WO2017166046A1 - Light hydrocarbon sweetening catalyst on the basis of alumina crystal surface regulation and preparation method therefor - Google Patents

Light hydrocarbon sweetening catalyst on the basis of alumina crystal surface regulation and preparation method therefor Download PDF

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WO2017166046A1
WO2017166046A1 PCT/CN2016/077660 CN2016077660W WO2017166046A1 WO 2017166046 A1 WO2017166046 A1 WO 2017166046A1 CN 2016077660 W CN2016077660 W CN 2016077660W WO 2017166046 A1 WO2017166046 A1 WO 2017166046A1
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alumina
catalyst
hydrothermal treatment
light hydrocarbon
nickel
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PCT/CN2016/077660
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French (fr)
Chinese (zh)
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鲍晓军
王磊
刘海燕
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中国石油大学(北京)
北京中石大格林催化科技有限公司
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Priority to PCT/CN2016/077660 priority Critical patent/WO2017166046A1/en
Publication of WO2017166046A1 publication Critical patent/WO2017166046A1/en

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    • B01J35/30—
    • 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
    • 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
    • B01J35/60—
    • 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
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C07C5/05—Partial hydrogenation
    • 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

Definitions

  • the invention relates to a light hydrocarbon desulfurization catalyst based on alumina crystal plane regulation and a preparation method thereof, and belongs to the technical field of petroleum product refining.
  • the desulfurization technology of light petroleum products has been following the Merox catalytic oxidative desulfurization process developed by UOP.
  • the principle is to remove the mercaptan by utilizing the weak acidity of thiol molecules and the easy oxidation of thiol anions to disulfides.
  • the main chemical reactions are:
  • CN101077984B discloses a method for deep desulfurization of liquefied petroleum gas, which is a caustic free deodorization technology
  • CN100462146C discloses a preparation method of a catalyst for converting mercaptan contained in gasoline, which belongs to an alkali-free deodorization technology, the above two
  • the technology needs to continuously add lye or water in the process of use, so it does not really solve the problem of deep desulfurization of light petroleum processing products and environmental pollution caused by liquid alkali discharge.
  • US 6,692,635 B2 discloses a process for producing gasoline having a low sulfur content, in which a new desulfurization technique is employed.
  • the technology feeds the whole fraction gasoline feedstock into a selective hydrogenation reactor to etherify the olefin or the diene in the gasoline to form a high-boiling sulfur-containing compound, and then selectively increases the concentration in a fractionator.
  • the hydrogen product is subjected to fractional distillation to obtain a light gasoline fraction containing no mercaptan and having a low total sulfur content, and a heavy gasoline fraction having a high sulfur content.
  • the technology is characterized by the effective removal of mercaptan from the light gasoline fraction and the transfer to the heavy gasoline fraction by the addition reaction of mercaptan and diolefin, and at the same time, the removal of mercaptan and the total sulfur content of light gasoline are realized.
  • the reduction overcomes the problem that the conventional Merox process cannot be deeply desulfurized and the presence of alkali residue is discharged.
  • CN1229838A discloses a method for converting hydrocarbon oil by using a feedstock oil and a hydrotreating catalyst Desulfurizing the mercaptan under the process conditions of hydrodesulfurization, the hydrorefining catalyst comprising tungsten oxide (molybdenum), nickel oxide and cobalt oxide supported on an alumina carrier, wherein the content of tungsten oxide (molybdenum) is 4 to 10 wt %, the content of nickel oxide is 1 to 5 wt%, the content of cobalt oxide is 0.01 to 0.1 wt%, and the ratio of the total number of atoms of nickel and cobalt to the total number of atoms of nickel, cobalt, tungsten (molybdenum) is 0.3 to 0.9.
  • the hydrorefining catalyst comprising tungsten oxide (molybdenum), nickel oxide and cobalt oxide supported on an alumina carrier, wherein the content of tungsten oxide (molybdenum) is 4 to 10 wt
  • the catalyst can reduce the thiol content from 212 ⁇ g/g to 10 ⁇ g/g when used to treat FCC gasoline, but the gasoline research octane number (RON) loss is 3.3 units, motor octane number (MON) loss. 3.0 units.
  • CN102451694A discloses a hydrodesulfurization catalyst and a preparation method and application thereof.
  • the catalyst uses alumina or silica-containing alumina as a carrier, phosphorus as an auxiliary component, copper and zinc as active components, and based on the catalyst quality, the phosphorus content of the promoter is 0.5-3.0 wt%, zinc oxide. The content is 3 to 15% by weight, and the content of copper oxide is 5 to 30% by weight. Due to the strong hydrogenation activity of the catalyst, the thiol content was reduced from 38 ⁇ g/g to 3 ⁇ g/g when the whole fraction FCC gasoline was used, and the olefin content was also reduced from 25 v% to 20 v%, and the RON loss was as high as 1.3. Units.
  • an object of the present invention is to provide a method of hydrothermal treatment of a ⁇ -alumina crystal face which enables the obtained ⁇ -alumina to have highly exposed (111) and (110) crystal faces.
  • Another object of the present invention is to provide a ⁇ -alumina controlled by hydrothermal treatment obtained by the method.
  • Still another object of the present invention is to provide a light hydrocarbon desulfurization catalyst using ⁇ -alumina controlled by the hydrothermal treatment as a carrier.
  • the catalyst can retain olefins in the raw materials in the case of efficiently removing thiols and/or diolefins in light fractions such as liquefied petroleum gas, FCC gasoline, catalytic pyrolysis gasoline and/or coking gasoline, and the octane number of gasoline is only RON. Reduce the value of about 0.3 points to achieve high value-added use of light hydrocarbons.
  • an aspect of the invention provides a method for hydrothermal treatment of a ⁇ -alumina crystal face, the method comprising: adding a ⁇ -alumina ( ⁇ -Al 2 O 3 ) raw material to an acidic aqueous solution, water Heat treatment, filtration, washing, drying and calcination to obtain ⁇ -alumina controlled by hydrothermal treatment.
  • the modified ⁇ -alumina obtained by the hydrothermal treatment of the ⁇ -alumina crystal surface of the present invention has significantly different physicochemical properties from the unmodified ⁇ -alumina, the most significant difference being hydrothermal modification.
  • the later ⁇ -alumina has higher crystallinity and exposes more (111) and (110) crystal faces on its surface. These two newly exposed crystal faces make hydrothermally modified ⁇ - Alumina has more acid centers and more bases at the same time.
  • the catalyst of the present invention can be prepared by using the hydrothermal treatment to adjust ⁇ -alumina, which has excellent properties as described below.
  • the temperature of the hydrothermal treatment is 120 to 200 ° C; preferably, the hydrothermal treatment is 3 to 12 h.
  • the calcination temperature is 400 to 550 ° C; preferably, the calcination is 5 to 15 h.
  • the ⁇ -alumina raw material in the hydrothermal treatment of the ⁇ -alumina crystal surface of the present invention, has a specific surface area of 200 to 400 m 2 /g and a pore volume of 0.3 to 0.8. Cm 3 /g.
  • the acidic aqueous solution comprises one of an aqueous solution of nitric acid, hydrochloric acid, an aqueous solution of oxalic acid, an aqueous solution of acetic acid and an aqueous solution of citric acid or
  • the acidic aqueous solution has a pH of 0 to 4; more preferably, the acidic aqueous solution used is an aqueous solution of nitric acid; more preferably, the acidic aqueous solution is an aqueous solution of nitric acid having a pH of 0 to 4.
  • the mass ratio of the ⁇ -alumina raw material to the acidic aqueous solution is 1:1 to 1:6; It is preferably 1:2 to 1:4.
  • the hydrothermal treatment in the hydrothermal treatment of the ⁇ -alumina crystal surface of the present invention, has a temperature of from 120 to 200 ° C, preferably from 160 to 200 ° C. Further preferably, the hydrothermal treatment time is from 3 to 12 h, for example from 5 to 12.
  • the washing is carried out using deionized water.
  • the drying temperature is 80 to 200 ° C, preferably 100 to 150 ° C.
  • the calcination is calcined at 100 to 550 ° C for 5 to 15 h; and the preferred calcination temperature is 400 to 550 ° C.
  • the hydrothermal treatment temperature is as described above, and the calcination temperature is as described above.
  • the hydrothermal treatment temperature and the time of the hydrothermal treatment are as described above, and the calcination temperature and the calcination time are as described above.
  • the kind of the acidic aqueous solution is as described above, and the hydrothermal treatment temperature is as described above.
  • the kind and amount of the acidic aqueous solution are as described above, and the hydrothermal treatment temperature and the hydrothermal treatment time are as described above.
  • the kind of the acidic aqueous solution is as described above, and the calcination temperature is as described above.
  • the kind and amount of the acidic aqueous solution are as described above, and the calcination temperature and the calcination time are as described above.
  • the kind of the acidic aqueous solution is as described above
  • the hydrothermal treatment temperature is as described above
  • the calcination temperature is as described above.
  • the kind and amount of the acidic aqueous solution are as described above
  • the hydrothermal treatment temperature and time are as described above
  • the calcination temperature and the calcination time are as described above.
  • the present invention provides a hydrothermally controlled ⁇ -alumina obtained by the hydrothermal treatment of a ⁇ -alumina crystal face.
  • the hydrothermally controlled ⁇ -alumina has higher crystallinity and more (111) and (110) crystal faces, and the two newly exposed crystal faces make water
  • the thermally modified gamma-alumina has more acid centers and more base centers.
  • the ⁇ -alumina after the hydrothermal treatment according to the present invention has a specific surface area of 150 to 300 m 2 /g and a pore volume of 0.3 to 1.0 cm 3 /g.
  • the present invention provides a light hydrocarbon desulfurization catalyst based on alumina crystal plane control, which is characterized in that ⁇ -alumina controlled by hydrothermal treatment according to the present invention is used as a carrier, and nickel and molybdenum are active. metal.
  • the active metal nickel is deposited on the crystal face (111) of the ⁇ -alumina after the hydrothermal treatment, and the active metal molybdenum is deposited on the crystal face (110) of the ⁇ -alumina controlled by the hydrothermal treatment. .
  • the light hydrocarbon desulfurization catalyst of the present invention is a highly active and highly selective catalyst which can be used to catalyze the action of mercaptans and diolefins (or olefins) in light hydrocarbons to form macromolecular sulfides.
  • the catalyst provided by the invention has high desulfurization activity, high hydrogenation selectivity of the diolefin, and the active component is not lost and is not easy to be deactivated, so the catalyst has a long operation period and has good industrial application prospects. .
  • the total weight of the catalyst is 100%, which comprises: 50 to 85 wt% of the hydrothermally controlled ⁇ -alumina;
  • nickel oxide 5 to 20% by weight of nickel oxide; preferably 10 to 20% by weight of nickel oxide, and
  • molybdenum oxide 2 to 15% by weight of molybdenum oxide; preferably 4 to 12% by weight of molybdenum oxide.
  • the light hydrocarbon desulfurization catalyst of the present invention based on 100% of the total weight of the catalyst, it comprises:
  • the carrier of the catalyst of the present invention is the ⁇ -alumina after the hydrothermal treatment of the present invention, and as described above, the ⁇ -alumina is characterized in that it has highly exposed (111) and (110) crystal faces, so that The active metal nickel (Ni) and molybdenum (Mo) in the catalyst of the invention can realize the crystal face selection and the preferred load on the ⁇ -alumina crystal face, and the metal Ni is excellent. It is first loaded on the newly exposed (111) crystal plane, while the metal Mo is preferentially loaded on the newly exposed (110) crystal plane. At the same time, the two active metals also form two different active crystal faces by the action of the modified ⁇ -alumina (111) and (110) crystal faces, respectively, thereby obtaining high activity and high selectivity.
  • a hydrocarbon desulfurization catalyst can retain olefins in the raw materials in the case of efficiently removing thiols and/or diolefins in light fractions such as liquefied petroleum gas, FCC gasoline, catalytic pyrolysis gasoline and coking gasoline, and the octane number RON of gasoline is only reduced by 0.3. At around the point, high value-added utilization of light hydrocarbons is achieved.
  • the present invention provides a method for preparing the light hydrocarbon desulfurization catalyst, the method comprising the steps of:
  • the auxiliary agent in the preparation method of the light hydrocarbon desulfurized alcohol catalyst of the present invention, is used in an amount of 1.0 to 3.5% by weight based on 100% by weight of the total of the catalyst carrier.
  • the aqueous solution of nitric acid has a mass fraction of 50 to 70% and an amount of 3.0 to 6.0% by weight.
  • the extrusion molding is to extrude the kneaded material into spherical particles, columnar particles or clover-like particles;
  • the particles have an equivalent diameter of from 2 to 10 mm.
  • the drying is carried out at a temperature of 80 to 150 ° C for 2 to 10 hours.
  • the calcination is carried out at a temperature of 300 to 600 ° C for 5 to 10 hours.
  • the drying is carried out at 70 to 140 ° C for 2 to 6 hours.
  • the calcination is calcined at 400 to 600 ° C for 3 to 10 h.
  • the calcination temperature and time in the step (a) are as described above, and the calcination temperature and time in the step (b) are as above. Said.
  • the precursor of the metallic nickel includes one of nickel nitrate, nickel acetate, nickel chloride and nickel sulfate or Several; preferably nickel nitrate and / or nickel acetate.
  • the precursor of the metal molybdenum comprises molybdate and/or molybdenum nitrate; preferably, the molybdate It is ammonium molybdate.
  • the precursor of the metallic nickel is nickel nitrate
  • the precursor of the metallic molybdenum is ammonium molybdate.
  • the auxiliary agent in the above catalyst preparation method may be a conventional pore former such as tianjing powder.
  • the impregnation method is a co-impregnation method or a stepwise impregnation method.
  • the co-impregnation method is an equal volume co-impregnation method; each step in the step-wise impregnation method is an equal volume impregnation method. More preferably, the impregnation method is an equal volume co-impregnation method.
  • the present invention provides the use of the light hydrocarbon desulfurization catalyst for applying the catalyst to the removal of mercaptans from liquefied petroleum gas, FCC gasoline, catalytic pyrolysis gasoline and/or coking gasoline and/or Or a diene; or the use of the catalyst to catalyze the selective hydrogenation of a diolefin.
  • the use of the light hydrocarbon desulfurization catalyst of the present invention can efficiently remove mercaptans and/or diolefins from light hydrocarbons such as liquefied petroleum gas, FCC gasoline, catalytic pyrolysis gasoline and/or coking gasoline.
  • light hydrocarbons such as liquefied petroleum gas, FCC gasoline, catalytic pyrolysis gasoline and/or coking gasoline.
  • the olefin in the raw material is retained, and the octane number RON of the gasoline is reduced by about 0.3 point, thereby achieving high added value utilization of the light hydrocarbon.
  • the present invention mainly provides a method for hydrothermal treatment of the ⁇ -alumina crystal face and a light hydrocarbon desulfurization catalyst based on the obtained hydrothermal treatment-controlled ⁇ -alumina.
  • the catalyst prepared by the hydrothermally modified ⁇ -alumina according to the invention has distinct physicochemical properties, and the most remarkable feature is that the two active metals realize the preferential selection of the crystal face on the ⁇ -alumina, that is, the metal Ni preferential load On the newly exposed (111) crystal plane, the metal Mo is preferentially loaded on the newly exposed (110) crystal plane.
  • the two active metals also form two different active crystal faces by respectively acting with the modified ⁇ -alumina (111) and (110) crystal faces.
  • Example 1 is a X-ray diffraction (XRD) spectrum of a hydrothermally treated ⁇ -alumina prepared by Example 1 and a non-hydrothermally treated ⁇ -alumina;
  • Example 2 is a transmission electron microscope (TEM) photograph of the hydrothermally treated ⁇ -alumina prepared in Example 1;
  • Example 3 is a TEM photograph of a catalyst RM-1 prepared by using the hydrothermally treated ⁇ -alumina prepared in Example 1;
  • Figure 4 is a TEM photograph of a catalyst PH-1 prepared by using a hydrothermally treated ⁇ -alumina
  • Figure 5 is a graph showing the evaluation results of the reaction properties of RM-1 and PH-1 catalysts for the desulfurization of gasoline simulating compounds (ethanethiol and isoamyl olefin);
  • Figure 6 is a graph comparing the sulfur distribution in the product catalyzed by the RM-1 catalyst with the sulfur distribution in the feedstock oil.
  • the present embodiment provides a light hydrocarbon desulfurization catalyst based on ⁇ -alumina crystal surface control and a preparation method thereof, which are implemented by the following steps:
  • FIG. 1 is a XRD spectrum of the hydrothermally treated ⁇ -alumina and the unhydrothermally treated ⁇ -alumina obtained in the present example.
  • 1(a) is an XRD spectrum of an alumina precursor boehmite (a product before calcination)
  • (b) of FIG. 1 is an XRD spectrum of the calcined alumina product. It can be seen from Fig. 1 that the peaks of the two products before and after hydrothermal treatment are basically the same as those of the boehmite and alumina standard XRD cards, and the characteristic diffraction peaks after hydrothermal treatment are obviously enhanced, especially in Fig. 1.
  • FIG. 2 is a TEM photograph of the hydrothermally treated ⁇ -alumina obtained in the present embodiment, wherein (a) and (b) of FIG. 2 are TEM photographs of the ⁇ 110 ⁇ crystal plane of the alumina, and FIG. 2(c) And (d) is a TEM photograph of the ⁇ 111 ⁇ crystal plane of alumina, and the above TEM photograph can prove that new (111) and (110) crystal faces appear on the surface of the ⁇ -alumina after hydrothermal treatment.
  • 100 g of the above hydrothermally treated ⁇ -alumina powder and 100 g of the above non-hydrothermally treated ⁇ -alumina powder were respectively kneaded with 2 g of phthalocyanine powder, 4.5 g of concentrated nitric acid having a mass fraction of 65%, and 50 g of water.
  • Spherical particles with a diameter of 3 mm are dried at 120 ° C for 4 h and calcined at 520 ° C for 3 h at constant temperature to obtain ⁇ - based on hydrothermal treatment.
  • Figure 3 and Figure 4 are TEM photographs of the two catalysts RM-1 and PH-1, respectively. It can be seen from the photograph that the active metal achieves the preferential selection of the crystal face in the RM-1 catalyst, that is, the active metal Ni preferential load. A (101) crystal plane is formed on the (111) crystal plane, and the active metal Mo is preferentially supported on the (110) crystal plane to form a (100) crystal plane. No similar selective loading of the active metal was observed in the PH-1 catalyst.
  • the present embodiment provides a light hydrocarbon desulfurization catalyst based on ⁇ -alumina crystal plane control and a preparation method thereof, which are implemented by the following steps:
  • ⁇ -alumina powder 100 g was mixed with 2 g of phthalocyanine powder, 4.5 g of concentrated nitric acid having a mass fraction of 65%, and 50 g of water to prepare spherical particles having a diameter of 2 mm and a length of 3 to 4 mm.
  • the catalyst carrier of this example was obtained by drying at 120 ° C for 4 h and calcining at 500 ° C for 5 h.
  • the present embodiment provides a light hydrocarbon desulfurization catalyst based on ⁇ -alumina crystal plane control and a preparation method thereof, which are implemented by the following steps:
  • Example ⁇ -alumina powder after hydrothermal treatment 1L of deionized water and 1g mass fraction of 65% concentrated nitric acid mixed to prepare a solution of nitric acid, to which was then added 2 O 3 powder 400g ⁇ -Al, the ⁇ -Al 2 O 3 surface area powder was 260m 2 / g, The pore volume is 0.78cm 3 /g, and the mixture is uniformly mixed and then charged into the reaction vessel. The mixture is heated in an oven at 180 ° C for 6 hours. The solid product is filtered, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours.
  • Example ⁇ -alumina powder after hydrothermal treatment 1L of deionized water and 1g mass fraction of 65% concentrated nitric acid mixed to prepare a solution of nitric acid, to which was then added 2 O 3 powder 400g ⁇ -Al, the ⁇ -Al 2 O 3 surface area powder was 260m 2 / g, The pore volume is 0.
  • ⁇ -alumina powder 100 g was mixed with 2 g of phthalocyanine powder, 4.5 g of concentrated nitric acid having a mass fraction of 65%, and 50 g of water to prepare a clover-shaped granule having a diameter of 2 mm and a length of 3 to 4 mm.
  • the catalyst carrier of this example was obtained by drying at 120 ° C for 4 h and calcining at 500 ° C for 5 h.
  • RM-1 and PH-1 catalyst particles with a diameter of 2 ⁇ 4mm were respectively loaded into the micro fixed bed reactor.
  • the pre-vulcanization conditions are: a pressure of 2.8 MPa, a hydrogen/presulfurized oil volume ratio of 200:1, a pre-sulfided oil liquid hour volume space velocity of 2 h -1 , a reactor temperature of a program control method, and a constant temperature of 150 ° C for 2 h.
  • Fig. 5 is a graph showing the evaluation results of the reaction properties of the two catalysts RM-1 and PH-1 for the desulfurization of simulated gasoline (ethyl mercaptan and isoamyl). It can be seen from Fig.
  • the RM-1 catalyst can catalyze the complete reaction of ethanethiol with a desulfurization rate of 100%; while the conversion of ethanethiol of the PH-1 catalyst is only 87.7%, which is significantly lower than that of the RM-1 catalyst.
  • the reaction products obtained on the two catalysts were identical, indicating that the reaction mechanisms of the two catalysts were the same.
  • the operation procedure in this embodiment is the same as that in the fourth embodiment, and the catalyst loading amount, the filling method, the pre-vulcanization conditions, the analysis method of the product, and the like are also the same as in the fourth embodiment.
  • the specific reaction conditions for catalytic cracking gasoline desulfurization are: pressure of 2.0 MPa, temperature of 130 ° C, hydrogen oil volume ratio of 10:1, liquid phase volume space velocity of 3.5 h -1 . The results obtained are shown in Table 1 below.
  • the operation steps in this example were the same as in Example 4.
  • the catalyst loading amount, the filling method, the pre-vulcanization conditions, and the analysis method of the product were also the same as in Example 4, but the reaction raw material was coking gasoline having a higher mercaptan content.
  • the specific reaction conditions of the mercaptan are: a pressure of 2.5 MPa, a reaction temperature of 135 ° C, a hydrogen oil volume ratio of 8:1, and a liquid volume volume velocity of 3 h -1 .
  • the results of the RM-2 catalyst evaluation product are shown in Table 2.
  • Table 2 and Table 1 are basically the same, which indicates that the catalyst coke gasoline also has excellent selectivity and desulfurization. Alcohol reactivity.
  • the operation procedure in this example was the same as in Example 4.
  • the catalyst loading amount, the charging method, the pre-vulcanization conditions, and the analysis method of the product were also the same as in Example 4, but the reaction raw material was liquefied petroleum gas.
  • the specific reaction conditions of the mercaptan are: a pressure of 2.0 MPa, a reaction temperature of 110 ° C, a hydrogen oil volume ratio of 6:1, and a liquid volume volume velocity of 3 h -1 .
  • the results of the reaction of the RM-3 catalyst for the liquefied petroleum gas desulfurization reaction are shown in Table 3.
  • composition raw material product Hydrogen sulfide, ppm 8.2 0 Methyl mercaptan, ppm 414.9 4.3 Ethyl mercaptan, ppm 217.5 1.7 Olefins, v% 59.74 57.74 Yield, wt% 94.57

Abstract

A light hydrocarbon sweetening catalyst on the basis of alumina crystal surface regulation and a preparation method therefor. The catalyst uses hydrothermally treated γ-alumina as a carrier, and nickel and molybdenum as active metals. The catalyst obtained from preparation can be used to catalyze a reaction between mercaptan and diene in light hydrocarbon to produce a macromolecular sulfide, as well as catalyze the selective hydrogenation of diene. Said catalyst has good activity, selectivity and resistance to inactivation.

Description

基于氧化铝晶面调控的轻质烃类脱硫醇催化剂及其制法Light hydrocarbon desulfurization catalyst based on alumina crystal plane control and preparation method thereof 技术领域Technical field
本发明涉及基于氧化铝晶面调控的轻质烃类脱硫醇催化剂及其制法，属于石油产品精制技术领域。The invention relates to a light hydrocarbon desulfurization catalyst based on alumina crystal plane regulation and a preparation method thereof, and belongs to the technical field of petroleum product refining.
背景技术Background technique
随着环保法规的日益严格，世界各国对石油加工产品的质量提出了越来越严格的要求，特别是对石油加工产品硫含量的限制越来越严格。轻质石油产品中所含的硫化物主要为硫醇(RSH)、硫醚(RSR)等，其中硫醇对产品质量的影响最大，不仅具有恶臭味，很强的腐蚀性，还会影响产品的安定性。With the increasingly strict environmental protection regulations, countries around the world have put more and more strict requirements on the quality of petroleum processing products, especially the restrictions on the sulfur content of petroleum processing products are becoming more and more strict. The sulfides contained in light petroleum products are mainly mercaptans (RSH), thioethers (RSR), etc. Among them, mercaptans have the greatest impact on product quality, not only have bad odor, but also strong corrosiveness, and also affect Product stability.
轻质石油产品的脱硫醇技术一直沿用UOP公司开发的Merox催化氧化脱硫醇工艺，其原理是利用硫醇分子的弱酸性和硫醇负离子易被氧化生成二硫化物这两个特性脱除硫醇，主要的化学反应为：The desulfurization technology of light petroleum products has been following the Merox catalytic oxidative desulfurization process developed by UOP. The principle is to remove the mercaptan by utilizing the weak acidity of thiol molecules and the easy oxidation of thiol anions to disulfides. The main chemical reactions are:
NaOH+RSH→RSNa+H2O          (1)NaOH+RSH→RSNa+H 2 O (1)
2RSNa+0.5O2+H2O→RSSR+2NaOH       (2)2RSNa+0.5O 2 +H 2 O→RSSR+2NaOH (2)
上述Merox工艺存在的主要问题是：仅能对硫醇进行转化，不能实现石油产品的深度脱硫；产生大量的碱渣排放，严重污染环境。The main problems of the above Merox process are: only the conversion of mercaptans can not achieve deep desulfurization of petroleum products; the production of a large amount of alkali residue discharge, seriously polluting the environment.
CN101077984B公开了一种液化石油气深度脱硫的方法，该方法为无苛性碱脱臭技术；CN100462146C公开了用于转化汽油所含硫醇的催化剂的制备方法，其属于无碱液脱臭技术，以上两种技术在使用过程中分别需要不断补加碱液或水，因而并没有真正解决轻质石油加工产品的深度脱硫问题和液体碱排放引起的环境污染问题。CN101077984B discloses a method for deep desulfurization of liquefied petroleum gas, which is a caustic free deodorization technology; CN100462146C discloses a preparation method of a catalyst for converting mercaptan contained in gasoline, which belongs to an alkali-free deodorization technology, the above two The technology needs to continuously add lye or water in the process of use, so it does not really solve the problem of deep desulfurization of light petroleum processing products and environmental pollution caused by liquid alkali discharge.
针对上述问题，US6692635B2公开了一种生产含硫量低的汽油的方法，该方法中采用新的脱硫醇技术。该技术将全馏分汽油原料通入一个选择性加氢反应器，使硫醇与汽油中的烯烃或者二烯烃发生醚化反应生成高沸点的含硫化合物，然后在一个分馏塔中对选择性加氢产物进行分馏，得到不含硫醇且总硫含量较低的轻汽油馏分和硫含量较高的重汽油馏分。该技术的特点是通过硫醇与二烯烃的加成反应实现硫醇从轻汽油馏分中的有效脱除和向重汽油馏分的转移，同时实现了硫醇的脱除和轻汽油总硫含量的降低，克服了传统Merox工艺不能深度脱硫和存在碱渣排放的问题。In response to the above problems, US 6,692,635 B2 discloses a process for producing gasoline having a low sulfur content, in which a new desulfurization technique is employed. The technology feeds the whole fraction gasoline feedstock into a selective hydrogenation reactor to etherify the olefin or the diene in the gasoline to form a high-boiling sulfur-containing compound, and then selectively increases the concentration in a fractionator. The hydrogen product is subjected to fractional distillation to obtain a light gasoline fraction containing no mercaptan and having a low total sulfur content, and a heavy gasoline fraction having a high sulfur content. The technology is characterized by the effective removal of mercaptan from the light gasoline fraction and the transfer to the heavy gasoline fraction by the addition reaction of mercaptan and diolefin, and at the same time, the removal of mercaptan and the total sulfur content of light gasoline are realized. The reduction overcomes the problem that the conventional Merox process cannot be deeply desulfurized and the presence of alkali residue is discharged.
CN1229838A公开了一种烃油的转化方法，该方法是将原料油与一种加氢精制催化剂 在加氢脱硫醇的工艺条件下脱硫醇，所述加氢精制催化剂含有负载在氧化铝载体上的氧化钨(钼)、氧化镍和氧化钴，其中氧化钨(钼)的含量为4～10wt％，氧化镍的含量为1～5wt％，氧化钴的含量为0.01～0.1wt％，镍和钴的总原子数与镍、钴、钨(钼)的总原子数之比为0.3～0.9。该催化剂在用于处理FCC汽油时，虽然可将硫醇含量从212μg/g降低到10μg/g，但汽油研究法辛烷值(RON)损失3.3个单位，马达法辛烷值(MON)损失3.0个单位。CN1229838A discloses a method for converting hydrocarbon oil by using a feedstock oil and a hydrotreating catalyst Desulfurizing the mercaptan under the process conditions of hydrodesulfurization, the hydrorefining catalyst comprising tungsten oxide (molybdenum), nickel oxide and cobalt oxide supported on an alumina carrier, wherein the content of tungsten oxide (molybdenum) is 4 to 10 wt %, the content of nickel oxide is 1 to 5 wt%, the content of cobalt oxide is 0.01 to 0.1 wt%, and the ratio of the total number of atoms of nickel and cobalt to the total number of atoms of nickel, cobalt, tungsten (molybdenum) is 0.3 to 0.9. The catalyst can reduce the thiol content from 212μg/g to 10μg/g when used to treat FCC gasoline, but the gasoline research octane number (RON) loss is 3.3 units, motor octane number (MON) loss. 3.0 units.
CN102451694A公开了一种加氢脱硫醇催化剂及其制备方法和应用。该催化剂以氧化铝或含硅氧化铝为载体，以磷为助剂组分，以铜和锌为活性组分，以催化剂质量为基准，助剂磷的含量为0.5～3.0wt％，氧化锌的含量为3～15wt％，氧化铜的含量为5～30wt％。因该催化剂具有很强的加氢活性，在用于处理全馏分FCC汽油时，硫醇含量由38μg/g降低到3μg/g，同时烯烃含量也由25v％降低到20v％，RON损失高达1.3个单位。CN102451694A discloses a hydrodesulfurization catalyst and a preparation method and application thereof. The catalyst uses alumina or silica-containing alumina as a carrier, phosphorus as an auxiliary component, copper and zinc as active components, and based on the catalyst quality, the phosphorus content of the promoter is 0.5-3.0 wt%, zinc oxide. The content is 3 to 15% by weight, and the content of copper oxide is 5 to 30% by weight. Due to the strong hydrogenation activity of the catalyst, the thiol content was reduced from 38 μg/g to 3 μg/g when the whole fraction FCC gasoline was used, and the olefin content was also reduced from 25 v% to 20 v%, and the RON loss was as high as 1.3. Units.
综上可知道，为克服以上现有技术的缺陷，寻找一种全新的加氢脱硫醇催化剂是本领域技术人员亟需解决的问题之一。In summary, in order to overcome the above drawbacks of the prior art, finding a new hydrodesulfurization catalyst is one of the problems that those skilled in the art need to solve.
发明内容Summary of the invention
为解决上述问题，本发明的目的在于提供水热处理调控γ-氧化铝晶面的方法，该方法能够使所得γ-氧化铝具有高度暴露的(111)和(110)晶面。In order to solve the above problems, an object of the present invention is to provide a method of hydrothermal treatment of a γ-alumina crystal face which enables the obtained γ-alumina to have highly exposed (111) and (110) crystal faces.
本发明的另一目的在于提供由所述方法得到的水热处理调控后的γ-氧化铝。Another object of the present invention is to provide a γ-alumina controlled by hydrothermal treatment obtained by the method.
本发明的再一目的在于提供以所述水热处理调控后的γ-氧化铝作为载体的轻质烃类脱硫醇催化剂。该催化剂可在高效脱除液化石油气、FCC汽油、催化裂解汽油和/或焦化汽油等轻馏分中的硫醇和/或二烯烃的情况下，保留原料中的烯烃，汽油的辛烷值RON只降低0.3个点左右，实现轻质烃类的高附加值利用。Still another object of the present invention is to provide a light hydrocarbon desulfurization catalyst using γ-alumina controlled by the hydrothermal treatment as a carrier. The catalyst can retain olefins in the raw materials in the case of efficiently removing thiols and/or diolefins in light fractions such as liquefied petroleum gas, FCC gasoline, catalytic pyrolysis gasoline and/or coking gasoline, and the octane number of gasoline is only RON. Reduce the value of about 0.3 points to achieve high value-added use of light hydrocarbons.
本发明的再一目的在于提供所述轻质烃类脱硫醇催化剂的制备方法与应用。It is still another object of the present invention to provide a process and application for the preparation of the light hydrocarbon desulfurization catalyst.
为实现上述目的，本发明一方面提供一种水热处理调控γ-氧化铝晶面的方法，所述方法包括：将γ-氧化铝(γ-Al2O3)原料加入到酸性水溶液中，水热处理，过滤、洗涤、干燥及焙烧得水热处理调控后的γ-氧化铝。In order to achieve the above object, an aspect of the invention provides a method for hydrothermal treatment of a γ-alumina crystal face, the method comprising: adding a γ-alumina (γ-Al 2 O 3 ) raw material to an acidic aqueous solution, water Heat treatment, filtration, washing, drying and calcination to obtain γ-alumina controlled by hydrothermal treatment.
由本发明所述水热处理调控γ-氧化铝晶面的方法得到的改性后γ-氧化铝与未改性的γ-氧化铝具有明显不同的物化性质，其中最显著的差别是水热改性后的γ-氧化铝具有更高的结晶度，并在其表面暴露出更多的(111)和(110)两种晶面，这两种新暴露的晶面使得水热改性后的γ-氧化铝同时具有更多的酸中心和更多的碱中心。应用该水热处理调控γ-氧化铝可制备出本发明所述催化剂，该催化剂具有如下所述的优良性能。 The modified γ-alumina obtained by the hydrothermal treatment of the γ-alumina crystal surface of the present invention has significantly different physicochemical properties from the unmodified γ-alumina, the most significant difference being hydrothermal modification. The later γ-alumina has higher crystallinity and exposes more (111) and (110) crystal faces on its surface. These two newly exposed crystal faces make hydrothermally modified γ - Alumina has more acid centers and more bases at the same time. The catalyst of the present invention can be prepared by using the hydrothermal treatment to adjust γ-alumina, which has excellent properties as described below.
根据本发明的具体实施方案，在本发明所述水热处理调控γ-氧化铝晶面的方法中，水热处理的温度为120～200℃；优选水热处理3～12h。According to a specific embodiment of the present invention, in the method of hydrothermal treatment of the γ-alumina crystal face of the present invention, the temperature of the hydrothermal treatment is 120 to 200 ° C; preferably, the hydrothermal treatment is 3 to 12 h.
根据本发明的具体实施方案，在本发明所述水热处理调控γ-氧化铝晶面的方法中，焙烧温度为400～550℃；优选焙烧5～15h。According to a specific embodiment of the present invention, in the method for hydrotreating the γ-alumina crystal face of the present invention, the calcination temperature is 400 to 550 ° C; preferably, the calcination is 5 to 15 h.
根据本发明的具体实施方案，在本发明所述水热处理调控γ-氧化铝晶面的方法中，所述γ-氧化铝原料的比表面积为200～400m2/g，孔容为0.3～0.8cm3/g。According to a specific embodiment of the present invention, in the hydrothermal treatment of the γ-alumina crystal surface of the present invention, the γ-alumina raw material has a specific surface area of 200 to 400 m 2 /g and a pore volume of 0.3 to 0.8. Cm 3 /g.
根据本发明的具体实施方案，在本发明所述水热处理调控γ-氧化铝晶面的方法中，所述酸性水溶液包括硝酸水溶液、盐酸、草酸水溶液、醋酸水溶液和柠檬酸水溶液中的一种或几种；优选地，所述酸性水溶液的pH值为0～4；进一步优选地，所用酸性水溶液为硝酸水溶液；更优选地，所述酸性水溶液为pH值为0～4的硝酸水溶液。According to a specific embodiment of the present invention, in the hydrothermal treatment of the γ-alumina crystal surface of the present invention, the acidic aqueous solution comprises one of an aqueous solution of nitric acid, hydrochloric acid, an aqueous solution of oxalic acid, an aqueous solution of acetic acid and an aqueous solution of citric acid or Preferably, the acidic aqueous solution has a pH of 0 to 4; more preferably, the acidic aqueous solution used is an aqueous solution of nitric acid; more preferably, the acidic aqueous solution is an aqueous solution of nitric acid having a pH of 0 to 4.
根据本发明的具体实施方案，在本发明所述水热处理调控γ-氧化铝晶面的方法中，所述γ-氧化铝原料与所述酸性水溶液的质量比为1:1～1:6；优选1:2～1:4。According to a specific embodiment of the present invention, in the method of hydrothermal treatment of the γ-alumina crystal surface of the present invention, the mass ratio of the γ-alumina raw material to the acidic aqueous solution is 1:1 to 1:6; It is preferably 1:2 to 1:4.
根据本发明的具体实施方案，在本发明所述水热处理调控γ-氧化铝晶面的方法中，水热处理的温度为120～200℃，优选160～200℃。进一步优选地，水热处理时间为3～12h，例如5～12。According to a specific embodiment of the present invention, in the hydrothermal treatment of the γ-alumina crystal surface of the present invention, the hydrothermal treatment has a temperature of from 120 to 200 ° C, preferably from 160 to 200 ° C. Further preferably, the hydrothermal treatment time is from 3 to 12 h, for example from 5 to 12.
根据本发明的具体实施方案，在本发明所述水热处理调控γ-氧化铝晶面的方法中，所述洗涤是采用去离子水洗涤。According to a particular embodiment of the invention, in the method of hydrothermal treatment of the gamma-alumina crystal face of the invention, the washing is carried out using deionized water.
根据本发明的具体实施方案，在本发明所述水热处理调控γ-氧化铝晶面的方法中，所述干燥的温度为80～200℃，优选100～150℃。According to a specific embodiment of the present invention, in the hydrothermal treatment of the present invention, the drying temperature is 80 to 200 ° C, preferably 100 to 150 ° C.
根据本发明的具体实施方案，在本发明所述水热处理调控γ-氧化铝晶面的方法中，所述焙烧是在100～550℃焙烧5～15h；优选的焙烧温度为400～550℃。According to a specific embodiment of the present invention, in the method of hydrothermal treatment of the γ-alumina crystal face of the present invention, the calcination is calcined at 100 to 550 ° C for 5 to 15 h; and the preferred calcination temperature is 400 to 550 ° C.
根据本发明的具体实施方案，在本发明所述水热处理调控γ-氧化铝晶面的方法中，水热处理温度如上所述，且焙烧温度如上所述。优选地，水热处理温度及水热处理的时间如上所述，且焙烧温度及焙烧时间如上所述。According to a specific embodiment of the present invention, in the method of hydrothermal treatment of the γ-alumina crystal face of the present invention, the hydrothermal treatment temperature is as described above, and the calcination temperature is as described above. Preferably, the hydrothermal treatment temperature and the time of the hydrothermal treatment are as described above, and the calcination temperature and the calcination time are as described above.
根据本发明的具体实施方案，在本发明所述水热处理调控γ-氧化铝晶面的方法中，酸性水溶液的种类如上所述，且水热处理温度如上所述。优选地，酸性水溶液的种类及用量如上所述，且水热处理温度及水热处理时间如上所述。According to a specific embodiment of the present invention, in the method of hydrothermal treatment of the γ-alumina crystal face of the present invention, the kind of the acidic aqueous solution is as described above, and the hydrothermal treatment temperature is as described above. Preferably, the kind and amount of the acidic aqueous solution are as described above, and the hydrothermal treatment temperature and the hydrothermal treatment time are as described above.
根据本发明的具体实施方案，在本发明所述水热处理调控γ-氧化铝晶面的方法中，酸性水溶液的种类如上所述，且焙烧温度如上所述。优选地，酸性水溶液的种类及用量如上所述，且焙烧温度及焙烧时间如上所述。 According to a specific embodiment of the present invention, in the method of hydrothermal treatment of the γ-alumina crystal face of the present invention, the kind of the acidic aqueous solution is as described above, and the calcination temperature is as described above. Preferably, the kind and amount of the acidic aqueous solution are as described above, and the calcination temperature and the calcination time are as described above.
根据本发明的具体实施方案，在本发明所述水热处理调控γ-氧化铝晶面的方法中，酸性水溶液的种类如上所述，水热处理温度如上所述，且焙烧温度如上所述。优选地，酸性水溶液的种类及用量如上所述，水热处理温度及时间如上所述，且焙烧温度及焙烧时间如上所述。According to a specific embodiment of the present invention, in the method of hydrothermal treatment of the γ-alumina crystal face of the present invention, the kind of the acidic aqueous solution is as described above, the hydrothermal treatment temperature is as described above, and the calcination temperature is as described above. Preferably, the kind and amount of the acidic aqueous solution are as described above, the hydrothermal treatment temperature and time are as described above, and the calcination temperature and the calcination time are as described above.
再一方面，本发明提供由所述水热处理调控γ-氧化铝晶面的方法得到的水热处理调控后的γ-氧化铝。相较于现有γ-氧化铝，该水热处理调控后的γ-氧化铝具有更高的结晶度以及更多的(111)和(110)晶面，这两种新暴露的晶面使得水热改性后的γ-氧化铝同时具有更多的酸中心和更多的碱中心。In still another aspect, the present invention provides a hydrothermally controlled γ-alumina obtained by the hydrothermal treatment of a γ-alumina crystal face. Compared with the existing γ-alumina, the hydrothermally controlled γ-alumina has higher crystallinity and more (111) and (110) crystal faces, and the two newly exposed crystal faces make water The thermally modified gamma-alumina has more acid centers and more base centers.
根据本发明的具体实施方案，本发明所述水热处理调控后的γ-氧化铝的比表面积为150～300m2/g，孔容为0.3～1.0cm3/g。According to a specific embodiment of the present invention, the γ-alumina after the hydrothermal treatment according to the present invention has a specific surface area of 150 to 300 m 2 /g and a pore volume of 0.3 to 1.0 cm 3 /g.
再一方面，本发明提供一种基于氧化铝晶面调控的轻质烃类脱硫醇催化剂，该催化剂是以本发明所述水热处理调控后的γ-氧化铝为载体，以镍及钼为活性金属。优选地，活性金属镍沉积于所述水热处理调控后的γ-氧化铝的晶面(111)上，活性金属钼沉积于所述水热处理调控后的γ-氧化铝的晶面(110)上。In a further aspect, the present invention provides a light hydrocarbon desulfurization catalyst based on alumina crystal plane control, which is characterized in that γ-alumina controlled by hydrothermal treatment according to the present invention is used as a carrier, and nickel and molybdenum are active. metal. Preferably, the active metal nickel is deposited on the crystal face (111) of the γ-alumina after the hydrothermal treatment, and the active metal molybdenum is deposited on the crystal face (110) of the γ-alumina controlled by the hydrothermal treatment. .
本发明所述轻质烃类脱硫醇催化剂为高活性和高选择性催化剂，其可用于催化轻质烃类中硫醇与二烯烃(或者烯烃)作用生成大分子硫化物。与现有催化剂相比，本发明所提供的催化剂脱硫醇活性高、双烯烃加氢选择性高，且活性组分不流失、不易失活，因而催化剂运转周期长，具有较好的工业应用前景。The light hydrocarbon desulfurization catalyst of the present invention is a highly active and highly selective catalyst which can be used to catalyze the action of mercaptans and diolefins (or olefins) in light hydrocarbons to form macromolecular sulfides. Compared with the existing catalyst, the catalyst provided by the invention has high desulfurization activity, high hydrogenation selectivity of the diolefin, and the active component is not lost and is not easy to be deactivated, so the catalyst has a long operation period and has good industrial application prospects. .
优选地，在本发明所述轻质烃类脱硫醇催化剂中，以该催化剂的总重量为100％计，其包括：50～85wt％的所述水热处理调控后的γ-氧化铝；Preferably, in the light hydrocarbon desulfurization catalyst of the present invention, the total weight of the catalyst is 100%, which comprises: 50 to 85 wt% of the hydrothermally controlled γ-alumina;
5～20wt％的氧化镍；优选10～20wt％的氧化镍，及5 to 20% by weight of nickel oxide; preferably 10 to 20% by weight of nickel oxide, and
2～15wt％的氧化钼；优选4～12wt％的氧化钼。2 to 15% by weight of molybdenum oxide; preferably 4 to 12% by weight of molybdenum oxide.
进一步优选地，在本发明所述轻质烃类脱硫醇催化剂中，以该催化剂的总重量为100％计，其包括：Further preferably, in the light hydrocarbon desulfurization catalyst of the present invention, based on 100% of the total weight of the catalyst, it comprises:
50～85wt％的所述水热处理调控后的γ-氧化铝；50 to 85 wt% of the hydrothermally controlled γ-alumina;
10～20wt％的氧化镍，及10 to 20% by weight of nickel oxide, and
4～12wt％的氧化钼。4 to 12% by weight of molybdenum oxide.
本发明所述催化剂的载体为本发明所述水热处理调控后的γ-氧化铝，如上所述，该γ-氧化铝的特征在于其具有高度暴露的(111)和(110)晶面，使得本发明所述催化剂中的活性金属镍(Ni)和钼(Mo)可在该γ-氧化铝晶面上实现晶面选择优选负载，金属Ni优 先负载在新暴露的(111)晶面上，而金属Mo优先负载在新暴露的(110)晶面上。同时，二种活性金属也通过分别与改性后的γ-氧化铝(111)和(110)晶面的作用形成了两种不同的活性晶面，从而获得了高活性和高选择性的轻质烃类脱硫醇催化剂。该催化剂可在高效脱除液化石油气、FCC汽油、催化裂解汽油和焦化汽油等轻馏分中的硫醇和/或二烯烃的情况下，保留原料中的烯烃，汽油的辛烷值RON只降低0.3个点左右，从而实现轻质烃类的高附加值利用。The carrier of the catalyst of the present invention is the γ-alumina after the hydrothermal treatment of the present invention, and as described above, the γ-alumina is characterized in that it has highly exposed (111) and (110) crystal faces, so that The active metal nickel (Ni) and molybdenum (Mo) in the catalyst of the invention can realize the crystal face selection and the preferred load on the γ-alumina crystal face, and the metal Ni is excellent. It is first loaded on the newly exposed (111) crystal plane, while the metal Mo is preferentially loaded on the newly exposed (110) crystal plane. At the same time, the two active metals also form two different active crystal faces by the action of the modified γ-alumina (111) and (110) crystal faces, respectively, thereby obtaining high activity and high selectivity. A hydrocarbon desulfurization catalyst. The catalyst can retain olefins in the raw materials in the case of efficiently removing thiols and/or diolefins in light fractions such as liquefied petroleum gas, FCC gasoline, catalytic pyrolysis gasoline and coking gasoline, and the octane number RON of gasoline is only reduced by 0.3. At around the point, high value-added utilization of light hydrocarbons is achieved.
再一方面，本发明提供所述轻质烃类脱硫醇催化剂的制备方法，所述方法包括如下步骤：In still another aspect, the present invention provides a method for preparing the light hydrocarbon desulfurization catalyst, the method comprising the steps of:
(a)将本发明所述水热处理调控后的γ-氧化铝、助剂和硝酸水溶液混合后混捏、挤压成型、干燥及焙烧，得催化剂载体；(a) mixing the γ-alumina, the auxiliary agent and the aqueous nitric acid solution after the hydrothermal treatment according to the present invention, kneading, extruding, drying and calcining to obtain a catalyst carrier;
(b)采用浸渍法将金属镍的前驱体、金属钼的前驱体负载在步骤(a)制得的催化剂载体上，干燥并焙烧后，得所述轻质烃类脱硫醇催化剂。(b) The precursor of the metallic nickel and the precursor of the metallic molybdenum are supported by the impregnation method on the catalyst carrier obtained in the step (a), dried and calcined to obtain the light hydrocarbon desulfurized alcohol catalyst.
根据本发明的具体实施方案，在本发明所述轻质烃类脱硫醇催化剂的制备方法中，以所述催化剂载体的总重量为100％计，所述助剂的用量为1.0～3.5wt％，所述硝酸水溶液的质量分数为50～70％，其用量为3.0～6.0wt％。According to a specific embodiment of the present invention, in the preparation method of the light hydrocarbon desulfurized alcohol catalyst of the present invention, the auxiliary agent is used in an amount of 1.0 to 3.5% by weight based on 100% by weight of the total of the catalyst carrier. The aqueous solution of nitric acid has a mass fraction of 50 to 70% and an amount of 3.0 to 6.0% by weight.
根据本发明的具体实施方案，在本发明所述轻质烃类脱硫醇催化剂的制备方法中，所述挤压成型是将混捏后的物料挤压成球状颗粒、柱状颗粒或三叶草状颗粒；优选地，所述颗粒的当量直径为2～10mm。According to a specific embodiment of the present invention, in the method for preparing a light hydrocarbon desulfurization catalyst according to the present invention, the extrusion molding is to extrude the kneaded material into spherical particles, columnar particles or clover-like particles; The particles have an equivalent diameter of from 2 to 10 mm.
根据本发明的具体实施方案，在本发明所述轻质烃类脱硫醇催化剂的制备方法的步骤(a)中，所述干燥是在温度为80～150℃干燥2～10h。According to a specific embodiment of the present invention, in the step (a) of the method for producing a light hydrocarbon desulfurized alcohol catalyst according to the present invention, the drying is carried out at a temperature of 80 to 150 ° C for 2 to 10 hours.
根据本发明的具体实施方案，在本发明所述轻质烃类脱硫醇催化剂的制备方法的步骤(a)中，所述焙烧是在温度为300～600℃焙烧5～10h。According to a specific embodiment of the present invention, in the step (a) of the method for producing a light hydrocarbon desulfurized alcohol catalyst according to the present invention, the calcination is carried out at a temperature of 300 to 600 ° C for 5 to 10 hours.
根据本发明的具体实施方案，在本发明所述轻质烃类脱硫醇催化剂的制备方法的步骤(b)中，所述干燥是在70～140℃干燥2～6h。According to a specific embodiment of the present invention, in the step (b) of the method for producing a light hydrocarbon desulfurized alcohol catalyst of the present invention, the drying is carried out at 70 to 140 ° C for 2 to 6 hours.
根据本发明的具体实施方案，在本发明所述轻质烃类脱硫醇催化剂的制备方法的步骤(b)中，所述焙烧是在400～600℃焙烧3～10h。According to a specific embodiment of the present invention, in the step (b) of the method for producing a light hydrocarbon desulfurized alcohol catalyst of the present invention, the calcination is calcined at 400 to 600 ° C for 3 to 10 h.
根据本发明的具体实施方案，在本发明所述轻质烃类脱硫醇催化剂的制备方法中，步骤(a)中的焙烧温度及时间如上所述，步骤(b)中的焙烧温度及时间如上所述。According to a specific embodiment of the present invention, in the preparation method of the light hydrocarbon desulfurization catalyst of the present invention, the calcination temperature and time in the step (a) are as described above, and the calcination temperature and time in the step (b) are as above. Said.
根据本发明的具体实施方案，在本发明所述轻质烃类脱硫醇催化剂的制备方法中，所述金属镍的前驱体包括硝酸镍、乙酸镍、氯化镍和硫酸镍中的一种或几种；优选硝酸镍和 /或乙酸镍。According to a specific embodiment of the present invention, in the method for producing a light hydrocarbon desulfurization catalyst according to the present invention, the precursor of the metallic nickel includes one of nickel nitrate, nickel acetate, nickel chloride and nickel sulfate or Several; preferably nickel nitrate and / or nickel acetate.
根据本发明的具体实施方案，在本发明所述轻质烃类脱硫醇催化剂的制备方法中，所述金属钼的前驱体包括钼酸盐和/或硝酸钼；优选地，所述钼酸盐为钼酸铵。According to a specific embodiment of the present invention, in the method for producing a light hydrocarbon desulfurization catalyst according to the present invention, the precursor of the metal molybdenum comprises molybdate and/or molybdenum nitrate; preferably, the molybdate It is ammonium molybdate.
优选地，在本发明所述轻质烃类脱硫醇催化剂的制备方法中，所述金属镍的前驱体为硝酸镍，所述金属钼的前驱体为钼酸铵。Preferably, in the method for preparing a light hydrocarbon desulfurization catalyst according to the present invention, the precursor of the metallic nickel is nickel nitrate, and the precursor of the metallic molybdenum is ammonium molybdate.
本发明所述轻质烃类脱硫醇催化剂的制备方法中，在上述催化剂制备方法中的助剂可以是常规的造孔剂，例如田菁粉。In the preparation method of the light hydrocarbon desulfurization catalyst of the present invention, the auxiliary agent in the above catalyst preparation method may be a conventional pore former such as tianjing powder.
根据本发明的具体实施方案，在本发明所述轻质烃类脱硫醇催化剂的制备方法中，所述浸渍法为共浸渍法或分步浸渍法。优选地，所述共浸渍法为等体积共浸渍法；所述分步浸渍法中每步均为等体积浸渍法。更优选地，所述浸渍法为等体积共浸渍法。According to a specific embodiment of the present invention, in the method for producing a light hydrocarbon desulfurized alcohol catalyst according to the present invention, the impregnation method is a co-impregnation method or a stepwise impregnation method. Preferably, the co-impregnation method is an equal volume co-impregnation method; each step in the step-wise impregnation method is an equal volume impregnation method. More preferably, the impregnation method is an equal volume co-impregnation method.
再一方面，本发明提供所述轻质烃类脱硫醇催化剂的应用，所述应用是将该催化剂应用于脱除液化石油气、FCC汽油、催化裂解汽油和/或焦化汽油中的硫醇和/或二烯烃；或所述应用是将该催化剂用于催化双烯烃选择性加氢。In still another aspect, the present invention provides the use of the light hydrocarbon desulfurization catalyst for applying the catalyst to the removal of mercaptans from liquefied petroleum gas, FCC gasoline, catalytic pyrolysis gasoline and/or coking gasoline and/or Or a diene; or the use of the catalyst to catalyze the selective hydrogenation of a diolefin.
如上所述，应用本发明所述轻质烃类脱硫醇催化剂可在高效脱除液化石油气、FCC汽油、催化裂解汽油和/或焦化汽油等轻质烃类中的硫醇和/或二烯烃的情况下，保留原料中的烯烃，汽油的辛烷值RON只降低0.3个点左右，实现轻质烃类的高附加值利用。As described above, the use of the light hydrocarbon desulfurization catalyst of the present invention can efficiently remove mercaptans and/or diolefins from light hydrocarbons such as liquefied petroleum gas, FCC gasoline, catalytic pyrolysis gasoline and/or coking gasoline. In this case, the olefin in the raw material is retained, and the octane number RON of the gasoline is reduced by about 0.3 point, thereby achieving high added value utilization of the light hydrocarbon.
综上所述，本发明主要提供水热处理调控γ-氧化铝晶面的方法以及基于所得水热处理调控后的γ-氧化铝的轻质烃类脱硫醇催化剂。基于本发明水热改性γ-氧化铝制备的催化剂具有明显不同的物化性质，其最显著的特点是两种活性金属在γ-氧化铝上实现了晶面选择优先负载，即金属Ni优先负载在新暴露的(111)晶面上，而金属Mo优先负载在新暴露的(110)晶面上。同时，二种活性金属也通过分别与改性γ-氧化铝(111)和(110)晶面的作用分别形成了两种不同的活性晶面。In summary, the present invention mainly provides a method for hydrothermal treatment of the γ-alumina crystal face and a light hydrocarbon desulfurization catalyst based on the obtained hydrothermal treatment-controlled γ-alumina. The catalyst prepared by the hydrothermally modified γ-alumina according to the invention has distinct physicochemical properties, and the most remarkable feature is that the two active metals realize the preferential selection of the crystal face on the γ-alumina, that is, the metal Ni preferential load On the newly exposed (111) crystal plane, the metal Mo is preferentially loaded on the newly exposed (110) crystal plane. At the same time, the two active metals also form two different active crystal faces by respectively acting with the modified γ-alumina (111) and (110) crystal faces.
附图说明DRAWINGS
图1为实施例1制备得到的经水热处理后的γ-氧化铝与未经水热处理的γ-氧化铝X射线衍射(XRD)谱图；1 is a X-ray diffraction (XRD) spectrum of a hydrothermally treated γ-alumina prepared by Example 1 and a non-hydrothermally treated γ-alumina;
图2为实施例1制备得到的经水热处理后的γ-氧化铝的透射电镜(TEM)照片；2 is a transmission electron microscope (TEM) photograph of the hydrothermally treated γ-alumina prepared in Example 1;
图3为实施例1制备得到的采用经水热处理后的γ-氧化铝所制得的催化剂RM-1的TEM照片；3 is a TEM photograph of a catalyst RM-1 prepared by using the hydrothermally treated γ-alumina prepared in Example 1;
图4为采用未经水热处理γ-氧化铝所制备的催化剂PH-1的TEM照片； Figure 4 is a TEM photograph of a catalyst PH-1 prepared by using a hydrothermally treated γ-alumina;
图5为RM-1和PH-1两种催化剂对汽油模拟化合物(乙硫醇和异戊烯烃)脱硫醇反应性能的评价结果；Figure 5 is a graph showing the evaluation results of the reaction properties of RM-1 and PH-1 catalysts for the desulfurization of gasoline simulating compounds (ethanethiol and isoamyl olefin);
图6为经RM-1催化剂催化后的产品中的硫分布与原料油中的硫分布的比较图。Figure 6 is a graph comparing the sulfur distribution in the product catalyzed by the RM-1 catalyst with the sulfur distribution in the feedstock oil.
具体实施方式detailed description
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现结合具体实施例及附图对本发明的技术方案进行以下详细说明，应理解这些实例仅用于说明本发明而不用于限制本发明的范围。The technical solutions of the present invention will be described in detail below with reference to the specific embodiments and the accompanying drawings. The scope of the invention.
实施例1Example 1
本实施例提供一种基于γ-氧化铝晶面调控的轻质烃类脱硫醇催化剂及其制备方法，其是通过以下步骤实施的：The present embodiment provides a light hydrocarbon desulfurization catalyst based on γ-alumina crystal surface control and a preparation method thereof, which are implemented by the following steps:
(1)γ-氧化铝原料的水热处理(1) Hydrothermal treatment of γ-alumina raw materials
将1L去离子水和1g质量分数为65％的浓硝酸混合，配制成硝酸溶液，然后向其中加入250gγ-Al2O3粉末，该γ-Al2O3粉末的比表面积为280m2/g，孔容为0.71cm3/g，混合均匀后装入反应釜中，在烘箱中于170℃恒温水热处理7h后，过滤出固体产物，于120℃干燥2h，然后520℃焙烧4h，即得本实施例经水热处理后的γ-氧化铝粉末。Mixing 1L of deionized water and 1g mass fraction of 65% concentrated nitric acid to prepare a nitric acid solution, and thereto was added 2 O 3 powder 250gγ-Al, the γ-Al 2 O 3 surface area powder was 280m 2 / g The pore volume is 0.71cm 3 /g, and the mixture is uniformly mixed and then charged into the reaction kettle. After heat treatment at 170 ° C for 7 hours in an oven, the solid product is filtered, dried at 120 ° C for 2 h, and then calcined at 520 ° C for 4 h. The γ-alumina powder after hydrothermal treatment of this example.
图1为本实施例所得经水热处理后的γ-氧化铝与未经水热处理的γ-氧化铝XRD谱图。其中图1中(a)为氧化铝前驱体薄水铝石(焙烧前的产物)的XRD谱图，而图1中(b)为焙烧后的氧化铝产物的XRD谱图。从图1中可以看出，水热处理前后的两种产物与薄水铝石、氧化铝标准XRD卡片的峰基本相同，同时经水热处理后的特征衍射峰出现了明显增强，尤其是图1中(a)出现的(131)和(151)衍射峰以及图1中(b)出现的(400)和(440)衍射峰强度都大幅增加，这表明经水热处理后的γ-氧化铝暴露出了新的晶面。1 is a XRD spectrum of the hydrothermally treated γ-alumina and the unhydrothermally treated γ-alumina obtained in the present example. 1(a) is an XRD spectrum of an alumina precursor boehmite (a product before calcination), and (b) of FIG. 1 is an XRD spectrum of the calcined alumina product. It can be seen from Fig. 1 that the peaks of the two products before and after hydrothermal treatment are basically the same as those of the boehmite and alumina standard XRD cards, and the characteristic diffraction peaks after hydrothermal treatment are obviously enhanced, especially in Fig. 1. (a) The (131) and (151) diffraction peaks appearing and the (400) and (440) diffraction peak intensities appearing in (b) of Figure 1 are greatly increased, indicating that the hydrothermally treated γ-alumina is exposed. A new crystal face.
图2为本实施例所得经水热处理后的γ-氧化铝的TEM照片，其中图2中(a)和(b)为氧化铝{110}晶面的TEM照片，而图2中(c)和(d)为氧化铝{111}晶面的TEM照片，上述TEM照片可以证明在经水热处理后的γ-氧化铝的表面出现了新的(111)和(110)晶面。2 is a TEM photograph of the hydrothermally treated γ-alumina obtained in the present embodiment, wherein (a) and (b) of FIG. 2 are TEM photographs of the {110} crystal plane of the alumina, and FIG. 2(c) And (d) is a TEM photograph of the {111} crystal plane of alumina, and the above TEM photograph can prove that new (111) and (110) crystal faces appear on the surface of the γ-alumina after hydrothermal treatment.
(2)催化剂载体的制备(2) Preparation of catalyst carrier
将100g上述经水热处理后的γ-氧化铝粉末和100g上述未经水热处理的γ-氧化铝粉末分别与2g田菁粉、4.5g质量分数为65％的浓硝酸、50g水混捏，制成直径为3mm的球形颗粒，在120℃干燥4h，在520℃恒温焙烧3h，分别得到基于经水热处理后的γ- 氧化铝制备的催化剂载体及基于未经水热处理的γ-氧化铝制备的催化剂载体。100 g of the above hydrothermally treated γ-alumina powder and 100 g of the above non-hydrothermally treated γ-alumina powder were respectively kneaded with 2 g of phthalocyanine powder, 4.5 g of concentrated nitric acid having a mass fraction of 65%, and 50 g of water. Spherical particles with a diameter of 3 mm are dried at 120 ° C for 4 h and calcined at 520 ° C for 3 h at constant temperature to obtain γ- based on hydrothermal treatment. A catalyst support prepared from alumina and a catalyst support prepared based on γ-alumina which has not been hydrothermally treated.
(3)轻质烃类脱硫醇催化剂的制备(3) Preparation of light hydrocarbon desulfurization catalyst
分别取78g上述两种催化剂载体，共浸渍负载50g硝酸镍和9g钼酸铵，干燥后在520℃恒温焙烧4h，然后冷却至室温，得编号为RM-1的基于经水热处理后的γ-氧化铝制备的轻质烃类脱硫醇催化剂，及编号为PH-1的基于未经水热处理的γ-氧化铝制备的轻质烃类脱硫醇催化剂。78g of the above two kinds of catalyst carriers were respectively taken, and 50 g of nickel nitrate and 9 g of ammonium molybdate were co-impregnated, dried, and then calcined at 520 ° C for 4 h, and then cooled to room temperature to obtain a hydrothermally-treated γ-numbered RM-1. A light hydrocarbon desulfurization catalyst prepared from alumina, and a light hydrocarbon desulfurization catalyst based on the non-hydrothermally treated gamma-alumina numbered PH-1.
图3和图4分别是RM-1和PH-1两种催化剂的TEM照片，从照片中可以看出，在RM-1催化剂中活性金属实现了晶面选择优先负载，即活性金属Ni优先负载于(111)晶面上生成(101)晶面，而活性金属Mo优先负载于(110)晶面上生成(100)晶面。而在PH-1催化剂中未观察到类似的活性金属的选择性负载现象。Figure 3 and Figure 4 are TEM photographs of the two catalysts RM-1 and PH-1, respectively. It can be seen from the photograph that the active metal achieves the preferential selection of the crystal face in the RM-1 catalyst, that is, the active metal Ni preferential load. A (101) crystal plane is formed on the (111) crystal plane, and the active metal Mo is preferentially supported on the (110) crystal plane to form a (100) crystal plane. No similar selective loading of the active metal was observed in the PH-1 catalyst.
实施例2Example 2
本实施例提供了一种基于γ-氧化铝晶面调控的轻质烃类脱硫醇催化剂及其制备方法，其是通过以下步骤实施的：The present embodiment provides a light hydrocarbon desulfurization catalyst based on γ-alumina crystal plane control and a preparation method thereof, which are implemented by the following steps:
(1)γ-氧化铝原料的水热处理(1) Hydrothermal treatment of γ-alumina raw materials
将1L去离子水和2g乙酸混合，配制成乙酸溶液，然后向其中加入400gγ-Al2O3粉末，该γ-Al2O3粉末的比表面积为320m2/g，孔容为0.75cm3/g，混合均匀后装入反应釜中，在烘箱中于190℃恒温水热处理5h，过滤出固体产物，于120℃干燥4h，在520℃恒温焙烧4h，即得本实施例经水热处理后的γ-氧化铝粉末。1L of deionized water and 2g of acetic acid is mixed, formulated as a solution of acetic acid, then adding 2 O 3 powder 400gγ-Al, the γ-Al 2 O 3 powder the specific surface area of 320m 2 / g, a pore volume of 0.75cm 3 /g, mixed uniformly, charged into the reaction vessel, hydrothermally treated at 190 ° C for 5 h in an oven, filtered to solid product, dried at 120 ° C for 4 h, and calcined at 520 ° C for 4 h, then the hydrothermal treatment of this example was obtained. Γ-alumina powder.
(2)催化剂载体的制备(2) Preparation of catalyst carrier
将100g上述经水热处理后的γ-氧化铝粉末与2g田菁粉、4.5g质量分数为65％的浓硝酸、50g水混捏，制成直径为2mm、长度为3～4mm的球形颗粒，在120℃干燥4h，在500℃恒温焙烧5h，即得本实施例催化剂载体。100 g of the above hydrothermally treated γ-alumina powder was mixed with 2 g of phthalocyanine powder, 4.5 g of concentrated nitric acid having a mass fraction of 65%, and 50 g of water to prepare spherical particles having a diameter of 2 mm and a length of 3 to 4 mm. The catalyst carrier of this example was obtained by drying at 120 ° C for 4 h and calcining at 500 ° C for 5 h.
(3)轻质烃类脱硫醇催化剂的制备(3) Preparation of light hydrocarbon desulfurization catalyst
取78g上述催化剂载体，分步负载56g硝酸镍和10g钼酸铵，干燥后在500℃恒温焙烧4h，然后冷却至室温，即得本实施例轻质烃类脱硫醇催化剂，编号为RM-2。78 g of the above catalyst carrier was taken, and 56 g of nickel nitrate and 10 g of ammonium molybdate were supported stepwise, dried and then calcined at 500 ° C for 4 h, and then cooled to room temperature to obtain a light hydrocarbon desulfurization catalyst of the present example, number RM-2. .
实施例3Example 3
本实施例提供了一种基于γ-氧化铝晶面调控的轻质烃类脱硫醇催化剂及其制备方法，其是通过以下步骤实施的：The present embodiment provides a light hydrocarbon desulfurization catalyst based on γ-alumina crystal plane control and a preparation method thereof, which are implemented by the following steps:
(1)γ-氧化铝原料的水热处理(1) Hydrothermal treatment of γ-alumina raw materials
将1L去离子水和1g质量分数为65％浓硝酸混合，配制成硝酸溶液，然后向其中加 入400gγ-Al2O3粉末，该γ-Al2O3粉末的比表面积为260m2/g，孔容为0.78cm3/g，混合均匀后装入反应釜中，在烘箱中于180℃恒温水热处理6h，过滤出固体产物，于120℃干燥4h，在500℃恒温焙烧4h，即得本实施例经水热处理后的γ-氧化铝粉末。1L of deionized water and 1g mass fraction of 65% concentrated nitric acid mixed to prepare a solution of nitric acid, to which was then added 2 O 3 powder 400gγ-Al, the γ-Al 2 O 3 surface area powder was 260m 2 / g, The pore volume is 0.78cm 3 /g, and the mixture is uniformly mixed and then charged into the reaction vessel. The mixture is heated in an oven at 180 ° C for 6 hours. The solid product is filtered, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours. Example γ-alumina powder after hydrothermal treatment.
(2)催化剂载体的制备(2) Preparation of catalyst carrier
将100g上述经水热处理后的γ-氧化铝粉末与2g田菁粉、4.5g质量分数为65％的浓硝酸、50g水混捏，制成直径为2mm、长度为3～4mm的三叶草形颗粒，于120℃干燥4h，在500℃恒温焙烧5h，即得本实施例催化剂载体。100 g of the above hydrothermally treated γ-alumina powder was mixed with 2 g of phthalocyanine powder, 4.5 g of concentrated nitric acid having a mass fraction of 65%, and 50 g of water to prepare a clover-shaped granule having a diameter of 2 mm and a length of 3 to 4 mm. The catalyst carrier of this example was obtained by drying at 120 ° C for 4 h and calcining at 500 ° C for 5 h.
(3)轻质烃类脱硫醇催化剂的制备(3) Preparation of light hydrocarbon desulfurization catalyst
取78g上述催化剂载体，共浸渍负载56g硝酸镍和9g钼酸铵，干燥后在500℃恒温焙烧4h，然后冷却至室温，即得本实施例轻质烃类脱硫醇催化剂，编号为RM-3。78 g of the above catalyst carrier was taken, and 56 g of nickel nitrate and 9 g of ammonium molybdate were co-impregnated, dried, and calcined at 500 ° C for 4 h, and then cooled to room temperature to obtain a light hydrocarbon desulfurization catalyst of the present example, number RM-3. .
实施例4Example 4
本实施例考察了RM-1和PH-1两种催化剂对模拟汽油化合物(乙硫醇和异戊烯烃)脱硫醇的反应性能，具体按照以下步骤实施：In this example, the performance of the two catalysts RM-1 and PH-1 for the desulfurization of simulated gasoline compounds (ethanethiol and isoamyl) was investigated, and the following steps were carried out:
分别将3g直径为2～4mm的RM-1和PH-1催化剂颗粒装填到微型固定床反应器中，在装填催化剂时，床层两端用石英砂填充；两种催化剂首先均经过预硫化处理，预硫化条件为：压力为2.8MPa，氢气/预硫化油的体积比为200:1，预硫化油的液时体积空速为2h-1，反应器温度采用程序控制方法，150℃恒温2h，230℃、260℃、290℃和320℃分别恒温4h；然后进行脱硫醇反应，反应条件为：压力为2.0MPa、温度为135℃、氢油体积比为10:1、液相体积空速为3.5h-1。3g of RM-1 and PH-1 catalyst particles with a diameter of 2~4mm were respectively loaded into the micro fixed bed reactor. When the catalyst was packed, the two ends of the bed were filled with quartz sand; both catalysts were first pre-vulcanized. The pre-vulcanization conditions are: a pressure of 2.8 MPa, a hydrogen/presulfurized oil volume ratio of 200:1, a pre-sulfided oil liquid hour volume space velocity of 2 h -1 , a reactor temperature of a program control method, and a constant temperature of 150 ° C for 2 h. 230 ° C, 260 ° C, 290 ° C and 320 ° C were respectively thermostated for 4 h; then desulfurization reaction was carried out under the conditions of a pressure of 2.0 MPa, a temperature of 135 ° C, a hydrogen oil volume ratio of 10:1, and a liquid volume volume velocity. It is 3.5h -1 .
进样稳定48h后采样分析，然后每隔8h对反应产品进行采样分析，采用气相色谱仪和硫质化学发光检测器(GC-SCD)检测样品的硫分布和硫醇含量。图5为本实施例RM-1和PH-1两种催化剂对模拟汽油(乙硫醇和异戊烯烃)脱硫醇反应性能的评价结果。从图5可以看出：RM-1催化剂可催化乙硫醇反应完全，脱硫醇率为100％；而PH-1催化剂的乙硫醇转化率只有87.7％，明显低于RM-1催化剂，在两个催化剂上获得的反应产物相同，表明两种催化剂的反应机理相同。The sample was sampled and stabilized for 48 hours, and then the reaction product was sampled and analyzed every 8 hours. The sulfur distribution and thiol content of the sample were detected by gas chromatography and sulfur chemiluminescence detector (GC-SCD). Fig. 5 is a graph showing the evaluation results of the reaction properties of the two catalysts RM-1 and PH-1 for the desulfurization of simulated gasoline (ethyl mercaptan and isoamyl). It can be seen from Fig. 5 that the RM-1 catalyst can catalyze the complete reaction of ethanethiol with a desulfurization rate of 100%; while the conversion of ethanethiol of the PH-1 catalyst is only 87.7%, which is significantly lower than that of the RM-1 catalyst. The reaction products obtained on the two catalysts were identical, indicating that the reaction mechanisms of the two catalysts were the same.
实施例5Example 5
本实施例考察了RM-1催化剂对催化裂化汽油的脱硫醇反应性能，具体按照以下步骤实施：In this example, the desulfurization reaction performance of the RM-1 catalyst for catalytic cracking gasoline was examined, and the following steps were specifically carried out:
本实施例中的操作步骤与实施例4相同，催化剂装填量、装填方式、预硫化条件以及产品的分析方法等也与实施例4相同。催化裂化汽油脱硫醇的具体反应条件为：压力为2.0 MPa、温度为130℃、氢油体积比为10:1、液相体积空速为3.5h-1。所得结果如下表1所示。The operation procedure in this embodiment is the same as that in the fourth embodiment, and the catalyst loading amount, the filling method, the pre-vulcanization conditions, the analysis method of the product, and the like are also the same as in the fourth embodiment. The specific reaction conditions for catalytic cracking gasoline desulfurization are: pressure of 2.0 MPa, temperature of 130 ° C, hydrogen oil volume ratio of 10:1, liquid phase volume space velocity of 3.5 h -1 . The results obtained are shown in Table 1 below.
表1 RM-1催化剂评价结果Table 1 RM-1 catalyst evaluation results
项目project FCC原料FCC raw materials RM-1反应产物RM-1 reaction product
密度，g/mLDensity, g/mL 0.7210.721 0.7250.725
硫，ppmSulfur, ppm 754754 746746
硫醇硫，ppmMercaptan sulfur, ppm 3131 22
烯烃含量，v％Olefin content, v% 55.4155.41 54.8954.89
辛烷值，RONOctane number, RON 88.2488.24 88.0888.08
汽油收率，wt％Gasoline yield, wt%   98.8998.89
由表1可以看出，经脱硫醇反应后，所得反应产物中的硫醇硫含量降低到10ppm以下，同时总硫含量保持基本不变，这表明该过程中只发生了硫转移即硫醇与二烯烃的醚化反应，而没有发生加氢脱硫反应；反应所得产物的烯烃含量也基本不变，这说明该催化剂具有良好的选择性，没有发生烯烃的加氢饱和，且产物的收率也在98.5％以上，汽油的辛烷值RON只降低0.3个点左右。图6为RM-1催化剂产品与原料油的硫分布谱图，由图6可以看出，原料中的低碳硫醇(甲硫醇、乙硫醇、异丙硫醇及正丙硫醇)全部发生了硫醚化发生，生成了高碳含硫化合物，而噻吩、甲基噻吩等噻吩类化合物的含量基本不变，这表明该催化剂具有优异的选择性和脱硫醇反应活性。It can be seen from Table 1 that after the mercaptan removal reaction, the mercaptan sulfur content in the obtained reaction product is reduced to less than 10 ppm, and the total sulfur content remains substantially unchanged, indicating that only sulfur transfer, ie, mercaptan, occurs during the process. The etherification reaction of the diene does not occur in the hydrodesulfurization reaction; the olefin content of the product obtained by the reaction is also substantially unchanged, which indicates that the catalyst has good selectivity, no hydrogenation of the olefin occurs, and the yield of the product is also Above 98.5%, the octane RON of gasoline is only reduced by about 0.3 points. Figure 6 is a sulfur distribution spectrum of the RM-1 catalyst product and the feedstock oil. As can be seen from Figure 6, the low-carbon mercaptans in the raw materials (methyl mercaptan, ethyl mercaptan, isopropyl mercaptan and n-propyl mercaptan) All of the thioetherification occurred, and a high-carbon sulfur-containing compound was formed, and the content of the thiophene compound such as thiophene or methylthiophene was substantially unchanged, indicating that the catalyst had excellent selectivity and dethiol-reactive activity.
实施例6Example 6
本实施例考察RM-2催化剂对焦化汽油的脱硫醇反应性能，具体按照以下步骤实施：In this example, the desulfurization reaction performance of the RM-2 catalyst for coking gasoline was examined, and the following steps were specifically carried out:
本实施例中的操作步骤与实施例4相同，催化剂装填量、装填方式、预硫化条件以及产品的分析方法等也与实施例4相同，但反应原料为硫醇含量更高的焦化汽油。其脱硫醇的具体反应条件为：压力为2.5MPa、反应温度为135℃、氢油体积比为8:1、液相体积空速为3h-1。RM-2催化剂评价产品的结果如表2所示。The operation steps in this example were the same as in Example 4. The catalyst loading amount, the filling method, the pre-vulcanization conditions, and the analysis method of the product were also the same as in Example 4, but the reaction raw material was coking gasoline having a higher mercaptan content. The specific reaction conditions of the mercaptan are: a pressure of 2.5 MPa, a reaction temperature of 135 ° C, a hydrogen oil volume ratio of 8:1, and a liquid volume volume velocity of 3 h -1 . The results of the RM-2 catalyst evaluation product are shown in Table 2.
表2 RM-2两种催化剂评价结果Table 2 RM-2 evaluation results of two catalysts
项目project 焦化汽油Coking gasoline RM-2反应产物RM-2 reaction product
密度，g/mLDensity, g/mL 0.7440.744 0.7400.740
硫，ppmSulfur, ppm 21102110 20982098
硫醇硫，ppmMercaptan sulfur, ppm 214214 77
烯烃含量，v％Olefin content, v% 32.7832.78 31.4231.42
辛烷值，RONOctane number, RON 72.4572.45 72.1272.12
汽油收率，wt％Gasoline yield, wt%   98.9898.98
表2与表1的结果基本相同，这表明该催化剂对焦化汽油也具有优异的选择性和脱硫 醇反应活性。The results in Table 2 and Table 1 are basically the same, which indicates that the catalyst coke gasoline also has excellent selectivity and desulfurization. Alcohol reactivity.
实施例7Example 7
本实施例考察RM-3催化剂对液化石油气的脱硫醇反应性能，具体按照以下步骤实施：In this example, the performance of the RM-3 catalyst for the desulfurization of liquefied petroleum gas was examined, and the following steps were specifically carried out:
本实施例中的操作步骤与实施例4相同，催化剂装填量、装填方式、预硫化条件以及产品的分析方法等也与实施例4相同，但反应原料为液化石油气。其脱硫醇具体反应条件为：压力为2.0MPa、反应温度为110℃、氢油体积比为6:1、液相体积空速为3h-1。RM-3催化剂催化液化石油气脱硫醇反应的反应结果如表3所示。The operation procedure in this example was the same as in Example 4. The catalyst loading amount, the charging method, the pre-vulcanization conditions, and the analysis method of the product were also the same as in Example 4, but the reaction raw material was liquefied petroleum gas. The specific reaction conditions of the mercaptan are: a pressure of 2.0 MPa, a reaction temperature of 110 ° C, a hydrogen oil volume ratio of 6:1, and a liquid volume volume velocity of 3 h -1 . The results of the reaction of the RM-3 catalyst for the liquefied petroleum gas desulfurization reaction are shown in Table 3.
表3 RM-3催化剂的反应结果Table 3 Reaction results of RM-3 catalyst
组成composition 原料raw material 产品product
硫化氢，ppmHydrogen sulfide, ppm 8.28.2 00
甲硫醇，ppmMethyl mercaptan, ppm 414.9414.9 4.34.3
乙硫醇，ppmEthyl mercaptan, ppm 217.5217.5 1.71.7
烯烃，v％Olefins, v% 59.7459.74 57.7457.74
收率，wt％Yield, wt%   94.5794.57
由表3可以看出，液化石油气中的硫化氢及硫醇基本被脱除，烯烃含量变化很小，这表明该催化剂对液化石油气也具有高的脱硫醇活性。It can be seen from Table 3 that the hydrogen sulfide and mercaptan in the liquefied petroleum gas are substantially removed, and the change in the olefin content is small, which indicates that the catalyst also has high dethiol activity for the liquefied petroleum gas.
最后说明的是：以上实施例仅用于说明本发明的实施过程和特点，而非限制本发明的技术方案，尽管参照上述实施例对本发明进行了详细说明，本领域的普通技术人员应当理解：依然可以对本发明进行修改或者等同替换，而不脱离本发明的精神和范围的任何修改或局部替换，均应涵盖在本发明的保护范围当中。 It is to be understood that the above embodiments are only used to illustrate the implementation process and features of the present invention, and are not intended to limit the technical solutions of the present invention. The invention may be modified or equivalently substituted without departing from the spirit and scope of the invention, and should be covered by the scope of the invention.

Claims (20)

  1. 水热处理调控γ-氧化铝晶面的方法，所述方法包括：将γ-氧化铝原料加入到酸性水溶液中，水热处理，过滤、洗涤、干燥及焙烧得水热处理调控后的γ-氧化铝。The method for hydrothermal treatment of γ-alumina crystal face comprises the steps of: adding γ-alumina raw material to an acidic aqueous solution, hydrothermal treatment, filtering, washing, drying and roasting to obtain γ-alumina controlled by hydrothermal treatment.
  2. 根据权利要求1所述的水热处理调控γ-氧化铝晶面的方法，其中，水热处理的温度为120～200℃；优选水热处理3～12h。The method for hydrotreating a γ-alumina crystal face according to claim 1, wherein the hydrothermal treatment has a temperature of from 120 to 200 ° C; preferably hydrothermal treatment for from 3 to 12 h.
  3. 根据权利要求1或2所述的水热处理调控γ-氧化铝晶面的方法，其中，焙烧温度为400～550℃；优选焙烧5～15h。The method for hydrotreating a γ-alumina crystal face according to claim 1 or 2, wherein the calcination temperature is 400 to 550 ° C; preferably, the calcination is 5 to 15 h.
  4. 根据权利要求1所述的水热处理调控γ-氧化铝晶面的方法，其中，所述γ-氧化铝原料的比表面积为200～400m2/g，孔容为0.3～0.8cm3/g。The method for hydrotreating a γ-alumina crystal face according to claim 1, wherein the γ-alumina raw material has a specific surface area of 200 to 400 m 2 /g and a pore volume of 0.3 to 0.8 cm 3 /g.
  5. 根据权利要求1或2所述的水热处理调控γ-氧化铝晶面的方法，其中，所述酸性水溶液包括硝酸水溶液、盐酸、草酸水溶液、醋酸水溶液和柠檬酸水溶液中的一种或几种；优选地，所述酸性水溶液的pH值为0～4。The hydrothermal treatment method for regulating a γ-alumina crystal face according to claim 1 or 2, wherein the acidic aqueous solution comprises one or more of an aqueous solution of nitric acid, hydrochloric acid, an aqueous solution of oxalic acid, an aqueous solution of acetic acid, and an aqueous solution of citric acid; Preferably, the acidic aqueous solution has a pH of from 0 to 4.
  6. 根据权利要求5所述的水热处理调控γ-氧化铝晶面的方法，其中，所述γ-氧化铝原料与所述酸性水溶液的质量比为1:1～1:6；优选地，水热处理的温度为120～200℃；焙烧温度为400～550℃。The hydrothermal treatment method according to claim 5, wherein the mass ratio of the γ-alumina raw material to the acidic aqueous solution is 1:1 to 1:6; preferably, hydrothermal treatment The temperature is 120 to 200 ° C; the baking temperature is 400 to 550 ° C.
  7. 水热处理调控后的γ-氧化铝，其是根据权利要求1～6中任一项所述的方法制备得到的；优选地，该水热处理调控后的γ-氧化铝的比表面积为150～300m2/g，孔容为0.3～1.0cm3/g。The γ-alumina after the hydrothermal treatment is prepared by the method according to any one of claims 1 to 6; preferably, the specific surface area of the γ-alumina after the hydrothermal treatment is 150 to 300 m 2 / g, the pore volume is 0.3 to 1.0 cm 3 /g.
  8. 基于氧化铝晶面调控的轻质烃类脱硫醇催化剂，其中，该催化剂是以权利要求7所述水热处理调控后的γ-氧化铝为载体，以镍及钼为活性金属。A light hydrocarbon desulfurization catalyst based on alumina crystal plane control, wherein the catalyst is a γ-alumina controlled by hydrothermal treatment according to claim 7, and nickel and molybdenum are active metals.
  9. 根据权利要求8所述的基于氧化铝晶面调控的轻质烃类脱硫醇催化剂，其中，The alumina-based surface-controlled light hydrocarbon desulfurization catalyst according to claim 8, wherein
    活性金属镍沉积于所述水热处理调控后的γ-氧化铝的晶面(111)上；The active metal nickel is deposited on the crystal face (111) of the γ-alumina after the hydrothermal treatment control;
    活性金属钼沉积于所述水热处理调控后的γ-氧化铝的晶面(110)上。The active metal molybdenum is deposited on the crystal face (110) of the γ-alumina after the hydrothermal treatment.
  10. 根据权利要求8或9所述的基于氧化铝晶面调控的轻质烃类脱硫醇催化剂，其中，以该催化剂的总重量为100％计，其包括：The alumina-based surface-controlled light hydrocarbon desulfurization catalyst according to claim 8 or 9, wherein, based on 100% of the total weight of the catalyst, it comprises:
    50～85wt％的所述水热处理调控后的γ-氧化铝；50 to 85 wt% of the hydrothermally controlled γ-alumina;
    5～20wt％的氧化镍；优选10～20wt％的氧化镍，及5 to 20% by weight of nickel oxide; preferably 10 to 20% by weight of nickel oxide, and
    2～15wt％的氧化钼；优选4～12wt％的氧化钼。2 to 15% by weight of molybdenum oxide; preferably 4 to 12% by weight of molybdenum oxide.
  11. 根据权利要求10所述的基于氧化铝晶面调控的轻质烃类脱硫醇催化剂，其中，以该催化剂的总重量为100％计，其包括： The alumina-based surface-controlled light hydrocarbon desulfurization catalyst according to claim 10, wherein, based on 100% of the total weight of the catalyst, it comprises:
    50～85wt％的所述水热处理调控后的γ-氧化铝；50 to 85 wt% of the hydrothermally controlled γ-alumina;
    10～20wt％的氧化镍，及10 to 20% by weight of nickel oxide, and
    4～12wt％的氧化钼。4 to 12% by weight of molybdenum oxide.
  12. 权利要求8～11中任一项所述基于氧化铝晶面调控的轻质烃类脱硫醇催化剂的制备方法，所述方法包括如下步骤：The method for preparing a light hydrocarbon desulfurization catalyst based on alumina crystal face according to any one of claims 8 to 11, wherein the method comprises the following steps:
    (a)将所述水热处理调控后的γ-氧化铝、助剂和硝酸水溶液混合后混捏、挤压成型、干燥及焙烧，得催化剂载体；(a) mixing the γ-alumina, the auxiliary agent and the aqueous nitric acid solution after the hydrothermal treatment, mixing, extruding, extruding, drying and calcining to obtain a catalyst carrier;
    (b)采用浸渍法将金属镍的前驱体、金属钼的前驱体负载在步骤(a)制得的催化剂载体上，干燥并焙烧后，得所述基于氧化铝晶面调控的轻质烃类脱硫醇催化剂。(b) supporting the precursor of metallic nickel and the precursor of metallic molybdenum on the catalyst carrier prepared in the step (a) by dipping, drying and calcining to obtain the light hydrocarbons controlled by the alumina crystal plane Desulfurization catalyst.
  13. 根据权利要求12所述的方法，其中，在步骤(a)中，以所述催化剂载体的总重量为100％计，所述助剂的用量为1.0～3.5wt％，所述硝酸水溶液的质量分数为50～70％，其用量为3.0～6.0wt％。The method according to claim 12, wherein in the step (a), the auxiliary agent is used in an amount of from 1.0 to 3.5% by weight based on the total weight of the catalyst carrier, and the quality of the aqueous solution of the nitric acid The fraction is 50 to 70%, and the amount thereof is 3.0 to 6.0% by weight.
  14. 根据权利要求12或13所述的方法，其中，所述挤压成型是将混捏后的物料挤压成球状颗粒、柱状颗粒或三叶草状颗粒；优选地，挤压成型后颗粒的当量直径为2～10mm。The method according to claim 12 or 13, wherein said extrusion molding extrudes the kneaded material into spherical particles, columnar particles or clover-like particles; preferably, the equivalent diameter of the particles after extrusion is 2 ~10mm.
  15. 根据权利要求12所述的方法，其中，在步骤(b)中，所述金属镍的前驱体包括硝酸镍、乙酸镍、氯化镍和硫酸镍中的一种或几种。The method according to claim 12, wherein in the step (b), the precursor of the metallic nickel comprises one or more of nickel nitrate, nickel acetate, nickel chloride and nickel sulfate.
  16. 根据权利要求12或15所述的方法，其中，所述金属钼的前驱体包括钼酸盐和/或硝酸钼。The method according to claim 12 or 15, wherein the precursor of the metallic molybdenum comprises molybdate and/or molybdenum nitrate.
  17. 根据权利要求12、13或15所述的方法，其中，所述浸渍法为共浸渍法或分步浸渍法。The method according to claim 12, 13 or 15, wherein the impregnation method is a co-impregnation method or a stepwise impregnation method.
  18. 根据权利要求12所述的方法，其中，步骤(a)中所述焙烧是在温度为300～600℃焙烧5～10h；步骤(b)中所述焙烧是在400～600℃焙烧3～10h。The method according to claim 12, wherein the calcination in the step (a) is calcination at a temperature of 300 to 600 ° C for 5 to 10 h; and the calcination in the step (b) is calcination at 400 to 600 ° C for 3 to 10 h. .
  19. 权利要求8～11中任一项所述的基于氧化铝晶面调控的轻质烃类脱硫醇催化剂或权利要求12～18中任一项所述的方法制备得到的基于氧化铝晶面调控的轻质烃类脱硫醇催化剂的应用，其中，所述应用是将该催化剂用于脱除液化石油气、FCC汽油、催化裂解汽油和/或焦化汽油中的硫醇和/或二烯烃。The alumina-based surface-controlled light hydrocarbon desulfurization catalyst according to any one of claims 8 to 11 or the alumina crystal face-based control prepared by the method according to any one of claims 12 to 18. Use of a light hydrocarbon desulfurization catalyst, wherein the application is to use the catalyst for the removal of mercaptans and/or diolefins from liquefied petroleum gas, FCC gasoline, catalytic pyrolysis gasoline and/or coking gasoline.
  20. 权利要求8～11中任一项所述的基于氧化铝晶面调控的轻质烃类脱硫醇催化剂或权利要求12～18中任一项所述的方法制备得到的基于氧化铝晶面调控的轻质烃类脱硫醇催化剂的应用，其中，所述应用是将该催化剂用于催化双烯烃选择性加氢。 The alumina-based surface-controlled light hydrocarbon desulfurization catalyst according to any one of claims 8 to 11 or the alumina crystal face-based control prepared by the method according to any one of claims 12 to 18. Use of a light hydrocarbon desulfurization catalyst wherein the application is to catalyze the selective hydrogenation of a diolefin.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112707420A (en) * 2019-10-25 2021-04-27 中国石油化工股份有限公司 Alumina material and preparation method thereof
CN113042021A (en) * 2019-12-27 2021-06-29 中国石油化工股份有限公司 Fluidized bed hydrogenation catalyst and preparation method thereof
CN113231067A (en) * 2021-05-28 2021-08-10 中国海洋石油集团有限公司 Dearsenic agent for hydrogenation of light distillate oil and preparation method and application thereof
CN113578350A (en) * 2020-04-30 2021-11-02 中国石油天然气股份有限公司 Completely-vulcanized hydrogenation modified catalyst, preparation method and application thereof
CN114177931A (en) * 2020-09-15 2022-03-15 中国石油化工股份有限公司 Gasoline desulfurization and olefin reduction catalyst and preparation method thereof
CN114471526A (en) * 2020-10-27 2022-05-13 中国石油化工股份有限公司 Reforming catalyst and preparation method and application thereof
CN114590828A (en) * 2020-12-02 2022-06-07 中国石油化工股份有限公司 Alumina material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1508223A (en) * 2002-12-19 2004-06-30 中国石油化工股份有限公司 Hydrotreating catalyst and preparing method thereof
US20150306585A1 (en) * 2012-11-14 2015-10-29 Universida Nacional Autónoma De México Supported catalysts for producing ultra-low sulphur fuel oils

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1508223A (en) * 2002-12-19 2004-06-30 中国石油化工股份有限公司 Hydrotreating catalyst and preparing method thereof
US20150306585A1 (en) * 2012-11-14 2015-10-29 Universida Nacional Autónoma De México Supported catalysts for producing ultra-low sulphur fuel oils

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ANTONY STANISLAUS ET AL.: "Preparation of a large pore alumina-based HDM catalyst by hydrothermal treatment and studies on pore enlargement mechanism", JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL, vol. 181, no. 1-2, 15 March 2002 (2002-03-15), pages 33 - 39, XP055426176, ISSN: 1381-1169 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112707420A (en) * 2019-10-25 2021-04-27 中国石油化工股份有限公司 Alumina material and preparation method thereof
CN113042021A (en) * 2019-12-27 2021-06-29 中国石油化工股份有限公司 Fluidized bed hydrogenation catalyst and preparation method thereof
CN113042021B (en) * 2019-12-27 2023-05-26 中国石油化工股份有限公司 Ebullated bed hydrogenation catalyst and preparation method thereof
CN113578350A (en) * 2020-04-30 2021-11-02 中国石油天然气股份有限公司 Completely-vulcanized hydrogenation modified catalyst, preparation method and application thereof
CN114177931A (en) * 2020-09-15 2022-03-15 中国石油化工股份有限公司 Gasoline desulfurization and olefin reduction catalyst and preparation method thereof
CN114177931B (en) * 2020-09-15 2023-07-28 中国石油化工股份有限公司 Catalyst for desulfurizing and reducing olefin of gasoline and preparation method thereof
CN114471526A (en) * 2020-10-27 2022-05-13 中国石油化工股份有限公司 Reforming catalyst and preparation method and application thereof
CN114590828A (en) * 2020-12-02 2022-06-07 中国石油化工股份有限公司 Alumina material and preparation method thereof
CN113231067A (en) * 2021-05-28 2021-08-10 中国海洋石油集团有限公司 Dearsenic agent for hydrogenation of light distillate oil and preparation method and application thereof
CN113231067B (en) * 2021-05-28 2023-08-22 中国海洋石油集团有限公司 Dearsenifying agent for light distillate oil hydrogenation and preparation method and application thereof

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