CN106928005B - Alkyne removing method by pre-depropanization and pre-hydrogenation process - Google Patents
Alkyne removing method by pre-depropanization and pre-hydrogenation process Download PDFInfo
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- CN106928005B CN106928005B CN201511032580.3A CN201511032580A CN106928005B CN 106928005 B CN106928005 B CN 106928005B CN 201511032580 A CN201511032580 A CN 201511032580A CN 106928005 B CN106928005 B CN 106928005B
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- catalyst
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- hydrogenation
- alumina
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 86
- 150000001345 alkine derivatives Chemical class 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 176
- 238000005470 impregnation Methods 0.000 claims abstract description 34
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000005977 Ethylene Substances 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000009467 reduction Effects 0.000 claims abstract description 17
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 claims abstract description 16
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 8
- 229910002555 FeNi Inorganic materials 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 46
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 30
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- 230000008569 process Effects 0.000 claims description 18
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- 230000032683 aging Effects 0.000 claims description 12
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 9
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- -1 ethylene, propylene Chemical group 0.000 description 6
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- IFYDWYVPVAMGRO-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)NCCCN(C)C IFYDWYVPVAMGRO-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
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- 238000002791 soaking Methods 0.000 description 4
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- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
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- 238000001228 spectrum Methods 0.000 description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000012692 Fe precursor Substances 0.000 description 2
- 229910021329 Fe4Al13 Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 150000001361 allenes Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
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- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
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- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
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- 238000007086 side reaction Methods 0.000 description 2
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- 229910018580 Al—Zr Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021007 Co2Al5 Inorganic materials 0.000 description 1
- 229910021214 Co2Al9 Inorganic materials 0.000 description 1
- 229910002515 CoAl Inorganic materials 0.000 description 1
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- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 229910021328 Fe2Al5 Inorganic materials 0.000 description 1
- 229910017372 Fe3Al Inorganic materials 0.000 description 1
- 229910015372 FeAl Inorganic materials 0.000 description 1
- 229910015370 FeAl2 Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- 229910002796 Si–Al Inorganic materials 0.000 description 1
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- 238000004220 aggregation Methods 0.000 description 1
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- 150000001342 alkaline earth metals Chemical class 0.000 description 1
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
- C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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Abstract
A method for removing alkyne in a pre-depropanization pre-hydrogenation process uses a Ti-Fe-Ni hydrogenation catalyst, wherein the volume of a hydrogenation raw material mainly comprises 15-25% of hydrogen, 30-45% of ethylene, 0.1-0.5% of propadiene, 0.5-1.0% of acetylene and 0.1-0.5% of propyne, the hydrogenation catalyst is a Ti-Fe-Ni selective hydrogenation catalyst, a carrier is a high-temperature-resistant inorganic oxide, the catalyst contains 5-15% of Fe and 0.5-3% of Ti + Ni, wherein the content of Ti and Ni is 1-1.5, the specific surface area of the catalyst is 10-300 m 2/g, the pore volume is 0.2-0.65 ml/g, Fe is loaded on the carrier in an impregnation mode, and is prepared by roasting and reduction in a hydrogen atmosphere, wherein the Fe mainly exists in an alpha-Fe 2 O 3 form and contains NiTi, FeNi and FeTi phases.
Description
Technical Field
The invention relates to a method for removing alkyne by hydrogenation before front-end depropanization, in particular to a method for hydrogenating and converting ethylene, propylene (MA) and allene (MA) contained in a front-end depropanized front-end hydrogenated ethylene material into propylene and allene by using a Ti-Fe-Ni hydrogenation catalyst.
Background
Polymer grade ethylene production is the tap of the petrochemical industry, and polymer grade ethylene and propylene are the most basic raw materials for downstream polymerization plants. The selective hydrogenation of acetylene has very important influence on the ethylene processing industry, the selectivity of the catalyst is excellent except ensuring that the content of the acetylene at the outlet of a hydrogenation reactor reaches the standard, the ethylene can be generated into ethane as little as possible, and the catalyst has important significance for improving the ethylene yield of the whole process and the economic benefit of a device.
The cracked carbon-dioxide fraction contains acetylene with a mole fraction of 0.5-2.5%, and a small amount of acetylene in ethylene reduces the activity of a polymerization catalyst and deteriorates the physical properties of a polymer when polyethylene is produced, so that the acetylene content in ethylene must be reduced to a certain limit before the ethylene can be used as a monomer for synthesizing a high polymer. Acetylene separation and conversion is therefore one of the important processes in the ethylene plant scheme.
the catalytic selective hydrogenation in the ethylene device is divided into front hydrogenation and back hydrogenation, wherein the front hydrogenation and the back hydrogenation of acetylene refer to that the hydrogenation reactor is positioned in front of the demethanizer and is front hydrogenation, and the hydrogenation reactor is positioned behind the demethanizer and is back hydrogenation relative to the position of the demethanizer. In the existing hydrogenation and alkyne removal of carbon-containing fraction, a process method adopting hydrogenation before carbon-containing is increasingly adopted, and the process method is characterized in that a hydrogenation reactor is arranged before a demethanizer, the process flow is hydrogenation before front depropanization, and the process method is characterized in that cracking fraction is subjected to gas-liquid phase separation, hydrogenation of fraction with less than three carbon atoms is carried out, acetylene is converted, most propadiene is removed,
The main reactions taking place in the reactor are as follows:
Main reaction
C2H2+H2→C2H4 (1)
MAPD+H2→CH3－CH＝CH2 (2)
MAPD is propine and propadiene
Side reactions
C2H4+H2→C2H6 (3)
C2H2+2H2→C2H6 (4)
2C2H2+H2→C4H6 (5)
C3H6+H2→C3H8 (6)
Among these applications, reactions (1) and (2) are desirable, which remove both acetylene, propyne and propadiene and yield increases in ethylene and propylene; reactions (3), (4), (5) and (6) are undesirable.
Due to the large amount of hydrogen in the reaction material, the selectivity of the catalyst is particularly important, otherwise, excessive side reactions can be caused, and the temperature of the catalytic reactor can be increased. Because the selectivity of the reaction is low at low airspeed, the temperature runaway is easily caused, the lowest safe airspeed at present is 4500/h, namely, when the airspeed of the device is lower than the value, the temperature runaway is easily caused in the reactor, and the operation of the device is threatened. The important difference between the carbon pre-hydrogenation process method and the carbon post-hydrogenation process method is that hydrogen is artificially added in the post-hydrogenation process method, and the reaction degree can be controlled by the hydrogen amount. In the prior hydrogenation process, the hydrogen content is higher, and hydrogen does not need to be prepared in the hydrogenation process, so that the control means for reaction is less, and the corresponding performance requirement on the catalyst is greatly improved.
For the front-end depropanization and front-end hydrogenation method, the selectivity of the catalyst is reduced along with the increase of the reaction temperature, when the selectivity of the catalyst is reduced to 1/3 at the initial reaction temperature, the highest use temperature of the catalyst is considered to be reached, the difference between the temperature and the initial reaction temperature is called the operation window of the catalyst, and the wider the temperature range is, the higher the operation safety of the catalyst is. Due to the selectivity limitation of the traditional catalyst, the operation window is only 10-15 ℃ generally.
at present, the hydrogenation before carbon dioxide mainly adopts an adiabatic bed reactor, and for the hydrogenation process before propane removal, a three-section adiabatic bed reactor is mainly adopted, the first two sections of reactors mainly remove most acetylene, and the third section of reactor is used for removing more than 50% of propyne (MA) and Propadiene (PD). Therefore, the acetylene at the outlet of the third section is less than 1 mu L/L, and the MAPD is less than 0.3% (v).
the patent US4484015 discloses a front-end depropanization front-end hydrogenation method, and the catalyst adopted in the method takes Pd as a main active component, takes alpha-alumina as a carrier, and is added with a promoter silver, so that a carbon dioxide hydrogenation catalyst with excellent performance is prepared by an impregnation method. The catalyst can effectively reduce excessive hydrogenation of ethylene and reduce the risk of temperature runaway of a bed layer. The catalyst disclosed in this patent is prepared by an impregnation method. Because the surface polar groups of the alpha-alumina carrier are few, the influence of the surface tension of the impregnating solution and the solvation effect is particularly obvious in the process of impregnating and drying the catalyst, and the precursor of the metal active component is deposited on the surface of the carrier in the form of aggregates. In addition, strong interaction cannot be formed between the metal salt species and the carrier after impregnation, and high-temperature roasting easily causes migration and aggregation of metal particles to form large grains.
Patent CN201110086174.0 discloses a selective hydrogenation method for carbon-reduced fraction, which adopts a catalyst comprising Pd as the main active component, alpha-alumina as the carrier, and silver as the promoter. The carrier is adsorbed with a specific high molecular compound, a high molecular coating layer is formed on the surface of the carrier in a certain thickness, the compound with a functional group reacts with the high molecular compound to enable the compound to have the functional group capable of being complexed with the active component, and the active component is ensured to be orderly and highly dispersed by the complexation reaction of the active component on the surface of the carrier. By adopting the method, the carrier adsorbs specific high molecular compounds, and the high molecular compounds are chemically adsorbed with the high molecular compounds through the hydroxyl groups of the alumina, and the amount of the high molecular compounds adsorbed by the carrier is limited by the number of the hydroxyl groups of the alumina; the functional polymer and Pd have weak complexing effect, sometimes the loading capacity of the active component can not meet the requirement, and part of the active component remains in the impregnation liquid, so that the cost of the catalyst is increased; the method for preparing the carbon dioxide hydrogenation catalyst also has the defect of complicated process flow.
CN2005800220708.2 discloses a selective hydrogenation catalyst for acetylene and diolefin in light olefin raw material, which is composed of a first component selected from copper, gold and silver and a second component selected from nickel, platinum, palladium, iron, cobalt, ruthenium and rhodium, and in addition, the catalyst also includes at least one inorganic salt and oxide selected from zirconium, lanthanide and alkaline earth metal mixture. The catalyst forms a fluorite structure after being calcined, used or regenerated. The total content of the catalyst oxide is 0.01-50%, and the preferred roasting temperature is 700-850 ℃. The addition of a third oxide, modified alumina or silica support, helps to increase catalyst selectivity and activity, selectivity after regeneration. The technology still takes copper, gold, silver, palladium and the like as active components and takes nickel, platinum, palladium, iron, cobalt, ruthenium, rhodium and the like as auxiliary components, and the regeneration performance of the catalyst is improved by modifying the oxide of the carrier.
CN102218323A discloses a hydrogenation catalyst for unsaturated hydrocarbons, the active component is a mixture of 5-15% of nickel oxide and 1-10% of other metal oxides, the other metal oxides can be one or more of molybdenum oxide, cobalt oxide and iron oxide, and in addition, 1-10% of an auxiliary agent is also included. The technology is mainly used for hydrogenating and converting ethylene, propylene, butylene and the like in the tail gas of the coal-to-liquid industry into saturated hydrocarbon, and has good deep hydrogenation capacity. The technology is mainly used for the total hydrogenation of ethylene, propylene, butylene and the like in various industrial tail gases rich in CO and hydrogen, and is not suitable for the selective hydrogenation of alkyne and dialkene.
ZL201080011940.0 discloses an ordered cobalt-aluminium and iron-aluminium compound as acetyleneA hydrogenation catalyst, wherein the intermetallic compound is selected from the group consisting of CoAl and CoAl3、Co2Al5、Co2Al9、o-Co4Al13、h-Co4Al13、m-Co4Al13、FeAl、FeAl2、Fe3Al、Fe2Al5、Fe4Al13Group (d) of (a). Among them, Fe is preferred4Al13And o-Co4Al13. The intermetallic compound is prepared by a hot melting method in solid chemistry. The hydrogenation performance of the catalyst is tested in a quartz tube furnace, the reaction temperature is 473K, and after the stable reaction is carried out for 20 hours, o-Co4Al13the catalyst has acetylene conversion rate up to 62%, ethylene selectivity up to 71%, and Fe4Al13The acetylene conversion rate on the catalyst reaches 40%, and the ethylene selectivity reaches 75%. The technology is used for preparing intermetallic compounds under the condition of high temperature, is used for selective hydrogenation of acetylene, has low acetylene conversion rate and high reaction temperature, and is not beneficial to industrial application. And the catalyst is prepared by a hot melting method, and the conditions are harsh.
In summary, the selective hydrogenation of low carbon alkynes and dienes mainly adopts noble metal catalysts, and a great deal of work is carried out on the research and development of non-noble metal catalysts, but the selective hydrogenation is far away from the industrial application. In order to solve the problem, the invention provides a novel Ti-Fe-Ni hydrogenation catalyst and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a method for removing alkyne in a front-end depropanization front-end hydrogenation process. In particular to a Ti-Fe-Ni hydrogenation catalyst which selectively hydrogenates acetylene contained in the tower top effluent of a front depropanizing tower to be completely converted into ethylene, and partially hydrogenates propyne (MA) and Propadiene (PD) to be converted into propylene without loss of the ethylene and the propylene.
The invention provides a front-depropanization front-hydrogenation removal method, which comprises the steps of enabling a material flowing out of the top of a front-depropanization tower to enter an adiabatic bed reactor for selective hydrogenation to remove acetylene contained in the material, partially hydrogenating propyne (MA) and Propadiene (PD) to convert the propyne (MA) and the Propadiene (PD) into propylene, and using the adiabatic bed reactor for selective hydrogenationThe reactor is filled with a Ti-Fe-Ni selective hydrogenation catalyst, the carrier is a high-temperature resistant inorganic oxide, the catalyst contains 5-15% of Fe, preferably 7-12% of Ti, 0.2-1.5% of Ti, preferably 0.5-1% of Ni, 0.5-1.8% of Ni, preferably 0.8-1.2% of Ti, and the specific surface of the catalyst is 10-300 m2The preferred concentration is 90-170 m/g2The pore volume is 0.2-0.65 ml/g, preferably 0.30-0.63 ml/g, wherein Fe is loaded on the carrier by a dipping mode, and is prepared by roasting at 300-700 ℃ and reducing at 200-500 ℃ in an atmosphere containing hydrogen; in the catalyst, Fe is mainly alpha-Fe2O3Exists in a form and contains a FeNi phase. Selecting the hydrogenation reaction conditions: the inlet temperature of the adiabatic bed reactor is 50-100 ℃, the reaction pressure is 1.5-4.0 MPa, and the volume space velocity is 10000-20000 h-1. Preferred hydrogenation conditions are: the inlet temperature of the adiabatic bed reactor is 60-95 ℃, the reaction pressure is 2.8-3.8 MPa, and the volume airspeed is 12000-18000 h-1。
The hydrogenation method adopts the hydrogenation catalyst, the carrier is a high-temperature-resistant inorganic oxide, the technical key point of the invention is that the catalyst contains Fe, and the catalyst is roasted and reduced, and the carrier has no special requirement, such as one or more of alumina, silicon oxide, zirconia, magnesia and the like. However, alumina or alumina-based carriers, which are composite carriers of alumina and other oxides, in which alumina accounts for 50% or more of the mass of the carrier, are also preferred, and for example, alumina and oxides such as silica, zirconia, magnesia, etc., and alumina-zirconia composite carriers, in which the alumina content is 60% or more, are also preferred. The alumina can be theta, alpha, gamma type or their mixture of multiple crystal forms, preferably alpha-Al2O3Or containing alpha-Al2O3Mixed crystal form alumina of (1).
The alkyne removing method adopts a Ti-Fe-Ni selective hydrogenation catalyst, and the preparation method comprises the following steps:
The catalyst is obtained by preparing impregnation liquid of Fe precursor aqueous solution and Ti and Ni precursor aqueous solution, respectively impregnating the carrier, respectively aging, drying and roasting or impregnating the carrier with mixed solution thereof, then aging, drying and roasting, and finally reducing.
The preferred conditions in the preparation method of the invention are:
The dipping temperature is 30-60 ℃, the loading time is 10-60 min, the pH value of the dipping solution is 1.5-5.0, the aging time is 30-120 min, the roasting temperature is 400-500 ℃, and the roasting time is 180-300 min.
In the present invention, the drying is preferably a temperature-raising drying, and the drying temperature program is set as follows:
In the present invention, the calcination, i.e. the activation process, is preferably temperature programmed calcination, and the calcination temperature program is set as follows:
The catalyst can be prepared by adopting any one impregnation mode of isometric impregnation, excessive impregnation, surface spray impregnation, vacuum impregnation and multiple impregnation.
The preparation method of the catalyst provided by the invention comprises the following specific steps:
(1) and measuring the water absorption of the carrier and then weighing the carrier.
(2) Accurately weighing a certain amount of Fe precursor (recommending soluble nitrate, chloride or sulfate) according to the load, preparing an impregnation solution according to the water absorption rate of the carrier and an impregnation method, adjusting the pH value of the impregnation solution to 1.5-5.0 according to requirements, and heating the solution to 30-60 ℃ for later use.
(3) When an isometric immersion or spray immersion method is adopted, the weighed carrier can be placed into a rotary drum, the rotating speed of the rotary drum is adjusted to be 25-30 r/min, the carrier is completely turned over, the prepared immersion liquid at the temperature of 30-60 ℃ is poured or sprayed onto the carrier at a certain speed, and the carrier is loaded for 5-10 min.
When an excessive impregnation method is adopted, the weighed carrier is placed in a container, then the prepared impregnation solution with the temperature of 30-60 ℃ is added, the container is quickly shaken, so that heat emitted in the adsorption process is quickly released, the active component is uniformly loaded on the carrier, and standing is carried out for 5-10 min so that the surface active component and the active component in the solution compete for adsorption balance.
When a vacuum impregnation method is adopted, the weighed carrier is placed in a cyclone evaporator, the vacuum is pumped, impregnation liquid with the temperature of 30-60 ℃ is added for impregnation for 5-10 min, and the carrier is heated in a water bath until the surface of the carrier is completely dried.
(4) Transferring the impregnated catalyst into a container, and aging the catalyst for 30-120 min at 25-60 ℃.
(5) Filtering out excessive solution after impregnation, and then drying in an oven by adopting a temperature programming method, wherein the drying temperature programming is as follows:
(6) Roasting and activating the dried catalyst in a muffle furnace or a tubular furnace, wherein the roasting temperature-rising program comprises the following steps:
The Ni component of the catalyst can be singly soaked by adopting the steps or can be prepared into a mixed solution with Fe and then is soaked together according to the steps; the Ti component is loaded by adopting the same steps, and the roasting temperature is 300-700 ℃, preferably 400-500 ℃.
The active component of the catalyst is mainly Fe, and the catalyst can be a non-noble metal catalyst, even can not contain cobalt, molybdenum and tungsten, so that the cost is greatly reduced, and the cost of the catalyst is far lower than that of a noble metal Pd catalyst.
In the method for preparing polymer-grade ethylene by hydrogenation, Fe element in the adopted hydrogenation catalyst can be Fe and Fe2O3、Fe3O4Several forms exist in FeO, but among them, alpha-Fe2O3The Fe content in the form is higher than that in the other forms, and preferably, it is 50% or more of the total Fe mass. In the invention, Ni is recommended to be added into the active composition containing iron, and the active composition is reduced after being roasted under specific conditions to form a FeNi phase, which is beneficial to the activation of hydrogen and improves the activity of the catalyst; in the present invention, it is recommended to add TiO to the iron-containing active component2The method is beneficial to the formation and dispersion of the catalyst active phase, and is beneficial to the stability of the active phase, and the selectivity and the coking resistance of the catalyst are improved.
The activation temperature of the catalyst in the invention is related to the active composition, content and carrier of the catalyst, and alpha-Fe is formed after the activation process2O3Fe in a form, and is relatively stable, and the activation temperature cannot be too high; on the other hand, the degree of activation determines the reduction conditions of the catalyst, and the catalyst provided by the invention still uses alpha-Fe2O3Fe in the form of Fe is a main component, and excessive reduction can influence the effect of the catalyst and the selectivity and is easy to coke.
The catalyst reduction of the present invention means that the calcined catalyst is reduced with a hydrogen-containing gas, H, before the catalyst is used2The volume content is preferably 10-50%, the reduction temperature is 250-500 ℃, the reduction time is 240-360 min, and the volume airspeed is 100-500 h-1The reduction pressure is 0.1-0.8 MPa; with the preferred proviso that N is used2+H2Reducing the mixed gas at the reduction temperature of 300-400 ℃ at a volume airspeed of 200-400 h-1The reduction pressure is preferably 0.1 to 0.5 MPa. The process is usually carried out before the selective hydrogenation reaction, and is preferably carried out outside the reactor, i.e., outside the selective hydrogenation reaction apparatus.
According to the method for removing acetylene by hydrogenation before front depropanization, disclosed by the invention, the adiabatic bed reactor is preferably a three-section series adiabatic bed reactor, acetylene contained in an ethylene material is selectively hydrogenated and completely converted into ethylene, and partial propyne (MA) and Propadiene (PD) are hydrogenated and converted into propylene without loss of ethylene.
When the adiabatic bed reactor is a three-section series reactor, the reaction conditions are as follows: the temperature of the first-stage inlet is 50-100 ℃, preferably 60-85 ℃, the temperature of the second-stage inlet is 50-100 ℃, preferably 75-90 ℃, and the temperature of the third-stage inlet is 50-100 ℃, preferably 80-95 ℃.
According to the alkyne removal method for preparing low-carbon olefin from methanol, the material for selective hydrogenation is the tower top effluent of a front depropanizing tower in the front depropanizing process. The raw materials mainly comprise: 30-40% of methane, 15-25% of hydrogen, 8-15% of ethane, 30-45% of ethylene, 5-10% of propane, 5-10% of propylene, 0.1-0.5% of propadiene, 0.5-1.0% of acetylene and 0.1-0.5% of propyne.
by adopting the alkyne-removing method, the catalyst has moderate reaction activity, good operation elasticity, good ethylene selectivity and far lower green oil generation amount than that of the noble metal catalyst.
Drawings
FIG. 1 is a flow diagram of a carbon dioxide hydrogenation process using a front-end depropanization process.
in the figure:
1-oil wash column; 2-water washing tower; 3-alkaline washing tower; 4-a dryer; 5-a front depropanizer; 6-hydrogenation adiabatic bed reactor before carbon dioxide; 7-a demethanizer; 8-heat exchanger.
FIG. 2 is the XRD spectrum (minus the carrier alpha-Al) of the catalyst in example 32O3Background).
FIG. 3 is the XRD spectrum (minus the carrier alpha-Al) of the catalyst of comparative example 22O3Background).
FIG. 4 is the XRD spectrum (minus the carrier alpha-Al) of the catalyst of comparative example 5 after reduction2O3background).
XRD measurement conditions:
German Bruker D8ADVANCE X-ray diffractometer
Tube voltage: 40kV current 40mA
Scanning: step size of 0.02 degree, frequency of 0.5s, scanning range of 4-120 degree, temperature of 25 degree C
Cu Ka 1 wavelength, diffraction angle 2 theta on abscissa and diffraction intensity on ordinate
The symbols in fig. 2 illustrate:
● is alpha-Fe2O3the tangle-solidup is FeNi, a xxx is Ti2O。
The symbols in fig. 3 illustrate:
● is alpha-Fe2O3Tangle-solidup is FeNi, diamond-solid is anatase.
Symbolic illustration in fig. 4:
^ is alpha-Fe, ■ is Fe3O4A t is Ti2O, and a-solidup is Ni.
As can be seen in FIG. 2, the Fe in the catalyst is mainly alpha-Fe2O3the relative content is 8.10%, and an FeNi phase appears at the same time.
As can be seen in fig. 3, Ti in the catalyst sinters with iron oxide, an anatase crystal phase appears, distribution and structure of active components are destroyed, and the catalyst activity decreases.
In FIG. 4, Fe mainly appears in the form of simple substance alpha-Fe, the relative content is 8.92%, and a small amount of Fe exists3O4And (4) forming.
Detailed Description
The analysis and test method comprises the following steps:
Specific surface area: GB/T-5816
pore volume: GB/T-5816
Content of Fe oxide in different crystal forms: XRD
The content of active components in the catalyst is as follows: atomic absorption method
The conversion and selectivity in the examples were calculated according to the following formulas:
Acetylene conversion (%). 100. times. delta. acetylene/inlet acetylene content
Ethylene selectivity (%). 100 x. DELTA. ethylene/. DELTA.acetylene
Example 1
100ml of clover-type alpha-alumina carrier with phi of 4.5 multiplied by 4.5mm is weighed and placed in a 1000ml beaker. Taking ferric nitrate, heating and dissolving in 60ml of deionized water, adjusting the pH value to be 2.5, keeping the temperature of an impregnation solution at 50 ℃, impregnating the surface of a carrier in an equal volume, quickly shaking the carrier for impregnation for 6min, standing for 30min until the adsorption is balanced, completely sealing the mouth of a beaker by using a preservative film, aging in a water bath at 60 ℃ for 30min, and then drying in an oven according to the following procedures:Transferring the catalyst into an evaporating dish, and activating the catalyst in a muffle furnace by adopting a programmed heating method, wherein the activating program comprises the following steps: Weighing nickel nitrate, impregnating according to the preparation steps, drying and activating. Then taking tetrabutyl titanate, carrying out loading according to the same method, and activating to obtain the catalyst.
The evaluation method comprises the following steps:
Before the catalyst is used, reducing the catalyst in a reducing furnace by using 40 percent of hydrogen and 60 percent of nitrogen at the reducing temperature of 400 ℃ and under the pressure of 0.5MPa for 4 hours. The hydrogenation scheme shown in figure 1 was used with the catalyst packed in an adiabatic bed reactor.
The reaction mass composition is shown in table 1:
Table 1 hydrogenation feed composition is shown in the table below
reaction conditions are as follows: material airspeed: 10000h-1(ii) a Operating pressure: 1.5 MPa.
adiabatic bed reactor, three-stage series process, catalyst preparation adopts the carrier physical property as shown in table 6, and catalyst behavior is shown in table 7.
Example 2
NaAlO is added at 50 deg.C2Solution and ZrCl4The solution is stirred and mixed, then is neutralized by nitric acid solution, is stirred for 10 hours, and is coprecipitated to generate uniform Al-Zr particles. The resultant was filtered, and Na contained therein was washed with deionized water+And Cl-And (3) ionizing, adding 15% polyvinyl alcohol serving as a pore-forming agent, and kneading and molding. Drying at 130 ℃ for 2h, and roasting at 650 ℃ for 4h to obtain the Zr-Al composite carrier. The mass ratio of alumina to zirconia in the carrier was 4: 1.
With alumina-zirconia composite carrierThe catalyst is prepared from the solid. Heating and dissolving ferric chloride and potassium chloride in deionized water, adjusting the pH value to be 2.0, soaking the carrier in excess at the temperature of 80 ℃, shaking a beaker for soaking for 10min, filtering out excessive soaking liquid, aging the catalyst in a water bath at the temperature of 60 ℃ for 50min, and then drying in an oven according to the following procedures:Activating the catalyst by adopting a programmed heating method, wherein the activating procedure comprises the following steps:
Before the catalyst is used, reducing the catalyst in a reducing furnace by using 30 percent of hydrogen and 60 percent of nitrogen at the reducing temperature of 550 ℃, under the pressure of 0.5MPa and for 4 hours. The hydrogenation scheme shown in figure 1 was used with the catalyst packed in an adiabatic bed reactor. The raw material composition is shown in table 2.
TABLE 2 hydrogenation feed composition
The physical properties of the carrier used for the catalyst preparation are shown in Table 6, and the operation of the catalyst is shown in Table 7.
Example 3
Spherical alumina with phi of 1.5mm is weighed to prepare the catalyst. Dissolving ferric nitrate in deionized water, adjusting the pH value to 3.0, keeping the temperature of the impregnation liquid at 40 ℃, spraying the carrier by a spraying pot, loading for 10min to uniformly load the active components, and then, in an oven, according to the following procedures: Activating the catalyst by adopting a programmed heating method, wherein the activating procedure comprises the following steps: To obtain a leached catalyst.
And (3) dissolving cerium nitrate, spraying and soaking the dissolved cerium nitrate on the surface of the first-soaked catalyst, drying and roasting to obtain the final catalyst by adopting the same method in the first step. And (3) drying procedure:And (3) roasting procedure:
Before the catalyst is used, reducing the catalyst in a reducing furnace by using 20 percent hydrogen at the reducing temperature of 400 ℃ and under the pressure of 0.5MPa for 4 h. XRD analysis of the reduced catalyst is shown in figure 2. The hydrogenation scheme shown in figure 1 was used with the catalyst packed in an adiabatic bed reactor.
Reaction conditions are as follows: airspeed of 18000h-1The operating pressure is 3.2MPa, and the catalyst loading is 50 ml.
The raw material composition is shown in table 3.
TABLE 3 hydrogenation feed composition
The physical properties of the carrier used for the catalyst preparation are shown in Table 6, and the catalyst operation results are shown in Table 7.
example 4
The spherical alumina-titania carrier with phi of 2.0mm is weighed and placed in a vacuum impregnation device. Dissolving ferric nitrate in deionized water, and adjusting the pH value to 3.5 for later use. Opening a vacuum pumping pump of a vacuum impregnation device until the vacuum degree is 0.1mmHg, then slowly adding the prepared impregnation liquid from a feeding port, finishing the addition for 5min, evaporating at 60 ℃ until the flowing moisture on the surface of the catalyst completely disappears, finishing the loading, and putting the loaded catalyst in an oven according to the following procedures:In a muffle furnace according to: To obtain a leached catalyst.
And (3) taking cerium nitrate, impregnating according to the same method, drying, and roasting to obtain the final catalyst. And (3) drying procedure:And (3) roasting procedure:
Before the catalyst is used, the catalyst is reduced by 15 percent hydrogen in a reducing furnace, the reducing temperature is 500 ℃, the pressure is 0.5MPa, and the reducing time is 4 hours. The hydrogenation scheme shown in figure 1 was used with the catalyst packed in an adiabatic bed reactor.
Reaction conditions are as follows: space velocity of 20000h-1The operating pressure is as follows: 3.8MPa, catalyst loading: 50 ml.
The composition of the starting materials for the reaction is shown in Table 4.
TABLE 4 hydrogenation feed composition
The physical properties of the carrier used for the catalyst preparation are shown in Table 6, and the catalyst operation results are shown in Table 7.
Example 5
a catalyst was prepared by weighing 100ml of an alumina carrier having a diameter of 4.0mm by the same method as in example 3. The activation temperature was 650 ℃.
Before the catalyst is used, the catalyst is reduced by 25 percent hydrogen in a reducing furnace, the temperature is 600 ℃, the pressure is 0.5MPa, and the reduction time is 4 h. The hydrogenation scheme shown in figure 1 was used, and the catalyst was packed in an adiabatic bed reactor.
reaction conditions are as follows: airspeed 12000h-1The operating pressure is as follows: 2.0MPa, catalyst loading: 50 ml.
The composition of the reaction raw materials is shown in Table 5.
TABLE 5 hydrogenation feed composition
The physical properties of the carrier used for the catalyst preparation are shown in Table 6, and the catalyst operation results are shown in Table 7.
Example 6
The commercial pseudo-boehmite, silica gel, zirconium oxychloride powder and extrusion aid are mixed according to the weight ratio of alumina: silicon oxide: uniformly mixing zirconium oxide in a ratio of 8:1:3, extruding the mixture on a strip extruding machine for forming, drying the mixture at 120 ℃, and roasting the mixture in a muffle furnace at 550 ℃ for 3 hours to obtain the Zr-Si-Al composite oxide carrier. The catalyst was prepared by the same method as in example 4.
Before the catalyst is used, 45% hydrogen and 55% nitrogen are used in a reducing furnace, the temperature is 450 ℃, the pressure is 0.5MPa, and the activation time is 4 h. The hydrogenation scheme shown in figure 1 was used, and the catalyst was packed in an adiabatic bed reactor.
reaction conditions are as follows: airspeed 16000h-1The operating pressure is as follows: 2.0MPa, catalyst loading: 50 ml.
the same materials as in example 4 were used for evaluation, and three stages of the series process were used for 100 hours of hydrogenation reaction, and the composition of the reaction raw materials was as shown in Table 1.
the physical properties of the carrier used for the catalyst preparation are shown in Table 6, and the catalyst operation results are shown in Table 7.
Comparative example 1
Taking an alumina carrier with phi of 4.0mm and a specific surface of 4.5m2The pore volume was 0.32 ml/g. The method comprises the steps of adopting an isometric impregnation method, impregnating a silver nitrate solution onto a carrier in an isometric manner, aging, drying and roasting to obtain a primary impregnated catalyst, then dissolving palladium chloride, impregnating in an isometric manner, aging, drying and roasting to obtain a final catalyst (PAH-01 hydrogenation catalyst of petrochemical research institute). The catalyst has Pd content of 0.050% and Ag content of 0.20%.
Catalyst and process for preparing sameReducing with hydrogen at 100 deg.C for 160min, pressure of 0.5MPa, and hydrogen space velocity of 100h-1. The hydrogenation scheme shown in figure 1 was used, and the catalyst was packed in an adiabatic bed reactor.
The raw material composition is the same as that of example 1, and the reaction conditions are as follows: airspeed 16000h-1The operating pressure is as follows: 3.5 MPa.
The physical properties of the carrier used for the catalyst preparation are shown in Table 6, and the reaction results are shown in Table 7.
Comparative example 2
The catalyst was prepared in the same manner as in example 1 using alumina of Φ 4.0mm as a carrier, and the catalyst activation temperature was 850 ℃.
Before the catalyst is used, the catalyst is reduced by 25 percent hydrogen in a reducing furnace, the temperature is 450 ℃, the pressure is 0.5MPa, and the activation time is 4 h. The hydrogenation scheme shown in figure 1 was used, and the catalyst was packed in an adiabatic bed reactor. The XRD diffraction pattern of the reduced catalyst is shown in figure 3.
The raw material composition is the same as that of example 2, and the reaction conditions are as follows: space velocity of 10000h-1The operating pressure is as follows: 3.0 MPa.
the physical properties of the carrier used for the catalyst preparation are shown in Table 6, and the reaction results are shown in Table 7.
comparative example 3
Alumina of phi 4.0mm was weighed as a carrier, and the catalyst with low iron content was prepared by the same method as in example 1, and activated at 450 ℃.
Before the catalyst is used, the catalyst is reduced by 45 percent hydrogen in a reducing furnace, the temperature is 450 ℃, the pressure is 0.5MPa, and the activation time is 4 h. The hydrogenation scheme shown in figure 1 was used, and the catalyst was packed in an adiabatic bed reactor.
The raw material composition is the same as that of example 3, and the reaction conditions are as follows: airspeed of 15000h-1the operating pressure is as follows: 3.0 MPa.
the physical properties of the carrier used for the catalyst preparation are shown in Table 6, and the reaction results are shown in Table 7.
comparative example 4
the same catalyst as in example 1 was used, and the catalyst was activated at 450 ℃ and then directly started without reduction with hydrogen. The hydrogenation scheme shown in figure 1 was used, and the catalyst was packed in an adiabatic bed reactor.
The raw material composition is the same as that of example 3, and the reaction conditions are as follows: airspeed of 18000h-1The operating pressure is as follows: 2.5 MPa.
The physical properties of the carrier used for the catalyst preparation are shown in Table 6, and the reaction results are shown in Table 7.
comparative example 5
The same catalyst as in example 1 was used and activated at 450 ℃.
The catalyst is reduced in a tubular furnace under the atmosphere of 30% hydrogen and 55% nitrogen at 850 ℃, the pressure of 0.5MPa and the activation time of 4 h. The hydrogenation scheme shown in figure 1 was used, and the catalyst was packed in an adiabatic bed reactor. The XRD diffraction pattern of the reduced catalyst is shown in figure 4.
Reaction conditions are as follows: airspeed of 15000h-1And the pressure is 2.0 MPa.
The catalyst properties are shown in Table 6, and the operating results are shown in Table 7.
TABLE 6 Process conditions and catalyst Properties
TABLE 7 physical Properties of catalysts of examples and comparative examples
the present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (16)
1. A process for removing alkyne from the front-end depropanizing hydrogenation features that the top effluent from front-end depropanizing tower is fed to adiabatic bedThe reactor is used for selective hydrogenation to remove alkyne and dialkene in the reactor, and is characterized in that a Ti-Fe-Ni selective hydrogenation catalyst is arranged in an adiabatic bed reactor, a carrier is a high-temperature-resistant inorganic oxide, the catalyst contains 5-15% of Fe, 0.2-1.5% of Ti and 0.5-1.8% of Ni by the mass of the catalyst being 100%, and the specific surface of the catalyst is 10-300 m2The pore volume is 0.2-0.65 mL/g, wherein Fe is loaded on the carrier by a dipping mode, and is prepared by roasting at 300-700 ℃ and reducing at 200-500 ℃ in an atmosphere containing hydrogen; in the catalyst, Fe is mainly alpha-Fe2O3Exists in a form and contains FeNi phase; selecting the hydrogenation reaction conditions: the inlet temperature of the adiabatic bed reactor is 50-100 ℃, the reaction pressure is 1.5-4.0 MPa, and the volume space velocity is 10000-20000 h-1。
2. The method of claim 1, wherein the catalyst is alpha-Fe2O3The Fe in the form accounts for more than 50% of the total weight of the Fe.
3. The method according to claim 1, wherein the carrier of the catalyst is alumina or a composite carrier of alumina and other oxides, the alumina accounts for more than 50% of the mass of the carrier in the composite carrier of alumina and other oxides, and the other oxides are silica, zirconia, magnesia or titania; the alumina is of the theta, alpha or gamma type.
4. The method according to claim 1, wherein the impregnation is an equal volume impregnation, an excess impregnation, a surface spray impregnation, a vacuum impregnation or a plurality of impregnations.
5. the method according to claim 1, wherein the catalyst is obtained by preparing an aqueous solution of a Fe-containing precursor, an aqueous solution of a Ni precursor, and an aqueous solution of a Ti precursor, impregnating the carrier with the aqueous solutions, aging, drying, and calcining the impregnated carrier, or impregnating the impregnated carrier with a mixed solution thereof, followed by aging, drying, and calcining, and finally reducing.
6. the method of claim 5, wherein: the dipping temperature is 30-60 ℃, the dipping time is 10-60 min, the pH value of the dipping solution is 1.5-5.0, the aging temperature is 30-60 ℃, the aging time is 30-120 min, the roasting temperature is 300-700 ℃, and the roasting time is 180-300 min.
7. The method of claim 5, wherein: the drying conditions were:
8. The method according to claim 1 or 5, characterized in that: the roasting is temperature programmed roasting, and the roasting temperature program is set as follows:
9. The method according to claim 1 or 5, characterized in that: catalyst reduction means that the calcined catalyst is reduced with a hydrogen-containing gas, H, before the catalyst is used2The content is 10-50%, the reduction temperature is 200-500 ℃, the reduction time is 240-360 min, and the volume airspeed is 100-500 h-1And the reduction pressure is 0.1-0.8 MPa.
10. The process according to claim 1, characterized in that the adiabatic bed reactor is a three-stage series reactor, the reaction conditions being: the temperature of the first section inlet is 50-100 ℃, the temperature of the second section inlet is 50-100 ℃, and the temperature of the third section inlet is 50-100 ℃.
11. The process of claim 1, wherein the feedstock subjected to selective hydrogenation is an overhead stream from a front-end depropanizer column, the feedstock consisting essentially of, by volume: 30-40% of methane, 15-25% of hydrogen, 8-15% of ethane, 30-45% of ethylene, 5-10% of propane, 5-10% of propylene, 0.1-0.5% of propadiene, 0.5-1.0% of acetylene and 0.1-0.5% of propyne.
12. The method according to claim 1, wherein the catalyst contains 7 to 12% Fe, 0.5 to 1% Ti, 0.8 to 1.2% Ni, and 90 to 170m of specific surface area based on 100% by mass of the catalyst2The pore volume is 0.30-0.63 mL/g; the selective hydrogenation reaction conditions are as follows: the inlet temperature of the adiabatic bed reactor is 60-95 ℃, the reaction pressure is 2.8-3.8 MPa, and the volume airspeed is 12000-18000 h-1。
13. The method according to claim 3, wherein the composite support of alumina and other oxides is an alumina-zirconia composite support; the alumina is alpha-Al2O3。
14. The method according to claim 6, wherein the calcination temperature is 400 to 500 ℃.
15. The method of claim 9, wherein the reducing conditions are with N2+H2The mixed gas is used for reducing the catalyst, the reduction temperature is 300-400 ℃, and the volume airspeed is 200-400 h-1The reduction pressure is 0.1-0.5 MPa.
16. The method of claim 10, wherein the reaction conditions are: the temperature of the first section inlet is 60-85 ℃, the temperature of the second section inlet is 75-90 ℃, and the temperature of the third section inlet is 80-95 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4547615A (en) * | 1983-06-16 | 1985-10-15 | Nippon Zeon Co. Ltd. | Process for producing conjugated diolefins |
| CN101821219A (en) * | 2007-09-19 | 2010-09-01 | 马克斯-普郎克科学促进学会 | Use of mixture of an ordered intermetallic compound and an inert material as a catalyst and corresponding hydrogenation processes |
| CN104245112A (en) * | 2012-04-18 | 2014-12-24 | 帝斯曼知识产权资产管理有限公司 | Device useful for hydrogenation reactions (III) |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4547615A (en) * | 1983-06-16 | 1985-10-15 | Nippon Zeon Co. Ltd. | Process for producing conjugated diolefins |
| CN101821219A (en) * | 2007-09-19 | 2010-09-01 | 马克斯-普郎克科学促进学会 | Use of mixture of an ordered intermetallic compound and an inert material as a catalyst and corresponding hydrogenation processes |
| CN104245112A (en) * | 2012-04-18 | 2014-12-24 | 帝斯曼知识产权资产管理有限公司 | Device useful for hydrogenation reactions (III) |
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