CN115106118A - Supported catalyst with function of catalyzing dehydrogenation of low-carbon alkane, preparation method and application thereof, and method for preparing low-carbon alkene - Google Patents
Supported catalyst with function of catalyzing dehydrogenation of low-carbon alkane, preparation method and application thereof, and method for preparing low-carbon alkene Download PDFInfo
- Publication number
- CN115106118A CN115106118A CN202110296713.7A CN202110296713A CN115106118A CN 115106118 A CN115106118 A CN 115106118A CN 202110296713 A CN202110296713 A CN 202110296713A CN 115106118 A CN115106118 A CN 115106118A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- active component
- alkane
- dehydrogenation
- molecular sieve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 121
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 13
- 150000003624 transition metals Chemical class 0.000 claims abstract description 13
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 11
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 239000002808 molecular sieve Substances 0.000 claims description 34
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 34
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 229910052710 silicon Inorganic materials 0.000 claims description 25
- 239000010703 silicon Substances 0.000 claims description 25
- 238000012986 modification Methods 0.000 claims description 24
- 230000004048 modification Effects 0.000 claims description 24
- 239000001294 propane Substances 0.000 claims description 22
- 150000001336 alkenes Chemical class 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 230000002209 hydrophobic effect Effects 0.000 claims description 17
- -1 small molecule organic compound Chemical class 0.000 claims description 17
- 238000011068 loading method Methods 0.000 claims description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 150000003384 small molecules Chemical class 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 4
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- 239000002994 raw material Substances 0.000 abstract description 4
- 125000001165 hydrophobic group Chemical group 0.000 abstract 1
- 229910052697 platinum Inorganic materials 0.000 abstract 1
- 238000002336 sorption--desorption measurement Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004846 x-ray emission Methods 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
- B01J29/0356—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
- C07C2529/035—Crystalline silica polymorphs, e.g. silicalites
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to the field of catalysts, and discloses a supported catalyst with a function of catalyzing dehydrogenation of low-carbon alkane, a preparation method and application thereof, and a method for preparing low-carbon alkene. The catalyst provided by the invention improves the adsorption/desorption speed of raw materials and products by modifying nonpolar and/or hydrophobic groups on the surface, thereby improving the catalytic performance and the one-way catalytic life of the catalyst. In addition, compared with the existing catalyst for low-carbon alkane dehydrogenation, the catalyst provided by the invention adopts transition metal to replace noble metal such as Pt or Cr as an active component, so that the cost of the catalyst is reduced, the pollution problem is avoided, and the high-efficiency, environment-friendly and sustainable production of the low-carbon alkane dehydrogenation industry is really realized.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a supported catalyst with a function of catalyzing dehydrogenation of low-carbon alkane, a preparation method and application thereof, and a method for preparing low-carbon olefin.
Background
At present, commercial low-carbon alkane dehydrogenation catalysts, such as propylene preparation catalysts by propane dehydrogenation, generally adopt catalysts which take alumina as a carrier and Pt and other precious metal main active components. However, these catalysts have poor stability and the noble metal itself has high cost, resulting in high catalyst cost. In addition, the single-pass catalytic life of the existing catalyst is short, so that the problem of frequent regeneration of the catalyst is caused, and the production energy consumption and the production cost are increased. Meanwhile, the existing fluidized bed process matched with the alumina catalyst also has the problems of complex reaction device and high construction cost.
The fixed bed process can greatly reduce the construction and operation cost of supporting facilities, thereby being widely concerned by the industry. The company LUMMUS has introduced Cr-series catalyst with Cr as main catalyst component for fixed bed production. However, the single pass catalytic life and catalytic performance of the catalyst still need to be further improved. Moreover, the Cr-series catalyst is easy to cause environmental pollution in use, and although a fixed bed production process with low cost is adopted, a pollution treatment device and a pollution treatment process are required to be matched in actual production, so that the production process of the low-carbon olefin by using the Cr-series catalyst is not only inconsistent with the sustainable development spirit, but also has high production cost.
The problems are not beneficial to the industrial development of the production of the low-carbon olefin, so that a novel green and environment-friendly catalyst which is good in stability, long in one-way catalytic life, simple in matching process and applicable to the preparation of the low-carbon olefin is urgently needed to be found.
Disclosure of Invention
The invention aims to overcome the problems in the prior art, and provides a supported catalyst with a function of catalyzing propane dehydrogenation, which adopts transition metal as an active component, reduces the cost of the catalyst, has no pollution problem, and can cause the product to be desorbed more quickly by changing the surface polarity and hydrophobicity of the catalyst, especially a carrier, so as to reduce the possibility of excessive dehydrogenation, reduce the carbon deposition speed and further improve the catalytic life. The catalyst has the characteristics of excellent catalytic performance, high stability, long one-way catalytic life, fast desorption of products, environmental protection and the like.
In order to achieve the above object, the present invention provides a supported catalyst having a function of catalyzing dehydrogenation of light alkane, the catalyst comprising a carrier and an active component supported on the carrier, the carrier being an all-silica molecular sieve, the active component being selected from transition metals excluding noble metals and chromium, and the surface of the catalyst having non-polar and/or hydrophobic modification.
In a second aspect, the present invention provides a process for preparing a supported catalyst having a function of catalyzing the dehydrogenation of propane, the process comprising the steps of:
(1) supporting an active component on a total silicon molecular sieve, wherein the active component is selected from transition metals excluding noble metals and chromium;
(2) and (2) carrying out surface nonpolar and/or hydrophobic modification on the product obtained in the step (1) to obtain the supported catalyst with the function of catalyzing the dehydrogenation of the low-carbon alkane.
In a third aspect, the present invention provides a catalyst prepared by the above method.
The invention provides the application of the catalyst and the method in catalyzing the dehydrogenation of the light alkane to prepare the light alkene;
wherein the lower alkane comprises an alkane having 5 or less carbon atoms;
and/or the lower olefins include olefins having 5 or less carbon atoms.
In a fifth aspect, the present invention provides a method for producing lower olefins, the method comprising: contacting the lower alkane with the catalyst as described above under conditions for dehydrogenation of the lower alkane;
wherein the lower alkane comprises an alkane having 5 or less carbon atoms;
and/or, the lower olefins include olefins having 5 or less carbon atoms.
According to the technical scheme, the beneficial effects obtained by the invention comprise that:
(1) the catalyst provided by the invention has the characteristics of high raw material conversion rate, high product selectivity and excellent catalytic performance, and has the characteristic of long one-way catalytic life, so that the production cost caused by frequent regeneration of the catalyst is reduced, and the catalyst is suitable for industrial production and popularization;
(2) the catalyst provided by the invention adopts transition metals such as Zn, Cu, Fe and the like as active components, so that the catalyst cost is reduced compared with the traditional noble metal catalyst, and the catalyst has the advantages of environmental protection compared with a Cr-series catalyst;
(3) the surface of the catalyst provided by the invention is modified by adopting non-polarity and/or hydrophobicity, so that the surface characteristics of the catalyst are improved on the premise of not changing the size, appearance and pore size structure of the catalyst, the product can be desorbed more quickly, the possibility of excessive dehydrogenation is reduced, the reaction efficiency is improved, and the catalytic performance and single-pass catalytic life of the catalyst are further improved.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, unless otherwise specified, the term "one-way life" means: the catalyst is maintained at the conditions of use for a period of time at an activity level, wherein the activity level includes feedstock conversion and product selectivity. Specifically, the single-pass lifetime is calculated from the start of the reaction to the time when any one of the indices of the conversion of the raw material and the selectivity of the product cannot be maintained stable. To a certain extent, the length of the one-way service life is positively correlated with the stability.
In the present invention, the "first" and the "second" of the "first drying" and the "second drying" are used only for the purpose of descriptively distinguishing the drying processes in the different steps.
The all-silicon molecular sieve (such as MFI type all-silicon molecular sieve) has weaker acidity, can inhibit isomerization and secondary hydrogenation reaction of intermediate products to a certain extent, and can reduce carbon deposition when being applied to a catalyst, thereby prolonging the service life of the catalyst to a certain extent. However, the MFI type all-silicon molecular sieve has smaller pore channels, so that the diffusion speed of raw materials and products is limited, and the carbon deposition speed is increased. The inventor of the invention skillfully discovers in research that the surface polarity and hydrophobicity of the all-silicon molecular sieve (and the catalyst prepared by the all-silicon molecular sieve) can be changed, the adsorption speed of reactants and products can be regulated, the reaction kinetic process can be optimized, the possibility of excessive dehydrogenation and secondary hydrogenation can be reduced, the carbon deposition speed can be reduced, and the service life of the catalyst can be prolonged.
The invention provides a supported catalyst with a function of catalyzing dehydrogenation of low-carbon alkane, which comprises a carrier and an active component loaded on the carrier, wherein the carrier is an all-silicon molecular sieve, the active component is selected from transition metals excluding noble metals and chromium, and the surface of the catalyst is provided with nonpolar and/or hydrophobic modification.
According to a preferred embodiment of the present invention, wherein the support is an MFI-type all-silica molecular sieve. The MFI-type all-silica molecular sieve can be prepared by a person skilled in the art according to the prior art, and can also be a related product obtained commercially. In addition, the MFI-type all-silica molecular sieve may also have a non-polar and/or hydrophobic surface modification.
Preferably, the specific surface area of the carrier is 200-600m 2 (ii) in terms of/g. Preferably 300-500m 2 (ii)/g, more preferably 400- 2 /g。
Preferably, the support has an average pore size of 2-10 nm. Preferably 2-5nm, more preferably 2-3 nm.
The present inventors have found during their research that a catalyst having a high catalytic activity and a long one-way lifetime and having a function of catalyzing dehydrogenation of a low-carbon alkane can be obtained by using a transition metal (e.g., Fe) as an active component and blending a carrier such as an all-silica molecular sieve (e.g., MFI-type all-silica molecular sieve). Compared with the precious metal catalyst (such as Pt catalyst) and Cr catalyst commonly used in the field, the catalyst prepared from the transition metal has the advantages of low cost and environmental protection.
According to a preferred embodiment of the invention, wherein the active component is selected from at least one of the group consisting of metals of groups VIIB, VIII, IB and IIB excluding transition metals of noble metals (e.g. Pt).
Preferably, the active component is selected from at least one of Zn, Fe, Cu, Ni and Mn.
More preferably, the active component is selected from at least one of Zn, Fe and Cu. More preferably Zn.
The content of the active component in the catalyst provided by the invention can be adjusted by those skilled in the art, for example, according to the actual production needs or the characteristics of the selected element of the active component. Preferably, the content of the active component is 1-10 wt% of the carrier in terms of metal element. Namely, the weight ratio of the active component to the carrier is 1:10-100 in terms of metal elements.
The inventor of the present invention has skillfully discovered in the process of research that the polarity and/or hydrophobicity of the surface of the catalyst (carrier) can be changed by grafting a polar and/or hydrophobic modification group provided by a small molecule organic compound (such as a small molecule benzene series, a small molecule liquid alkane, etc.) to the surface of the catalyst (carrier), but the characteristics of the size, the appearance, the pore size structure, etc. of the catalyst (carrier) are not changed, and the catalytic performance of the catalyst is not negatively influenced.
According to a preferred embodiment of the invention, wherein the non-polar and/or hydrophobic modification is achieved by grafting non-polar and/or hydrophobic modification groups onto the surface of the catalyst.
Preferably, the modifying group is provided by a small molecule organic compound.
More preferably, the modifying group is provided by at least one of a small molecule benzene series and/or a small molecule liquid alkane. Preferably at least one of methylcyclohexane, hexane, toluene and p-xylene.
According to a preferred embodiment of the present invention, wherein the weight ratio of the small molecule organic compound to the catalyst (support) is 3 to 10: 1.
preferably, the amount of grafting of the modifying group is such that the content of the grafting group is 0.01 to 3% by weight of the catalyst. Preferably 0.01 to 0.2 wt%, more preferably 0.08 to 0.12 wt%.
According to the preferred embodiment of the invention, wherein the specific surface area of the catalyst is 200-600m 2 (ii) in terms of/g. Preferably 300-500m 2 (ii)/g, more preferably 300- 2 /g。
According to a preferred embodiment of the present invention, wherein the active component of the catalyst is present in the catalyst in the oxidized state. The active component in the catalyst plays a catalytic role in a reduction state.
Preferably, before use, the method further comprises the step of reducing the catalyst.
More preferably, the reducing conditions include: h 2 Reducing for 1-5h at the temperature of 500-600 ℃ under the atmosphere.
In a second aspect, the present invention provides a process for preparing a supported catalyst having a function of catalyzing the dehydrogenation of propane, the process comprising the steps of:
(1) loading an active component on a full silicon molecular sieve, wherein the active component is selected from transition metals excluding noble metals and chromium;
(2) and (2) carrying out surface nonpolar and/or hydrophobic modification on the product obtained in the step (1) to obtain the supported catalyst with the function of catalyzing the dehydrogenation of the low-carbon alkane.
According to a preferred embodiment of the present invention, step (1) comprises loading an active component precursor on the all-silicon molecular sieve by an impregnation method, and then sequentially performing first drying and calcination to obtain the catalyst.
According to a preferred embodiment of the present invention, in step (1), the all-silicon molecular sieve is an MFI-type all-silicon molecular sieve.
Preferably, the specific surface area of the MFI-type all-silicon molecular sieve is 200-600m 2 (ii) in terms of/g. Preferably 300-500m 2 /g, more preferably 300-450m 2 /g。
Preferably, the average pore diameter of the MFI-type all-silica molecular sieve is 2 to 10 nm. Preferably 2-5nm, more preferably 2.5-4 nm.
Any existing MFI-type all-silica molecular sieve having the above characteristics can be suitable for use in the methods provided herein. For example, the MFI-type all-silicon molecular sieve may be a self-prepared MFI-type all-silicon molecular sieve having the above-mentioned characteristics according to the prior art, or a commercially available related product having the above-mentioned characteristics.
According to a preferred embodiment of the present invention, in the step (1), at least one of the active components selected from the group consisting of metals of groups VIIB, VIII, IB, and IIB does not include a transition metal of a noble metal (e.g., Pt, etc.).
Preferably, the active component is selected from at least one of Zn, Fe, Cu, Ni and Mn.
More preferably, the active component is selected from at least one of Zn, Fe and Cu. More preferably Zn.
According to a preferred embodiment of the present invention, in the step (1), the active component precursor is used in an amount such that the amount of the active component supported on the carrier is 1 to 10% by weight based on the metal element. Namely, the weight ratio of the active component to the carrier calculated by the metal element is 1: 10-100.
Preferably, the active component precursor comprises a water-soluble inorganic salt of the active component. Preferably at least one of carbonate, nitrate and chloride of the active component. More preferably Zn (NO) 3 ) 2 、Cu(NO 3 ) 2 、Fe(NO 3 ) 3 And hydrates thereof.
According to a preferred embodiment of the present invention, in step (1), the impregnation method adopts an equal volume impregnation method and/or an excess impregnation method, preferably an excess impregnation method.
According to a preferred embodiment of the present invention, wherein the conditions of the first drying include: the temperature is 80-120 ℃, and the time is 2-3 h.
According to a preferred embodiment of the present invention, wherein the firing conditions include: raising the temperature to 500-600 ℃ at the temperature raising rate of 5-8 ℃/min, and then roasting for 1-5h at the temperature.
According to a preferred embodiment of the present invention, wherein, in step (2), the non-polar and/or hydrophobic modification is achieved by grafting a non-polar and/or hydrophobic modification group on the surface of the catalyst.
Preferably, the non-polar and/or hydrophobic modification is performed in a manner comprising: and (2) contacting the product obtained in the step (1) with a small molecular organic compound, heating and refluxing, and then sequentially carrying out washing, solid-liquid separation and secondary drying.
Any small molecule organic compound with weak polarity or non-polarity can be suitable for the method provided by the invention. According to a preferred embodiment of the present invention, in the step (2), the small molecule organic compound comprises a small molecule benzene series and/or a small molecule liquid alkane, and more preferably comprises at least one of toluene, p-xylene, hexane and methylcyclohexane.
According to a preferred embodiment of the present invention, in the step (2), the amount of the small molecular organic compound is such that the weight ratio of the all-silicon molecular sieve to the small molecular organic compound is 1: 3-10.
According to a preferred embodiment of the present invention, in the step (2), the heating reflux condition includes: the temperature is 50-60 ℃, and the time is 20-30 h.
According to a preferred embodiment of the present invention, wherein said washing is performed with said small molecule organic compound of the same kind contacted with the product obtained in said step (1). Any amount of the small molecule organic compound may be used in the washing step as long as the purpose of dissolving the above organic solvent can be achieved.
Preferably, the small-molecule organic compound used for washing is used in an amount of 5-10: 1.
more preferably, the washing may be repeated 2 to 3 times in order to achieve the above object.
Any existing solid-liquid separation method suitable for catalyst preparation can be applied to the method provided by the invention. According to a preferred embodiment of the present invention, in the step (2), solid-liquid separation is performed by filtration.
According to a preferred embodiment of the present invention, in the step (2), the conditions of the second drying include: the temperature is 60-80 ℃ and the time is 2-5 h.
A third aspect of the invention provides a catalyst prepared according to the method as described above.
In a fourth aspect, the present invention provides the use of the catalyst or the preparation method as described above in the preparation of light olefins by dehydrogenation of light alkanes. The lower alkane includes an alkane having 5 or less carbon atoms (for example, propane). The lower olefins include olefins having 5 or less carbon atoms (e.g., propylene).
Because the MFI type catalyst has the characteristic of shape selection selectivity, the catalyst prepared by taking the MFI type catalyst as the carrier is particularly suitable for the reaction of preparing propylene by propane dehydrogenation. Therefore, the catalyst or the method provided by the invention and described above is preferably applied to the preparation of propylene by propane dehydrogenation.
In a fifth aspect, the present invention provides a method for producing lower olefins, the method comprising: the lower alkane is contacted with the catalyst as described above under conditions for dehydrogenation of the lower alkane. The lower alkane includes an alkane having 5 or less carbon atoms (for example, propane). The lower olefins include olefins having 5 or less carbon atoms (e.g., propylene).
According to a preferred embodiment of the present invention, the dehydrogenation conditions of the lower alkane comprise: the temperature is 550-650 ℃, the pressure is 0.08-0.12MPa, and the mass space velocity of the gas is 1-3h -1 。
Preferably, the lower alkane is propane.
Preferably, the lower olefin is propylene.
According to a preferred embodiment of the present invention, wherein H may also be employed in the method 2 As a diluent gas, and H 2 The volume ratio of the low-carbon alkane to the low-carbon alkane is 1: 2-4.
The present invention will be described in detail below by way of examples. It should be understood that the following examples are only intended to further illustrate and explain the present invention, and are not intended to limit the present invention.
In the following examples, MFI-type all-silicon molecular sieves are available from Aldrich and have a specific surface area of 480m 2 In terms of a/g, the mean pore diameter is 2.3 nm. Other conventional instrumentation and chemicals are commercially available from normal chemical instrumentation and reagent suppliers.
In the following examples, the conditions of the vacuum rotary evaporation method are: the water bath is carried out at 60 ℃ and the vacuum degree is 95 kPa.
Example 1
(1) Active ingredient loading
Zn (NO) is selected 3 ) 2 Dissolving the precursor as active component in water to obtain solution. And loading an active component precursor on the MFI type all-silicon molecular sieve by adopting a vacuum rotary evaporation method, wherein the active component precursor is used in an amount such that the loading amount of Zn accounts for 5 wt% of the weight of the carrier. After solid-liquid separation is carried out by adopting a filtering mode, the obtained solid phase is sequentially subjected to first drying and roasting. The concrete conditions are as follows: first drying: the temperature is 120 ℃, and the time is 2 h; roasting: heating to 550 ℃ at a heating rate of 5 ℃/min, and then roasting for 3 h.
(2) Surface modification
Mixing the product obtained in the step (1) with toluene according to the weight ratio of 1:4, and heating and refluxing for 24h at 60 ℃. The product obtained was then washed 3 times with toluene. After filtering the washing product, carrying out vacuum drying on the obtained solid phase, wherein the specific conditions are as follows: the temperature is 90 ℃, the time is 2h, and the vacuum degree is 95 kPa.
The obtained product was crushed to 40 to 60 mesh to obtain catalyst a 1.
Example 2
(1) Active ingredient loading
Selecting Fe (NO) 3 ) 3 Dissolving the precursor as an active component in water to prepare a solution. And loading an active component precursor on the MFI type all-silicon molecular sieve by adopting a vacuum rotary evaporation method, wherein the active component precursor is used in an amount such that the loading amount of Fe accounts for 5 wt% of the weight of the carrier. After solid-liquid separation by filtration, the obtained solid phase is sequentially subjected to primary drying and bakingAnd (6) burning. The concrete conditions are as follows: first drying: the temperature is 120 ℃, and the time is 2 h; roasting: heating to 550 ℃ at a heating rate of 5 ℃/min, and then roasting for 3 h.
(2) Surface modification
Mixing the product obtained in the step (1) with toluene according to the weight ratio of 1:4, and heating and refluxing for 24h at 60 ℃. The product obtained was then washed 3 times with toluene. After filtering the washing product, carrying out vacuum drying on the obtained solid phase under the specific conditions: the temperature is 90 ℃, the time is 2h, and the vacuum degree is 95 kPa.
The obtained product was crushed to 40 to 60 mesh to obtain catalyst a 2.
Example 3
(1) Active ingredient loading
Selecting Cu (NO) 3 ) 2 Dissolving the active precursor in water to prepare a solution. And loading an active component precursor on the MFI type all-silicon molecular sieve by adopting a vacuum rotary evaporation method, wherein the active component precursor is used in an amount such that the Cu loading amount accounts for 5 wt% of the carrier weight. After solid-liquid separation is carried out by adopting a filtering mode, the obtained solid phase is sequentially subjected to first drying and roasting. The concrete conditions are as follows: first drying: the temperature is 120 ℃, and the time is 2 h; roasting: heating to 550 ℃ at a heating rate of 5 ℃/min, and then roasting for 3 h.
(2) Surface modification
Mixing the product obtained in the step (1) with toluene according to the weight ratio of 1:4,
heated and refluxed for 24h at 60 ℃. The product obtained was then washed 3 times with toluene. After filtering the washing product, carrying out vacuum drying on the obtained solid phase under the specific conditions: the temperature is 90 ℃, the time is 2h, and the vacuum degree is 95 kPa.
The obtained product was crushed to 40 to 60 mesh to obtain catalyst a 3.
Example 4
The procedure was as in example 1, with the active component precursor being used in such an amount that the Zn loading was 10 wt% of the support weight. Catalyst a4 was obtained.
Example 5
The procedure was the same as in example 2, with the active component precursor being used in such an amount that the loading of Fe was 10 wt% of the support weight. Catalyst a5 was obtained.
Example 6
The procedure was the same as in example 3, with the active component precursor being used in such an amount that the loading of Cu was 10 wt% of the weight of the support. Catalyst A6 was obtained.
Comparative example 1
The method of example 1 was used except that alumina (available from national medicine, with an average pore diameter of 4.1nm) was used as the carrier. Catalyst D1 was obtained.
Comparative example 2
The method of example 1 was employed except that the product obtained in step (1) was used directly for the catalytic reaction without being subjected to the surface modification treatment of step (2). Catalyst D2 was obtained.
Test example 1
The catalysts obtained in examples and comparative examples were subjected to catalyst characteristic tests such as specific surface area and graft amount of the modifying group by nitrogen adsorption test method, and the results are detailed in table 1. Wherein, the grafting amount of the modifying group is the percentage of the modifying group grafted on the surface of the catalyst in the total weight of the catalyst, and is obtained by detecting with X-ray fluorescence spectrometry (the testing instrument is purchased from Pasnake company, and the model is ZTIUM).
Table 1 results of catalyst characteristic test
| Catalyst and process for preparing same | Specific surface area (m) 2 /g) | Graft amount of modifying group (% by weight) |
| A1 | 420 | 0.1 |
| A2 | 435 | 0.12 |
| A3 | 413 | 0.11 |
| A4 | 350 | 0.09 |
| A5 | 360 | 0.08 |
| A6 | 335 | 0.085 |
| D1 | 265 | 0.14 |
| D2 | 440 | / |
Test example 2
In the following test examples, the analysis of the reaction product composition was carried out on a gas chromatograph from Agilent under the model number 7890A, in which propane and propylene were detected by means of an alumina column FID detector. The method for calculating the conversion rate of the propane adopts a normalization method, and the main formula is as follows:
propane conversion-moles of propane converted/moles of propane fed
Propylene selectivity-moles of propylene converted/moles of propane converted
The single-pass lifetime refers to the total length of time from the start of the reaction to the end when any one of the indices of propane conversion and propylene selectivity cannot be maintained stable. The normal pressure means 0.1. + -. 0.02MPa (gauge pressure).
The propane conversion and propylene selectivity are both average values over the single pass life.
Before use, the catalyst is reduced, and the specific conditions are as follows: h 2 Reducing for 3h at 600 ℃ under the atmosphere and the gas flow rate of 30 ml/min.
Evaluation of the performance of the catalyst propane dehydrogenation to propylene was carried out on a fixed-bed microreactor (from de retton, texas). Filling 0.5g of catalyst, the diameter of a reaction tube is 10mm, the reaction temperature is 600 ℃, the reaction pressure is normal pressure, hydrogen is used as diluent gas, and the volume ratio of the hydrogen to the propane is 1:4, gas mass space velocity of 3h -1 . The results are detailed in table 2.
TABLE 2 results of the determination of catalytic Activity of the catalyst
| Catalyst and process for preparing same | Propane conversion (%) | Propylene selectivity (%) | Single pass catalytic life (h) |
| A1 | 35 | 80 | ＞300 |
| A2 | 23 | 75 | ＞300 |
| A3 | 25 | 72 | ＞300 |
| A4 | 38 | 77 | ＞300 |
| A5 | 25 | 75 | ＞300 |
| A6 | 28 | 70 | ＞300 |
| D1 | 36 | 78 | 10 |
| D2 | 33 | 78 | 150 |
The total test time of the test was 300h, no significant performance degradation occurred for catalysts a1-a6 over the test time, and therefore the single pass catalytic life results were recorded as over 300h (> 300 h).
Further detection shows that no acetylenic substance is detected in the product, which indicates that the catalyst provided by the invention effectively avoids the occurrence of an excessive dehydrogenation condition in the production process.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A supported catalyst with a function of catalyzing dehydrogenation of low-carbon alkane comprises a carrier and an active component loaded on the carrier, and is characterized in that the carrier is an all-silicon molecular sieve, the active component is selected from transition metals excluding noble metals and chromium, and the surface of the catalyst is provided with nonpolar and/or hydrophobic modification.
2. The catalyst of claim 1, wherein the support is an MFI-type all-silica molecular sieve;
preferably, the specific surface area of the catalyst is 200-600m 2 /g。
3. The catalyst of claim 1 or 2, wherein the active component is selected from at least one of group VIIB, VIII, IB, and IIB metals;
preferably, the active component is selected from at least one of Zn, Fe, Cu, Ni and Mn, preferably at least one of Zn, Fe and Cu;
preferably, the active component is present in an amount of 1 to 10% by weight, calculated as metallic element, based on the weight of the support.
4. The catalyst according to any one of claims 1-3, wherein the non-polar and/or hydrophobic modification is achieved by grafting non-polar and/or hydrophobic modification groups on the surface of the catalyst;
preferably, the modifying group is provided by a small molecule organic compound;
preferably, the amount of grafting of the modifying group is such that the content of the grafting group is from 0.01 to 3% by weight of the catalyst;
more preferably, the modifying group is provided by at least one of small molecule benzene series and/or small molecule liquid alkane, preferably at least one of methylcyclohexane, n-hexane, toluene and p-xylene.
5. A method for preparing a supported catalyst having a function of catalyzing propane dehydrogenation, comprising the steps of:
(1) supporting an active component on a total silicon molecular sieve, wherein the active component is selected from transition metals excluding noble metals and chromium;
(2) and (2) carrying out surface nonpolar and/or hydrophobic modification on the product obtained in the step (1) to obtain the supported catalyst with the function of catalyzing the dehydrogenation of the low-carbon alkane.
6. The method as claimed in claim 5, wherein the step (1) comprises loading an active component precursor on the all-silicon molecular sieve by an impregnation method, and then sequentially performing first drying and roasting;
preferably, the all-silicon molecular sieve is an MFI-type all-silicon molecular sieve;
preferably, the active component is selected from at least one of group VIIB, VIII, IB, and IIB metals;
more preferably, the active component precursor is used in an amount such that the amount of the active component supported on the carrier is 1 to 10% by weight, based on the metal element, based on the weight of the carrier;
more preferably, the active component precursor comprises a water-soluble inorganic salt of the active component, preferably at least one of a carbonate, nitrate and chloride of the active component, more preferably Zn (NO) 3 ) 2 、Cu(NO 3 ) 2 、Fe(NO 3 ) 3 And hydrates thereof.
7. The method according to claim 6, wherein in step (1), the impregnation method adopts an equal volume impregnation method and/or an excess impregnation method, preferably an excess impregnation method;
and/or, the conditions of the first drying include: the temperature is 80-120 ℃, and the time is 2-3 h;
and/or the roasting mode is as follows: raising the temperature to 500-600 ℃ at the temperature raising rate of 5-8 ℃/min, and then roasting for 1-5h at the temperature.
8. The process according to claim 5, wherein in step (2), the non-polar and/or hydrophobic modification is achieved by grafting non-polar and/or hydrophobic modification groups on the catalyst surface;
preferably, the non-polar and/or hydrophobic modification is performed in a manner comprising: contacting the product obtained in the step (1) with a small molecular organic compound, heating and refluxing, and then sequentially carrying out washing, solid-liquid separation and secondary drying;
more preferably, the small molecule organic compound comprises a small molecule benzene series and/or a small molecule liquid alkane, and more preferably comprises at least one of toluene, p-xylene, n-hexane and methylcyclohexane;
more preferably, the weight ratio of the all-silicon molecular sieve to the small-molecule organic compound is 1: 3-10;
more preferably, the conditions of the heating reflux include: the temperature is 50-60 ℃, and the time is 20-30 h;
more preferably, the washing is carried out with the small molecule organic compound in contact with the product obtained in step (1);
more preferably, the conditions of the second drying include: the temperature is 60-80 ℃, and the time is 2-5 h.
9. A catalyst prepared according to the process of any one of claims 5 to 8.
10. Use of the catalyst of any one of claims 1-4 and 9 for the catalytic dehydrogenation of lower alkanes to lower olefins;
wherein the lower alkane comprises an alkane having 5 or less carbon atoms;
and/or, the lower olefins include olefins having 5 or less carbon atoms.
11. A process for producing lower olefins, the process comprising: contacting a lower alkane with the catalyst of any one of claims 1-4 and 9 under conditions for dehydrogenation of the lower alkane;
wherein the lower alkane comprises an alkane having 5 or less carbon atoms;
and/or, the lower olefins include olefins having 5 or less carbon atoms.
12. The method of claim 11, wherein the conditions for dehydrogenation of the lower alkane comprise: the temperature is 550-650 ℃, the pressure is 0.08-0.12MPa, and the mass space velocity of the gas is 1-5h -1 ；
Preferably, the lower alkane is propane;
preferably, the lower olefin is propylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110296713.7A CN115106118B (en) | 2021-03-19 | 2021-03-19 | Supported catalyst with function of catalyzing dehydrogenation of low-carbon alkane, preparation method and application thereof, and method for preparing low-carbon olefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110296713.7A CN115106118B (en) | 2021-03-19 | 2021-03-19 | Supported catalyst with function of catalyzing dehydrogenation of low-carbon alkane, preparation method and application thereof, and method for preparing low-carbon olefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115106118A true CN115106118A (en) | 2022-09-27 |
| CN115106118B CN115106118B (en) | 2024-02-13 |
Family
ID=83323366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110296713.7A Active CN115106118B (en) | 2021-03-19 | 2021-03-19 | Supported catalyst with function of catalyzing dehydrogenation of low-carbon alkane, preparation method and application thereof, and method for preparing low-carbon olefin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115106118B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105712837A (en) * | 2014-12-05 | 2016-06-29 | 中国科学院大连化学物理研究所 | Method for preparing organic oxygenated compounds by hydrocarbon catalytic selective oxidation |
| CN105772092A (en) * | 2016-03-21 | 2016-07-20 | 中国科学技术大学 | Modified catalyst and preparation method thereof |
| CN106669703A (en) * | 2015-11-05 | 2017-05-17 | 中国石油化工股份有限公司大连石油化工研究院 | SiO2 modified low carbon alkane dehydrogenation catalyst and preparation method thereof |
| CN110614116A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Non-noble metal low-carbon alkane dehydrogenation catalyst, preparation method thereof and method for preparing low-carbon olefin by low-carbon alkane dehydrogenation |
| CN111085208A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Non-noble metal low-carbon alkane dehydrogenation catalyst with spherical double-mesoporous composite carrier and preparation method and application thereof |
| CN111672532A (en) * | 2019-03-11 | 2020-09-18 | 中国石油化工股份有限公司 | Catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof |
-
2021
- 2021-03-19 CN CN202110296713.7A patent/CN115106118B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105712837A (en) * | 2014-12-05 | 2016-06-29 | 中国科学院大连化学物理研究所 | Method for preparing organic oxygenated compounds by hydrocarbon catalytic selective oxidation |
| CN106669703A (en) * | 2015-11-05 | 2017-05-17 | 中国石油化工股份有限公司大连石油化工研究院 | SiO2 modified low carbon alkane dehydrogenation catalyst and preparation method thereof |
| CN105772092A (en) * | 2016-03-21 | 2016-07-20 | 中国科学技术大学 | Modified catalyst and preparation method thereof |
| CN110614116A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Non-noble metal low-carbon alkane dehydrogenation catalyst, preparation method thereof and method for preparing low-carbon olefin by low-carbon alkane dehydrogenation |
| CN111085208A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Non-noble metal low-carbon alkane dehydrogenation catalyst with spherical double-mesoporous composite carrier and preparation method and application thereof |
| CN111672532A (en) * | 2019-03-11 | 2020-09-18 | 中国石油化工股份有限公司 | Catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115106118B (en) | 2024-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109225306B (en) | Monoatomic catalyst for preparing low-carbon olefin by dehydrogenation of low-carbon hydrocarbon and catalytic method | |
| JP6636162B2 (en) | Palladium-based hydrogenation catalyst, method for producing the same, and use thereof | |
| Zhu et al. | A hollow Mo/HZSM-5 zeolite capsule catalyst: preparation and enhanced catalytic properties in methane dehydroaromatization | |
| CA2778386C (en) | Catalyst for synthesis of hydrocarbons from co and h2 and preparation method thereof | |
| US6084140A (en) | Catalyst for selective hydrogenation of highly unsaturated hydrocarbon compound in olefin compound | |
| CN108620092A (en) | Monatomic alloy catalysts of PtCu of alumina load and its preparation method and application | |
| CN108435239B (en) | Catalyst for coproducing olefin and aromatic hydrocarbon and preparation method and application thereof | |
| CN110013854A (en) | The preparation and the application in C5/C9 Petropols catalytic hydrogenation of a kind of load-type nickel series catalysts | |
| CN106866328A (en) | A kind of method of methyl alcohol high selectivity aromatic hydrocarbons | |
| CN112191261A (en) | Heterogeneous catalyst for catalytic hydrogenation reaction of C5 petroleum resin and application thereof | |
| CN102757306B (en) | Preparation method of cyclohexanone | |
| Tang et al. | Enhancement of Pt catalytic activity in the hydrogenation of aldehydes | |
| CN115106118B (en) | Supported catalyst with function of catalyzing dehydrogenation of low-carbon alkane, preparation method and application thereof, and method for preparing low-carbon olefin | |
| CN113649030B (en) | Hydrodehalogenation catalyst and preparation method of chlorotrifluoroethylene and trifluoroethylene | |
| WO2015152159A1 (en) | Method for producing unsaturated hydrocarbon | |
| CN105732266A (en) | Selective hydrogenation method of trace amount of acetylene in methanol to olefin (MTO) apparatus | |
| CN115106116A (en) | Catalyst with catalytic dehydrogenation function, preparation method and application thereof, and method for preparing propylene | |
| CN113856739A (en) | Catalyst with dehydrogenation function, preparation method and application thereof, and method for generating low-carbon olefin by dehydrogenation of low-carbon alkane | |
| CN115106119A (en) | Catalyst for catalyzing propane dehydrogenation, preparation method and application thereof, and method for preparing propylene | |
| CN105732271A (en) | Front-hydrogenation method of trace amount of acetylene in methanol to olefin (MTO) apparatus | |
| CN112934232B (en) | Catalyst for selective hydrogenation of carbon three fractions | |
| CN112939723B (en) | Alkyne removing method for carbon three-fraction selective hydrogenation process | |
| CN115138356B (en) | Application of dehydrogenation catalyst in ethylbenzene direct dehydrogenation reaction and dehydrogenation method | |
| CN112675872B (en) | Hydrogenation catalyst before deethanization before carbon dioxide fraction | |
| CN112844405B (en) | Catalyst for selective hydrogenation of light hydrocarbon cracking carbon-enriched fraction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |