CN112138706A - Sulfur-tolerant hydrogenation catalyst for hydrogen transfer system and preparation method thereof - Google Patents

Sulfur-tolerant hydrogenation catalyst for hydrogen transfer system and preparation method thereof Download PDF

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CN112138706A
CN112138706A CN202010964150.XA CN202010964150A CN112138706A CN 112138706 A CN112138706 A CN 112138706A CN 202010964150 A CN202010964150 A CN 202010964150A CN 112138706 A CN112138706 A CN 112138706A
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sulfur
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郭洪臣
张晓彤
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Dalian University of Technology
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0325—Noble metals
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • 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
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a sulfur-resistant hydrogenation catalyst for a hydrogen transfer system and a preparation method thereof. The hydrogen storage carrier of the hydrogen transfer system is toluene and methylcyclohexane, and the hydrogenation catalyst is a supported platinum catalyst. The catalyst is prepared by taking an aqueous solution of platinum salt as a metal precursor and a high-silicon molecular sieve as a carrier through an impregnation method, and is roasted in an oxidizing atmosphere to obtain the catalyst with the oxidation state platinum accounting for 60-95%. The catalyst has good sulfur resistance, so that a hydrogen transfer system can continuously and stably carry out toluene hydrogenation reaction under the condition that the raw material toluene contains 1-10ppm of sulfur-containing impurities, and the catalyst does not need to be regenerated frequently.

Description

Sulfur-tolerant hydrogenation catalyst for hydrogen transfer system and preparation method thereof
Technical Field
The invention belongs to the technical field of hydrogen energy, and particularly relates to a sulfur-resistant type supported platinum catalyst for a hydrogen transfer system and a preparation method thereof.
Background
As is well known, hydrogen energy has the advantages of environmental friendliness, abundant resources, high heat value, good combustion performance, high potential economic benefit and the like, is considered as an energy carrier with the most development potential in future energy structures, and has very wide application and important commercial value. However, hydrogen is flammable and explosive, so that the utilization of hydrogen energy depends not only on hydrogen production technology but also on safe and economical storage and transportation technology. In order to use hydrogen gas more safely, researchers have proposed pressure hydrogen storage, low temperature liquefied hydrogen storageSolid material physical adsorption hydrogen storage, solid hydride chemical adsorption hydrogen storage, organic liquid hydrogen storage and other hydrogen storage technologies. The mass hydrogen storage density of the pressurized hydrogen storage is lower, generally 1-5 wt%, and the high-pressure container has a limited service life, and the hydrogen stored for a long period is easy to leak to cause safety accidents, so that the pressurized hydrogen storage can not be applied under the condition of large scale, long distance or long period. Although cryogenic liquefied hydrogen storage has a desirable hydrogen storage density (about 10 wt%), liquefied hydrogen is too costly (17 kWh of electricity is consumed for 1kg of hydrogen to be liquefied) and cannot be stored for a long period of time. The solid material physically adsorbs hydrogen storage and is represented by a carbon material. According to the reports of Materials Science and Engineering 2002,20(1),31, the mass fraction of hydrogen stored in single-walled carbon nanotubes at-179 ℃ and 6MPa can reach as high as 9.8 wt%. However, the current technology for producing carbon materials in large scale is not mature and has higher cost, and the temperature and pressure in the hydrogen storage process have more rigorous requirements, so that the method is difficult to be widely applied. The solid hydride chemical adsorption hydrogen storage comprises metal hydride, composite aluminum hydride, borohydride and the like, and the mass hydrogen storage density of most of the existing hydrogen storage alloys is only 2-3 wt%. But light metal alloys such as MgH2The hydrogen storage density can reach 7.6 wt%. However, the Mg-based alloy has problems of a low hydrogen absorption/desorption rate and a high temperature required for hydrogen desorption. Moreover, the metal alloy generally has the serious problems of easy pulverization and the like in the hydrogen absorption and desorption process. In conclusion, considering the comprehensive factors of hydrogen storage density, hydrogen storage cycle reversibility, hydrogen storage energy consumption, hydrogen absorption and desorption rate, safety and the like, the organic liquid hydrogen transportation system is considered to be an ideal solution. An organic liquid hydrogen transfer system is a hydrogen storage and release technology based on the reversible hydrogenation-dehydrogenation catalytic reaction principle. Organic hydrogen storage liquids can be broadly classified into three categories: cycloalkanes, nitrogen-containing heterocyclic compounds, and other organic hydrogen storage liquids (e.g., methanol, ethanol, formic acid, and the like). Considering the stability, toxicity, boiling point, hydrogen storage density, dehydrogenation enthalpy and price of organic hydrogen storage liquids in a comprehensive manner, methylcyclohexane-toluene-hydrogen cycle (MTH) is one of the systems most suitable for large-scale, remote, long-period transport of hydrogen. Methylcyclohexane-toluene-hydrogen storage technologies are currently commercialized in Japan. Downstream of the hydrogen energy industry chain, future hydrogen energy will be primarily applied to hydrogen combustionFuel cell automobiles/forklifts, distributed power generation, emergency power sources, industrial hydrogenation reaction raw materials and high-energy density fuels (such as liquid fuel rockets) and the like.
During the hydrogenation process of the MTH hydrogen transport system, a certain amount of sulfur-containing impurities are usually contained in toluene because trace amounts of sulfur-containing impurities (such as thiophene and its derivatives) in toluene are difficult to remove. GB/T3406-2010 stipulates that the total sulfur content of petroleum toluene is not more than 2mg/Kg (2ppm), but GB/T2284-2009 stipulates that the total sulfur content of coking toluene of first-class products and superior products is not more than 150mg/Kg (150ppm) and 2mg/Kg (2ppm), respectively. That is, sulfur is inevitably contained in both petroleum-based toluene and coal-based toluene. The sulfur resistance of the hydrogenation catalyst is improved, the desulfurization severity of the toluene raw material is reduced, the raw material cost of the toluene for the hydrogen transportation system is reduced, and the popularization of the hydrogen transportation technology is facilitated.
The following patents relate to hydrogenation catalysts for organic liquid hydrogen storage systems. Patent CN 104555914A (application date: 2015 1/2015 6) mainly discloses a medium of a liquid hydrogen storage system, and in the examples, discloses that an active component of a hydrogenation catalyst for organic liquid hydrogen storage is Ru, and a carrier is Al2O3Wherein contents relating to sulfur resistance are not contained, and the main component of the catalyst used is different from the present invention.
To date, few chinese patents have been made relating to organic liquid hydrogen transport systems. The hydrogen storage carrier used in the organic hydrogen storage circulation is toluene, and the essence of the hydrogen storage carrier is aromatic hydrocarbon hydrogenation reaction. Toluene, as one of the aromatic hydrocarbons, can be catalytically hydrogenated using an aromatic hydrogenation catalyst. The following patents relate to sulfur resistance of aromatic hydrogenation catalysts:
patent CN 1706917A (application date: 5/25/2005) discloses a sulfur-tolerant catalyst for preparing diesel oil by coal tar hydrogenation, which comprises a first-stage catalyst and a second-stage catalyst, wherein the first-stage hydrodesulfurization, denitrification and cracking catalyst comprises 3-8% of molybdenum oxide, 2-5% of cobalt oxide, 3-6% of nickel oxide and silicon carbide, and the second-stage hydrogenation deep dearomatization catalyst comprises 3-5% of platinum, 2-5% of palladium and silicon carbide. The invention mainly prevents sulfur poisoning of the second-level aromatic hydrogenation catalyst through the first-level catalyst desulfurization.
The sulfur resistance of the catalysts in the following patents all stem from the specific composition of the catalyst:
patent CN 105772034A (application date: 12/15/2014) discloses a preparation method of a polycyclic aromatic hydrocarbon hydrogenation catalyst, wherein the main component is molybdenum disulfide, and the catalyst has sulfur resistance.
Patent CN 102335621A (application date: 7/15/2011) discloses a heteropolyacid-containing aromatic hydrogenation catalyst with high sulfur resistance and high activity, wherein the catalyst comprises heteropolyacid cesium, a hydrogenation component and a carrier. The heteropoly acid cesium is phosphotungstic acid cesium or silicotungstic acid tungsten, the hydrogenation component is Ni, and the carrier is porous silicon dioxide.
Patent CN 101085934 a (application date: 2006, 6, 7) discloses a coal-to-liquid oil boiling bed hydrogenation catalyst, the carrier contains alumina fiber and phosphorus and boron auxiliary agent, and the active component is shown as Ni oxide in the specification.
Patent CN 101376830a (application date: 8/27/2007) discloses a hydrogenation catalyst carrier capable of removing heteroatoms such as nitrogen, sulfur and the like in heavy oil fraction, which contains alumina fiber and phosphorus promoter.
Patent CN 1769379A (application date: 10/29/2004) discloses a hydrofining catalyst with strong sulfur and nitrogen poisoning resistance, wherein the main active component of the catalyst is Ni, the auxiliary agent is Mo, and the carrier is SiO modified by Ti2。
The composition of the catalyst used in the above invention is significantly different from that of the present invention, and the necessary technical features corresponding to the improvement of the sulfur resistance in the above invention are also significantly different from that of the present invention.
The catalysts disclosed in the following patents, similar to the catalyst components used in the present invention, all contain a noble metal and a silica support: patent CN 1267233A (application date: 6/16/1998) discloses a catalyst for hydrogenating middle distillate aromatics and having a high sulfur content resistance, which catalyst comprises two parts, a platinum group metal and a silica-alumina support.
Patent CN 1351117 a (application date 2000,10, 26) discloses a diesel aromatics hydrogenation saturation catalyst, which has high sulfur and nitrogen resistance, wherein the hydrogenation metal components are noble metals (Pt, Pd, Ir, Rh) and at least one non-noble metal (Ni, W, Mo, Co), the carrier is inorganic refractory oxide and modified Y zeolite, and the hydrogenation metal components are in a reduction state when the catalyst is used for aromatics hydrogenation saturation reaction.
Patent CN 1566282A (application date: 6/30/2003) discloses a method for deeply dearomatizing hydrocarbon oil, which uses VIII group noble metal as active metal component, and one or more selected from zeolite, heat-resistant inorganic oxide, active carbon, carbon fiber and clay as carrier, and the obtained catalyst has good sulfur and nitrogen poisoning resistance.
Patent CN 101489668A (application date: 6/18/2007) discloses a catalyst for saturated aromatics, a sulfur tolerant aromatics hydrogenation catalyst composition comprising a noble metal component and a support, wherein the support comprises zirconia, silica and optionally alumina.
Patent CN 105727941A (application date: 12/10/2014) discloses a sulfur-resistant aromatic saturated hydrogenation catalyst, which consists of noble metal and inorganic porous material, wherein the noble metal is one or more of Pt, Pd, Ru and Re, and the carrier is alumina, silica or alumina-silica combination.
In addition to the above patent documents, the following publications relate to methods for improving the sulfur resistance of platinum-based aromatic hydrocarbon hydrogenation catalysts, and are mainly classified into two types: (1) adding a second metal component such as Pd, Ru and Ir to adjust the electronic environment of Pt, wherein the Pt-Pd alloy has a remarkable sulfur resistance effect; (2) increasing the amount of catalyst acid, such as increasing the number of medium strength acid centers by introducing Al, B, where the introduction of Al changes the amount of carrier acid is more abundant.
The publications Energ Fuel 1997,11(3),656-661, J Catal1998,177(2),208-216, 1999,185(2), L199-L201, Catal Lett 2001,75(1-2),37-43, J Catal2001,202(1),163-168, ApplCatal a-Gen 2002,225(1-2),223-237, J Jpn Petroleum Inst 2004,47(3),222-223, pplCatal a-2005,290 (1-2),73-80, ApplCatal a-Gen 2005, 249 (2),249 257, InEngChem Res 2007,46(12),4186-4192 and Catal Lett 2008,122(3-4),214-222 all report that the addition of Pt-Pd alloy to platinum-based catalyst results in the increase in the sulfur tolerance of the aromatic catalyst. In addition, ApplCatal a-Gen 2004,267(1-2), 111-.
Since Ir, Ru, Pd and Pt are noble metals, the addition of a second noble metal to increase the sulfur resistance of the catalyst further increases the cost of the catalyst, which is not advantageous for industrial use.
The publications J Catal1997,169(2),480-489, ApplCatal a-Gen 2000,192(2),253-261, J Phys Chem B2000, 104(49),11644-11649, J Catal2001,201(1),60-69, Catal Today 2002,74(3-4),281-290, J Catal2008,257(1),125-133, Catal Commun2013,35,6-10, Energ Fuel 2014,28(11),6788-6792 and Catal Sci. Technol.2014,4(7),2081-2090 all report that the addition of Al increases the acid amount of the medium-strength acid of the catalyst, thereby increasing the sulfur resistance. In addition, ApplCatal a-Gen 1999,185(2), L199-L201 and RscAdv2017,7(66),41460-41470 reported respectively the enhancement of sulfur resistance by the addition of B and P to increase the acid content of medium strength acids. However, since the acid strength of the added acid sites is difficult to control, this method of increasing the acidity of the catalyst to increase the sulfur resistance of the catalyst is likely to cause side reactions in the hydrogen storage carrier.
In summary, the prior art mainly includes two types in terms of improving the sulfur resistance of the aromatic hydrogenation catalyst: (1) adding a second metal component, such as Pd, Ru and Ir, to adjust the electronic environment of Pt; (2) the amount of catalyst acid is increased, such as by introducing Al, B, P to increase the number of medium strength acid centers. In addition, no specific measures for imparting sulfur resistance to a toluene hydrogenation catalyst have been proposed for a methylcyclohexane-toluene-hydrogen (MTH) hydrogen transport system. According to the sulfur resistance solution of the moving aromatic hydrogenation catalyst, the catalyst cost is greatly increased due to the use of a noble metal auxiliary agent, or acid components are introduced to generate acid catalytic side reaction impurities in the hydrogenation reaction of the MTH system, so that the hydrogen transfer system cannot be in closed cycle.
Disclosure of Invention
Aiming at the problems that the conventional toluene hydrogenation catalyst in a methylcyclohexane-toluene-hydrogen (MTH) hydrogen transfer system does not have sulfur resistance, is easy to generate sulfur poisoning and inactivation and causes insufficient catalyst stability, the invention provides a method for enhancing the sulfur resistance of the toluene hydrogenation catalyst.
Specifically, the invention provides a platinum catalyst with a platinum active component with a high oxidation state ratio and a preparation method thereof. The carrier of the catalyst is ordered porous high silicon oxide, and the active component is platinum, its oxidation state platinum (PtO and PtO)2) The amount of the platinum accounts for 60-95% of the total amount of the platinum. We found through comparative studies that: when the proportion of the platinum in the oxidation state reaches 60-95% of the platinum loading amount, the sulfur resistance of the platinum-loaded catalyst prepared on the silicon oxide carrier can be obviously improved, so that the hydrogenation stability and the service life of the catalyst can be obviously improved. And an effective method for increasing the platinum oxide content in the silica-supported platinum catalyst is to calcine the catalyst in an oxidizing atmosphere. The hydrogenation catalyst has good sulfur resistance and stability when being used in a hydrogen transportation system.
It is known that, in the past, a toluene hydrogenation catalyst is generally pre-reduced before being used, so that an oxidized platinum species is reduced to elemental Pt, and most of hydrogenation active centers in the reaction are elemental platinum. In contrast to the current practice, the present invention oxidizes the catalyst in an oxygen-rich atmosphere to produce a supported platinum catalyst having an oxidation state platinum content as high as 60-95% which is used as a catalyst for the hydrogenation of toluene. According to the invention, through comparison research, the reduced silicon oxide supported platinum catalyst (taking simple substance Pt as a main active center) is very sensitive to sulfur-containing impurities, and the active center is easily and strongly adsorbed and occupied by sulfide to lose the capacity of adsorbing and activating other reactants, so that irreversible poisoning inactivation of the catalyst is caused. In contrast, oxidized silica supported platinum catalysts are available as PtO and PtO2The active center is a main active center and is not easily and strongly adsorbed and occupied by sulfide, so that the catalyst has good catalytic activity and sulfur resistance, and contains 1-10ppm of sulfur-containing impurities in tolueneIn this case, the hydrogenation reaction of toluene can be continuously and stably carried out.
The technical scheme of the invention is as follows:
a preparation method of a sulfur-resistant hydrogenation catalyst for a hydrogen transport system comprises the following specific steps:
(1) pretreatment of a carrier: the carrier is one or a mixture of more than two of an all-silicon zeolite molecular sieve S-1, an all-silicon mesoporous molecular sieve MCM-41, SBA-15 and a titanium silicalite molecular sieve TS-1, and the S-1 zeolite molecular sieve is preferred. The carrier pretreatment is to carry out drying and roasting treatment on the carrier before use. The drying temperature is 80-200 ℃, and preferably 100-120 ℃; the drying time is 0.5-100 hours, and the preferable time is 3-24 hours; the roasting temperature is 300-550 ℃, and preferably 350-450 ℃; the roasting time is 0.5 to 24 hours, preferably 3 to 6 hours.
The invention selects the all-silicon zeolite molecular sieve or the all-silicon mesoporous molecular sieve as the carrier, and mainly avoids the acidic influence caused by the aluminum-containing zeolite molecular sieve and the aluminum-containing mesoporous molecular sieve. Although high silica alumina has fewer acid centers than zeolitic molecular sieves and mesoporous molecular sieves, the use of such supports still destroys the hydrogen selectivity of the catalysts produced. Compared with mesoporous molecular sieves such as MCM-41 and the like, the S-1 molecular sieve has the main advantages of good framework thermal stability and hydrothermal stability, and is favorable for preparing a catalyst with high stability and long service life.
S-1, MCM-41, SBA-15, TS-1 can be synthesized according to the following patents and literature. ChemSoc Farad T182 (1986),785, Chemistry & Industry (1986)786-787 et al relate to the synthesis of S-1; j Am ChemSoc114(1992),10834-10843, US5260501-A, et al, relates to the synthesis of MCM-41; chem Lett (1999)131-132, Chem Mater11(1999)492-500, etc., are involved in the synthesis of SBA-15; studies in Surface Science and Catalysis, Vol.84; zeolite 16: 108-; zeolite 19: 246-; applied Catalysis A, General 185(1999) 11-18; catalysis Today 74(2002) 65-75; ind, eng, chem, res, 2011,50, 8485-; microporous and Mesoporous Materials 162(2012) 105-114; chinese invention patent (application number) 201110295555.x, 201110295596.9 and the like relate to hydrothermal synthesis of TS-1 by a cheap method. Engineers familiar with the art may prepare S-1, MCM-41, SBA-15, TS-1 synthetically on their own, or may purchase the corresponding commercial products S-1, MCM-41, SBA-15, TS-1.
The purpose of carrier pretreatment is to remove water and other impurities adsorbed in pores of the carrier, and the pretreated carrier is more favorable for metal ions to enter the pore channels of the molecular sieve through capillary condensation in the impregnation process.
(2) Preparing a loaded metal solution: the load metal solution is a metal platinum salt solution, and the metal platinum salt is one or a mixture of tetraammineplatinum nitrate and platinum acetylacetonate. Tetraammineplatinum nitrate complexes containing divalent platinum ions are preferred. The concentration of platinum ions in the supported metal solution is 0.005-0.4 mol/L, preferably 0.01-0.20 mol/L. Deionized water is used for preparing the supported metal solution, and the solution preparation is carried out at room temperature. In order to ensure the uniformity of the solution, mechanical stirring is adopted in the solution preparation process. The exact concentration of the formulated solution was determined by inductively coupled plasma emission spectroscopy (ICP-AES).
In fact, other soluble salts containing platinum ions, such as platinum chloride, chloroplatinic acid, may also be used in providing divalent platinum ions. However, the invention has not been selected in consideration of the possibility that chloride ions and sulfate ions, etc. may cause an increase in the acidity of the catalyst and cause poisoning of the noble metal.
(3) The catalyst was prepared by an excess impregnation method. The process is as follows: firstly, pouring the carrier pretreated in the step (1) into the supported metal solution containing platinum metal ions prepared in the step (2) at room temperature under mechanical stirring, and stirring the mixture until the mixture is uniform to obtain slurry. And then, heating the slurry to 70-90 ℃, and continuously stirring for 2-8 hours. When the catalyst is prepared by the excess impregnation method, the amount of the supported metal solution and the concentration of the metal ions in the supported metal solution are used to control the metal loading. The final finished catalyst contains platinum in an amount of 0.1-2.0 wt%, preferably 0.3-1.0 wt%, and silica in an amount of 98.0-99.9 wt%, preferably 99.0-99.7 wt%.
(4) Oxidation of the active center. First, the catalyst is separated and recovered from the impregnation slurry treated in the step (3)And (3) a solid. And then drying and oxidizing the recovered catalyst solid, wherein the temperature rise rate in the drying and oxidizing processes is not more than 10 ℃/min in order to avoid the aggregation of metal particles caused by overhigh temperature rise rate. The drying temperature is 80-200 ℃, and preferably 100-120 ℃; the drying time is 0.5-100 hours, and the preferable time is 3-24 hours; the oxidation process is as follows: calcining in an oxidizing atmosphere at atmospheric pressure, the oxidizing atmosphere comprising: an oxygen/inert gas mixture with an oxygen volume fraction of 21 to 99.9%, wherein the inert gas is preferably nitrogen. Although helium, argon, xenon, etc. can achieve similar results, the use of noble gases can result in higher manufacturing costs. The oxidation temperature is 300-550 ℃ (preferably 350-450 ℃), and the oxidation time is 0.5-6 hours, preferably 1-3 hours. The specific surface area of the oxidized catalyst solid is 350-450 m2(iv)/g, the metal average particle diameter is in the range of 2.0 + -1.0 nm.
(II) characterization of the catalyst:
the valence state of Pt was determined by X-ray photoelectron spectroscopy (XPS). Obtaining Pt 4f in catalyst by XPS5/2And Pt 4f7/2Energy spectrum and deconvolution analysis are carried out. Determination of Pt 4f5/2、Pt 4f7/2In the category of Pt, PtO and PtO2Peak area of (A), calculation of Pt, PtO and PtO2The ratio of the active ingredients to the total amount of the active ingredients.
(III) evaluation of catalyst Activity, selectivity, and Sulfur resistance:
a batch kettle type stainless steel high-pressure reactor is adopted for the toluene hydrogenation experiment, and 0.198mol of cyclohexane, 1-10ppm of benzothiophene/toluene mixed solution (wherein the mass amount of toluene is 0.011mol) and 0.5g of Pt/S-1 catalyst are added into a 100mL reactor. Cyclohexane is used as a solvent, so that the system can be prevented from being heated rapidly due to heat release in the hydrogenation reaction process. The reaction temperature is 90-160 ℃, the hydrogen partial pressure is 1.5MPa, and the hydrogen partial pressure is H2The molar ratio/toluene was about 3.1. After the reaction system is heated to the specified temperature and reacts for 15min, the heating is stopped and the reaction kettle is placed in an ice bath for cooling. The product was analyzed by off-line chromatography. The chromatographic conditions are as follows: a hydrogen Flame Ionization Detector (FID) and an HP-5 column (30 m.times.0.320 mm.times.0.25 m) were used for liquid phase product analysis, and a thermal conductivity cell detector (TCD) and TDX-01 packed column were used for gas phase product analysis.
The toluene conversion, methylcyclohexane selectivity and hydrogenation rate were calculated as follows:
Figure BDA0002681610330000061
Figure BDA0002681610330000062
Figure BDA0002681610330000063
wherein n is1Is the amount of material of toluene in the product, n2Is the amount of toluene in the starting material, n3Is the amount of methylcyclohexane species in the product, mPtRepresents the mass of Pt in the catalyst, and t is the reaction time.
The invention has the outstanding advantages that the sulfur resistance of the catalyst is obviously improved only by adjusting the valence state of the active center of the catalyst, and a second auxiliary agent metal component is not required to be added, thereby greatly simplifying the process flow of catalyst processing and being beneficial to obviously reducing the preparation cost of the catalyst.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited by the examples.
Example 1:
(1) 1g of the S-1 zeolite molecular sieve support was dried at 110 ℃ for 6 hours and then calcined at 400 ℃ for 2 hours.
(2) 0.018g of tetraammineplatinum (II) nitrate was dissolved in 1.5mL of deionized water at room temperature with mechanical stirring to give a supported metal solution in which the concentration of the metal platinum salt was 0.03 mol/L.
(3) And (2) pouring the carrier pretreated in the step (1) into the supported metal solution containing the platinum metal ions prepared in the step (2) at room temperature under mechanical stirring, and stirring until the mixture is uniform. The mixture was then heated to 80 ℃ and the stirring was continued for 4 hours.
(4) The solid product was centrifuged and dried in an oven at 110 ℃ for 6 hours at a temperature rise rate of 5 ℃/min. Next, the mixture was calcined at 300 ℃ for 2 hours in an oxygen atmosphere at a temperature rise rate of 5 ℃/min. Obtaining finished catalyst Pt/S-1-O2。
(5) The product analysis was carried out according to the procedure in the above-mentioned protocol-evaluation of catalyst activity, selectivity and sulphur resistance ". Wherein the concentration of benzothiophene/toluene is 10ppm, the reaction temperature is 130 ℃, the reaction time is 15 minutes, the average toluene conversion rate, the methylcyclohexane selectivity and the hydrogenation rate are respectively 100 percent after 5 times of reaction, 100 percent and 68027mmol/gPt/min。
Comparative example 1:
example 1 was repeated, but in step (4), calcination was not carried out in an oxygen atmosphere but in a hydrogen atmosphere at a temperature of not 300 ℃ but 100 ℃ and 200 ℃ and 300 ℃ respectively to obtain Pt/S-1-H as a catalyst2-100，Pt/S-1-H2-200，Pt/S-1-H2300, calculating the average toluene conversion, methylcyclohexane selectivity and hydrogenation rate as follows:
Figure BDA0002681610330000071
generally, the oxidized form of Pt in the catalyst can be reduced only at 300-500 deg.C, and the Pt is difficult to be reduced at 100 deg.C, so Pt/S-1-H2In-100, the platinum still takes the oxidation state as the main part, and the catalyst keeps better activity and sulfur resistance. The partially small oxidized platinum nanoclusters are reduced at 200 deg.C, so Pt/S-1-H2The proportion of oxidized platinum in-200 is reduced, and the catalyst maintains better activity and sulfur resistance.
Comparative example 2:
example 1 was repeated, but in step (4) instead of calcination in an oxygen atmosphere, reduction was carried out with 0.05mol/L aqueous sodium borohydride solution to give the catalyst Pt/S-1-NaBH4. Calculating the average toluene conversion, the methylcyclohexane selectivity and the hydrogenation rate respectively18%, 100%, 12245mmol/gPt/min。
The reduction degree of chemical reduction of sodium borohydride is lower than that of high-temperature thermal reduction of hydrogen. Therefore, relative to Pt/S-1-H2-300，Pt/S-1-NaBH4The proportion of platinum in a medium oxidation state is large, and the platinum shows better stability in the toluene hydrogenation reaction.
Example 2:
example 1 was repeated, but in step (1) all-silicon MCM-41, SBA-15, TS-1 was used alone as the support, and S-1 and SBA-15, MCM-41, SBA-15 and TS-1 were used in combination as the support, wherein the mass ratio of S-1 to SBA-15 was 1: 1, the mass ratio of MCM-41, SBA-15 to TS-1 is 1: 1: 1, the obtained catalysts are respectively 1-5 in number. The average toluene conversion, methylcyclohexane selectivity, and hydrogenation rate are calculated as follows:
Figure BDA0002681610330000081
example 3:
example 1 was repeated, but the catalyst numbers obtained in step (2) were 6 to 8, respectively, at platinum ion concentrations of 0.005, 0.20 and 0.40mol/L, respectively. The average toluene conversion, methylcyclohexane selectivity, and hydrogenation rate are calculated as follows:
Figure BDA0002681610330000082
example 4:
example 1 was repeated, but platinum acetylacetonate was used as the metal platinum salt in step (2), and the catalyst obtained was numbered 9. The average toluene conversion, methylcyclohexane selectivity and hydrogenation rate were calculated to be 100%, 100% and 68027mmol/g, respectivelyPt/min。
Example 5:
example 1 was repeated, but in step (4), the calcination atmosphere was air, oxygen/argon (60% by volume), oxygen/xenon (80% by volume), oxygen/helium (90% by volume), the calcination temperature was 300 ℃, the calcination time was 3 hours, and the obtained catalysts were 10 to 12 in number, respectively. The average toluene conversion, methylcyclohexane selectivity, and hydrogenation rate are calculated as follows:
Figure BDA0002681610330000091
example 6:
example 1 was repeated, but in step (4), the calcination temperatures were 300, 450, and 550 ℃, the calcination times were 0.5, 3, and 6 hours, respectively, and the obtained catalysts were 14 to 16 in number, respectively. The average toluene conversion, methylcyclohexane selectivity, and hydrogenation rate are calculated as follows:
Figure BDA0002681610330000092
example 7:
example 1 was repeated, but in step (5) the benzothiophene/toluene concentration was not 10ppm, but 2ppm, 5ppm and 100ppm, respectively. The obtained catalysts are respectively 17-19 in number. The average toluene conversion, methylcyclohexane selectivity, and hydrogenation rate are calculated as follows:
Figure BDA0002681610330000093
Figure BDA0002681610330000101
example 8:
repeating the example 1, circularly carrying out hydrogenation reaction for 10 times, carrying out no treatment on the catalyst after each reaction is finished, and respectively recording the toluene conversion rate, the methylcyclohexane selectivity and the hydrogenation rate of 1-10 times of reaction as follows:
Figure BDA0002681610330000102
example 9:
example 1 was repeated with the finished catalyst Pt/S-1-O2、Pt/S-1-Air、Pt/S-1-NaBH4、Pt/S-1-H2300 ICP-AES, nitrogen physisorption and XPS characterization. The platinum loading in the finished catalyst was about 0.6 wt%, and the specific surface area was about 420m2(g) Pt 4f thereof5/2、Pt 4f7/2Deconvolution to obtain platinum (PtO and PtO) in oxidation state2) The amounts of the materials accounted for 92.5%, 79.5%, 65.9%, 41.5%, respectively, of the total platinum atom material.
Example 10:
example 1 was repeated, but in step (4), calcination was not carried out in an oxidizing atmosphere at normal pressure, but in an oxygen atmosphere at 3MPa, to give a catalyst No. 20. XPS characterization of Pt 4f5/2、Pt 4f7/2Deconvolution to obtain platinum (PtO and PtO) in oxidation state2) The amounts of the species each accounted for 100% of the total platinum atom species. The average toluene conversion, methylcyclohexane selectivity, and hydrogenation rate are calculated as follows: 80%, 100% and 54422mmol/gPt/min。
In practical application, the proportion of the oxidation state platinum does not need to reach 100 percent to meet the requirement of a hydrogen transport system on the sulfur resistance of the catalyst. It is difficult to prepare a catalyst having a platinum in an oxidized state of 100% by calcination in an oxidizing atmosphere at normal pressure, and when the ratio of platinum in an oxidized state in the catalyst is increased, the sulfur resistance of the catalyst is improved but the activity for hydrogenation of toluene is lowered. When the proportion of platinum in the oxidized state reaches 100%, the activity thereof is remarkably reduced under the same reaction conditions.

Claims (10)

1. A preparation method of a sulfur-resistant hydrogenation catalyst for a hydrogen transfer system is characterized by comprising the following specific steps:
(1) pretreatment of a carrier: the carrier is one or a mixture of more than two of an all-silicon zeolite molecular sieve S-1, an all-silicon mesoporous molecular sieve MCM-41, SBA-15 and a titanium-silicon zeolite molecular sieve TS-1, and the carrier pretreatment is to dry and roast the carrier before use; the drying temperature is 80-200 ℃; the drying time is 0.5-100 hours; the roasting temperature is 300-550 ℃; the roasting time is 0.5-24 hours;
(2) preparing a loaded metal solution: the load metal solution is a metal platinum salt solution, and the concentration of platinum ions in the load metal solution is 0.005-0.4 mol/L;
(3) preparation of catalyst by excess impregnation
Firstly, pouring the carrier pretreated in the step (1) into the supported metal solution containing platinum metal ions prepared in the step (2) at room temperature under mechanical stirring, and stirring uniformly to obtain slurry; then, heating the slurry to 70-90 ℃, and continuously stirring for 2-8 hours;
when the catalyst is prepared by an excess impregnation method, controlling the metal loading capacity by using the using amount of the loaded metal solution and the concentration of metal ions in the loaded metal solution; the mass range of platinum in the finally obtained finished catalyst is 0.1-2.0 wt%, and the mass range of silicon dioxide is 98.0-99.9 wt%;
(4) oxidation of active centres
Firstly, separating and recovering catalyst solid from the impregnation slurry treated in the step (3); then drying and oxidizing the recovered catalyst solid, wherein the heating rate in the drying and oxidizing processes is not more than 10 ℃/min; the drying temperature is 80-200 ℃; the drying time is 0.5-100 hours; the oxidation process is as follows: roasting in an oxidizing atmosphere at normal pressure, wherein the oxidizing temperature is 300-550 ℃, and the oxidizing time is 0.5-6 hours.
2. The method for preparing the sulfur-tolerant hydrogenation catalyst for the hydrogen transportation system according to claim 1, wherein in the step (1), the drying temperature is 100-120 ℃, and the drying time is 3-24 hours; the roasting temperature is 350-450 ℃, and the roasting time is 3-6 hours.
3. The method for preparing a sulfur-tolerant hydrogenation catalyst for a hydrogen transportation system according to claim 1 or 2, wherein in the step (2), the metal platinum salt is one or a mixture of tetraammineplatinum nitrate and platinum acetylacetonate; the concentration of platinum ions in the supported metal solution is 0.01-0.20 mol/L.
4. The method for preparing a sulfur-tolerant hydrogenation catalyst for a hydrogen transportation system according to claim 1 or 2, wherein in the step (3), the mass range of platinum in the final catalyst is 0.3-1.0 wt%, and the mass range of silica is 99.0-99.7 wt%.
5. The method for preparing a sulfur-tolerant hydrogenation catalyst for a hydrogen transportation system according to claim 3, wherein in the step (3), the mass range of platinum in the final catalyst is 0.3-1.0 wt%, and the mass range of silica is 99.0-99.7 wt%.
6. The method for preparing a sulfur-tolerant hydrogenation catalyst for a hydrogen transportation system according to claim 1,2 or 5, wherein in the step (4), the drying temperature is 100-120 ℃, the drying time is 3-24 hours, and the oxidizing atmosphere comprises: oxygen/inert gas mixed gas with the oxygen volume fraction of 21-99.9%; the oxidation temperature is 350-450 ℃, and the oxidation time is 1-3 hours.
7. The method for preparing a sulfur-tolerant hydrogenation catalyst for a hydrogen transportation system according to claim 3, wherein in the step (4), the drying temperature is 100-120 ℃, the drying time is 3-24 hours, and the oxidizing atmosphere comprises: oxygen/inert gas mixed gas with the oxygen volume fraction of 21-99.9%; the oxidation temperature is 350-450 ℃, and the oxidation time is 1-3 hours.
8. The method for preparing a sulfur-tolerant hydrogenation catalyst for a hydrogen transportation system according to claim 4, wherein in the step (4), the drying temperature is 100-120 ℃, the drying time is 3-24 hours, and the oxidizing atmosphere comprises: oxygen/inert gas mixed gas with the oxygen volume fraction of 21-99.9%; the oxidation temperature is 350-450 ℃, and the oxidation time is 1-3 hours.
9. The method for preparing a sulfur-tolerant hydrogenation catalyst for a hydrogen transportation system according to claim 1,2, 5, 7 or 8, wherein in the step (4), the specific surface area of the oxidized catalyst solid is 350-450 m2(iv)/g, the metal average particle diameter is in the range of 2.0 + -1.0 nm.
10. A sulfur tolerant hydrogenation catalyst for use in a hydrogen transport system, wherein said sulfur tolerant hydrogenation catalyst is prepared by the process of any one of claims 1 to 9.
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