst is above-mentioned acetylene ring trimerization benzene catalyst or is obtained using the above method
To acetylene ring trimerization benzene catalyst.Specifically, it is anti-that above-mentioned acetylene ring trimerization benzene catalyst is first packed into fixed bed
It answers in device, for a period of time with nitrogen purging reaction unit, so that the conditions warrant in reaction unit is anhydrous and oxygen-free state, then
Above-mentioned catalyst is carried out to in-situ activation under hydrogen atmosphere and certain temperature and handles one section, so that ɑ-Al2O3Supported palladium cobalt chromium is urged
Palladium oxide, cobalt/cobalt oxide and chromated oxide in agent are reduced to metallic state, obtain metallic state catalyst.
According to one embodiment of present invention, in-situ activation processing temperature be 600~800 degrees Celsius, the time be 1~
3h.Inventors have found that reduction reaction formation monometallic will not occur for metal oxide if the temperature of in-situ activation processing is too low,
And if the temperature too Gao Zehui of in-situ activation processing makes carrier collapse, and destroys skeleton.If the time is too short, reduction reaction can not be anti-
Should completely, the time is too long, wastes energy.
Sb: metallic state catalyst is contacted with the gaseous mixture containing acetylene and nitrogen
In the step, metallic state catalyst is contacted with the gaseous mixture containing acetylene and nitrogen, controls the flow of gaseous mixture
And reaction temperature, to obtain benzene.Specifically, the gaseous mixture containing acetylene and nitrogen is passed into fixed bed reactors and gold
Belong to the contact of state catalyst, while controlling the flow of reaction temperature and gaseous mixture, obtains benzene.Second alkyne conversion is made using this method
Rate is up to 70% or more, and the selectivity of benzene is up to 80% or more.
According to one embodiment of present invention, the volume ratio of acetylene and nitrogen is (20~50): (50~80) in gaseous mixture.
Inventors have found that concentration of acetylene can be made excessively high if the volume ratio of acetylene in gaseous mixture and nitrogen is excessively high, so that reaction heat collects very much
In, can not quick release, there is temperature runaway phenomenon, and if the volume ratio of acetylene in gaseous mixture and nitrogen is too low second alkyne conversion imitate
Rate reduces, and improves production cost indirectly.
Still another embodiment in accordance with the present invention, reaction temperature are 150~300 degrees Celsius.Inventors have found that if reaction temperature
Height is spent, then monometallic clustering phenomena can occur, leads to catalyst activity reduction, and catalyst does not reach if temperature is too low
Catalysis reaction will not occur for active site.
According to still another embodiment of the invention, the air speed of gaseous mixture is 200~2000h-1.Inventors have found that if mixing
The air speed of gas is excessively high, can reduce the conversion ratio of acetylene, too low, can reduce production efficiency.
The method of acetylene ring trimerization benzene according to an embodiment of the present invention, under conditions of only acetylene and nitrogen participate in,
By using above-mentioned acetylene ring trimerization benzene catalyst, benzene can be converted the acetylene to, and the conversion ratio of acetylene is up to 70%
More than, for the selectivity of benzene up to 80% or more, unreacted acetylene is reusable, while entire reaction condition is more mild,
It is easy to operate, it is suitable for industrialized production.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without limiting the invention in any way.
Embodiment 1
Supported catalyst Pb/Co/Cr/ ɑ-Al2O3Preparation: weigh 10g carrier ɑ-Al2O3, add it to the chlorine of 10mL
Change in aqueous palladium, palladium chloride load capacity is denoted as ɑ-Al with palladium2O30.06%, at room temperature impregnate 6 hours, then in air gas
It is 8 hours dry under 100~120 degrees Celsius in atmosphere, it is crushed and ɑ-Al is made2O3Loaded palladium catalyst is denoted as Pb (0.06)/ɑ-
Al2O3；Then this catalyst is added in the cobalt chloride solution of 10mL, chlorination cobalt loading is denoted as ɑ-Al with cobalt2O3's
0.12%, it impregnates at room temperature 6 hours, it is then 8 hours dry under 100~120 degrees Celsius in air atmosphere, it is crushed and is made
ɑ-Al2O3Supported palladium Co catalysts are denoted as Pb (0.06)/Co (0.12)/ɑ-Al2O3；Then this catalyst is added to 10mL's
In chromium trichloride aqueous solution, chromium trichloride load capacity is denoted as ɑ-Al with chromium2O30.06%, at room temperature impregnate 6 hours, then exist
It is 8 hours dry under 100~120 degrees Celsius in air atmosphere, it is crushed and roasts the obtained acetylene ring three of 5h under 450 degrees Celsius
Gather benzene catalyst processed, is denoted as Pb (0.06)/Co (0.12)/Cr (0.06)/ɑ-Al2O3, through tabletting, broken and sieve as 20~
It is spare after 40 mesh.
The reaction of acetylene benzene carries out on fixed-bed reactor, the stainless steel reactor for the use of internal diameter being 10mm, reaction
Pressure is normal pressure.By 2g supported catalyst Pb (0.06)/Co (0.12)/Cr (0.06)/ɑ-Al2O3It is fitted into fixed bed reactors,
Catalyst is purged 20 minutes on reaction unit with nitrogen before reaction, guaranteeing reaction environment is anhydrous and oxygen-free state.Then
By catalyst in hydrogen atmosphere 700 degrees Celsius of lower reductase 12 h, be cooled to 200 degrees Celsius and be passed through volume group as 50%C2H2+
50%N2Gaseous mixture, the air speed of gaseous mixture is 1000h-1.The flow of gas has mass flowmenter control, reaction 4 in experiment
It as a child sampled afterwards, and detected product using gas chromatograph, the conversion ratio of acetylene is 53%, and the selectivity of benzene is 86%.
Embodiment 2
Supported catalyst Pb/Co/Cr/ ɑ-Al2O3Preparation: weigh 10g carrier ɑ-Al2O3, add it to the chlorine of 10mL
Change in aqueous palladium, palladium chloride load capacity is denoted as ɑ-Al with palladium2O30.12%, at room temperature impregnate 6 hours, then in air gas
It is 8 hours dry under 100~120 degrees Celsius in atmosphere, it is crushed and ɑ-Al is made2O3Loaded palladium catalyst is denoted as Pb (0.12)/ɑ-
Al2O3；Then this catalyst is added in the cobalt chloride solution of 10mL, chlorination cobalt loading is denoted as ɑ-Al with cobalt2O3's
0.24%, it impregnates at room temperature 6 hours, it is then 8 hours dry under 100~120 degrees Celsius in air atmosphere, it is crushed and is made
ɑ-Al2O3Supported palladium Co catalysts are denoted as Pb (0.12)/Co (0.24)/ɑ-Al2O3；Then this catalyst is added to 10mL's
In chromium trichloride aqueous solution, chromium trichloride load capacity is denoted as ɑ-Al with chromium2O30.06%, at room temperature impregnate 6 hours, then exist
It is 8 hours dry under 100~120 degrees Celsius in air atmosphere, it is crushed and roasts the obtained acetylene ring three of 5h under 450 degrees Celsius
Gather benzene catalyst processed, is denoted as Pb (0.12)/Co (0.24)/Cr (0.06)/ɑ-Al2O3, through tabletting, broken and sieve as 20~
It is spare after 40 mesh.
The reaction of acetylene benzene carries out on fixed-bed reactor, the stainless steel reactor for the use of internal diameter being 10mm, reaction
Pressure is normal pressure.By 2g supported catalyst Pb (0.12)/Co (0.24)/Cr (0.06)/ɑ-Al2O3It is fitted into fixed bed reactors,
Catalyst is purged 20 minutes on reaction unit with nitrogen before reaction, guaranteeing reaction environment is anhydrous and oxygen-free state.Then
By catalyst in hydrogen atmosphere 700 degrees Celsius of lower reductase 12 h, be cooled to 200 degrees Celsius and be passed through volume group as 50%C2H2+
50%N2Gaseous mixture, the air speed of gaseous mixture is 1000h-1.The flow of gas has mass flowmenter control, reaction 4 in experiment
It as a child sampled afterwards, and detected product using gas chromatograph, the conversion ratio of acetylene is 62%, and the selectivity of benzene is 80%.
Embodiment 3
Supported catalyst Pb/Co/Cr/ ɑ-Al2O3Preparation: weigh 10g carrier ɑ-Al2O3, add it to the chlorine of 10mL
Change in aqueous palladium, palladium chloride load capacity is denoted as ɑ-Al with palladium2O31%, at room temperature impregnate 6 hours, then in air atmosphere
It is 8 hours dry under 100~120 degrees Celsius, it is crushed and ɑ-Al is made2O3Loaded palladium catalyst is denoted as Pb (1)/ɑ-Al2O3；So
This catalyst is added in the cobalt chloride solution of 10mL afterwards, chlorination cobalt loading is denoted as ɑ-Al with cobalt2O32%, at room temperature
Dipping 6 hours, it is then 8 hours dry under 100~120 degrees Celsius in air atmosphere, it is crushed and ɑ-Al is made2O3Supported palladium
Co catalysts are denoted as Pb (1)/Co (2)/ɑ-Al2O3；Then this catalyst is added in the chromium trichloride aqueous solution of 10mL, three
Chromium chloride load capacity is denoted as ɑ-Al with chromium2O31%, impregnate at room temperature 6 hours, it is then 100~120 Celsius in air atmosphere
Degree is lower 8 hours dry, is crushed and is roasted under 450 degrees Celsius the obtained acetylene ring trimerization benzene catalyst of 5h, be denoted as Pb
(1)/Co(2)/Cr(1)/ɑ-Al2O3, through tabletting, it is broken and after sieving as 20~40 mesh it is spare.
The reaction of acetylene benzene carries out on fixed-bed reactor, the stainless steel reactor for the use of internal diameter being 10mm, reaction
Pressure is normal pressure.By 2g supported catalyst Pb (1)/Co (2)/Cr (1)/ɑ-Al2O3It is fitted into fixed bed reactors, it will before reacting
Catalyst is purged 20 minutes on reaction unit with nitrogen, and guaranteeing reaction environment is anhydrous and oxygen-free state.Then by catalyst
700 degrees Celsius of lower reductase 12 h in hydrogen atmosphere are cooled to 200 degrees Celsius and are passed through volume group as 30%C2H2+ 70%N2It is mixed
Gas is closed, the air speed of gaseous mixture is 600h-1.The flow of gas has mass flowmenter control in experiment, and reaction 4 as a child took afterwards
Sample detects product using gas chromatograph, and the conversion ratio of acetylene is 70%, and the selectivity of benzene is 88%.
Embodiment 4
Supported catalyst Pb/Co/Cr/ ɑ-Al2O3Preparation: weigh 10g carrier ɑ-Al2O3, add it to the chlorine of 10mL
Change in aqueous palladium, palladium chloride load capacity is denoted as ɑ-Al with palladium2O32%, at room temperature impregnate 6 hours, then in air atmosphere
It is 8 hours dry under 100~120 degrees Celsius, it is crushed and ɑ-Al is made2O3Loaded palladium catalyst is denoted as Pb (2)/ɑ-Al2O3；So
This catalyst is added in the cobalt chloride solution of 10mL afterwards, chlorination cobalt loading is denoted as ɑ-Al with cobalt2O33%, at room temperature
Dipping 6 hours, it is then 8 hours dry under 100~120 degrees Celsius in air atmosphere, it is crushed and ɑ-Al is made2O3Supported palladium
Co catalysts are denoted as Pb (2)/Co (3)/ɑ-Al2O3；Then this catalyst is added in the chromium trichloride aqueous solution of 10mL, three
Chromium chloride load capacity is denoted as ɑ-Al with chromium2O32%, impregnate at room temperature 6 hours, it is then 100~120 Celsius in air atmosphere
Degree is lower 8 hours dry, is crushed and is roasted under 450 degrees Celsius the obtained acetylene ring trimerization benzene catalyst of 5h, be denoted as Pb
(2)/Co(3)/Cr(2)/ɑ-Al2O3, through tabletting, it is broken and after sieving as 20~40 mesh it is spare.
The reaction of acetylene benzene carries out on fixed-bed reactor, the stainless steel reactor for the use of internal diameter being 10mm, reaction
Pressure is normal pressure.By 2g supported catalyst Pb (2)/Co (3)/Cr (2)/ɑ-Al2O3It is fitted into fixed bed reactors, it will before reacting
Catalyst is purged 20 minutes on reaction unit with nitrogen, and guaranteeing reaction environment is anhydrous and oxygen-free state.Then by catalyst
700 degrees Celsius of lower reductase 12 h in hydrogen atmosphere are cooled to 200 degrees Celsius and are passed through volume group as 30%C2H2+ 70%N2It is mixed
Gas is closed, the air speed of gaseous mixture is 600h-1.The flow of gas has mass flowmenter control in experiment, and reaction 4 as a child took afterwards
Sample detects product using gas chromatograph, and the conversion ratio of acetylene is 72%, and the selectivity of benzene is 82%.
Embodiment 5
Supported catalyst Pb/Co/Cr/ ɑ-Al2O3Preparation: weigh 10g carrier ɑ-Al2O3, add it to the chlorine of 10mL
Change in aqueous palladium, palladium chloride load capacity is denoted as ɑ-Al with palladium2O30.06%, at room temperature impregnate 6 hours, then in air gas
It is 8 hours dry under 100~120 degrees Celsius in atmosphere, it is crushed and ɑ-Al is made2O3Loaded palladium catalyst is denoted as Pb (0.06)/ɑ-
Al2O3；Then this catalyst is added in the cobalt chloride solution of 10mL, chlorination cobalt loading is denoted as ɑ-Al with cobalt2O3's
0.12%, it impregnates at room temperature 6 hours, it is then 8 hours dry under 100~120 degrees Celsius in air atmosphere, it is crushed and is made
ɑ-Al2O3Supported palladium Co catalysts are denoted as Pb (0.06)/Co (0.12)/ɑ-Al2O3；Then this catalyst is added to 10mL's
In chromium trichloride aqueous solution, chromium trichloride load capacity is denoted as ɑ-Al with chromium2O30.06%, at room temperature impregnate 6 hours, then exist
It is 8 hours dry under 100~120 degrees Celsius in air atmosphere, it is crushed and roasts the obtained acetylene ring three of 5h under 450 degrees Celsius
Gather benzene catalyst processed, is denoted as Pb (0.06)/Co (0.12)/Cr (0.06)/ɑ-Al2O3, through tabletting, broken and sieve as 20~
It is spare after 40 mesh.
The reaction of acetylene benzene carries out on fixed-bed reactor, the stainless steel reactor for the use of internal diameter being 10mm, reaction
Pressure is normal pressure.By 2g supported catalyst Pb (0.06)/Co (0.12)/Cr (0.06)/ɑ-Al2O3It is fitted into fixed bed reactors,
Catalyst is purged 20 minutes on reaction unit with nitrogen before reaction, guaranteeing reaction environment is anhydrous and oxygen-free state.Then
By catalyst in hydrogen atmosphere 700 degrees Celsius of lower reductase 12 h, be cooled to 200 degrees Celsius and be passed through volume group as 50%C2H2+
50%N2Gaseous mixture, the air speed of gaseous mixture is 600h-1.The flow of gas has mass flowmenter control in experiment, and reaction 4 is small
When after sample, detect product using gas chromatograph, the conversion ratio of acetylene is 61%, and the selectivity of benzene is 87%.
1 it is found that the conversion ratio of acetylene reduces when the flow of acetylene increases in conjunction with the embodiments, and the selectivity of benzene maintains not
Become.When the effective component of catalyst is too low, the conversion ratio of acetylene is affected by acetylene flow.
Embodiment 6
Supported catalyst Pb/Co/Cr/ ɑ-Al2O3Preparation: weigh 10g carrier ɑ-Al2O3, add it to the chlorine of 10mL
Change in aqueous palladium, palladium chloride load capacity is denoted as ɑ-Al with palladium2O32%, at room temperature impregnate 6 hours, then in air atmosphere
It is 8 hours dry under 100~120 degrees Celsius, it is crushed and ɑ-Al is made2O3Loaded palladium catalyst is denoted as Pb (2)/ɑ-Al2O3；So
This catalyst is added in the cobalt chloride solution of 10mL afterwards, chlorination cobalt loading is denoted as ɑ-Al with cobalt2O33%, at room temperature
Dipping 6 hours, it is then 8 hours dry under 100~120 degrees Celsius in air atmosphere, it is crushed and ɑ-Al is made2O3Supported palladium
Co catalysts are denoted as Pb (2)/Co (3)/ɑ-Al2O3；Then this catalyst is added in the chromium trichloride aqueous solution of 10mL, three
Chromium chloride load capacity is denoted as ɑ-Al with chromium2O32%, impregnate at room temperature 6 hours, it is then 100~120 Celsius in air atmosphere
Degree is lower 8 hours dry, is crushed and is roasted under 450 degrees Celsius the obtained acetylene ring trimerization benzene catalyst of 5h, be denoted as Pb
(2)/Co(3)/Cr(2)/ɑ-Al2O3, through tabletting, it is broken and after sieving as 20~40 mesh it is spare.
The reaction of acetylene benzene carries out on fixed-bed reactor, the stainless steel reactor for the use of internal diameter being 10mm, reaction
Pressure is normal pressure.By 2g supported catalyst Pb (2)/Co (3)/Cr (2)/ɑ-Al2O3It is fitted into fixed bed reactors, it will before reacting
Catalyst is purged 20 minutes on reaction unit with nitrogen, and guaranteeing reaction environment is anhydrous and oxygen-free state.Then by catalyst
700 degrees Celsius of lower reductase 12 h in hydrogen atmosphere are cooled to 200 degrees Celsius and are passed through volume group as 30%C2H2+ 70%N2It is mixed
Gas is closed, the air speed of gaseous mixture is 600h-1.The flow of gas has mass flowmenter control in experiment, and reaction 12 as a child took afterwards
Sample detects product using gas chromatograph, and the conversion ratio of acetylene is 70%, and the selectivity of benzene is 86%.
It 4 is found in conjunction with the embodiments it is found that extending to sampling in 12 hours between when reacted, the conversion ratio and benzene of acetylene in product
Selectivity be still able to maintain preferably, it can be seen that this catalyst system lasts a long time.
Comparative example 1
Supported catalyst Co/Cr/ ɑ-Al2O3Preparation: weigh 10g carrier ɑ-Al2O3, add it to the chlorination of 10mL
In cobalt aqueous solution, chlorination cobalt loading is denoted as ɑ-Al with cobalt2O30.12%, at room temperature impregnate 6 hours, then in air atmosphere
In it is 8 hours dry under 100~120 degrees Celsius, is crushed obtained ɑ-Al2O3Load cobalt catalyst is denoted as Co (0.12)/ɑ-
Al2O3；Then this catalyst is added in the chromium trichloride aqueous solution of 10mL, chromium trichloride load capacity is denoted as ɑ-Al with chromium2O3
0.06%, impregnate 6 hours, then crushed simultaneously dry 8 hours under 100~120 degrees Celsius in air atmosphere at room temperature
5h is roasted under 450 degrees Celsius, and ɑ-Al is made2O3Supported Co chrome catalysts are denoted as Co (0.12)/Cr (0.06)/ɑ-Al2O3, warp
Tabletting, broken and to sieve be spare after 20~40 mesh.
The reaction of acetylene benzene carries out on fixed-bed reactor, the stainless steel reactor for the use of internal diameter being 10mm, reaction
Pressure is normal pressure.By 2g supported catalyst Co (0.12)/Cr (0.06)/ɑ-Al2O3It is fitted into fixed bed reactors, it will before reacting
Catalyst is purged 20 minutes on reaction unit with nitrogen, and guaranteeing reaction environment is anhydrous and oxygen-free state.Then by catalyst
700 degrees Celsius of lower reductase 12 h in hydrogen atmosphere are cooled to 200 degrees Celsius and are passed through volume group as 30%C2H2+ 70%N2It is mixed
Gas is closed, the air speed of gaseous mixture is 600h-1.The flow of gas has mass flowmenter control in experiment, and reaction 4 as a child took afterwards
Sample detects product using gas chromatograph, and the conversion ratio of acetylene is 10%, and the selectivity of benzene is 0%.
1 it is found that when not having palladium in catalyst, conversion of alkyne is substantially reduced, and is generated without benzene in conjunction with the embodiments.Table
Bright palladium is most important ingredient in catalyst.
Comparative example 2
Supported catalyst Pb/Co/Cr/ γ-Al2O3Preparation: weigh 10g carrier γ-Al2O3, add it to 10mL's
In palladium chloride aqueous solution, palladium chloride load capacity is denoted as γ-Al with palladium2O30.06%, at room temperature impregnate 6 hours, then in air
It is 8 hours dry under 100~120 degrees Celsius in atmosphere, it is crushed and γ-Al is made2O3Loaded palladium catalyst, be denoted as Pb (0.06)/
γ-Al2O3；Then this catalyst is added in the cobalt chloride solution of 10mL, chlorination cobalt loading is denoted as γ-Al with cobalt2O3
0.12%, impregnate at room temperature 6 hours, then crushed system dry 8 hours under 100~120 degrees Celsius in air atmosphere
Obtain γ-Al2O3Supported palladium Co catalysts are denoted as Pb (0.06)/Co (0.12)/γ-Al2O3；Then this catalyst is added to
In the chromium trichloride aqueous solution of 10mL, chromium trichloride load capacity is denoted as γ-Al with chromium2O30.06%, at room temperature impregnate 6 hours,
Then 8 hours dry under 100~120 degrees Celsius in air atmosphere, it is crushed and roasting 5h is made under 450 degrees Celsius
γ-Al2O3The palladium cobalt chrome catalysts of load are denoted as Pb (0.06)/Co (0.12)/Cr (0.06)/γ-Al2O3, through tabletting, it is crushed
And it is spare after 20~40 mesh for sieving.
The reaction of acetylene benzene carries out on fixed-bed reactor, the stainless steel reactor for the use of internal diameter being 10mm, reaction
Pressure is normal pressure.By 2g supported catalyst Pb (0.06)/Co (0.12)/Cr (0.06)/γ-Al2O3It is packed into fixed bed reactors
In, catalyst is purged 20 minutes on reaction unit with nitrogen before reaction, guaranteeing reaction environment is anhydrous and oxygen-free state.So
Afterwards by catalyst in hydrogen atmosphere 700 degrees Celsius of lower reductase 12 h, be cooled to 200 degrees Celsius and be passed through volume group as 30%C2H2+
70%N2Gaseous mixture, the air speed of gaseous mixture is 600h-1.The flow of gas has mass flowmenter control in experiment, and reaction 4 is small
When after sample, detect product using gas chromatograph, the conversion ratio of acetylene is 44%, and the selectivity of benzene is 61%.
1 it is found that when using γ-Al in conjunction with the embodiments2O3Instead of ɑ-Al2O3After carrier, the conversion ratio and benzene of acetylene are selected
Property decrease, show that the specific surface area of carrier has large effect to this catalysis reaction.γ-Al2O3Specific surface area it is smaller,
Keep the metallic catalyst being supported on carrier limited, to reduce the active principle of catalyst, and then affects reaction.
Comparative example 3
Supported catalyst Pb/Co/ ɑ-Al2O3Preparation: weigh 10g carrier ɑ-Al2O3, add it to the chlorination of 10mL
In aqueous palladium, palladium chloride load capacity is denoted as ɑ-Al with palladium2O30.06%, at room temperature impregnate 6 hours, then in air atmosphere
In it is 8 hours dry under 100~120 degrees Celsius, is crushed obtained ɑ-Al2O3Loaded palladium catalyst is denoted as Pb (0.06)/ɑ-
Al2O3；Then this catalyst is added in the cobalt chloride solution of 10mL, chlorination cobalt loading is denoted as ɑ-Al with cobalt2O3's
0.12%, impregnate at room temperature 6 hours, then in air atmosphere dry 8 hours under 100~120 degrees Celsius, crushed and
5h is roasted under 450 degrees Celsius, and ɑ-Al is made2O3Supported palladium Co catalysts are denoted as Pb (0.06)/Co (0.12)/ɑ-Al2O3, through pressing
Piece, broken and to sieve be spare after 20~40 mesh.
The reaction of acetylene benzene carries out on fixed-bed reactor, the stainless steel reactor for the use of internal diameter being 10mm, reaction
Pressure is normal pressure.By 2g supported catalyst Pb (0.06)/Co (0.12)/ɑ-Al2O3It is fitted into fixed bed reactors, it will before reacting
Catalyst is purged 20 minutes on reaction unit with nitrogen, and guaranteeing reaction environment is anhydrous and oxygen-free state.Then by catalyst
700 degrees Celsius of lower reductase 12 h in hydrogen atmosphere are cooled to 300 degrees Celsius and are passed through volume group as 30%C2H2+ 70%N2It is mixed
Gas is closed, the air speed of gaseous mixture is 600h-1.The flow of gas has mass flowmenter control in experiment, and reaction 4 as a child took afterwards
Sample detects product using gas chromatograph, and the conversion ratio of acetylene is 51%, and the selectivity of benzene is 22%.
1 it is found that acetylene is still able to maintain preferable conversion ratio, benzene when in catalyst system without crome metal in conjunction with the embodiments
Selectivity substantially reduce, show that chromium can greatly improve the selectivity of benzene, reduce the generation of reaction impurities.
Comparative example 4
Supported catalyst Pb/Co/Cr/ ɑ-Al2O3Preparation: weigh 10g carrier ɑ-Al2O3, add it to the chlorine of 10mL
Change in aqueous palladium, palladium chloride load capacity is denoted as ɑ-Al with palladium2O30.01%, at room temperature impregnate 6 hours, then in air gas
It is 8 hours dry under 100~120 degrees Celsius in atmosphere, it is crushed and ɑ-Al is made2O3Loaded palladium catalyst is denoted as Pb (0.01)/ɑ-
Al2O3；Then this catalyst is added in the cobalt chloride solution of 10mL, chlorination cobalt loading is denoted as ɑ-Al with cobalt2O3's
0.24%, it impregnates at room temperature 6 hours, it is then 8 hours dry under 100~120 degrees Celsius in air atmosphere, it is crushed and is made
ɑ-Al2O3Supported palladium Co catalysts are denoted as Pb (0.01)/Co (0.24)/ɑ-Al2O3；Then this catalyst is added to 10mL's
In chromium trichloride aqueous solution, chromium trichloride load capacity is denoted as ɑ-Al with chromium2O30.06%, at room temperature impregnate 6 hours, then exist
It is 8 hours dry under 100~120 degrees Celsius in air atmosphere, it is crushed and roasts the obtained acetylene ring three of 5h under 450 degrees Celsius
Gather benzene catalyst processed, is denoted as Pb (0.01)/Co (0.24)/Cr (0.06)/ɑ-Al2O3, through tabletting, broken and sieve as 20~
It is spare after 40 mesh.
The reaction of acetylene benzene carries out on fixed-bed reactor, the stainless steel reactor for the use of internal diameter being 10mm, reaction
Pressure is normal pressure.By 2g supported catalyst Pb (0.01)/Co (0.24)/Cr (0.06)/ɑ-Al2O3It is fitted into fixed bed reactors,
Catalyst is purged 20 minutes on reaction unit with nitrogen before reaction, guaranteeing reaction environment is anhydrous and oxygen-free state.Then
By catalyst in hydrogen atmosphere 700 degrees Celsius of lower reductase 12 h, be cooled to 200 degrees Celsius and be passed through volume group as 50%C2H2+
50%N2Gaseous mixture, the air speed of gaseous mixture is 1000h-1.The flow of gas has mass flowmenter control, reaction 4 in experiment
It as a child sampled afterwards, and detected product using gas chromatograph, the conversion ratio of acetylene is 21%, and the selectivity of benzene is 71%.
2 it is found that conversion of alkyne substantially reduces when palladium catalyst content is too low in conjunction with the embodiments, benzene product amount also phase
It should reduce, show that certain palladium content has a major impact rate of catalysis reaction, too low palladium content can reduce reaction rate, no
Conducive to reaction.
Comparative example 5
Supported catalyst Pb/Co/Cr/ ɑ-Al2O3Preparation: weigh 10g carrier ɑ-Al2O3, add it to the chlorine of 10mL
Change in aqueous palladium, palladium chloride load capacity is denoted as ɑ-Al with palladium2O34%, at room temperature impregnate 6 hours, then in air atmosphere
It is 8 hours dry under 100~120 degrees Celsius, it is crushed and ɑ-Al is made2O3Loaded palladium catalyst is denoted as Pb (4)/ɑ-Al2O3；So
This catalyst is added in the cobalt chloride solution of 10mL afterwards, chlorination cobalt loading is denoted as ɑ-Al with cobalt2O30.24%, room
It is temperature lower dipping 6 hours, then 8 hours dry under 100~120 degrees Celsius in air atmosphere, it is crushed and ɑ-Al is made2O3It is negative
Palladium Co catalysts are carried, Pb (4)/Co (0.24)/ɑ-Al is denoted as2O3；Then the chromium trichloride for this catalyst being added to 10mL is water-soluble
In liquid, chromium trichloride load capacity is denoted as ɑ-Al with chromium2O30.06%, at room temperature impregnate 6 hours, then 100 in air atmosphere
It is 8 hours dry under~120 degrees Celsius, it is crushed and roasts the obtained acetylene ring trimerization benzene catalysis of 5h under 450 degrees Celsius
Agent is denoted as Pb (4)/Co (0.24)/Cr (0.06)/ɑ-Al2O3, through tabletting, it is broken and after sieving as 20~40 mesh it is spare.
The reaction of acetylene benzene carries out on fixed-bed reactor, the stainless steel reactor for the use of internal diameter being 10mm, reaction
Pressure is normal pressure.By 2g supported catalyst Pb (4)/Co (0.24)/Cr (0.06)/ɑ-Al2O3It is fitted into fixed bed reactors, instead
Catalyst is purged 20 minutes on reaction unit with nitrogen before answering, guaranteeing reaction environment is anhydrous and oxygen-free state.Then will
Catalyst 700 degrees Celsius of lower reductase 12 h in hydrogen atmosphere are cooled to 200 degrees Celsius and are passed through volume group as 50%C2H2+ 50%
N2Gaseous mixture, the air speed of gaseous mixture is 1000h-1.The flow of gas has mass flowmenter control in experiment, reacts 4 hours
It is sampled after time, detects product using gas chromatograph, the conversion ratio of acetylene is 36%, and the selectivity of benzene is 70%.
2 it is found that conversion of alkyne reduces instead when palladium catalyst too high levels in conjunction with the embodiments, benzene product amount also phase
It should reduce.This is because excessively packing phenomenon can then occur for palladium content, effective monoatomic metal palladium content is reduced instead, into
And conversion ratio is caused to reduce, while also increasing cost.Therefore excessive palladium is unfavorable for reacting.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of acetylene ring trimerization benzene catalyst characterized by comprising cobalt, palladium, chromium and ɑ-Al2O3Carrier, wherein base
In the ɑ-Al2O3The quality of carrier, the load capacity of the cobalt are 0.1~3wt%, the load capacity of the palladium is 0.03~
2wt%, the load capacity of the chromium are 0.05~3wt%.
2. catalyst according to claim 1, which is characterized in that be based on the ɑ-Al2O3The quality of carrier, the cobalt
Load capacity is 0.1~1.5wt%, and the load capacity of the palladium is 0.03~1.8wt%, the load capacity of the chromium is 0.05~
1.5wt%.
3. catalyst according to claim 1 or 2, which is characterized in that be based on the ɑ-Al2O3The quality of carrier, the cobalt
Load capacity be 0.1~1.0wt%, the load capacity of the palladium is 0.05~1.5wt%, the load capacity of the chromium is 0.08~
1.0wt%.
4. a kind of method for preparing acetylene ring trimerization benzene catalyst described in any one of claim 1-3, which is characterized in that
Include:
(1) palladium salt is mixed with water, to obtain palladium salt solution；
(2) cobalt salt is mixed with water, to obtain cobalt salt solution；
(3) chromic salts is mixed with water, to obtain chromium salt solution；
(4) by ɑ-Al2O3Carrier and the palladium salt solution are mixed with dipping, crushed after being dried, to obtain ɑ-Al2O3Load palladium catalysis
Agent；
(5) by the ɑ-Al2O3Loaded palladium catalyst and the cobalt salt solution are mixed with dipping, crushed after being dried, to obtain ɑ-
Al2O3Supported palladium Co catalysts；
(6) by the ɑ-Al2O3Supported palladium Co catalysts and the chromium salt solution are mixed with dipping, and crushed after being dried simultaneously roasts, so as to
Obtain acetylene ring trimerization benzene catalyst.
5. according to the method described in claim 4, it is characterized in that, the palladium salt is selected from palladium chloride, nitre in step (1)
At least one of sour palladium；
Optional, in step (2), the cobalt salt is selected from least one of cobalt chloride, cobalt nitrate；
Optional, in step (3), the chromic salts is selected from least one of chromium trichloride, chromic nitrate.
6. method according to claim 4 or 5, which is characterized in that in step (6), the temperature of the roasting is 350~
500 degrees Celsius, the time is 3~6h.
7. a kind of method of acetylene ring trimerization benzene characterized by comprising
(a) under anhydrous, anaerobic state, catalyst is subjected to in-situ activation processing in hydrogen atmosphere, to obtain metallic state
Catalyst；
(b) the metallic state catalyst is contacted with the gaseous mixture containing acetylene and nitrogen, controls flow and the reaction of gaseous mixture
Temperature, to obtain benzene,
Wherein, the catalyst is for acetylene ring trimerization benzene catalyst of any of claims 1-3 or using power
The catalyst that benefit requires method described in any one of 4-6 to prepare.
8. the method according to the description of claim 7 is characterized in that in step (a), the temperature of the in-situ activation processing is
600~800 degrees Celsius, the time is 1~3h.
9. the method according to the description of claim 7 is characterized in that in step (b), acetylene described in the gaseous mixture and institute
The volume ratio for stating nitrogen is (20~50): (50~80).
10. the method according to the description of claim 7 is characterized in that the volume space velocity of the gaseous mixture is 200-2000h-1。
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| CN102159520A (en) * | 2008-07-31 | 2011-08-17 | 国际人造丝公司 | Process for catalytically producing ethylene directly from acetic acid in single reaction zone |
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| US3812196A (en) * | 1970-11-30 | 1974-05-21 | Mitsubishi Petrochemical Co | Catalytic steam dealkylation |
| US3992468A (en) * | 1974-03-01 | 1976-11-16 | Institut Francais Du Petrole, Des Carburants Et Lubrifiants Et Entreprise De Recherches Et D'activities Petrolieres Elf | Process for the catalytic hydrodealkylation of alkylaromatic hydrocarbons |
| CN101116820A (en) * | 2007-08-30 | 2008-02-06 | 汉能科技有限公司 | Method for preparing un-equipartition combustion catalyst |
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