WO2023179036A1 - 复合氧化物、复合氧化物的制备方法、加氢催化剂及其应用 - Google Patents

复合氧化物、复合氧化物的制备方法、加氢催化剂及其应用 Download PDF

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WO2023179036A1
WO2023179036A1 PCT/CN2022/129813 CN2022129813W WO2023179036A1 WO 2023179036 A1 WO2023179036 A1 WO 2023179036A1 CN 2022129813 W CN2022129813 W CN 2022129813W WO 2023179036 A1 WO2023179036 A1 WO 2023179036A1
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composite oxide
solution
titanium dioxide
catalyst
range
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French (fr)
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杜周
刘艳惠
张富春
刘宗语
季静
任玉梅
杨光
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中国石油化工股份有限公司
中石化(北京)化工研究院有限公司
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Publication of WO2023179036A1 publication Critical patent/WO2023179036A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/12—Alkadienes
    • C07C11/16—Alkadienes with four carbon atoms
    • C07C11/167—1, 3-Butadiene
    • 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
    • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel

Definitions

  • the invention relates to a composite oxide, a preparation method of the composite oxide, a hydrogenation catalyst and its application. Specifically, it can be used to hydrogenate and remove alkynes in the C 4 fraction and increase the production of butadiene.
  • C4 fraction refers to a mixture of various alkanes, olefins, diolefins and alkynes containing four carbon atoms. It is mainly derived from the refinery gas produced in the petroleum refining process and the by-product of the cracking of petroleum hydrocarbons to ethylene.
  • Cracking C4 contains n-butane, isobutane, 1-butene, trans-2-butene, cis-2-butene, isobutene, 1,2-butadiene, 1,3-butadiene, methyl Saturated hydrocarbons and unsaturated hydrocarbons such as ethyl acetylene, ethyl acetylene and vinyl acetylene are mainly used in industry to produce 1,3-butadiene, isobutylene and 1-butene.
  • the cracked carbon four fraction a by-product of high-temperature cracking of hydrocarbons to produce ethylene, usually contains 40%-60% mass fraction of butadiene.
  • Butadiene is an important monomer in the synthetic rubber industry.
  • Butadiene is extracted from the cracked carbon four fraction.
  • Solvent extraction methods are usually used, such as acetonitrile method, N-methylpyrrolidone method and dimethylformamide method. At present, these methods basically meet the requirements for butadiene purity.
  • alkynes in mixed carbon tetrahydrocarbon fractions can be removed by catalytic selective hydrogenation.
  • the catalysts used mainly tend to use precious metal catalysts represented by palladium, platinum, silver, etc., followed by non-noble metal catalysts represented by copper and nickel.
  • the selective hydrogenation of alkynes in hydrocarbon streams depends on the composition of the raw materials and the target products, and the catalysts and reaction conditions selected are also different.
  • a good selective hydrogenation catalyst should also have good stability, that is, the catalyst must have the ability to resist impurities and colloids, so as to extend the life of the catalyst. Therefore, the carrier is required to have lower acidity, smaller specific surface area and larger pore size.
  • adding some additives during the preparation of the catalyst can also extend the service life of the catalyst.
  • Precious metal catalysts generally use palladium catalysts supported on carriers (usually alumina), and add other cocatalyst components, such as gold, silver, chromium, copper, iron, rhodium, lithium, potassium, and lead or zinc.
  • Precious metal catalysts have good low-temperature activity and mild reaction conditions.
  • their shortcomings are that the active components of the catalyst are easy to lose, are expensive, are not easy to regenerate, and have slightly poor hydrogenation selectivity.
  • Non-noble metal catalysts need to react at higher temperatures, and the hydrogenation conditions are more stringent. However, they are simple to prepare, easy to regenerate repeatedly, and the cost is relatively low, so they still have certain research and development value.
  • the semi-hydrogenated free radicals adsorbed on the catalyst react with adjacent alkynes or dienes to form a viscous polymer (commonly known as green oil), which is mainly composed of C 6 and above
  • green oil which is mainly composed of C 6 and above
  • the compound composition covers the surface of the catalyst and blocks the micropores on the surface of the catalyst, reducing the activity of the catalyst and affecting the service life of the catalyst.
  • conjugated dienes such as 1,3-butadiene
  • the polymerization reaction proceeds more easily, thereby deactivating the catalyst in a short time, so that the catalyst must be regenerated frequently before it can be reused.
  • the structure and shape of catalytic materials based on TiO 2 can greatly affect the light absorption efficiency of the material.
  • Coral reefs have excellent light-absorbing and reflective structures, thus providing a three-dimensional (3D) environment for many plants and animals on the seafloor, absorbing small particles and supporting approximately a quarter of all known marine life.
  • Coral-like 3D hierarchical structures can have higher specific surface areas, resulting in more active sites and stronger light-harvesting capabilities, and have been shown to have better photocatalytic performance than other structures.
  • the performance of TiO2- supported catalysts can be improved by using specific catalytic materials with a coral reef-like morphology.
  • the purpose of the present invention is to provide a non-noble metal selective hydrogenation catalyst with high low-temperature activity, high selectivity and high stability. Compared with precious metal selective hydrogenation and alkyne removal catalysts, the catalyst investment cost of the present disclosure can be saved by more than 80%, and the catalyst has better resistance to impurity poisoning and raw material adaptability.
  • the present invention provides a composite oxide, which includes aluminum oxide and titanium dioxide, the specific surface area of the composite oxide is expressed as X m 2 /g, and the average pore diameter of the composite oxide is expressed as Y nm , wherein the ratio of Preferably, the ratio of X to Y is 5 to 15. Further preferably, the ratio of X to Y is 5 to 10.
  • titanium dioxide in the anatase crystal phase accounts for 96wt%-100wt% of the total titanium dioxide.
  • titanium dioxide in the anatase crystal phase accounts for 97wt%-100wt% of the total titanium dioxide.
  • titanium dioxide in the anatase crystal phase accounts for 98wt%-100wt% of the total titanium dioxide.
  • titanium dioxide in the anatase crystal phase accounts for 99wt%-100wt% of the total titanium dioxide.
  • the proportion of titanium dioxide in the anatase crystal phase to the total titanium dioxide can be measured through X-ray diffraction analysis.
  • the specific surface area of the composite oxide can be measured by the BET method.
  • the average pore size of the composite oxide can be measured by the nitrogen adsorption isotherm curve method.
  • the diffraction peak area representing the crystal structure of anatase titanium dioxide, measured by X-ray diffraction analysis accounts for 95 wt % to 100 wt % of the diffraction peak areas of all titanium dioxide crystal structures.
  • the diffraction peak area representing the crystal structure of anatase titanium dioxide, measured by X-ray diffraction analysis accounts for 96 wt % to 100 wt % of the diffraction peak areas of all titanium dioxide crystal structures.
  • the diffraction peak area representing the crystal structure of anatase titanium dioxide, measured by X-ray diffraction analysis accounts for 97 wt % to 100 wt % of the diffraction peak areas of all titanium dioxide crystal structures.
  • the diffraction peak area representing the crystal structure of anatase titanium dioxide, measured by X-ray diffraction analysis accounts for 98 wt % to 100 wt % of the diffraction peak areas of all titanium dioxide crystal structures.
  • the pore volume of the composite oxide measured using the P/Po single-point desorption curve is Z mL/g, and the ratio of X to Z is 220 to 400, preferably 250 to 350. In some embodiments, the ratio of
  • X is from 90 to 150. In some embodiments, X is 90, 100, 110, 120, 130, 140, 150, or a range consisting of any two thereof.
  • Y is from 9 to 20, preferably from 12 to 16. In some embodiments, Y is 12, 13, 14, 15, 16, or a range consisting of any two thereof.
  • the proportion of pores with pore diameters in the range of 10-20 nm to all pores is at least 85% by volume.
  • Z is from 0.3 to 0.5, preferably from 0.3 to 0.4. In some embodiments, Z is 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, or a range consisting of any two thereof.
  • the composite oxide contains 5 wt% to 21 wt% titanium dioxide, based on the total weight of the composite oxide. In some embodiments, the composite oxide contains 5wt%, 6wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, 21wt% or within the range of any two of them. Titanium dioxide.
  • the composite oxide contains 79 wt% to 95 wt% aluminum oxide, based on the total weight of the composite oxide.
  • the composite oxide has a coral plexus-like 3D layered structure.
  • the 3D hierarchical structure of coral clusters can have a higher specific surface area, resulting in more active sites and stronger light-harvesting capabilities.
  • the present invention provides a method for preparing a composite oxide, through which an alumina-titanium dioxide composite oxide with a 3D microscopic morphology of coral clusters can be obtained.
  • the preparation method of the present invention includes the following steps:
  • Step 1 Dissolve the soluble aluminum source in water to form an aluminum source solution, dissolve the titanium source in an acid solution to form a titanium source solution, and mix ammonium salt and alkali solution to form a mixed alkali solution;
  • Step II (a) Add the titanium source solution and the mixed alkali solution to the aluminum source solution, so that the resulting mixed solution maintains the first pH value for a first period of time; (b) Add the titanium source solution and the mixed alkali solution to the mixed solution Adding additional mixed alkali solution to maintain the resulting mixed solution at a second pH value for a second period of time; (c) adding additional titanium source solution to the mixed solution to maintain the resulting mixed solution at a third pH value for a second period of time; Three time periods;
  • Step III After step II.(c), increase the temperature of the mixed liquid and maintain it for a fourth period of time to obtain a precipitate;
  • Step IV The precipitate is dried and roasted to obtain a composite oxide containing alumina and titanium dioxide.
  • the precipitate is also washed and filtered (to remove unnecessary impurities) before drying.
  • the composite oxide thus obtained has the composition and structural characteristics described in the first aspect of the invention.
  • the first pH value is less than 5, preferably between 3 and 4.
  • the second pH value is greater than 8.5, preferably between 9 and 10.
  • the third pH value is greater than 7 and less than 9, preferably 7.5 to 8.5.
  • the first time period, the second time period and the third time period are respectively 5 minutes to 20 minutes, preferably 10 minutes to 15 minutes.
  • the fourth time period is from 20 minutes to 60 minutes.
  • the operating temperature is from 25°C to 60°C, preferably from 50°C to 60°C.
  • the temperature in said step III, is increased to 80°C to 150°C, preferably 80°C to 100°C. In some embodiments, in step III, the temperature is increased to 80°C, 85°C, 90°C, 92°C, or 95°C.
  • the drying temperature is 110°C to 130°C. Drying time is 4-12h, preferably 6-10h
  • the calcination temperature is 800°C to 1000°C. In some embodiments, in step IV, the calcination temperature is in the range of 800°C, 850°C, 900°C, 950°C, or any two thereof.
  • the roasting time is 4-12h, preferably 5-8h
  • the aluminum source solution has an aluminum concentration of 0.5 to 2.5 mol/L.
  • the aluminum source is a soluble aluminum salt, and one or more of aluminum sulfate, aluminum chloride, aluminum nitrate, and organic aluminum such as aluminum isopropoxide, aluminum sec-butoxide, aluminum monoacetate, and aluminum diacetate can be selected. kind.
  • the titanium concentration of the titanium source solution is 0.2 to 1.2moL/L.
  • the titanium source is a soluble titanium source, which can be selected from titanium salts such as titanium acetate, hydrochloride, sulfate, nitrate or titanate esters such as tetraethyl titanate and tetra-n-propyl titanate. , tetraisopropyl titanate and tetrabutyl titanate.
  • the ammonium salt concentration of the mixed alkali solution is 0.1 to 0.3moL/L.
  • the ammonium salt may be selected from one or more types of ammonium bicarbonate, ammonium carbonate, and organic ammonium salts.
  • the alkali concentration is 0.2 to 0.4moL/L.
  • the alkali solution can be selected from ammonia, sodium hydroxide, potassium hydroxide and organic bases such as triethylamine, N,N-2 toluidine, pyridine and quinoline.
  • the acid solution can be one or more selected from sulfuric acid, nitric acid, hydrochloric acid, and organic acids such as formic acid, acetic acid, citric acid, and oxalic acid.
  • the reactant input ratios in steps II(a), II(b) and II(c) are as follows:
  • the titanium source solution charging ratio in steps II(a) and II(c) can be 1:4-2:3.
  • the feeding amount of the titanium source solution in step II(a) accounts for 20%-40% of the total titanium source solution feeding volume in the method
  • the feeding amount in step II(c) accounts for 20%-40% of the total titanium source solution feeding volume in the method. 60%-80% of the total titanium source solution feeding volume
  • the feeding ratio of the mixed alkali solution in steps II(a) and II(b) can be in the range of 2:1 to 1:2, or in the range of 1.5:1 to 1:1.
  • the input amount of the mixed alkali solution in step II(a) accounts for 33%-67%, preferably 50%-60%
  • the input amount in step II(b) accounts for 33%-670%, preferably 40%-50% , relative to the total feed volume in II(a) and II(b).
  • the precipitate washing process includes washing with deionized water until acid ions cannot be detected, the drying temperature is 100°C to 120°C, and the drying time is 4°C to 12h, The calcination temperature is 800°C to 1000°C.
  • the composite oxide prepared by the method provided by the present invention contains 5wt% to 21wt% titanium dioxide, and the titanium dioxide and alumina are uniformly mixed. And the inventor was surprised to find that the surface microstructure of the composite oxide showed a 3D layered structure of coral clusters.
  • the coral-like 3D layered structure can make the composite oxide have a higher specific surface area, thereby having more active sites and stronger electron capture ability, which helps to promote the catalytic effect of TiO 2 as an electron promoter, Thereby improving the overall performance of the catalyst such as activity and selectivity.
  • the roasting temperature of TiO 2 starts to produce rutile from 500°C, and most of the crystal phase of TiO 2 above 700°C changes from anatase phase to rutile phase.
  • the composite oxide prepared by the method provided by the present invention is roasted at a high temperature of 800°C or higher, it is found through X-ray diffraction analysis that anatase titanium dioxide accounts for 95wt%-100wt% of all crystal phases of TiO2 . Breaks common sense.
  • TiO 2 existing in the form of anatase in the composite oxide has an electron induction effect and can effectively induce a decrease in the electron cloud density of the active metal Ni in the prepared catalyst (compared to the rutile phase generated by high-temperature roasting), thus Enhance the adsorption capacity of alkynes in the reaction raw materials and improve the selective hydrogenation activity and selectivity of the catalyst.
  • the present invention also provides an application of a composite oxide, which includes the use of the composite oxide prepared according to the first aspect of the present invention or the composite oxide prepared by the method of the second aspect as a catalyst carrier.
  • the type of catalyst is not particularly limited.
  • the present invention provides a hydrogenation catalyst, which includes a composite oxide according to the first aspect of the present invention or a composite oxide prepared according to the method according to the second aspect, and an active component, such as Palladium, nickel, iron or cobalt.
  • the hydrogenation metal is nickel.
  • the hydrogenation catalyst may have a nickel content of 8-25 wt%, preferably 12-20 wt%.
  • the hydrogenation catalyst includes palladium, which may be present in an amount of 0.1-2 wt%, such as 0.15-1.5 wt%.
  • the present invention also provides an alkyne selective hydrogenation method, which hydrogenation method includes performing alkyne selective hydrogenation on distillate oil in the presence of the hydrogenation catalyst described in the third aspect to increase the production of butylene.
  • Alkene wherein the distillate oil includes C4 distillate oil, preferably the high-alkyne tail gas produced by a butadiene extraction unit.
  • the reaction temperature is 20°C to 40°C
  • the molar ratio of hydrogen to alkyne is 1:1 to 2.5:1
  • the pressure is 0.5MPa to 0.8MPa
  • the circulation ratio is 10 :1 to 30:1.
  • the catalyst provided by the invention exhibits high vinyl acetylene conversion rate and high 1,3-butadiene selectivity in the selective hydrogenation of alkynes.
  • Figure 1 shows the 3D microscopic morphology of the coral cluster of the alumina-titanium dioxide composite oxide prepared in Example 1.
  • Figure 2 shows the XRD pattern of the alumina-titanium dioxide composite oxide prepared in Example 1.
  • the raw materials or components used in the present invention can be prepared through commercial channels or conventional methods.
  • the ASAP ⁇ 2020 adsorption instrument (N 2 adsorption and desorption method) of the American Mike Instrument Company was used to determine the specific surface area and pore structure of the composite oxide. Before testing, the composite oxide sample was degassed at 623K for 4 hours, and nitrogen was adsorbed at liquid nitrogen temperature. AMSM software was used to process the sample data, and the Brunauer-Emmet-Teller (BET) method was used to obtain the specific surface area of the sample. The Barrett-Joyner-Halenda (BJH) method was used to obtain the average pore diameter based on the nitrogen adsorption isotherm curve, and the P/Po single-point desorption curve was used to obtain the pore volume.
  • BET Brunauer-Emmet-Teller
  • BJH Barrett-Joyner-Halenda
  • the morphology of the composite oxide was observed using FEI's QUANTA 200 scanning electron microscope.
  • the crystal phase structure of the composite oxide was characterized using an EMPYREAN X-ray diffractometer from PANalytical Corporation of the Netherlands.
  • Cu K ⁇ is the radiation source X-ray tube voltage 40kV, light tube current 40mA, slit width 10mm, scanning range: 5-90°, scanning speed: 0.013°/s.
  • the temperature was raised to 92°C, maintained for 20 minutes, filtered, and the filter cake was repeatedly washed 5 times with 20 times the volume of deionized water.
  • the washed filter cake was dried at 110°C for 6 hours and roasted at 850°C for 5 hours. 114.3g of composite oxide with a TiO2 content of 15.0wt% was obtained.
  • FIG. 1 shows the surface micromorphology of the composite oxide exhibits a 3D layered structure of coral clusters.
  • Figure 2 shows the XRD pattern of the alumina-titanium dioxide composite oxide prepared in Example 1.
  • Dissolve 32.15g Ti(SO 4 ) 2 in deionized water add 5 mL (98%) concentrated sulfuric acid, and prepare 500 mL of dilute sulfuric acid solution of titanium sulfate.
  • Example 2 Repeat the preparation process of the titanium dioxide-alumina composite oxide in Example 1, except that 379.79g Al(NO 3) 3 is dissolved in deionized water to prepare 1000 mL of aluminum nitrate solution. Dissolve 25.99g Ti(OCH 3 CH 2 ) 4 in absolute ethanol to prepare 500 mL of tetraethyl titanate ethanol solution. Finally, 9.1% alumina-titanium dioxide composite oxide was obtained.
  • Example 2 Repeat the preparation process of the titanium dioxide-alumina composite oxide in Example 1, except that 396.92g Al(NO 3 ) 3 is dissolved in deionized water to prepare 1000 mL of aluminum nitrate solution. Dissolve 6.13g TiO(OH) 2 in the sulfuric acid solution, add deionized water, and prepare 500 mL of dilute sulfuric acid solution of metatitanic acid. Finally, 5.0% alumina-titanium dioxide composite oxide was obtained.
  • Example 2 Repeat the preparation process of the titanium dioxide-alumina composite oxide in Example 1, except that 396.92g Al(NO 3 ) 3 is dissolved in deionized water to prepare 1000 mL of aluminum nitrate solution. Dissolve 6.13g TiO(OH) 2 in the sulfuric acid solution, add deionized water, and prepare 500 mL of dilute sulfuric acid solution of metatitanic acid. The filter cake baking temperature is changed to 800°C, and finally 5.0% alumina-titanium dioxide composite oxide is obtained. .
  • Example 2 Repeat the preparation process of the titanium dioxide-alumina composite oxide in Example 1, except that 374.13g AlCl3 ⁇ 6H 2 O is dissolved in deionized water to prepare 1000 mL of aluminum chloride solution. Dissolve 59.99g Ti(OCH 3 CH 2 ) 4 in absolute ethanol to prepare 500 mL of tetraethyl titanate ethanol solution. Finally, 21.0% alumina-titanium dioxide composite oxide was obtained.
  • Dissolve 24.5g TiO(OH) 2 in the sulfuric acid solution add deionized water to prepare 1000 mL of dilute sulfuric acid solution of metatitanic acid.
  • Control the flow rate of the mixed alkali solution to keep the pH value of the precipitate in the range of 5.0-6.0 for 8 minutes then increase the flow rate of the mixed alkali solution to keep the pH value of the mixed solution in the range of 8.5-9.5 for 8 minutes, and then Reduce the flow rate of the mixed alkali solution to keep the pH value of the mixed solution in the range of 5.0-6.0 for 8 minutes, then increase the flow rate of the mixed alkali solution to keep the pH value of the precipitate in the range of 8.5-9.5, and repeat this until the solution A1 and B1 are all added dropwise.
  • solution A1 Take 401.88g of analytically pure AlCl 3 ⁇ 6H 2 O and dissolve it in 1000ml of deionized water to prepare solution A1; take 43.25g of chemically pure Ti(OCH 2 CH 3 ) 4 and dissolve it in 500ml of benzene (benzene content is 99.8 (Wt )%), prepare solution B1; take 18g of analytically pure NH 4 HCO 3 , dissolve it in 600 ml of deionized water, add 250 ml of ammonia water with a concentration of 24-28 wt%, stir and mix evenly, and then add deionized water to prepare 1000 ml of solution C1.
  • the N2 adsorption-desorption method was used to determine the specific surface area and pore structure of the composite oxide on the carrier prepared above.
  • Example 4 90% Example 5 85% Example 6 85% Comparative example 1 78% Comparative example 2 34% Comparative example 3 82%
  • the impregnation time is 0.5 h. After filtering, drying at 110°C for 5 h and roasting at 550°C for 5 h. Then use 100 mL of 12.24 g Ni/100 mL of nickel nitrate aqueous solution to impregnate 100 g of the above-mentioned calcined catalyst precursor.
  • the impregnation time is 0.5 h. After drying, it is dried at 110°C for 4 hours and roasted at 550°C for 6 hours to obtain a Ni content of 19.82%. Ni/Al 2 O 3 -TiO 2 Catalyst B.
  • the impregnation time is 0.5 h. After filtering, drying at 110°C for 5 h and roasting at 550°C for 5 h. Then use 100mL of 20gNi/100mL nickel nitrate aqueous solution to impregnate 100g of the above-mentioned calcined catalyst precursor. The impregnation time is 0.5h. After drying, it is dried at 110°C for 4h and roasted at 550°C for 6h to obtain a Ni content of 25% Ni/ Al 2 O 3 -TiO 2 Catalyst D.
  • the impregnation time is 0.5 h. After filtering, drying at 110°C for 5 h and roasting at 550°C for 5 h. Then use 100 mL of 12.24 g Ni/100 mL of nickel nitrate aqueous solution to impregnate 100 g of the above-mentioned calcined catalyst precursor.
  • the impregnation time is 0.5 h. After drying, it is dried at 110°C for 4 hours and roasted at 550°C for 6 hours to obtain a Ni content of 19.82%. Ni/Al 2 O 3 -TiO 2 Catalyst E.
  • the impregnation time is 0.5 h. After filtering, drying at 110°C for 5 h and roasting at 550°C for 5 h. Then use 100 mL of 12.24 g Ni/100 mL of nickel nitrate aqueous solution to impregnate 100 g of the above-mentioned calcined catalyst precursor. The impregnation time is 0.5 h. After drying, it is dried at 110°C for 4 hours and roasted at 550°C for 6 hours to obtain a Ni content of 19.82%. Ni/Al 2 O 3 -TiO 2 Catalyst F.
  • Example 1 Immerse 100g of the composite oxide prepared in Example 1 into 85mL of a palladium chloride aqueous solution with a palladium atom content of 0.32g/100mL, take it out after 1.5 hours, filter out the impregnated composite carrier, and use 120mL of a palladium chloride solution with a concentration of 10wt%.
  • the hydrazine hydrate aqueous solution is reduced at room temperature for 1 hour, rinsed repeatedly with deionized water until the chloride ions are washed away, drained and dried at 120°C for 6 hours, and then roasted at 480°C for 4 hours to obtain a palladium content of A Pd/Al 2 O 3 -TiO 2 catalyst H with a Pd content of 0.3% was obtained.
  • This example is the application of the catalyst in the selective hydrogenation reaction of butadiene extraction tail gas.
  • the catalysts used in this example are catalysts A-K.
  • the raw material used in this example is butadiene extraction tail gas from a certain plant.
  • the composition is shown in Table 3.
  • the fixed-bed small-scale evaluation device of Tuochuan Scientific Research Equipment Co., Ltd. is used, and 50 mL of catalyst is loaded to perform selective hydrogenation reaction of butadiene extraction tail gas.
  • reaction pressure is 0.5 to 0.7MPa
  • hydrogen volume is 1.92L/h
  • reactor inlet temperature is 25°C
  • circulation ratio is 20:1
  • raw material feed volume is 25mL/h.
  • Catalysts A to K were evaluated under the same conditions, and the results of hydrogenation and acetylene removal are shown in Table 4.
  • the catalyst provided by the present invention exhibits a high conversion rate of vinyl acetylene and a high selectivity of 1,3-butadiene. Because the vinyl acetylene in the hydrogenated product can be controlled within a lower range, the hydrogenated product can be directly returned to the extraction system to increase butadiene production.
  • Example 7 Catalyst A prepared in Example 7 was used to conduct a long-term stability experiment under the same conditions as in Example 15.
  • the stability evaluation experimental data for 1000 hours is as follows in Table 5:
  • the catalyst provided by the present invention exhibits high stability for the selective hydrogenation reaction of butadiene tail gas feedstock with high acetylene content.
  • the hydrogenation catalyst of the present invention not only has high 1,3-butadiene selectivity (%) and vinyl acetylene conversion rate (%), but also can be maintained at a high level for a long time, so it is suitable for long-term operation.

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Abstract

本发明涉及一种复合氧化物，其包括60-95wt％的氧化铝和5-40wt％的二氧化钛，所述复合氧化物的通过BET法测定的比表面积表示为X m 2/g，所述复合氧化物的通过氮气吸附等温曲线法测定的平均孔径表示为Y nm，其中X与Y的比值为5至30，并且通过X射线衍射法测定，所述复合氧化物中锐钛矿晶相的二氧化钛占总的二氧化钛的95wt％-100wt％，其中X在50-200的范围内，优选X在60-180的范围内,更优选在80-150的范围内,Y在5-25nm的范围内。本发明还提供了包含所述复合氧化物的加氢催化剂，其表现出很高的乙烯基乙炔转化率和高的1,3-丁二烯选择性。

Description

复合氧化物、复合氧化物的制备方法、加氢催化剂及其应用 技术领域
本发明涉及一种复合氧化物、复合氧化物的制备方法、加氢催化剂及其应用，具体可用于加氢脱除C 4馏分中的炔烃并增产丁二烯。
背景技术
碳四馏份是指含有四个碳原子的多种烷烃、烯烃、二烯烃和炔烃的混合物，主要来源于石油炼制过程产生的炼厂气和石油烃类裂解制乙烯过程的副产品，裂解碳四中含有正丁烷、异丁烷、1-丁烯，反-2-丁烯、顺-2-丁烯，异丁烯、1，2-丁二烯、1，3-丁二烯、甲基乙炔、乙基乙炔、乙烯基乙炔等饱合烃和不饱和烃，工业上主要用来生产1，3-丁二烯、异丁烯和1-丁烯。
烃类高温裂解制乙烯副产的裂解碳四馏分中通常含有质量分数40％-60％的丁二烯，丁二烯是合成橡胶工业的重要单体，从裂解碳四馏分中提取丁二烯通常采用溶剂抽提法，如乙腈法、N-甲基吡咯烷酮法和二甲基甲酰胺法，目前，这些方法基本满足对丁二烯纯度的要求。
由于裂解深度及裂解技术等因素的影响，裂解碳四馏分中炔烃含量呈逐渐增加趋势，导致抽提过程中丁二烯的损失增大和能托增加。同时，随着有机合成工业技术的发展，对丁二烯中炔烃含量的限制更加严格，这些因素均导致丁二烯抽提装置的经济性变差，在抽提丁二烯时，将块烃选择性加氢后回收部分丁二烯，不仅可以达到变废为宝的目的，而且减少炔烃排放和防止环境污染也起到重要作用。
目前，混合碳四烃馏分中的炔烃可以采用催化选择加氢的方法除去。所用催化剂主要倾向于使用以钯、铂、银等为代表的贵金属催化剂，其次是以铜、镍为代表的非贵金属催化剂。
烃类物流中炔烃的选择加氢因原料组成的不同和目的产物的不同，所选择的催化剂和反应条件亦有所不同。一种好的选择加氢催化剂除了要有较高的加氢活性外，还应具有良好的稳定性，即催化剂要有抗杂质及抗胶质的能力，这样才能延长催化剂的寿命。因此，要求载体要有较低的酸性、较小的比表面积和较大的孔径。另外，在催化剂的制备中，加入一些助剂也能延长催化剂的使用寿命。
贵金属催化剂一般大量地采用负载在载体(通常采用氧化铝)上的钯催化剂，并添加其他的助催化剂组分，如金、银、铬、铜、铁、铑、锂、钾，还有铅或锌。贵金属催化剂 低温活性好，反应条件温和，但其不足之处在于催化剂活性组分易流失、价格昂贵，不易再生，加氢选择性稍差。非贵金属催化剂需在较高的温度下反应，加氢条件较苛刻，但其制备简单，便于反复再生，且成本相对较低，因此仍具有一定的研究开发价值。在这类加氢反应过程中，吸附在催化剂上的半氢化状态自由基与相邻的炔烃或二烯烃反应生成一种粘稠状的聚合物(俗称绿油)，它主要由C 6以上的化合物组成，因其覆盖在催化剂的表面，堵塞了催化剂表面的微孔，使催化剂活性下降，影响催化剂的使用寿命。尤其对于共轭二烯烃(如1，3-丁二烯)，其聚合反应更容易进行，从而使催化剂在短时间内失活，这样催化剂必须经常再生才能重复使用。
在碳四炔烃选择加氢领域的应用研究中，人们意识到对于高浓度的炔烃含量的原料，使用镍基选择加氢催化剂更加安全高效，但是镍基选择加氢催化剂的活性与选择性相比贵金属钯基催化剂而言有一定的差距，使得其应用受到限制。因此，对于炔烃选择加氢用非贵金属催化剂，还需要进一步提高该催化剂的活性和选择性，针对催化剂使用过程中的绿油问题进行对策研究，并延长催化剂寿命。对于炔烃选择加氢使用非贵金属加氢催化剂，可以提高催化剂的抗杂质中毒能力和稳定性，具有经济价值。
根据光催化剂领域的研究表明，以TiO 2为主的催化材料的结构和形状能够极大地影响材料的光吸收效率。珊瑚礁具有出色的吸光和反射结构，因此为海底的许多动植物提供了三维(3D)环境，并可以吸收小颗粒，支撑大约四分之一的已知海洋生物生活。珊瑚状的3D分层结构可以具有更高的比表面积，从而具有更多的活性位点和更强的光捕获能力，并且已被证明具有比其他结构更好的光催化性能。使用特定的类似珊瑚礁形貌的催化材料可以提高以TiO 2为载体的催化剂性能。
发明内容
针对现有技术的不足，本发明的目的在于提供一种低温活性高、选择性高、稳定性高的非贵金属选择加氢催化剂。相比于贵金属选择加氢除炔催化剂，本公开的催化剂投资成本可以节省80％以上，并且催化剂具有较好的抗杂质中毒能力和原料适应性。
在第一方面，本发明提供了一种复合氧化物，其包括氧化铝和二氧化钛，所述复合氧化物的比表面积表示为X m 2/g，所述复合氧化物的平均孔径表示为Y nm，其中X与Y的比值为5至30；并且其中所述复合氧化物中，锐钛矿晶相的二氧化钛占总的二氧化钛的95wt％-100wt％。优选地，X与Y的比值为5至15。进一步优选地，X与Y的比值为5至10。优选地，所述复合氧化物中，锐钛矿晶相的二氧化钛占总的二氧化钛的96wt％-100wt％。优选地，所述复合氧化物中，锐钛矿晶相的二氧化钛占总的二氧化钛的 97wt％-100wt％。优选地，所述复合氧化物中，锐钛矿晶相的二氧化钛占总的二氧化钛的98wt％-100wt％。优选地，所述复合氧化物中，锐钛矿晶相的二氧化钛占总的二氧化钛的99wt％-100wt％。
本发明中，锐钛矿晶相的二氧化钛占总的二氧化钛的比例可以通过X射线衍射分析测量。
本发明中，复合氧化物的比表面积可以通过BET法测定。
本发明中，复合氧化物的平均孔径可以通过氮气吸附等温曲线法测定。
在本发明的一些实施方案中，通过X射线衍射分析测量的表示锐钛矿型二氧化钛的晶体结构的衍射峰面积占所有的二氧化钛晶体结构的衍射峰面积的95wt％-100wt％。
在本发明的一些实施方案中，通过X射线衍射分析测量的表示锐钛矿型二氧化钛的晶体结构的衍射峰面积占所有的二氧化钛晶体结构的衍射峰面积的96wt％-100wt％。
在本发明的一些实施方案中，通过X射线衍射分析测量的表示锐钛矿型二氧化钛的晶体结构的衍射峰面积占所有的二氧化钛晶体结构的衍射峰面积的97wt％-100wt％。
在本发明的一些实施方案中，通过X射线衍射分析测量的表示锐钛矿型二氧化钛的晶体结构的衍射峰面积占所有的二氧化钛晶体结构的衍射峰面积的98wt％-100wt％。
在本发明的一些实施方案中，所述复合氧化物的采用P/Po单点脱附曲线测定的孔容为Z mL/g，X与Z的比值为220至400，优选为250至350。在一些实施例中，X与Z的比值为250、260、270、280、290、300、310、320、330、340、350或在其中任意二者组成的范围内。
在本发明的一些实施方案中，X为90至150。在一些实施例中，X为90、100、110、120、130、140、150或在其中任意二者组成的范围内。
在本发明的一些实施方案中，Y为9至20，优选为12至16。在一些实施例中，Y为12、13、14、15、16或在其中任意二者组成的范围内。
在本发明的一些实施方案中，在所述复合氧化物中，按体积计，孔径在10-20nm范围的孔占所有孔的比例为至少85％。
在本发明的一些实施方案中，Z为0.3至0.5，优选为0.3至0.4。在一些实施例中，Z为0.31、0.32、0.33、0.34、0.35、0.36、0.37、0.38、0.39、0.40或在其中任意二者组成的范围内。
在本发明的一些实施方案中，所述复合氧化物中含有5wt％至21wt％的二氧化钛，基于复合氧化物的总重量计。在一些实施例中，所述复合氧化物中含有5wt％、6wt％、8wt％、10wt％、12wt％、15wt％、18wt％、20wt％、21wt％或在其中任意二者组成的范围内的二 氧化钛。
根据本发明的一些实施方式，所述复合氧化物中含有79wt％至95wt％的氧化铝，基于复合氧化物的总重量计。
在本发明的一些实施方案中，所述复合氧化物具有珊瑚丛状3D分层结构。珊瑚丛状的3D分层结构可以具有更高的比表面积，从而具有更多的活性位点和更强的光捕获能力。
在第二方面，本发明提供了一种复合氧化物的制备方法，通过该制备方法可以得到具有珊瑚丛3D微观形貌的氧化铝-二氧化钛复合氧化物。本发明的制备方法包括以下步骤：
步骤I.将可溶性铝源溶解于水中形成铝源溶液，将钛源溶解于酸溶液中形成钛源溶液，将铵盐和碱液混合形成混合碱溶液；
步骤II.(a)向所述铝源溶液中加入所述钛源溶液和所述混合碱溶液，使得到的混合液在第一pH值保持第一时间段；(b)向所述混合液加入附加的混合碱溶液，使得到的混合液在第二pH值保持第二时间段；(c)向所述混合液加入附加的钛源溶液，使得到的混合液在第三pH值保持第三时间段；
步骤III.在步骤II.(c)之后，将所述混合液的温度升高，保持第四时间段，得到沉淀物；
步骤IV.将所述沉淀物进行干燥和焙烧，得到含有氧化铝和二氧化钛的复合氧化物，优选地，在干燥之前还进行洗涤和过滤(以除去不需要的杂质)。
如此得到的复合氧化物具有在本发明第一方面中所描述的组成和结构特征。
在本发明方法的一些实施方案中，在所述步骤II中，第一pH值小于5，优选为3至4。在本发明方法的一些实施方案中，在所述步骤II中，第二pH值大于8.5，优选为9至10。在本发明方法的一些实施方案中，在所述步骤II中，第三pH值为大于7且小于9，优选为7.5至8.5。
在本发明方法的一些实施方案中，在所述步骤II中，第一时间段、第二时间段和第三时间段分别为5分钟至20分钟，优选10分钟至15分钟。
在本发明方法的一些实施方案中，在所述步骤III中，第四时间段为20分钟至60分钟。
在本发明方法的一些实施方案中，在所述步骤II中，操作温度为25℃至60℃，优选50℃至60℃。
在本发明方法的一些实施方案中，在所述步骤III中，将温度升高至80℃至150℃，优选80℃至100℃。在一些实施例中，在所述步骤III中，将温度升高至80℃、85℃、90℃、92℃或95℃。
在本发明方法的一些实施方案中，所述步骤IV中，干燥温度为110℃至130℃。干燥时间为4-12h，优选6-10h
在本发明方法的一些实施方案中，所述步骤IV中，焙烧温度为800℃至1000℃。在一些实施例中，所述步骤IV中，焙烧温度为800℃、850℃、900℃、950℃或其中任意二者组成的范围内。焙烧时间为4-12h，优选5-8h
在本发明方法的一些实施方案中，所述的铝源溶液的铝浓度为0.5至2.5mol/L。所述的铝源为可溶性铝盐，可选择硫酸铝、氯化铝和硝酸铝、以及有机铝如异丙醇铝、仲丁醇铝、一乙酸铝、二乙酸铝盐中的一种或者多种。
在本发明方法的一些实施方案中，所述的钛源溶液的钛浓度为0.2至1.2moL/L。所述的钛源为可溶性钛源，可选自钛盐如钛的乙酸盐、盐酸盐、硫酸盐、硝酸盐或选自钛酸酯如钛酸四乙酯、钛酸四正丙酯、钛酸四异丙酯和钛酸四丁酯。
在本发明方法的一些实施方案中，所述混合碱溶液的铵盐浓度为0.1至0.3moL/L。所述的铵盐可以选自碳酸氢铵、碳酸铵、和有机铵盐的一种或者多种。
在本发明方法的一些实施方案中，所述的碱液浓度为0.2至0.4moL/L。所述的碱液可选择氨水、氢氧化钠、氢氧化钾和有机碱如三乙胺、N,N-2甲苯胺，吡啶，喹啉的一种或者多种。
在本发明方法的一些实施方案中，所述的酸溶液可选择硫酸、硝酸、盐酸、和有机酸如甲酸、乙酸、柠檬酸、草酸的一种或者多种。
在本发明方法的一些实施方案中，步骤II(a)、II(b)和II(c)中反应物投料比如下：
钛源溶液在步骤II(a)、II(c)中投料比可以为1:4-2:3。或者，钛源溶液在步骤II(a)中的投料量占在所述方法中总钛源溶液投料体积的20％-40％，在步骤II(c)中的投料量占在所述方法中总钛源溶液投料体积的60％-80％，
混合碱溶液在步骤II(a)、II(b)中投料比可以为2：1至1:2的范围内，或者在1.5:1至1:1的范围内。或者，混合碱溶液在步骤II(a)中投料量占33％-67％，优选50％-60％，在步骤II(b)中投料量占33％-670％，优选40％-50％，相对于在II(a)和II(b)中总投料体积计。
在本发明方法的一些实施方案中，所述步骤IV中，沉淀物洗涤过程包括用去离子水洗涤至酸根离子测不出，干燥温度为100℃至120℃，干燥时间为4℃至12h，焙烧温度为800℃至1000℃。
根据本发明所提供的方法制备的复合氧化物，复合物中含有5wt％至21wt％的二氧化钛，二氧化钛与氧化铝均匀混合。并且本发明人惊讶的发现：该复合氧化物表面微观形貌呈珊瑚丛3D分层结构。珊瑚状的3D分层结构可以使得复合氧化物具有更高的比表面积， 从而具有更多的活性位点和更强的电子捕获能力，有助于促进TiO 2作为电子助剂的助催化作用，从而提高催化剂的活性和选择性等综合性能。
此外，一般认为TiO 2的焙烧温度从500℃开始产生金红石，700℃以上TiO 2的晶相绝大部分由锐钛矿相转为金红石相。本发明所提供的方法制备的复合氧化物，在800℃或更高的高温焙烧后，通过X-射线衍射分析测量发现，锐钛矿型二氧化钛占TiO 2所有晶相的95wt％-100wt％，打破了常识。据信在复合氧化物中，以锐钛矿形态存在的TiO 2具有电子诱导效应，能够(与高温焙烧生成的金红石相相比)有效诱导制备的催化剂中的活性金属Ni电子云密度下降，从而增强对反应原料中炔烃的吸附能力，提高催化剂的选择加氢活性和选择性。
在第三方面，本发明还提供了一种复合氧化物的应用，其包括根据本发明第一方面所述的复合氧化物或者第二方面所述方法制备的复合氧化物作为催化剂载体的应用。
根据本发明，所述催化剂的类型不受特殊限制。
在一些实施方案中，本发明提供了一种加氢催化剂，其包括根据本发明第一方面所述的复合氧化物或根据第二方面所述的方法制备的复合氧化物以及活性组分，例如钯、镍、铁或钴。
根据本发明加氢催化剂的一些实施方式，所述加氢金属是镍。在一些实施方案中，所述加氢催化剂的镍含量可以为8-25wt％，优选12-20wt％。在其它一些实施方案中，所述加氢催化剂包含钯，其含量可以为0.1-2wt％，例如0.15-1.5wt％。
在第四方面，本发明还提供了一种炔烃选择加氢方法，该加氢方法包括将馏分油在第三方面所述的加氢催化剂的存在下进行炔烃选择加氢以增产丁二烯，其中所述馏分油包括C4馏分油，优选丁二烯抽提装置副产的高炔烃尾气。
进一步地，在炔烃选择加氢的过程中，反应温度为20℃至40℃，氢气与炔烃的摩尔比为1:1至2.5:1，压力为0.5MPa至0.8MPa，循环比为10：1至30:1。
本发明提供的催化剂在炔烃选择加氢中表现出很高的乙烯基乙炔转化率和高的1,3-丁二烯选择性。
附图简要说明
图1显示了实施例1制备的氧化铝-二氧化钛复合氧化物的珊瑚丛3D微观形貌。
图2显示了实施例1中制备的氧化铝-二氧化钛复合氧化物的XRD谱图。
具体实施方式
为使本发明容易理解，下面将结合实施例来详细说明本发明，这些实施例仅起说明性 作用，并不局限于本发明的应用范围。
本发明中所使用的原料或组分若无特殊说明均可以通过商业途径或常规方法制得。
采用美国麦克仪器公司的ASAP·2020型吸附仪(N 2吸脱附法)来测定复合氧化物的比表面积和孔结构。测试前将复合氧化物样品在623K下脱气4h，液氮温度下吸附氮气，使用AMSM软件来处理样品数据，使用Brunauer-Emmet-Teller(BET)方法得到样品的比表面积。采用Barrett-Joyner-Halenda(BJH)法根据氮气吸附等温曲线得到平均孔径，采用P/Po单点脱附曲线得到孔容。
使用FEI公司的QUANTA 200型扫描电镜来观察复合氧化物形貌。
采用荷兰帕纳科公司，EMPYREAN型X射线衍射仪对复合氧化物的晶相结构进行表征。Cu Kα为辐射源X光管电压40kV，光管电流40mA，狭缝宽度10mm，扫描范围：5-90°，扫描速度：0.013°/s。
实施例1
取328.02gAl 2(SO 4) 3溶于去离子水中制得1000mL的硫酸铝溶液。取21.14gTiO(OH) 2溶于16mL 98wt％硫酸溶液中，加入去离子水制得500mL偏钛酸的稀硫酸溶液。取18gNH 4HCO 3溶于600mL的去离子水中制得碳酸氢铵溶液，再加入250mL浓度为27wt％的氨水，搅拌混合均匀，加去离子水配置成1000mL的混碱溶液。
在常压，55℃的温度下，将230mL上述偏钛酸的稀硫酸溶液与360mL混碱溶液并流加入制备的1000mL的硫酸铝溶液中，保持强烈的搅拌，保持混合溶液pH值在3至4的范围内15min。然后，加入另外320mL混碱溶液使得pH＝9至10，在此范围内停留15min。然后，加入剩余的上述偏钛酸的稀硫酸溶液，pH调整到7.5至8.5，停留6min至10min。然后，使温度上升至92℃，保持20min，过滤，将滤饼使用20倍体积的去离子水反复洗涤5次，将洗涤后的滤饼110℃烘干6h，于850℃焙烧5h。得到114.3gTiO 2含量为15.0wt％的复合氧化物。
通过图1的SEM可以看出复合氧化物表面微观形貌呈珊瑚丛3D分层结构。图2显示了实施例1中制备的氧化铝-二氧化钛复合氧化物的XRD谱图。对于二氧化钛而言，仅在2θ＝25.4°出现了锐钛矿的特征衍射峰而未在其他位置出现其他晶相的衍射峰，表明复合氧化物中的TiO 2组分都是以锐钛矿晶相形式存在的，也就是说，锐钛矿晶相的二氧化钛占总的二氧化钛的100wt％。
实施例2
取256.04gAl 2(SO 4) 3溶于去离子水中制得1000mL的硫酸铝溶液。取32.15gTi(SO 4) 2溶于,溶于去离子水，加入5mL(98％)浓硫酸，制得500mL硫酸钛的稀硫酸溶液。取18gNH 4HCO 3溶于600mL的去离子水中制得碳酸氢铵溶液，再加入250mL浓度为27wt％的氨水，搅拌混合均匀，加去离子水配置成1000mL的混碱溶液。
在常压，在60℃的温度下，将280mL上述硫酸钛的稀硫酸溶液与320mL混碱溶液并流加入1000mL的硫酸铝溶液中，保持强烈的搅拌，保持混合溶液pH值在3至4的范围内15min。继续加入240mL混碱溶液，使得pH＝9至10，在此范围内停留15min。然后，加入剩余的上述硫酸钛的稀硫酸溶液，pH调整到7.5至8.5。将温度上升至85℃，保持40min，过滤，将滤饼使用20倍体积的去离子水洗涤反复洗涤5次，将洗涤后的滤饼110℃烘干6h，于950℃焙烧5h。得到到86.8gTiO 2含量为12.3％的氧化铝-二氧化钛复合氧化物。
实施例3
重复实施例1中的二氧化钛-氧化铝复合氧化物的制备过程，不同之处在于取379.79gAl(NO 3)3溶于去离子水中，制得1000mL的硝酸铝溶液。取25.99gTi(OCH 3CH 2) 4溶于无水乙醇中，制得500mL钛酸四乙酯乙醇溶液。最终得到9.1％的氧化铝-二氧化钛复合氧化物。
实施例4
重复实施例1中的二氧化钛-氧化铝复合氧化物的制备过程，不同之处在于取396.92gAl(NO 3) 3溶于去离子水中，制得1000mL的硝酸铝溶液。取6.13gTiO(OH) 2溶于硫酸溶液中，加入去离子水，制得500mL偏钛酸的稀硫酸溶液。最终得到5.0％的氧化铝-二氧化钛复合氧化物。
实施例5
重复实施例1中的二氧化钛-氧化铝复合氧化物的制备过程，不同之处在于取396.92gAl(NO 3) 3溶于去离子水中，制得1000mL的硝酸铝溶液。取6.13gTiO(OH) 2溶于硫酸溶液中，加入去离子水，制得500mL偏钛酸的稀硫酸溶液，滤饼焙烧温度改为800℃，最终得到5.0％的氧化铝-二氧化钛复合氧化物。
实施例6
重复实施例1中的二氧化钛-氧化铝复合氧化物的制备过程，不同之处在于取374.13gAlCl3·6H 2O溶于去离子水中，制得1000mL的氯化铝溶液。取59.99gTi(OCH 3CH 2) 4溶于无水乙醇中，制得500mL钛酸四乙酯乙醇溶液。最终得到21.0％的氧化铝-二氧化钛复合氧化物。
扫描电镜和XRD测试结果表明，实施例2-6制备的复合氧化物与实施例1类似，其表面微观形貌呈珊瑚丛3D分层结构，并且复合氧化物中的TiO 2组分都是以锐钛矿晶相形式存在。
对比例1
取268.46gAl 2(SO 4) 3溶于去离子水中制得1000mL的硫酸铝溶液。取24.5gTiO(OH) 2溶于硫酸溶液中，加入去离子水制得1000mL偏钛酸的稀硫酸溶液。取18gNH 4HCO 3溶于600mL的去离子水中制得碳酸氢铵溶液，再加入250mL浓度为24-28wt％的氨水，搅拌混合均匀，加去离子水配置成1000mL的混碱溶液。
在常压，温度为70-75℃的条件下，将上述硫酸铝的去离子水溶液、偏钛酸的稀硫酸溶液、混合碱溶液三种溶液并流共沉淀。控制溶液混合碱溶液的流量，使沉淀物的pH值在5.0-6.0范围内保持8分钟，再加大混合碱溶液的流量，使混合溶液的pH值在8.5-9.5范围内保持8分钟，然后减少混合碱溶液的流量，使混合溶液的pH值在5.0-6.0范围内保持8分钟，再加大混合碱溶液的流量，使沉淀物的pH值在8.5-9.5范围内，如此反复，直至溶液A1和B1全部滴加完。反应液在70℃下，静置30分钟，过滤，用滤饼体积的15倍的去离子水洗涤滤饼30分钟，再过滤，再洗涤，此过程重复四次，最后将滤饼在100-120℃下干燥8-12小时，于950℃下焙烧5小时，得到二氧化钛-氧化铝复合物。其结构和性能结果见表1。
对比例2
取分析纯的401.88gAlCl 3·6H 2O，溶于1000ml的去离子水中，制得溶液A1；取化学纯的43.25gTi(OCH 2CH 3) 4，溶于500ml苯(苯含量为99.8(Wt)％)中，制得溶液B1；取分析纯的NH 4HCO 318g，溶于600ml的去离子水中，加入250ml浓度为24-28wt％的氨水，搅拌混合均匀，再加入去离子水配制成1000ml的溶液C1。
在常压，温度为70-75℃的条件下，将A1、B1和C1三种溶液并流共沉淀。控制溶液C1的流量，使沉淀物的pH值在5.0-6.0范围内保持8分钟，再加大溶液C1的流量，使混合溶液的pH值在8.5-9.5范围内保持8分钟，然后减少溶液C1的流量，使混合溶液 的pH值在5.0-6.0范围内保持8分钟，再加大溶液C1的流量，使沉淀物的pH值在8.5-9.5范围内，如此反复，直至溶液A1和B1全部滴加完。反应液在70℃下，静置30分钟，过滤，用滤饼体积的15倍的去离子水洗涤滤饼30分钟，再过滤，再洗涤，此过程重复四次，最后将滤饼在100-120℃下干燥8-12小时，于550℃下焙烧5小时，得到42.7g二氧化钛-氧化铝复合物。其结构和性能结果见表1。
对比例3
重复对比例2中的二氧化钛-氧化铝复合氧化物的制备过程，不同之处在于干燥后的焙烧温度改为950℃。
扫描电镜和XRD测试结果表明，对比例1-3制备的复合氧化物不具有珊瑚丛3D分层结构，且TiO 2晶相主要为金红石晶相的二氧化钛。
对上述制备的载体采用N 2吸脱附法测定复合氧化物的比表面积和孔结构。
表1 二氧化钛-氧化铝复合物分析数据
Figure PCTCN2022129813-appb-000001
表2 二氧化钛-氧化铝复合物载体的孔分布
  孔径在10-20nm范围的孔占所有孔的比例，按体积计
实施例1 86％
实施例2 88％
实施例3 89％
实施例4 90％
实施例5 85％
实施例6 85％
对比例1 78％
对比例2 34％
对比例3 82％
催化剂的制备
实施例7
取100mL 24.72gNi/100mL的硝酸镍水溶液浸渍上述实施例1中制备的156g复合氧化物，浸渍时间为1h，110℃烘干6h，滤干后于600℃焙烧4h，制得Ni含量13.68％的Ni/Al 2O 3-TiO 2催化剂A。
实施例8
取100mL20.0gNi/100mL的硝酸镍水溶液浸渍上述实施例1中上述制备的180g复合氧化物，浸渍时间为0.5h，滤干后110℃烘干5h，于550℃焙烧5h。然后再使用100mL12.24gNi/100mL的硝酸镍水溶液浸渍100g上述已焙烧后的催化剂前驱体，浸渍时间为0.5h，滤干后110℃烘干4h，于550℃焙烧6h制得Ni含量为19.82％Ni/Al 2O 3-TiO 2催化剂B。
实施例9
取100mL13.56gNi/100mL的硝酸镍水溶液浸渍上述实施例6中制备的156g复合氧化物，浸渍时间为1h，110℃烘干6h，滤干后于600℃焙烧4h，制得Ni含量8％Ni/Al 2O 3-TiO 2催化剂C。
实施例10
取100mL20.0gNi/100mL的硝酸镍水溶液浸渍上述实施例4中上述制备的180g复合氧化物，浸渍时间为0.5h，滤干后110℃烘干5h，于550℃焙烧5h。然后再使用100mL20gNi/100mL的硝酸镍水溶液浸渍100g上述已焙烧后的催化剂前驱体，浸渍时间为0.5h，滤干后110℃烘干4h，于550℃焙烧6h制得Ni含量为25％Ni/Al 2O 3-TiO 2催化剂D。
实施例11
取100mL20.0gNi/100mL的硝酸镍水溶液浸渍上述实施例2中上述制备的180g复合氧化物，浸渍时间为0.5h，滤干后110℃烘干5h，于550℃焙烧5h。然后再使用100mL12.24gNi/100mL的硝酸镍水溶液浸渍100g上述已焙烧后的催化剂前驱体，浸渍时间为0.5h，滤干后110℃烘干4h，于550℃焙烧6h制得Ni含量为19.82％Ni/Al 2O 3-TiO 2催化剂E。
实施例12
取100mL20.0gNi/100mL的硝酸镍水溶液浸渍上述实施例3中上述制备的180g复合氧化物，浸渍时间为0.5h，滤干后110℃烘干5h，于550℃焙烧5h。然后再使用100mL12.24gNi/100mL的硝酸镍水溶液浸渍100g上述已焙烧后的催化剂前驱体，浸渍时间为0.5h，滤干后110℃烘干4h，于550℃焙烧6h制得Ni含量为19.82％Ni/Al 2O 3-TiO 2催化剂F。
实施例13
取100mL 24.72gNi/100mL的硝酸镍水溶液浸渍上述实施例5中制备的156g复合氧化物，浸渍时间为1h，110℃烘干6h，滤干后于600℃焙烧4h，制得Ni含量13.68％的Ni/Al 2O 3-TiO 2催化剂G。
实施例14
将100g在实施例1中制备的复合氧化物浸入85mL钯原子计含量为0.32g/100mL的氯化钯水溶液中，1.5小时后取出，滤出浸渍的复合物载体，用120mL浓度为10wt％的水合肼水溶液在室温下还原1小时，用去离子水反复冲洗，到洗净氯离子为止，沥干水分后于120C下干燥6小时，然后于480℃下焙烧4小时，制得钯含量为制得Pd含量为0.3％的Pd/Al 2O 3-TiO 2催化剂H。
对比例4
取100mL24.72gNi/100mL的硝酸镍水溶液浸渍上述对比例1中156g上述制备的复合氧化物，浸渍时间为1h，滤干后110℃烘干6h，于600℃焙烧4h，制得Ni含量为13.68％Ni/Al 2O 3-TiO 2催化剂I。
对比例5
取100mL24.72gNi/100mL的硝酸镍水溶液浸渍上述对比例2中156g上述制备的复合氧化物，浸渍时间为1h，滤干后110℃烘干6h，于600℃焙烧4h，制得Ni含量为13.68％Ni/Al 2O 3-TiO 2催化剂J。
对比例6
取100mL24.72Ni/100mL的硝酸镍水溶液浸渍上述对比例3中156g上述制备的复合氧化物，浸渍时间为1h，滤干后110℃烘干6h，于600℃焙烧4h，制得Ni含量为13.68％Ni/Al 2O 3-TiO 2催化剂K。
实施例15
本实施例为催化剂在丁二烯抽提尾气选择加氢反应中的应用。
本实施例所用催化剂为催化剂A-K。
本实施例所用原料为某厂的丁二烯抽提尾气。组成见表3。
表3 某厂的丁二烯抽提尾气组成
序号 组成 wt％
1 异丁烷 2.658
2 正丁烷 5.652
3 反-2-丁烯 5.994
4 正丁烯 24.635
5 异丁烯 31.445
6 顺-2-丁烯 2.986
7 1,3-丁二烯 3.162
8 1,2-丁二烯 0
9 乙烯基乙炔(VA) 20.563
10 乙基乙炔(EA) 2.344
本实施例使用拓川科研设备有限公司的固定床小试评价装置，装填50mL催化剂，进行丁二烯抽提尾气选择加氢反应。
反应条件：反应压力为0.5至0.7MPa，氢气量为1.92L/h，反应器入口温度为25℃，循环比为20:1，原料进料量为25mL/h。
将催化剂A-K分别在相同的条件下进行评价，得到加氢除炔结果见表4。
表4 丁二烯抽提尾气选择加氢结果
Figure PCTCN2022129813-appb-000002
**1.3-丁二烯选择性＝(产物中的1.3-丁二烯-原料中的1.3-丁二烯)/(原料中乙烯基乙炔-产物中乙烯基乙炔)
由上表可以看出，本发明提供的催化剂表现出很高的乙烯基乙炔转化率，以及高的1,3-丁二烯选择性。因为加氢产品中的乙烯基乙炔可以控制在较低的范围内，所以加氢产品可以直接返回萃取系统以实现丁二烯的增产。
实施例16
使用实施例7制备的催化剂A，在与实施例15相同的情况下进行长周期稳定性实验，1000h的稳定性评价实验数据如下表5：
表5
实验时间(h) 1,3-丁二烯选择性(％) 乙烯基乙炔转化率(％)
96 44.38 80.72
192 43.65 82.74
288 42.97 81.62
384 42.12 81.53
480 43.38 81.08
576 44.85 80.45
672 44.38 80.49
768 43.57 81.27
864 44.81 80.72
960 42.76 81.67
1056 42.59 81.76
由表5可以看出，本发明提供的催化剂对高炔烃含量的丁二烯尾气原料选择加氢反应表现出很高的稳定性。本发明的加氢催化剂不仅具有高的1,3-丁二烯选择性(％)和乙烯基乙炔转化率(％)，而且可以长时间保持在较高水平，因此适合长周期运行。
应当注意的是，以上所述的实施例仅用于解释本发明，并不构成对本发明的任何限制。通过参照典型实施例对本发明进行了描述，但应当理解为其中所用的词语为描述性和解释性词汇，而不是限定性词汇。可以按规定在本发明权利要求的范围内对本发明作出修改，以及在不背离本发明的范围和精神内对本发明进行修订。尽管其中描述的本发明涉及特定的方法、材料和实施例，但是并不意味着本发明限于其中公开的特定例，相反，本发明可扩展至其他所有具有相同功能的方法和应用。

Claims (10)

  1. 一种复合氧化物，其包括60-95wt％的氧化铝和5-40wt％的二氧化钛，所述复合氧化物的通过BET法测定的比表面积表示为X m 2/g，所述复合氧化物的通过氮气吸附等温曲线法测定的平均孔径表示为Y nm，其中X与Y的比值为5至30，并且通过X射线衍射法测定，所述复合氧化物中锐钛矿晶相的二氧化钛占总的二氧化钛的95wt％-100wt％，其中X在50-200的范围内，优选X在60-180的范围内,更优选在80-150的范围内,Y在5-25nm的范围内。
  2. 根据权利要求1所述的复合氧化物，其特征在于，所述复合氧化物的孔容表示为Z mL/g，其中Z在0.3至0.5的范围内，并且其中X与Z的比值为220至400，优选为250至350。
  3. 根据权利要求1或2所述的复合氧化物，其具有以下特征至少之一：
    -X为90至150；
    -Y为9至20，优选为12至16；
    -至少85％的孔的孔径在10-20nm的范围内
    -Z为0.3至0.4；和/或所述复合氧化物中含有5wt％至21wt％的二氧化钛；和
    -所述复合氧化物具有珊瑚丛状3D分层结构。
  4. 一种复合氧化物的制备方法，包括以下步骤：
    步骤I.将可溶性铝源溶解于水中形成铝源溶液，将钛源溶解于酸溶液中形成钛源溶液，将铵盐和碱液混合形成混合碱溶液；
    步骤II.(a)向所述铝源溶液中加入所述钛源溶液和所述混合碱溶液，使得到的混合液在第一pH值保持第一时间段；(b)向所述混合液中添加附加量的混合碱溶液，使得到的混合液在第二pH值保持第二时间段；(c)向所述混合液中添加附加量的钛盐溶液，使得到的混合液在第三pH值保持第三时间段；
    步骤III.在步骤II.(c)之后，将所述混合液的温度升高，保持第四时间段，得到沉淀物；
    步骤IV.将所述沉淀物进行干燥和焙烧，得到含有氧化铝和二氧化钛的复合氧化物，优选地，在干燥之前还进行洗涤和过滤。
  5. 根据权利要求4所述的方法，其特征在于，在所述步骤II中，第一pH值小于5，优选为3至4，第二pH值大于8.5，优选为9至10，第三pH值为大于7且小于9，优选为7.5至8.5。
  6. 根据权利要求4或5所述的方法，其特征在于，第一时间段、第二时间段和第三时间段分别为5分钟至20分钟，优选10分钟至15分钟；和/或
    第四时间段为20分钟至60分钟。
  7. 根据权利要求4-6中任一项所述的方法，其特征在于，所述步骤II中，操作温度为25℃至60℃；和/或所述步骤III中，将温度升高至80℃至150℃；和/或所述步骤IV中，干燥温度为110℃至130℃，和/或焙烧温度为800℃至1000℃。
  8. 一种权利要求1-3中任一项所述的复合氧化物或根据权利要求4-7中任一项所述的方法制备的复合氧化物作为催化剂载体的应用。
  9. 一种加氢催化剂，包括权利要求1-3中任一项所述的复合氧化物或根据权利要求4-7中任一项所述的方法制备的复合氧化物和活性组分，优选地，所述活性组分是镍，并且优选地催化剂中镍含量为8-25wt％，更优选地，催化剂中镍含量为12-20wt％。
  10. 一种炔烃选择加氢方法，包括将馏分油在权利要求9所述的加氢催化剂的存在下进行炔烃选择加氢以增产丁二烯，其中所述馏分油C4馏分油，优选丁二烯抽提装置副产的高炔烃尾气；优选地，在炔烃选择加氢的过程中，反应温度为20℃至40℃，氢气与炔烃的摩尔比为1:1至2.5:1，压力为0.5MPa至0.8MPa，循环比为10：1至30:1。
PCT/CN2022/129813 2022-03-24 2022-11-04 复合氧化物、复合氧化物的制备方法、加氢催化剂及其应用 WO2023179036A1 (zh)

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