CN114425361B - Paraffin hydrofining catalyst and preparation method thereof - Google Patents
Paraffin hydrofining catalyst and preparation method thereof Download PDFInfo
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- CN114425361B CN114425361B CN202011182296.5A CN202011182296A CN114425361B CN 114425361 B CN114425361 B CN 114425361B CN 202011182296 A CN202011182296 A CN 202011182296A CN 114425361 B CN114425361 B CN 114425361B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 110
- 239000012188 paraffin wax Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 78
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 55
- 230000000149 penetrating effect Effects 0.000 claims abstract description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 23
- 239000011230 binding agent Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000010335 hydrothermal treatment Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000008213 purified water Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004375 Dextrin Substances 0.000 claims description 3
- 229920001353 Dextrin Polymers 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 235000019425 dextrin Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 229910010293 ceramic material Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052799 carbon Inorganic materials 0.000 abstract description 13
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 10
- 239000001993 wax Substances 0.000 abstract description 9
- 239000012528 membrane Substances 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 4
- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
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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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B01J35/635—
-
- B01J35/647—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1081—Alkanes
- C10G2300/1085—Solid paraffins
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a paraffin hydrofining catalyst and a preparation method thereof. The catalyst comprises a catalyst body composed of a carrier and an active component carried on the carrier, wherein the outer surface of the catalyst body is provided with a macroporous alumina layer; the pore volume difference between the catalyst body and macroporous alumina is more than 0.40cm 3 And/g. The invention coats macroporous alumina on the surface of the paraffin hydrofining catalyst body. In the hydrogenation process, the generated carbon deposit is firstly deposited in the alumina pore canal on the surface, and the membrane layer is provided with the penetrating pore canal, so that the carbon deposit can not block the pore canal, wax can enter the catalyst body for hydrogenation reaction, the carbon deposit resistance of the catalyst is improved, meanwhile, the stability of the catalyst is good, and the service life of the catalyst is prolonged.
Description
Technical Field
The invention relates to a paraffin hydrofining catalyst and a preparation method thereof.
Background
The paraffin wax is solid at normal temperature and has relatively large average molecular weight of 300-500 and carbon number of 20-30. The paraffin hydrorefining is mainly characterized in that raw material wax is mixed with hydrogen in a certain proportion at a certain temperature to enter a reactor, and under the action of a catalyst, the hydrogen and hetero atoms such as S, N, O and the like in the raw material wax react chemically to correspondingly generate H 2 S、NH 3 、H 2 O, etc., to remove impurities. Regarding the paraffin hydrofining catalyst, molybdenum is generally used as a main metal component, and tungsten is also used as a main metal component. In addition to the main metal component, the hydrotreating catalyst alsoA second metal component such as nickel or cobalt is employed.
CN111097489a discloses a paraffin hydrofining catalyst and a preparation method thereof. The carrier of the catalyst comprises alumina, layered clay and a Y-type molecular sieve, nickel and molybdenum are used as active metal components, the content of the molybdenum oxide is 2.0-35.0% and the content of the nickel oxide is 0.5-20.0% based on the mass of the catalyst, the dispersity of the active metal components is IMo/IAl and INi/IAl is 0.15-0.30, and INi/IAl is 0.07-0.15. The paraffin hydrofining catalyst improves the utilization rate of active metal from the angle of improving the dispersity of the active metal.
CN1393528A discloses a paraffin hydrofining catalyst, its preparation method and application. The carrier is characterized in that the surface of the alumina is chemically treated to contain titanium dioxide, so that the characteristics of the carrier are improved; the active component of the catalyst adopts a one-step impregnation method of W-Mo-Ni solution, and the metal components reach the common competitive adsorption, so that the special paraffin hydrofining catalyst with higher activity is prepared.
Paraffin hydrofinishing catalysts are used in industrial settings, which typically result in reduced catalyst life due to the deposition of carbon deposits. Therefore, the development of the paraffin hydrofining catalyst with long service life and carbon deposit resistance has very important significance.
Disclosure of Invention
The invention aims to provide a paraffin hydrofining catalyst and a preparation method thereof, which can prolong the service life of the paraffin hydrofining catalyst and improve the running period of a paraffin hydrogenation device.
In the hydrogenation process of the conventional paraffin hydrofining catalyst, as the service time of the catalyst is prolonged, deposited carbon blocks pore channels to cover active sites, so that the utilization rate of active metal is reduced, and the service life of the catalyst is shortened.
The invention provides a paraffin hydrofining catalyst, which comprises a catalyst body composed of a carrier and active components carried on the carrier, wherein the outer surface of the catalyst body is provided with a macroporous alumina layer. The pore volume difference between the catalyst body and macroporous alumina is more than 0.40cm 3 Preferably 0.45 to 0.55 cm/g 3 /g。
The macroporous alumina layer has a pore volume of more than 0.80cm 3 Preferably 0.85 to 0.95 cm per gram (mercury intrusion) 3 And/g, the pore volume of the pores with the pore diameter of more than 30nm accounts for 20-60 percent of the total pore volume, preferably 40-55 percent, and can accommodate more carbon deposition.
The macroporous alumina layer has a thickness of 1-400 μm, preferably 60-180 μm.
The catalyst body is characterized by comprising the following components: pore volume of more than 0.35cm 3 And/g, wherein the content of tungsten oxide is 2.0% -25.0%, the content of molybdenum oxide is 2.0% -20.0% and the content of nickel oxide is 0.4% -8.0% based on the mass of the catalyst body.
The invention also provides a preparation method of the paraffin hydrofining catalyst, which comprises the following steps:
(1) Preparing a paraffin hydrofining catalyst as a catalyst body;
(2) Adding the catalyst body in the step (1) into macroporous pseudo-boehmite gel, stirring and soaking, wrapping the gel on the surface, taking out, and drying;
(3) Roasting the catalyst particles obtained in the step (2) to obtain the paraffin hydrofining catalyst.
The paraffin hydrofining catalyst in the step (1) has a pore volume of more than 0.35cm 3 The active metal in the catalyst is preferably tungsten, molybdenum and/or nickel, the content of tungsten oxide is 2.0% -25.0%, the content of molybdenum oxide is 2.0% -20.0% and the content of nickel oxide is 0.4% -8.0% based on the mass of the catalyst body.
The catalyst body is preferably immersed in the binder solution prior to addition of the catalyst body to the macroporous pseudo-boehmite gel in step (2). The adhesive solution consists of an adhesive and purified water. The mass content of the binder in the binder solution is 1% -80%, preferably 2% -30%. The adhesive can be one or more of starch, dextrin, polyvinyl alcohol or carboxymethyl cellulose.
Preferably, the catalyst body is immersed in the binder solution for 10 to 50 seconds, the excess binder solution is drained off, and the catalyst body is left to stand at room temperature for 15 to 60 minutes.
The macroporous pseudo-boehmite gel described in step (2) has the following properties of being converted into macroporous alumina: pore volume of more than 0.80cm 3 And/g (mercury intrusion method), has a through pore, and the pore volume of pores with the pore diameter of more than 30nm accounts for 20-60% of the total pore volume, and can accommodate more carbon deposition. Wherein the macroporous pseudo-boehmite gel is converted into macroporous alumina by roasting at 450-650 ℃ for 3-6 hours. The macroporous pseudo-boehmite gel can be prepared by adopting an inorganic aluminum source as a raw material, not adding a template agent, adjusting the pH value to 2.8-3.2, and performing hydrothermal treatment at 180-300 ℃ for 3-6 hours. The concentration of alumina in the macroporous pseudo-boehmite gel is 20 g/L-100 g/L, preferably 20 g/L-70 g/L.
And (3) adding the catalyst particles in the step (2) into macroporous pseudo-boehmite gel, stirring, soaking for 10 s-20 min, taking out after coating the gel on the surface, centrifuging by using a centrifuge to remove superfluous gel on the surface, and drying for 2-12 hours at 80-150 ℃. The thickness of the alumina film layer can be controlled by controlling the concentration, soaking time and centrifuging time of alumina in the macroporous pseudo-boehmite gel.
And (3) heating the roasting in the step (3) by adopting a temperature programming mode. The roasting conditions are as follows: the temperature rising rate is 1 ℃/min-3 ℃/min, the roasting temperature is 450-650 ℃ and the roasting time is 3-6 hours. After calcination, an alumina coating layer of 1 to 400 μm, preferably 60 to 180 μm, may be formed on the catalyst surface.
The invention has the advantage that macroporous alumina is coated on the surface of the paraffin hydrofining catalyst body. In the hydrogenation process, the generated carbon deposit is firstly deposited in the alumina pore canal on the surface, and the membrane layer is provided with the penetrating pore canal, so that the carbon deposit can not block the pore canal, wax can enter the catalyst body for hydrogenation reaction, the carbon deposit resistance of the catalyst is improved, meanwhile, the stability of the catalyst is good, and the service life of the catalyst is prolonged.
The pore volume of macroporous alumina on the outer layer of the catalyst body is 0.40cm larger than that of the catalyst body 3 /g, which ensures that even if carbon deposition occurs in macroporous aluminaThe blocking of pore canal of the outer macroporous alumina can be caused, so that the wax can be ensured to normally enter the catalyst body for hydrogenation reaction.
Detailed Description
The operation and effect of the process according to the invention are further illustrated, but not limited, by the following examples.
The pore volume, pore diameter and specific surface area of the external surface macroporous alumina referred in the examples and the comparative examples are all obtained by mercury intrusion test, and the pore volume, pore diameter and specific surface area of the desulfurization catalyst and the carrier are obtained by nitrogen adsorption and desorption experiments.
Example 1
(1) 200g of paraffin hydrofining catalyst with a pore volume of 0.40cm was prepared 3 Per gram, the content of tungsten oxide in the catalyst is 10.5 percent, the content of molybdenum oxide is 18.0 percent, and the content of nickel oxide is 4.5 percent
(2) Preparing an adhesive solution: dissolving 20 g of starch in 500 g of purified water under the condition of heating and stirring, and uniformly stirring and dissolving;
(3) Preparing macroporous pseudo-boehmite gel: 20 g of aluminum sulfate was weighed, the pH value was adjusted to 3.0, and the mixture was subjected to hydrothermal treatment at 180℃for 3 hours. The concentration of alumina in the macroporous pseudo-boehmite was 25 g/L.
(4) Immersing the dried catalyst particles in the step (1) in the adhesive in the step (2) for 20 seconds, taking out, draining excessive adhesive solution, and standing for 30 minutes at room temperature.
(5) Adding the catalyst particles obtained in the step (4) into the macroporous pseudo-boehmite gel obtained in the step (3), stirring for 2min, taking out after the gel is wrapped on the surface, centrifuging for 3min by a high-speed centrifuge, and drying at 120 ℃ for 5 h.
(6) Roasting: roasting for 4 hours at a temperature rising rate of 1 ℃/min to 500 ℃ by adopting a temperature programming mode to obtain the paraffin hydrofining catalyst A, wherein the thickness of the macroporous alumina film layer is 117 mu m, and the pore volume is 0.87cm 3 And/g, wherein the pore volume of pores with the pore diameter of more than 30nm accounts for 45% of the total pore volume. The pore volume difference of the macroporous alumina film layer and the paraffin hydrofining catalyst body is 0.47cm 3 /g。
Example 2
The same as in example 1, except that the pH was adjusted to 2.9 in the step (3), and the hydrothermal treatment was carried out at 180℃for 3.5 hours. The concentration of alumina in the macroporous pseudo-boehmite is 70 g/L, thus obtaining the paraffin hydrofining catalyst B coated with alumina, the thickness of the macroporous alumina film layer is 165 mu m, and the pore volume is 0.90cm 3 And/g, wherein the pore volume occupied by pores with the pore diameter of more than 30nm is 49% of the total pore volume. The pore volume difference between the macroporous alumina and the catalyst body is 0.50cm 3 And/g. Other properties are the same as in example 1.
Example 3
As in example 1, except that 20 g of dextrin was dissolved in 100g of purified water under heating and stirring in the step (2) to prepare a binder solution, the soaking time in the binder in the step (4) was 10S, and the solution was left at room temperature for 50 minutes. In the step (3), the pH value is adjusted to 3.1, and the mixture is subjected to hydrothermal treatment at 250 ℃ for 5 hours. The concentration of alumina in the macroporous pseudo-boehmite is 40g/L, thus obtaining the paraffin hydrofining catalyst C coated with alumina, the thickness of the macroporous alumina film layer is 135 mu m, and the pore volume is 0.89cm 3 And/g, wherein the pore volume occupied by pores with the pore diameter of more than 30nm is 47% of the total pore volume. The pore volume difference between the macroporous alumina and the catalyst body is 0.49cm 3 And/g. Other properties are the same as in example 1.
Example 4
The same procedure as in example 1 was followed except that the catalyst particles in step (5) were immersed in the macroporous pseudo-boehmite gel of step (3) and stirred for 2 minutes, the gel was packed on the surface and then taken out, centrifuged with a high-speed centrifuge for 6 minutes, and then dried at 90℃for 8 hours. Roasting for 5 hours at the temperature rising rate of 2 ℃/min to 600 ℃ to obtain the paraffin hydrofining catalyst D coated with alumina, wherein the thickness of the macroporous alumina membrane layer is 84 mu m, and the pore volume is 0.88cm 3 And/g, wherein the pore volume occupied by pores with the pore diameter of more than 30nm is 46% of the total pore volume. The pore volume difference between the macroporous alumina and the catalyst body is 0.48cm 3 And/g. Other properties are the same as in example 1.
Example 5
As in example 1, except that the concentration of alumina in the macroporous pseudo-boehmite in the step (3) was adjusted to 50 g/L, while in the step (5)Immersing the medium catalyst particles into macroporous pseudo-boehmite gel in the step (3), stirring for 18min, wrapping the gel on the surface, taking out, centrifuging for 6min by a high-speed centrifuge to obtain the paraffin hydrofining catalyst E wrapped with alumina, wherein the thickness of a macroporous alumina membrane layer is 141 mu m, and the pore volume is 0.87cm 3 And/g, wherein the pore volume of pores with the pore diameter of more than 30nm accounts for 45% of the total pore volume. The pore volume difference between the macroporous alumina and the catalyst body is 0.47cm 3 And/g. Other properties are the same as in example 1.
Example 6
As in example 1, only steps (1) (3) (5) (6) and no steps (2) and (4) were carried out, and the paraffin hydrofining catalyst F coated with alumina was obtained, wherein the thickness of the macroporous alumina film layer was 27 μm, and other properties were the same as in example 1.
Comparative example 1
Directly taking the step (1) to obtain the paraffin hydrofining catalyst, and marking the paraffin hydrofining catalyst as a paraffin hydrofining catalyst D1.
Comparative example 2
As in example 1, 2L of an aqueous sodium metaaluminate solution (as Al 2 O 3 A concentration of 15g/100 mL) and 3L of an aqueous solution of aluminum sulfate (in terms of Al 2 O 3 The concentration of the alumina film is 3g/100 mL) is gelled at the gelling temperature of 60 ℃ and the gelling pH value of 7.3, and the obtained alumina film layer does not have penetrating pore channels. Finally, pseudo-boehmite gel is obtained, and the paraffin hydrofining catalyst D2 is prepared. The thickness of the macroporous alumina film layer is 127 mu m, and the pore volume is 0.65cm 3 The pore volume of the pores with the pore diameter more than 30nm is 14 percent of the total pore volume, and the pore volume difference value between macroporous alumina and the catalyst body is 0.25cm 3 /g。
The catalysts of the above examples are respectively evaluated by adopting a small paraffin hydrofining evaluation device, and the reaction process conditions are as follows: the reaction pressure is 6.5MPa, the reaction temperature is 255 ℃, and the LHSV is 1.0h -1 The hydrogen wax ratio was 300. The properties of the corresponding hydrofinished product after 2000 hours of operation of the starting wax are shown in Table 1.
Table 1 raw wax and properties of each hydrorefined product
| Catalyst numbering | Raw material wax | A | F | D1 | D2 |
| Melting point, DEG C | 59.55 | 59.45 | 59.45 | 59.40 | 59.35 |
| Oil content, wt% | 0.20 | 0.20 | 0.21 | 0.23 | 0.24 |
| Color (Sai's) number | -13 | +30 | +29 | +28 | +27 |
| Penetration (25 ℃ C.)/10 -1 mm | 15 | 15 | 15 | 16 | 17 |
| Light stability, number | 7 | 2～3 | 2～3 | 4 | 4 |
| Thermal stability, number | -16 | 29 | 28 | 27 | 26 |
| Easy carbide | Failure to pass | Qualified product | Qualified product | Qualified product | Qualified product |
As can be seen from Table 1, the paraffin hydrofining catalyst prepared by the invention has better hydrogenation performance than the comparative agent, the hydrogenation activity decay is slower after 2000 hours of operation, and the catalyst still has better hydrogenation performance, thus providing guarantee for prolonging the operation period of the device.
Claims (15)
1. A catalyst for hydrorefining paraffin is characterized in thatThe catalyst comprises a catalyst body composed of a carrier and an active component supported on the carrier, wherein the outer surface of the catalyst body is provided with a macroporous alumina layer; the pore volume difference between the catalyst body and macroporous alumina is more than 0.40cm 3 /g; the macroporous alumina layer has the following properties: pore volume of more than 0.80cm 3 And/g, the porous ceramic material has penetrating pore canal, and the pore volume of pores with the pore diameter of more than 30nm accounts for 20-60% of the total pore volume.
2. The catalyst according to claim 1, wherein the pore volume difference between the catalyst body and the macroporous alumina is 0.45-0.55 cm 3 /g。
3. The catalyst of claim 1, wherein the macroporous alumina layer has a pore volume of 0.85 cm to 0.95 cm 3 /g。
4. The catalyst of claim 1, wherein the macropore alumina layer has pores with a pore diameter of > 30nm accounting for 40% -55% of the total pore volume.
5. The catalyst of claim 1, wherein the macroporous alumina layer has a thickness of 1 to 400 μm.
6. The catalyst of claim 1, wherein the macroporous alumina layer has a thickness of 60-180 μm.
7. A process for preparing the catalyst of any one of claims 1 to 6, comprising the steps of:
(1) Preparing a paraffin hydrofining catalyst as a catalyst body;
(2) Adding the catalyst body in the step (1) into macroporous pseudo-boehmite gel, stirring and soaking, wrapping the gel on the surface, taking out, and drying;
(3) Roasting the catalyst particles obtained in the step (2) to obtain the paraffin hydrofining catalyst.
8. The preparation method according to claim 7, wherein the catalyst body is immersed in a binder solution before the catalyst body is added to the macroporous pseudo-boehmite gel in the step (2), the binder solution is composed of a binder and purified water, and the mass content of the binder in the binder solution is 1% -80%.
9. The preparation method according to claim 8, wherein the mass content of the binder in the binder solution is 2% to 30%.
10. The method according to claim 8, wherein the binder is one or more of starch, dextrin, polyvinyl alcohol, and carboxymethyl cellulose.
11. The preparation method according to claim 8, wherein the catalyst body is immersed in the binder solution for 10 to 50 seconds, the excess binder solution is leached off, and the catalyst body is left at room temperature for 15 to 60 minutes.
12. The preparation method of claim 7, wherein the macroporous pseudo-boehmite gel in the step (2) is prepared by taking an inorganic aluminum source as a raw material, not adding a template agent, adjusting the pH value to 2.8-3.2, and performing hydrothermal treatment at 180-300 ℃ for 3-6 hours.
13. The method according to claim 7, wherein the concentration of alumina in the macroporous pseudo-boehmite gel in the step (2) is 20. 20 g/L to 100 g/L.
14. The method according to claim 7, wherein the concentration of alumina in the macroporous pseudo-boehmite gel in the step (2) is 20. 20 g/L to 70 g/L.
15. The preparation method of claim 7, wherein in the step (2), the catalyst body in the step (1) is added into macroporous pseudo-boehmite gel, stirred and soaked for 10 s-20 min, the surface is taken out after being wrapped with gel, the gel with superfluous surface is removed by centrifugation by using a centrifuge, and the catalyst body is dried for 2-12 hours at 80-150 ℃.
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| US5914290A (en) * | 1996-06-28 | 1999-06-22 | China Petrochemical Corporation | Distillate hydrofining catalyst and a process for the preparation of the same |
| CN102485847A (en) * | 2010-12-03 | 2012-06-06 | 中国石油天然气股份有限公司 | Method for hydrorefining petroleum wax |
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| CN104549430A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrogenation catalyst as well as preparation method and application thereof |
| CN111097489A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and its preparation |
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| JPH0427439A (en) * | 1990-05-21 | 1992-01-30 | Sumitomo Metal Mining Co Ltd | Catalyst for hydrodesulfurization |
| US5914290A (en) * | 1996-06-28 | 1999-06-22 | China Petrochemical Corporation | Distillate hydrofining catalyst and a process for the preparation of the same |
| CN102485847A (en) * | 2010-12-03 | 2012-06-06 | 中国石油天然气股份有限公司 | Method for hydrorefining petroleum wax |
| CN103301888A (en) * | 2013-06-21 | 2013-09-18 | 中国海洋石油总公司 | Preparation method of catalyst carrier for hydrotreating pretreatment of wax oil |
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