CN110314675B - TiO 2 Modified alumina-based magnesium aluminate spinel, preparation method thereof and sulfur-tolerant shift catalyst - Google Patents

TiO 2 Modified alumina-based magnesium aluminate spinel, preparation method thereof and sulfur-tolerant shift catalyst Download PDF

Info

Publication number
CN110314675B
CN110314675B CN201810264420.9A CN201810264420A CN110314675B CN 110314675 B CN110314675 B CN 110314675B CN 201810264420 A CN201810264420 A CN 201810264420A CN 110314675 B CN110314675 B CN 110314675B
Authority
CN
China
Prior art keywords
tio
magnesium
carrier
catalyst
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810264420.9A
Other languages
Chinese (zh)
Other versions
CN110314675A (en
Inventor
李海千
邓甜音
蒋明哲
赵华博
田大勇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
Original Assignee
China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Energy Investment Corp Ltd, National Institute of Clean and Low Carbon Energy filed Critical China Energy Investment Corp Ltd
Priority to CN201810264420.9A priority Critical patent/CN110314675B/en
Publication of CN110314675A publication Critical patent/CN110314675A/en
Application granted granted Critical
Publication of CN110314675B publication Critical patent/CN110314675B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/005—Spinels
    • 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
    • B01J21/10—Magnesium; 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
    • B01J23/76—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
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8872—Alkali or alkaline earth 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the field of sulfur-resistant shift catalysts and discloses TiO 2 Modified alumina-based magnesium aluminate spinel, a preparation method thereof and a sulfur-tolerant shift catalyst. TiO prepared by the method of the invention 2 The modified alumina-based magnesium aluminate spinel avoids the use of organic solvents and reduces the preparation cost. Using the TiO 2 The modified alumina-based magnesia-alumina spinel is used as a carrier, the prepared catalyst overcomes the defect of easy hydration, widens the application range of the catalyst, and has better activity and stability within the temperature range of 200-500 ℃.

Description

TiO 2 Modified alumina-based magnesium aluminate spinel, preparation method thereof and sulfur-tolerant shift catalyst
Technical Field
The invention relates to the field of sulfur-resistant shift catalysts, in particular to TiO 2 Modified alumina-based magnesium aluminate spinel, a preparation method thereof and a sulfur-tolerant shift catalyst.
Background
The CO shift reaction is widely applied to industries of methanol preparation from coal, ammonia synthesis, hydrogen production and the like, and is used for modulating CO and H in synthesis gas 2 To meet the requirements of different chemical processes. Compared with the traditional Fe-Cr based high-temperature transformation catalyst and Cu-Zn based low-temperature transformation catalyst, the cobalt-molybdenum based sulfur-tolerant transformation catalyst has high transformation activity, wide use temperature range and no influence of sulfur poisoning, thereby being widely applied. The existing Co-Mo based sulfur-tolerant shift catalyst is mainly divided into two main categories, one is a cobalt-molybdenum shift catalyst without alkali metal auxiliary agent. The catalysts mostly adopt magnesium aluminate spinel as a carrier, such as K8-11 catalyst widely used by BASF company in Germany. The catalyst has higher strength, is suitable for reaction under the conditions of high temperature, high pressure (3-8Mpa) and high water-gas ratio, but has poorer low-temperature activity, and requires higher sulfur content in the shift gas, otherwise, the activity is seriously degraded. Another class is Co-Mo based shift catalysts containing an alkali metal promoter (mainly potassium), such as those disclosed in US3850840A and CN87107892A, among others. The catalyst has better activity under the conditions of low temperature and low sulfur, but the existence of potassium can promote the hydration reaction of carrier alumina at high temperature, and the structural stability of the catalyst is influenced, so that the activity of the catalyst is seriously degraded.
By mixing TiO with 2 The introduction of the modified Co-Mo catalyst into the carrier is an effective method for solving the problems of poor low-temperature activity, water resistance and performance of the existing Co-Mo catalyst. CN1429763A prepared by using a catalyst prepared from TiO 2 、MgO、 Al 2 O 3 The cobalt-molybdenum shift catalyst is prepared by a composite carrier consisting of four components of cement, and the catalyst does not contain alkali metal but has better low temperature (250 ℃ C.) -300 ℃ C.) and low sulfur (C.), (>0.01v/v) activity. CN103447049B discloses a potassium-free cobalt-molybdenum shift catalyst using aluminum-titanium-based magnesium aluminate spinel as a carrier, compared with a titanium-free catalyst, the titanium-containing catalyst has better activity stability and is suitable for shift of synthesis gas with high CO content (more than or equal to 60%). CN1096494A discloses a wide-temperature and wide-sulfur type sulfur-tolerant carbon monoxide shift catalyst without alkali metal promoter, wherein the carrier is composed of magnesium oxide, aluminum oxide and titanium dioxide, and is prepared by a suspension precipitation method. TiO is directly used for CN1087192C and CN102151574B 2 As carrier for preparing sulfur-resistant shift catalyst with excellent hydration resistanceEnergy, low temperature activity and structural stability.
However, in the method provided by the invention, most of the titanium-containing substance is added into the carrier in a solid mode and is prepared by a kneading method, so that the titanium raw material cannot be well combined with other elements, the utilization efficiency is low, and the exertion of the effect is limited. CN103447049B although the titanium element was introduced by impregnation method, since it uses organic titanium or TiCl 4 Is a titanium source, needs volatile organic matters as a solvent, has high preparation cost and is not beneficial to industrial production.
Disclosure of Invention
The invention aims to overcome the problems of poor bonding and low utilization rate when Ti is introduced into a carrier in a solid mode in the prior art and to overcome the defects of poor bonding and low utilization rate when organic titanium or TiCl is used 4 Provides TiO for the problems of organic solvent requirement and high cost in titanium source 2 Modified alumina-based magnesium aluminate spinel, a preparation method thereof and a sulfur-tolerant shift catalyst.
In order to achieve the above object, the present invention provides, in a first aspect, a TiO 2 A process for the preparation of a modified alumina-based magnesium aluminate spinel, the process comprising the steps of:
(1) loading magnesium compound on gamma-Al by dipping method 2 O 3 Drying and roasting the substrate;
(2) impregnating TiOSO 4 Loading the substrate prepared in the step (1) and then drying; and
(3) and (3) placing the matrix prepared in the step (2) in an ammonia water solution for heat treatment, and then drying and roasting.
In a second aspect, the present invention provides TiO prepared by the process of the first aspect 2 Modified alumina-based magnesium aluminate spinels.
In a third aspect, the invention provides a sulfur tolerant shift catalyst comprising a carrier and an active component supported on the carrier, wherein the carrier is the TiO described in the second aspect of the invention 2 The modified alumina-based magnesium aluminate spinel comprises cobalt, molybdenum and potassium as active components.
The invention uses water-soluble TiOSO 4 Preparation of TiO as a starting Material 2 The modified alumina-based magnesium aluminate spinel avoids the use of organic solvents, reduces the preparation cost, has good titanium dispersibility, and can cover the alumina-based magnesium aluminate spinel to the maximum extent.
The catalyst of the present invention uses the above TiO 2 The modified alumina-based magnesia-alumina spinel is used as a carrier, overcomes the defect that a potassium-containing catalyst is easy to hydrate under severe conditions, widens the application range of the catalyst, and ensures that the catalyst has better activity and stability within a wider temperature range of 200-500 ℃.
Drawings
Figure 1 is an XRD pattern after hydrothermal treatment of the catalyst of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The invention provides a TiO compound 2 A process for the preparation of a modified alumina-based magnesium aluminate spinel, the process comprising the steps of:
(1) loading magnesium compound on gamma-Al by dipping method 2 O 3 Drying and roasting the substrate;
(2) impregnating TiOSO 4 Loading the substrate prepared in the step (1) and then drying; and
(3) and (3) placing the matrix prepared in the step (2) into an ammonia water solution for heat treatment, and then drying and roasting.
In the present invention, the gamma-Al 2 O 3 Matrix, magnesium compound, TiOSO 4 Respectively with Al 2 O 3 、MgO、 TiO 2 The mass ratio is 100: 1-20: 1-15, preferably 100: 1-15: 1-8.
In the present invention, the gamma-Al 2 O 3 The substrate may be in various shapes commonly used in the art, such as a ball shape, a teethed ball shape, or a bar shape, preferably a ball shape.
In the present invention, in step (1), the impregnation method is preferably an equal-volume impregnation method.
In the present invention, the impregnation liquid used in the impregnation process contains a magnesium compound and optionally one or more selected from a lanthanum compound, a calcium compound, a zirconium compound, and a cerium compound;
preferably, the magnesium compound may be a water-soluble salt, for example, may be selected from one or more of, but not limited to, magnesium nitrate, magnesium chloride, magnesium acetate, and magnesium bicarbonate. The lanthanum compound, the calcium compound, the zirconium compound and the cerium compound may be water-soluble salts of the corresponding elements, and the lanthanum compound may be, for example, one or more selected from lanthanum chloride, lanthanum nitrate, lanthanum acetate and lanthanum sulfate; the calcium compound may be selected, for example, from one or more of calcium chloride and calcium nitrate, and the zirconium compound may be selected, for example, from one or more of zirconium chloride and zirconium nitrate; the cerium compound may be selected, for example, from one or more of cerium trichloride and cerium nitrate.
In the present invention, the drying conditions in step (1) include: the temperature is 100-150 ℃, and the time is 6-18 h; the roasting conditions comprise: the temperature is 400 ℃ and 1000 ℃, and the time is 1-5 h. In the present invention, alumina-based magnesium aluminate spinel particles are obtained after the drying and firing step in step (1).
In the present invention, in the step (2), TiOSO is used 4 And (2) carrying out solution impregnation on the alumina-based magnesium aluminate spinel particles obtained in the step (1), wherein the impregnation method is preferably an equal-volume impregnation method.
In the present invention, in the step (2), the drying conditions include: the temperature is 80-150 ℃ and the time is 3-12 h.
In the present invention, TiOSO is added 4 After being dipped on alumina-based magnesium aluminate spinel, the aluminum aluminate spinel needs to be thermally treated in dilute ammonia water. Preferably, in the step (3), the heat treatment conditions include: heat treating at 50-100 deg.C for 1-5 hrThe pH of the aqueous ammonia solution in the process is maintained at greater than 11.
During the treatment, the following reactions occur:
TiOSO 4 +2NH 3 ·H 2 O＝TiO(OH) 2 ↓+(NH 4 ) 2 SO 4
TiO(OH) 2 ＝TiO 2 +H 2 O
3(NH 4 ) 2 SO 4 ＝4NH 3 ↑+3SO 2 ↑+N 2 ↑+6H 2 O
in the present invention, the aqueous ammonia solution used in step (3) may be an aqueous ammonia solution having any suitable concentration range as long as it is ensured that the pH of the aqueous ammonia solution is maintained at a value of more than 11 during the heat treatment, and may be, for example, 0.1 to 0.5 mol/L.
Compared with the conventional kneading method which uses titanium-containing solid such as metatitanic acid as a starting material, the method has better titanium dispersibility, can cover the alumina-based magnesia-alumina spinel to the maximum extent, and enhances the hydration resistance of the catalyst carrier; with the use of TiCl 4 Or an organic titanium such as tetrabutyl titanate, using a water-soluble TiOSO 4 The raw materials are adopted, the use of organic solvents is avoided, and the preparation cost is reduced. Furthermore, the sulfate ion introduced into the carrier of the present invention can be formed by (NH) 4 ) 2 SO 4 And then the catalyst is removed in a roasting mode, does not need a large amount of water washing, and is simple and easy to implement.
In the present invention, the drying conditions in step (3) include: the temperature is 100-150 ℃, and the time is 6-18 h; the roasting conditions comprise: the temperature is 500-600 ℃, and the time is 1-5 h.
The invention also provides TiO prepared by the method 2 Modified alumina-based magnesium aluminate spinels.
With the above TiO 2 The modified alumina-based magnesia-alumina spinel is used as a carrier, and active components Co, Mo and K can be loaded on the carrier by an impregnation method to prepare the sulfur-resistant shift catalyst, wherein the impregnation liquid contains a cobalt compound, a molybdenum compound and a potassium compoundThe compound (I) is prepared. The cobalt compound may be a soluble cobalt salt, for example, may be one or more of cobalt nitrate, cobalt acetate, cobalt chloride, cobalt sulfate, and cobalt hydroxycarbonate; the molybdenum compound may be a soluble molybdenum salt, and may be, for example, one or more of ammonium molybdate, sodium molybdate, potassium molybdate, and phosphomolybdic acid, preferably ammonium molybdate; the potassium compound may be a soluble potassium salt, and may be one or more of potassium carbonate, potassium chloride, potassium hydroxide, and potassium nitrate, for example, with potassium carbonate being preferred.
The components in the catalyst are preferably introduced by an isometric impregnation method, so that the catalyst has the advantages of high utilization efficiency of the components, uniform dispersion and simple and convenient operation.
In the present invention, an impregnation method is used to load an active component to TiO 2 Drying and roasting the modified alumina-based magnesia-alumina spinel carrier to obtain the sulfur-resistant shift catalyst. The drying conditions may be those commonly used in the art, and preferably include: the temperature is 100-; the time is 8-18h, more preferably 12 h. The firing conditions may be firing conditions commonly used in the art, and preferably include: the temperature is 450-600 ℃, more preferably 550-600 ℃; the time is 2-5 h.
The invention provides a sulfur-tolerant shift catalyst comprising the above TiO 2 The modified alumina-based magnesium aluminate spinel carrier comprises a modified alumina-based magnesium aluminate spinel carrier and active components loaded on the carrier, wherein the active components are cobalt, molybdenum and potassium.
Preferably, the carrier is contained in an amount of 60 to 95 wt%, the cobalt component is contained in an amount of 1 to 10 wt% in terms of oxide, the molybdenum component is contained in an amount of 2 to 20 wt% in terms of molybdenum trioxide, and the potassium component is contained in an amount of 1 to 15 wt% in terms of potassium oxide, based on the total weight of the catalyst.
Preferably, the carrier has a magnesium content, expressed as MgO, of from 1 to 15 wt.%, based on the total weight of the carrier, for example, from 2, 5, 7, 10, 12, 15 wt.%, and any value within the compositional range of any two of the above, preferably, from 1 to 10 wt.%, expressed as MgO; with TiO 2 The titanium content is 1-10% by weight, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10% by weight and any value within the range of any two of the foregoing, preferably TiO 2 The titanium content is 1-8 wt%; with Al 2 O 3 The aluminum content is 80 to 95 wt.%, and may be, for example, 85, 87, 89, 92 wt.%, or any value within the range defined by any two of the foregoing.
The catalyst provided by the invention has better strength, water resistance and performance, is free from water and phase change when used at high temperature (250-500 ℃), has excellent low-temperature activity (200-250 ℃), is wide in use temperature range, and has better activity and stability within a wider temperature range of 200-500 ℃.
The present invention will be described in detail below by way of examples.
The raw materials used in the following examples are as follows:
spherical gamma-Al 2 O 3 : a product purchased from Ziboruifeng chemical company and having a specific surface area of 200m 2 The water absorption rate is 63 percent, wherein the water absorption rate is 110N per particle and the water absorption rate is 7 nm.
Technical grade magnesium nitrate hexahydrate: a product available from star chemical ltd, shanxi, handed over from city.
Titanyl sulfate: a product purchased from Shanghai Yi Huai chemical Co., Ltd.
The water absorption test described in the examples was carried out by a method commonly used in the art.
Example 1
740g of spherical gamma-Al is weighed 2 O 3 Carrier, water absorption 63%. 364g of industrial-grade magnesium nitrate hexahydrate is taken, dissolved by water and then is added to 466 ml. The magnesium nitrate solution was immersed in 740g of gamma-Al in equal volume 2 O 3 Drying the carrier at 120 ℃ for 12h, and roasting the carrier at 800 ℃ for 3h to obtain 813g of alumina-based magnesia-alumina spinel carrier, wherein the water absorption rate is measured to be 56%. 61g of titanyl sulfate is dissolved in water to reach the constant volume of 455ml, and the solution is dipped on the alumina-based magnesium aluminate spinel carrier in the same volume and dried for 12 hours at the temperature of 120 ℃. The dried carrier is cooled to room temperature and then is placed at 70 ℃ for heat treatment for 3h in 0.5mol/L ammonia solution. After thatDrying at 120 deg.C for 12 hr, and calcining at 550 deg.C for 3 hr to obtain TiO 2 828g of modified alumina-based magnesia alumina spinel carrier, based on the total weight of the carrier, has a magnesium content of 6.9 wt.% in terms of MgO, calculated as TiO 2 The titanium content was 3.7 wt%, the balance being γ -Al 2 O 3 Water absorption: 50 percent.
Preparing 64.34g of basic cobalt carbonate, 106.55g of ammonium heptamolybdate and 97.47g of potassium carbonate into co-impregnation liquid by a conventional method, and impregnating the co-impregnation liquid into the TiO in equal volume 2 Drying the modified alumina-based magnesia-alumina spinel on a carrier at 120 ℃ for 12h, and roasting the carrier at 600 ℃ for 3h to obtain a catalyst finished product A1. Based on the total weight of the catalyst, the cobalt component was present in an amount of 4 wt.% as an oxide, the molybdenum component was present in an amount of 8.5 wt.% as molybdenum trioxide, and the potassium component was present in an amount of 6.5 wt.% as potassium oxide.
Example 2
A sulfur tolerant shift catalyst A2 was prepared in a similar manner to example 1, except that TiO was prepared in accordance with the following procedure 2 Modified alumina-based magnesium aluminate spinel support:
679g of spherical gamma-Al are weighed 2 O 3 Carrier, water absorption 63%. 527g of industrial grade magnesium nitrate hexahydrate is taken, dissolved by water and then fixed to 428 ml. Magnesium nitrate solution was immersed in 679g of gamma-Al in equal volume 2 O 3 Drying the carrier for 15h at 110 ℃, and roasting the carrier for 3h at 900 ℃ to obtain 762g of alumina-based magnesia-alumina spinel carrier, wherein the water absorption rate is measured to be 52%. 132g of titanyl sulfate is dissolved in water to reach the constant volume of 396ml, and the solution is dipped on the alumina-based magnesium aluminate spinel carrier in the same volume and dried for 12 hours at the temperature of 120 ℃. The dried carrier is cooled to room temperature and then placed at 60 ℃ for heat treatment for 4h in 0.3mol/L ammonia solution. Then drying the mixture at 120 ℃ for 12h, and roasting the dried mixture at 500 ℃ for 5h to obtain TiO 2 The modified alumina-based magnesia-alumina spinel carrier has a magnesium content of 10 wt% calculated by MgO and TiO content based on the total weight of the carrier 2 The titanium content was 8 wt%, the balance being γ -Al 2 O 3 Water absorption: and 48 percent.
Example 3
In accordance with and implementExample 1A sulfur tolerant shift catalyst A3 was prepared in a similar manner except that TiO was prepared according to the following procedure 2 Modified alumina-based magnesium aluminate spinel support:
687g of spherical gamma-Al are weighed 2 O 3 Carrier, water absorption 63%. 500g of magnesium chloride hexahydrate is taken, dissolved by water and then the volume is adjusted to 433 ml. Soaking magnesium chloride solution in 687g of gamma-Al in the same volume 2 O 3 Drying the carrier at 100 ℃ for 12h, and roasting the carrier at 500 ℃ for 3h to obtain 787g of alumina-based magnesia-alumina spinel carrier, wherein the water absorption rate is measured to be 50%. 82g of titanyl sulfate is dissolved in water to achieve a constant volume of 394ml, dipped on the alumina-based magnesium aluminate spinel carrier in an equal volume, and dried for 12 hours at 120 ℃. The dried carrier is cooled to room temperature and then is placed at 80 ℃ for heat treatment for 3h in 0.3mol/L ammonia solution. Then drying the mixture at 120 ℃ for 12h, and roasting the dried mixture at 500 ℃ for 5h to obtain TiO 2 The modified alumina-based magnesia-alumina spinel carrier comprises the following components by taking the total weight of the carrier as a reference: the magnesium content, calculated as MgO, is 12% by weight, calculated as TiO 2 The titanium content was 5 wt%, the remainder being γ -Al 2 O 3 Water absorption: 50 percent.
Example 4
A sulfur tolerant shift catalyst a4 was prepared in a similar manner to example 1, except that the active component was supported according to the following procedure:
taking 287g of cobalt nitrate hexahydrate, 206g of sodium molybdate and 110g of potassium hydroxide, preparing a co-impregnation liquid according to a conventional method, and impregnating the co-impregnation liquid into the TiO in equal volume 2 Drying the modified alumina-based magnesia-alumina spinel on a carrier at 120 ℃ for 12h, and roasting the carrier at 550 ℃ for 3h to obtain a catalyst finished product A4. Based on the total weight of the catalyst, the cobalt component was present in an amount of 8 wt.% as an oxide, the molybdenum component was present in an amount of 12 wt.% as molybdenum trioxide, and the potassium component was present in an amount of 9 wt.% as potassium oxide.
Comparative example 1
A sulfur tolerant shift catalyst was prepared in a similar manner to example 1, except that there was no Ti-supporting step in comparative example 1. Finally obtaining the finished catalyst D1.
Comparative example 2
A sulfur tolerant shift catalyst was prepared in a similar manner to example 1 except that TiO was used in comparative example 2 2 、Al 2 O 3 Mixing with MgO to obtain TiO 2 A modified magnesium aluminate spinel carrier. Finally obtaining the finished catalyst D2.
Test example
1. Atmospheric activity of the catalyst
The evaluation conditions of the normal pressure activity of the catalyst are as follows: the loading of the catalyst is 0.5g, the granularity is 20-40 meshes, the reaction pressure is 0.1Mpa, and the gas airspeed is 6000h -1 The reaction temperature is 200-500 ℃, and the feed gas composition is as follows: CO 81.45%, H 2 9.92％，N 2 8.55％，H 2 S0.08%, water to gas ratio 1.0, characterizing catalyst activity with CO conversion.
In-situ vulcanization is required before catalyst activity evaluation, wherein the vulcanization conditions are as follows: h 2 /H 2 S (99.2%/0.8% (v/v)), 50ml/min, pressure 0.1MPa, temperature 450 deg.C, and vulcanization time 5 h.
The CO conversion rate is calculated by the formula X CO ＝[(C 1 -C 2 )/C 1 ]*100％，C 1 CO concentration (v/v, dry basis (water vapor removal)) at the reactor inlet C 2 CO concentration (v/v, dry basis (water vapor removed)) at the reactor outlet.
The catalysts A1-A4 and D1-D2 were each tested for their normal pressure activity at different temperatures (200 ℃, 300 ℃, 400 ℃, 500 ℃) in accordance with the above-mentioned methods, and the results are shown in Table 1.
TABLE 1
Figure BDA0001611022860000101
2. Evaluation of hydration resistance of catalyst
Putting the catalysts A1, D1 and D2 into a hydrothermal kettle, adding a certain amount of deionized water, sealing, heating to 200 ℃ for hydrothermal treatment for 15 hours, drying, detecting the phase change by XRD, and expressing the strength of the hydration resistance of the catalysts by the amplitude of the phase change.
As shown in Table 1, catalysts A1-A4 all had higher activity at 200 ℃ and 500 ℃ and D1 catalyst was severely deactivated at a high temperature of 500 ℃ as compared with comparative catalysts D1 and D2, while the catalyst of the present invention had substantially no change in activity and the activity at 500 ℃ was maintained at 65% or more.
As shown in fig. 1, after hydrothermal treatment, the catalysts a1 and D1 both undergo significant hydration reaction of the supported alumina, but the hydration peak of the a1 catalyst alumina is smaller, indicating that it has better hydration resistance.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (11)

1. TiO 2 2 A process for the preparation of a modified alumina-based magnesium aluminate spinel, the process comprising the steps of:
(1) loading magnesium compound on gamma-Al by dipping method 2 O 3 Drying and roasting the substrate;
(2) impregnating TiOSO 4 Loading the substrate prepared in the step (1) and then drying; and
(3) and (3) placing the matrix prepared in the step (2) into an ammonia water solution for heat treatment, and then drying and roasting.
2. The method of claim 1, wherein the γ -Al is 2 O 3 Matrix, magnesium compound, TiOSO 4 Respectively with Al 2 O 3 、MgO、TiO 2 The mass ratio is 100: 1-20: 1-15.
3. The method according to claim 1, wherein, in step (1), the impregnation method is an equal-volume impregnation method,
and/or the impregnation liquid used in the impregnation process contains a magnesium compound and optionally one or more selected from a lanthanum compound, a calcium compound, a zirconium compound and a cerium compound;
and/or, the magnesium compound is selected from one or more of magnesium nitrate, magnesium chloride, magnesium acetate and magnesium bicarbonate.
4. The method according to claim 1 or 3, wherein in step (1), the drying conditions comprise: the temperature is 100-150 ℃, and the time is 6-18 h; the roasting conditions comprise: the temperature is 400 ℃ and 1000 ℃, and the time is 1-5 h.
5. The method according to claim 1, wherein, in the step (2), the impregnation method is an equal-volume impregnation method.
6. The method of claim 1 or 5, wherein in step (2), the drying conditions comprise: the temperature is 80-150 ℃ and the time is 3-12 h.
7. The method according to claim 1, wherein, in step (3), the conditions of the heat treatment include: the temperature is 50-100 deg.C, the time is 1-5h, and the pH value of ammonia water solution is kept above 11 during heat treatment.
8. The method of claim 1, wherein, in step (3), the drying conditions comprise: the temperature is 100-150 ℃, and the time is 6-18 h; the roasting conditions comprise: the temperature is 500-600 ℃, and the time is 1-5 h.
9. TiO prepared by the process of any one of claims 1 to 8 2 Modified alumina-based magnesium aluminate spinels.
10. A sulfur tolerant shift catalyst comprising a carrier and an active component supported on the carrier, wherein the carrier is the TiO according to claim 9 2 Modified alumina-based magnesiumThe aluminum spinel comprises cobalt, molybdenum and potassium as active components.
11. The catalyst of claim 10, wherein the support is present in an amount of 60 to 95 wt%, the cobalt component is present in an amount of 1 to 10 wt% as an oxide, the molybdenum component is present in an amount of 2 to 20 wt% as molybdenum trioxide, and the potassium component is present in an amount of 1 to 15 wt% as potassium oxide, based on the total weight of the catalyst;
and/or in the carrier, the magnesium content calculated by MgO is 1-15 wt% based on the total weight of the carrier, and the magnesium content is TiO 2 The titanium content is 1-10 wt.% calculated as Al 2 O 3 The calculated aluminum content is 80-95 wt.%.
CN201810264420.9A 2018-03-28 2018-03-28 TiO 2 Modified alumina-based magnesium aluminate spinel, preparation method thereof and sulfur-tolerant shift catalyst Active CN110314675B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810264420.9A CN110314675B (en) 2018-03-28 2018-03-28 TiO 2 Modified alumina-based magnesium aluminate spinel, preparation method thereof and sulfur-tolerant shift catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810264420.9A CN110314675B (en) 2018-03-28 2018-03-28 TiO 2 Modified alumina-based magnesium aluminate spinel, preparation method thereof and sulfur-tolerant shift catalyst

Publications (2)

Publication Number Publication Date
CN110314675A CN110314675A (en) 2019-10-11
CN110314675B true CN110314675B (en) 2022-09-02

Family

ID=68109974

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810264420.9A Active CN110314675B (en) 2018-03-28 2018-03-28 TiO 2 Modified alumina-based magnesium aluminate spinel, preparation method thereof and sulfur-tolerant shift catalyst

Country Status (1)

Country Link
CN (1) CN110314675B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112090435B (en) * 2019-06-18 2023-01-03 国家能源投资集团有限责任公司 Cobalt-molybdenum-based sulfur-tolerant shift catalyst and preparation method and application thereof
CN111410543B (en) * 2020-04-24 2021-08-13 朔州西廊煤炭科技有限公司 Method for preparing functional ceramic engineering material combustion-supporting catalyst by utilizing coal solid waste or bauxite solid waste
CN113880124A (en) * 2020-07-01 2022-01-04 中国石油天然气股份有限公司 Method for preparing magnesium aluminate spinel by impregnation
CN114471589A (en) * 2020-10-27 2022-05-13 中国石油化工股份有限公司 Catalyst, method for sulfur-tolerant shift catalytic reaction and method for preparing methane
CN112517008B (en) * 2020-12-29 2023-10-27 福州大学 Preparation method of Fe-doped magnesia-alumina spinel catalyst and application of Fe-doped magnesia-alumina spinel catalyst in desulfurization field

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102049257A (en) * 2009-10-27 2011-05-11 中国石油化工股份有限公司 Catalyst for simultaneously reducing SO2 and NO with CO as well as preparation and application of catalyst
CN107398262A (en) * 2016-05-19 2017-11-28 神华集团有限责任公司 Catalyst for methanation in presence of sulfur and preparation method thereof and magnesium aluminate spinel complex carrier and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102049257A (en) * 2009-10-27 2011-05-11 中国石油化工股份有限公司 Catalyst for simultaneously reducing SO2 and NO with CO as well as preparation and application of catalyst
CN107398262A (en) * 2016-05-19 2017-11-28 神华集团有限责任公司 Catalyst for methanation in presence of sulfur and preparation method thereof and magnesium aluminate spinel complex carrier and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Mechanism of Solid-state Reaction Between Magnesium -Oxide and Aluminum Oxide and Between Magnesium Oxide and Ferric Oxide;R. E. CARTER;《Journal of The American Ceramic Society》;19610331;第44卷(第3期);全文 *

Also Published As

Publication number Publication date
CN110314675A (en) 2019-10-11

Similar Documents

Publication Publication Date Title
CN110314675B (en) TiO 2 Modified alumina-based magnesium aluminate spinel, preparation method thereof and sulfur-tolerant shift catalyst
JPH10194742A (en) Zirconium-cerium-based compound oxide and its production
JP2016510687A (en) Nickel hexaaluminate-containing catalyst for reforming hydrocarbons in the presence of carbon dioxide
CN111943242B (en) Mesoporous gamma-Al 2 O 3 Preparation method of carrier and mesoporous gamma-Al 2 O 3 Carrier
CN106179381B (en) The preparation method of Hydrobon catalyst
JP5746716B2 (en) Porous alumina material, method for producing the same, and catalyst
JPH0230740B2 (en)
CN104607199B (en) A kind of low temperature sulfur tolerant shift Catalysts and its preparation method
CN109289831A (en) The catalyst of preparing propylene by dehydrogenating propane and preparation method thereof with high anti-carbon
CN114471589A (en) Catalyst, method for sulfur-tolerant shift catalytic reaction and method for preparing methane
CN108863706A (en) A kind of selection method of hydrotreating of the C-4-fraction containing alkynes
CN102962104A (en) Composite carrier of exhaust gas cleaning catalyst and preparation method of carrier
CN104549399B (en) Shell catalyst for 1, 4-butanediol vapor-phase dehydrogenation and application of shell catalyst
CN110697768A (en) Mesoporous TiO 22Material, catalyst, preparation method of material and catalyst, and denitration method
CN110237852B (en) Sulfate ion-containing titanium compound modified sulfur-tolerant shift catalyst and preparation method thereof
JPS60226414A (en) Production of lanthanum-alumina based compound oxide
CN106179383B (en) The preparation method of hydrotreating catalyst
CN112439451B (en) Low-temperature sulfur-tolerant shift catalyst, and preparation method and application thereof
CN106179480B (en) A kind of Hydrobon catalyst composition and preparation method thereof
CN108654630B (en) Sulfur-tolerant shift catalyst and preparation method thereof
CN106179389B (en) Hydrobon catalyst and preparation method thereof
CN110935460A (en) High-selectivity hydrodesulfurization catalyst and preparation method thereof
CN112387276A (en) Supported ruthenium cluster catalyst for ammonia synthesis and preparation method and application thereof
CN106179380B (en) A kind of Hydrobon catalyst and preparation method thereof
JPS6283315A (en) Production of gamma-alumina having superior heat stability

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information
CB02 Change of applicant information

Address after: 100011 Beijing Dongcheng District, West Binhe Road, No. 22

Applicant after: CHINA ENERGY INVESTMENT Corp.,Ltd.

Applicant after: Beijing low carbon clean energy research institute

Address before: 100011 Beijing Dongcheng District, West Binhe Road, No. 22

Applicant before: CHINA ENERGY INVESTMENT Corp.,Ltd.

Applicant before: Beijing low carbon clean energy research institute

GR01 Patent grant
GR01 Patent grant