CN111097434A - Paraffin hydrofining catalyst and preparation method thereof - Google Patents
Paraffin hydrofining catalyst and preparation method thereof Download PDFInfo
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- CN111097434A CN111097434A CN201811257841.5A CN201811257841A CN111097434A CN 111097434 A CN111097434 A CN 111097434A CN 201811257841 A CN201811257841 A CN 201811257841A CN 111097434 A CN111097434 A CN 111097434A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 239000012188 paraffin wax Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 238000005470 impregnation Methods 0.000 claims description 19
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- -1 phosphate ester Chemical class 0.000 claims description 4
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 claims description 3
- CKQGJVKHBSPKST-UHFFFAOYSA-N [Ni].P#[Mo] Chemical compound [Ni].P#[Mo] CKQGJVKHBSPKST-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- FFZANLXOAFSSGC-UHFFFAOYSA-N phosphide(1-) Chemical compound [P-] FFZANLXOAFSSGC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011734 sodium Substances 0.000 description 7
- 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 6
- 229920000193 polymethacrylate Polymers 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- 150000007942 carboxylates Chemical class 0.000 description 5
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012169 petroleum derived wax Substances 0.000 description 2
- 235000019381 petroleum wax Nutrition 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
- 238000005303 weighing Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910015338 MoNi Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- 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
-
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/28—Phosphorising
-
- 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
- B01J37/32—Freeze drying, i.e. lyophilisation
-
- 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
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/42—Refining of petroleum waxes
- C10G73/44—Refining of petroleum waxes in the presence of hydrogen or hydrogen-generating compounds
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a paraffin hydrofining catalyst and a preparation method thereof. The method comprises the following steps: (1) preparing a paraffin hydrofining catalyst carrier; (2) impregnating the catalyst carrier obtained in the step (1) with a phosphorus-containing solution, and then drying; (3) and (3) impregnating the dried carrier in the step (2) with an active metal solution containing a carboxyl polymer, and then drying and roasting to obtain the catalyst. The paraffin hydrofining catalyst prepared by the method has high utilization rate of active metals, high dispersion degree of the active metals and high activity.
Description
Technical Field
The invention relates to a preparation method of a catalyst, in particular to a paraffin hydrofining catalyst and a preparation method thereof.
Background
The paraffin takes normal paraffin as a main component, is solid at normal temperature, has a large average molecular weight of generally 300-500 and has carbon number of C20-C30. Hydrogenation of paraffinsThe refining process includes mixing material wax with hydrogen in certain proportion at certain temperature, reaction of hydrogen with S, N, O and other hetero atoms in the material wax to produce H2S、NH3、H2O, etc. to remove impurities. As for the paraffin wax hydrorefining catalyst, molybdenum is generally used as a main metal component, and tungsten is also used as a main metal component. In addition to the primary metal component, the hydrotreating catalyst employs a secondary metal component such as nickel or cobalt.
The raw material cost of the active metals in paraffin hydrofinishing catalysts is a large proportion of the cost of the catalyst, particularly in recent years the price of molybdenum (also including tungsten) has continued to rise. Molybdenum has been MoNi/Al2O3The price of the paraffin wax hydrofining catalyst forms the most main part. Therefore, how to increase the utilization rate of the active metal and reduce the cost of the paraffin hydrofining catalyst is one of the important issues in the field.
US 4186078A is prepared by adding a large amount of silicon to a carrier (containing SiO)25 to 25 wt%) to prepare SiO2- Al2O3Carrier to ensure that the carrier has larger specific surface, larger pore diameter and more concentrated pore distribution. However, the catalyst prepared by this method has a low active metal utilization rate because the amount of the active metal dispersed on the carrier is not sufficiently high.
CN 1249329A discloses a petroleum wax hydrofining catalyst and a preparation method thereof, and the method uses a mixed solution containing molybdenum, nickel and phosphorus to dip gamma-Al2O3Then drying and roasting, wherein the gamma-Al2O3The preparation of the carrier is that α -AlO (OH) of acid sol is kneaded, extruded to form, dried and roasted to prepare the carrier, the concentration of the mixed solution of molybdenum, nickel and phosphorus used in the preparation of the method is high, especially the mass concentration of molybdenum, in addition, the method can not reduce the distribution of active metal in catalyst pores and can not improve the dispersion degree of the active metal nickel, thereby the utilization rate of the active metal is low.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a paraffin hydrofining catalyst and a preparation method thereof. The paraffin hydrofining catalyst prepared by the method has high utilization rate of active metals, high dispersion degree of the active metals and high activity.
The invention provides a preparation method of a paraffin hydrofining catalyst, which comprises the following steps:
(1) preparing a paraffin hydrofining catalyst carrier;
(2) impregnating the catalyst carrier obtained in the step (1) with a phosphorus-containing solution, and then drying;
(3) and (3) impregnating the dried carrier in the step (2) with an active metal solution containing a carboxyl polymer, and then drying and roasting to obtain the catalyst.
The catalyst obtained by the method of the invention has the carrier of alumina, the active metal components of nickel and molybdenum, and based on the mass of the catalyst, the content of the molybdenum oxide is 2.0-35.0%, preferably 12.0-25.0%, more preferably 15.0-25.0%, the content of the nickel oxide is 0.5-20.0%, preferably 4.0-10.0%, more preferably 5.0-10.0%, and the content of the phosphorus is 0.01-6.00%, preferably 0.10-3.00%.
In the method, the specific surface area of the paraffin hydrofining catalyst carrier in the step (1) is 150-400 m2The pore volume is 0.68-1.10 mL/g, and the average pore diameter is 10-18 nm.
The carrier of the paraffin hydrofining catalyst is preferably an alumina carrier and can be prepared by a conventional method. The preparation method of the alumina carrier can be as follows: the preparation method comprises the steps of adding an extrusion aid, an adhesive and a proper amount of water into macroporous pseudo-boehmite, fully kneading, molding, drying and roasting to obtain the paraffin hydrofining catalyst carrier, wherein the extrusion aid and the adhesive are commonly used in the field.
In the method, the phosphorus-containing solution in the step (2) is one or more of phosphate radical, monohydrogen phosphate, dihydrogen phosphate, six-coordinate phosphorus anion and phosphate ester in the solution. Wherein the mass concentration of the phosphorus-containing solution is 0.01-15.00%, preferably 0.01-5.00%.
In the above method, the impregnation in the step (2) may be an isovolumetric impregnation method or an over-volumetric impregnation method. The impregnation is preferably carried out at a temperature of from 20 ℃ to 80 ℃.
The drying process described in step (2) is preferably freeze drying. The freeze drying comprises the following specific operations: and (3) cooling to-20 to-90 ℃ at a cooling rate of 0.1 to 20 ℃/min, and carrying out freeze drying for 2 to 96 hours, preferably 3 to 36 hours.
In the above method, the carboxyl group-containing polymer in the step (3) contains one or more carboxyl groups in its repeating unit; the carboxyl-containing polymer is a liquid compound or a soluble polymer. The carboxyl-containing polymer corresponds to the following general formula:
wherein, R1, R2 and R3 are at least one of hydrogen, aliphatic alkyl or substituted derivatives thereof, acyl or substituted derivatives thereof, hydroxyl and carboxyl independently. Further, the carbon number of the aliphatic alkyl is 1-5, the carbon number of the acyl is 1-6, and the carbon number of the carboxyl is 1-6; wherein M is at least one of H, Na and K, and n is a natural number not less than 1.
In the active metal solution containing the carboxyl-containing polymer, the content of the carboxyl-containing polymer is 0.1-30.0 g/100mL, preferably 0.1-10.0 g/100mL, calculated by carboxylate radical.
In the method, the active metal solution in the step (3) is a molybdenum-nickel-phosphorus solution. The drying condition is drying for 2-15 hours at 80-150 ℃ in air, and the roasting condition is roasting for 3-5 hours at 350-650 ℃.
In another aspect, the invention provides a catalyst for hydrorefining paraffin wax prepared by the above method. The catalyst takes alumina as a carrier, takes nickel and molybdenum as active metal components, and takes the mass of the catalyst as a reference, the content of the molybdenum oxide is 2.0-35.0 percent, preferably 12.0-25.0 percent, further preferably 15.0-25.0 percent, the content of the nickel oxide is 0.5-20.0 percent, preferably 4.0-10.0 percent,further preferably 5.0-10.0%, and the content of phosphorus is 0.01-6.00%, preferably 0.10-3.00%; the dispersion degree of the active metal component is as follows: i isMo/IAl0.140 to 0.30, preferably 0.140 to 0.200; i isNi/IAl0.065 to 0.150, preferably 0.065 to 0.100.
Wherein, the IMo/IAl、INi/IAlRespectively represent the number ratio of active metal atoms and aluminum atoms on the surface of the catalyst.
The active metal dispersion degree is obtained by analyzing the active metal components on the surface of the catalyst by an X photoelectron spectrometer, in particular to an American MultilAB2000 photoelectron spectrometer. The larger the value of the dispersion, the more uniform the dispersion of the active metal.
Compared with the prior art, the invention has the following advantages:
the method of the invention uses phosphoric acid-containing solution to pre-impregnate the carrier, so that the generated aluminum phosphate blocks partial small holes, the content of active metal entering the small holes is reduced, the method is beneficial to generating synergistic effect with the carboxyl-containing polymer which is subsequently impregnated, and the metal dispersity is improved.
Due to the action of carboxylate anions on a macromolecular chain, strong electrostatic force exists near the macromolecular chain, so that the electrostatic attraction between the carboxylate and cations on the macromolecular chain is far larger than that between the corresponding monomer carboxylate and the same cations, and the constraint action of the carboxylate on the cations is increased along with the increase of the dissociation degree of the polymer, the increase of the cation valence and the decrease of the ion radius. Thus, the carboxyl group-containing polymer binds divalent metal ions more strongly than monovalent metal ions. After the carboxyl-containing polymer is added into the active metal impregnation liquid, the dissociated macromolecular anions are combined with divalent nickel ions to play a role in fixing the nickel ions, and meanwhile, the macromolecular ions combined with the nickel ions still have negative charges and are mutually and electrostatically repelled with phosphomolybdic acid radicals in the impregnation liquid to play a role in dispersing the active metal molybdenum.
Detailed Description
The following examples are given to further illustrate the effects and effects of the method of the present invention, but are not limited thereto.
Example 1
(1) Weighing 500g of macroporous pseudo-boehmite, adding 15g of sesbania powder, 15g of methylcellulose and 15g of acetic acid, uniformly mixing, adding a proper amount of deionized water, and kneading and molding at room temperature. After forming, drying at 120 ℃ for 4 hours, and roasting at 750 ℃ for 3 hours to obtain the catalyst carrier. The specific surface area of the calcined catalyst carrier is 303 m2The pore volume is 1.02 mL/g, and the average pore diameter is 16 nm;
(2) weighing 100g of the catalyst carrier prepared in the step (1), soaking the catalyst carrier in 200mL of 1.00 mass percent disodium hydrogen phosphate solution at 60 ℃ for 3 hours, filtering out redundant solution, cooling to-40 ℃ at a cooling rate of 0.3 ℃/min, and freeze-drying for 5 hours;
(3) ammonium molybdate, nickel nitrate and phosphoric acid are added into water to be dissolved, and then sodium polymethacrylate is added to obtain an impregnation solution, wherein the content of molybdenum oxide is 48.7g/100mL, the content of nickel oxide is 9.8g/100mL, the content of phosphorus is 2.1g/100mL, and the content of sodium polymethacrylate is 0.5 g/100mL calculated by carboxylate radical. And (3) dipping the dried catalyst carrier in the step (2) by using a prepared dipping solution for 2 hours, then drying for 5 hours at the temperature of 120 ℃, and then roasting for 4 hours at the temperature of 500 ℃ to obtain the paraffin hydrofining catalyst A.
Example 2
The same procedure as in example 1 was repeated, except that the sodium polymethacrylate concentration of the impregnation solution prepared in step (3) was 1.0g/100mL in terms of carboxylate group and the impregnation time was 3 hours. Thus obtaining the paraffin hydrofining catalyst B.
Example 3
The same as example 1 except that in the step (2), when the support was impregnated with the disodium hydrogenphosphate solution, the disodium hydrogenphosphate solution was used in an amount of 0.10% by mass; the drying conditions were: cooling to-30 deg.C at a rate of 0.5 deg.C/min, and freeze drying for 3 hr. Thus obtaining the paraffin hydrofining catalyst C.
Example 4
The same procedure as in example 1 was repeated except that in the step (2), when the support was impregnated with the disodium hydrogenphosphate solution, the disodium hydrogenphosphate solution was used in an amount of 0.10% by mass under the drying conditions: cooling to-50 deg.C at a rate of 0.5 deg.C/min, and freeze drying for 5 hr; the content of the sodium polymethacrylate in the impregnation liquid prepared in the step (3) is 1.0g/100mL in terms of carboxylate radical, and the impregnation time is 3 hours. Thus obtaining the paraffin hydrofining catalyst D.
Example 5
The same procedure as in example 1 was repeated, except that in the step (3), ammonium molybdate, nickel nitrate and phosphoric acid were dissolved in water, and then polymethacrylic acid was added to obtain an impregnation solution containing molybdenum oxide in an amount of 50.2g/100mL, nickel oxide in an amount of 10.3g/100mL, phosphorus in an amount of 2.2g/100mL and polymethacrylic acid in an amount of 0.5 g/100mL in terms of carboxylate groups. And (3) dipping the dried catalyst carrier in the step (2) by using a prepared dipping solution for 3 hours, then drying for 5 hours at the temperature of 120 ℃, and then roasting for 4 hours at the temperature of 500 ℃ to obtain the paraffin hydrofining catalyst E.
Comparative example 1
The same procedure as in example 1 was repeated except that the impregnation solution prepared in step (3) of example 1 was used to impregnate the catalyst support obtained in step (1) without impregnating the phosphorus-containing solution prepared in step (2). Obtaining the paraffin hydrofining catalyst F.
Comparative example 2
The procedure is otherwise the same as in example 1, except that the impregnation solution in step (3) does not contain sodium polymethacrylate. To obtain the paraffin hydrofining catalyst G.
Comparative example 3
The same procedure as in example 1 was repeated except that the phosphorus-containing solution was not impregnated in step (2) and sodium polymethacrylate was not present in the impregnation solution in step (3). Obtaining the paraffin hydrofining catalyst H. The properties of the catalysts prepared in the above examples and comparative examples are shown in Table 1.
TABLE 1 Properties of catalysts prepared in examples and comparative examples
| Catalyst numbering | A | B | C | D | E | F | G | H |
| Specific surface area, m2/g | 153 | 155 | 161 | 164 | 155 | 160 | 156 | 161 |
| Pore volume, mL/g | 0.60 | 0.58 | 0.60 | 0.56 | 0.57 | 0.60 | 0.55 | 0.60 |
| Several pore diameters, nm | 10.0 | 9.8 | 10.5 | 10.3 | 10.1 | 11.0 | 9.9 | 10.5 |
| MoO3，w% | 18.4 | 18.5 | 18.2 | 18.1 | 19.0 | 18.6 | 18.3 | 18.7 |
| NiO，w% | 5.3 | 5.2 | 5.0 | 5.1 | 5.6 | 5.4 | 5.1 | 5.5 |
| P，w% | 1.6 | 1.6 | 1.0 | 1.1 | 1.7 | 1.0 | 1.6 | 1.0 |
| Degree of dispersion of active metal | ||||||||
| IMo/IAl | 0.1487 | 0.1580 | 0.1453 | 0.1544 | 0.1593 | 0.1274 | 0.0856 | 0.0812 |
| INi/IAl | 0.0708 | 0.0758 | 0.0679 | 0.0723 | 0.0824 | 0.0604 | 0.0549 | 0.0487 |
Note: i isMo/IAl、INi/IAlRespectively represent the number ratio of active metal atoms and aluminum atoms on the surface of the catalyst.
The degree of dispersion of the active metal in the catalysts obtained in the above examples and comparative examples was measured by using a u.s.multilab 2000 photoelectron spectrometer.
The catalysts in the above examples were evaluated by a small paraffin hydrofining evaluation device under the following reaction conditions: the reaction pressure is 6.0MPa, the reaction temperature is 260 ℃, and the LHSV is 1.0h-1The hydrogen wax ratio was 300. The raw material properties and the product properties are shown in Table 2.
TABLE 2 raw wax and hydrorefined product Properties
| Catalyst numbering | Raw material wax | A | B | C | D | E | F | G | H |
| Melting point of | 59.50 | 59.55 | 59.55 | 59.55 | 59.55 | 59.55 | 59.50 | 59.50 | 59.50 |
| Oil content, wt% | 0.56 | 0.55 | 0.55 | 0.55 | 0.55 | 0.55 | 0.56 | 0.56 | 0.57 |
| Color (Sai's), number | -10 | +30 | +30 | +30 | +30 | +30 | +28 | +26 | +25 |
| Penetration (25 ℃ C.)/10-1mm | 16 | 16 | 16 | 16 | 16 | 16 | 17 | 17 | 18 |
| Light stability No. | 6～7 | 3 | 3 | 3 | 3 | 3 | 3～4 | 3～4 | 4 |
| Heat stability No. 1 | -2 | 26 | 26 | 26 | 26 | 27 | 24 | 22 | 22 |
| Easily carbonized substance | Fail to be qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified |
As can be seen from Table 2, the catalyst prepared by the present invention has excellent effect on hydrogenation of petroleum wax. Compared with the comparative example, the refined wax obtained by adopting the paraffin hydrofining catalyst prepared by the invention has less oil content, the color reaches No. 30, and the light stability and the heat stability are both better than those of the comparative example.
Claims (13)
1. A preparation method of a paraffin hydrofining catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing a paraffin hydrofining catalyst carrier;
(2) impregnating the catalyst carrier obtained in the step (1) with a phosphorus-containing solution, and then drying;
(3) and (3) impregnating the dried carrier in the step (2) with an active metal solution containing a carboxyl polymer, and then drying and roasting to obtain the catalyst.
2. The method of claim 1, wherein: in the catalyst obtained in the step (3), the carrier is alumina, the active metal component is nickel and molybdenum, and based on the mass of the catalyst, the content of the molybdenum oxide is 2.0-35.0%, preferably 12.0-25.0%, more preferably 15.0-25.0%, the content of the nickel oxide is 0.5-20.0%, preferably 4.0-10.0%, more preferably 5.0-10.0%, and the content of the phosphorus is 0.01-6.00%, preferably 0.10-3.00%.
3. A method according to claim 1 or 2, characterized in that: the specific surface area of the paraffin hydrofining catalyst carrier in the step (1) is 150-400 m2(ii) a pore volume of 0.68 to 1.10mL/g, average poreThe diameter is 10-18 nm.
4. A method according to claim 1 or 2, characterized in that: the phosphorus-containing solution in the step (2) is one or more of phosphate radical, phosphoric acid monobasic radical, phosphoric acid dibasic radical, six-coordinate phosphorus anion and phosphate ester in the solution; the mass concentration of the phosphorus-containing solution is 0.01-15.00%, preferably 0.01-5.00%.
5. A method according to claim 1 or 2, characterized in that: the impregnation in the step (2) is an isometric impregnation method or an over-volume impregnation method; the impregnation is preferably carried out at 20-80 ℃, and the drying process adopts freeze drying.
6. The method of claim 5, wherein: the freeze drying comprises the following steps: and (3) reducing the temperature to-20 to-90 ℃ at a cooling rate of 0.1 to 20 ℃/min, and carrying out freeze drying for 2 to 96 hours, preferably 3 to 36 hours.
7. The method of claim 1, wherein: the carboxyl group-containing polymer in the step (3) which contains one or more carboxyl groups in the repeating unit; the carboxyl-containing polymer is a liquid compound or a soluble polymer.
8. The method of claim 1 or 7, wherein: the carboxyl-containing polymer corresponds to the following general formula:
wherein, R1, R2 and R3 are at least one of hydrogen, aliphatic alkyl or substituted derivatives thereof, acyl or substituted derivatives thereof, hydroxyl and carboxyl independently; the carbon number of the aliphatic alkyl is 1-5, the carbon number of the acyl is 1-6, and the carbon number of the carboxyl is 1-6; wherein M is at least one of H, Na and K, and n is a natural number not less than 1.
9. The method of claim 1 or 7, wherein: in the active metal solution containing the carboxyl-containing polymer, the content of the carboxyl-containing polymer is 0.1-30.0 g/100mL, preferably 0.1-10.0 g/100mL, calculated by carboxylate radical.
10. The method of claim 1, wherein: and (4) the active metal solution in the step (3) is a molybdenum-nickel-phosphorus solution.
11. The method of claim 1, wherein: the drying condition in the step (3) is drying for 2-15 hours at 80-150 ℃ in air, and the roasting condition is roasting for 3-5 hours at 350-650 ℃.
12. A catalyst for hydrorefining paraffin wax, which is characterized in that: prepared by the process of any one of claims 1 to 11.
13. A paraffin hydrofinishing catalyst according to claim 12, wherein: the dispersion degree of the active metal components of the catalyst is as follows: i isMo/IAl0.140 to 0.30, preferably 0.140 to 0.200; i isNi/IAl0.065 to 0.150, preferably 0.065 to 0.100.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040186014A1 (en) * | 2001-07-10 | 2004-09-23 | Takayuki Tsukada | Hydro-refining catalyst, carrier for use therein and method for production thereof |
| CN1887420A (en) * | 2006-07-26 | 2007-01-03 | 中国石油大庆石化公司研究院 | Petroleum wax hydrofining catalyst and its prepn process |
| 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 |
| CN105665027A (en) * | 2015-12-29 | 2016-06-15 | 四川大学 | Preparation method of high-dispersing supported metal nano catalyst |
| CN106140310A (en) * | 2015-03-30 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and hydrogenation method for hydrocarbon oils |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040186014A1 (en) * | 2001-07-10 | 2004-09-23 | Takayuki Tsukada | Hydro-refining catalyst, carrier for use therein and method for production thereof |
| CN1887420A (en) * | 2006-07-26 | 2007-01-03 | 中国石油大庆石化公司研究院 | Petroleum wax hydrofining catalyst and its prepn process |
| 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 |
| CN106140310A (en) * | 2015-03-30 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and hydrogenation method for hydrocarbon oils |
| CN105665027A (en) * | 2015-12-29 | 2016-06-15 | 四川大学 | Preparation method of high-dispersing supported metal nano catalyst |
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