CN112337487A - Deoxygenation catalyst and preparation method and application thereof - Google Patents

Deoxygenation catalyst and preparation method and application thereof Download PDF

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Publication number
CN112337487A
CN112337487A CN201910731413.XA CN201910731413A CN112337487A CN 112337487 A CN112337487 A CN 112337487A CN 201910731413 A CN201910731413 A CN 201910731413A CN 112337487 A CN112337487 A CN 112337487A
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China
Prior art keywords
catalyst
deoxidation
mos
deoxygenation
pts
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吕顺丰
李彤
王世亮
秦燕璜
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Priority to CN201910731413.XA priority Critical patent/CN112337487A/en
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • B01J27/0515—Molybdenum with iron group metals or platinum group metals
    • 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
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction

Abstract

The invention relates to the field of deoxidation catalysts, and discloses a preparation method of a deoxidation catalyst, the deoxidation catalyst prepared by the preparation method and application of the deoxidation catalyst. The method comprises the following steps: mixing MoS2Mixing with carrier to obtain mixture containing MoS2The vector of (1); to the MoS-containing2By introducing the active ingredient PtS into the carrierxObtaining a deoxidation catalyst precursor; and sequentially molding and roasting the deoxidation catalyst precursor to obtain the deoxidation catalyst. The preparation method can improve the content of the Mo element in the prepared deoxidation catalyst, can avoid the problem that hydrogen, hydrogen sulfide and other explosive toxic gases are used in the production process of the traditional deoxidation catalyst, can ensure that the active components Pt and Mo are in a completely vulcanized state, obviously improves the performance of the deoxidation catalyst, and can predictably prolong the service life.

Description

Deoxygenation catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of deoxidation catalysts, in particular to a preparation method of a deoxidation catalyst, a deoxidation catalyst prepared by the preparation method and application of the deoxidation catalyst.
Background
The synthesis gas is an important raw material for producing butanol and octanol through oxo synthesis reaction, and is a mixed gas of carbon monoxide and hydrogen. The composition is generally expressed as the volume ratio of hydrogen to carbon monoxide, and H is produced in the oxo process2The molar ratio to CO is between 1-1.2: 1. The synthesis gas is produced by a high-temperature coke and steam reforming method, a natural gas steam reforming method, a light naphtha reforming method, a heavy oil partial oxidation method, and the like. The synthesis gas produced by these processes contains trace amounts of impurities such as oxygen. The presence of oxygen oxidizes triphenylphosphine, which is a ligand of the oxo catalyst, into phosphine oxide, so that the activity of the oxo rhodium-phosphine complex catalyst is reduced. In order to prevent trace impurity oxygen from entering the hydroformylation reactor, trace oxygen in the synthesis gas must be purified to 0.1 to 1ppm (mole, the same applies hereinafter) using a deoxygenation catalyst. With the improvement of the production process of butanol and octanol, the requirement on the purification of trace oxygen in the synthesis gas is higher and higher. Therefore, it is necessary to develop a highly efficient deoxygenation catalyst capable of deeply purifying the trace oxygen content of the syngas to less than or equal to 0.1 ppm.
The principle of deoxidation of synthesis gas applied to the related patent documents and industrial production is to remove a trace amount of oxygen by reacting oxygen impurity mixed in synthesis gas with hydrogen gas to generate water vapor under the action of a catalyst containing noble metals such as Pd and Pt.
CN1768936A discloses PtS with platinum sulfide as active componentxThe preparation method of the supported deoxygenation catalyst comprises the following steps: (1) preparation of platinum Pt catalyst: loading platinum on a carrier by using a platinum-containing solution by adopting a spraying method or an impregnation method to obtain a platinum catalyst, wherein the platinum content is 0.01-0.5% (wt) based on the total weight of the catalyst; (2) reduction and vulcanization: heating the Pt catalyst obtained in the step (1), and introducing H2Reduction to H2Adding a vulcanizing agent into the mixture for vulcanization, and after the vulcanization is finished, enabling the molar ratio x of S/Pt in the catalyst to be 0.1-50; (3) purging and cooling: continuously introducing hydrogen until tail gas H2Middle H2The S content is less than 0.1ppm, and the temperature is reduced to room temperature in a hydrogen atmosphere to obtain the PtSxAnd (3) a deoxygenation catalyst.
CN1724155A discloses a sulfur-resistant catalytic deoxidizer and a production method thereof, which is a catalytic deoxidizer taking active alumina as a carrier and metal platinum and molybdenum as composite active components and a preparation method thereof, wherein the metal platinum accounts for 0.03 to 0.5 percent of the total weight of the catalyst and the molybdenum accounts for 0.5 to 15 percent of the total weight of the catalyst in percentage by weight. The preparation of the catalyst comprises the following steps: a. the specific surface area is 250m2More than g, pore volume of 0.40cm3Drying the activated alumina carrier with more than/g and the average pore diameter of 5-20 nm; b. dissolving the calculated amount of chloroplatinic acid into a certain amount of deionized water, uniformly stirring, adjusting the pH value to 7.0-10.0, and adding the calculated amount of ammonium molybdate solution; c. dipping the activated alumina carrier according to an equal volume method, wherein the dipping time is 6-12 hours, and placing the alumina carrier at room temperature for 12-24 hours; d. drying the water in an air atmosphere of 110-120 ℃; e. the temperature is programmed to 400-800 ℃ within 6 hours, and the mixture is roasted for 6-9 hours; f. the catalyst needs pre-reduction before use, and the reduction is realized in a hydrogen atmosphere: gradually heating to 280 ℃ by using nitrogen with 5-10% of hydrogen-containing gas volume ratio, staying for 4 hours, and then heating to 450 ℃ until the reduction is complete; g. after the reduction is finished, 0.5 percent of hydrogen sulfide is added into nitrogen to be vulcanized for more than 4 hours at 180 ℃ to obtain the finished deoxidizer.
Most nearly synthesis gas deoxygenation catalysts prepared by the prior art use platinum and molybdenum as active components and alumina as a carrier. In order to be suitable for purifying trace oxygen in sulfur-containing synthesis gas, in the production process of the deoxidation catalyst, active components Pt and Mo are reduced to be in a zero-valent metal state, and then hydrogen sulfide gas is adopted to carry out high-temperature vulcanization reaction on the zero-valent active components Pt and Mo, namely explosive gas (hydrogen) and toxic gas (hydrogen sulfide) are used in the production process.
In addition, in the prior art, the active component Mo is loaded by adopting an impregnation method, so that the content of the molybdenum element cannot reach a very high content. Furthermore, since the gas-solid reaction rate with hydrogen sulfide is slow when the zero-valent active components Pt and Mo are sulfided, it is not possible to ensure that the zero-valent active components Pt and Mo are completely sulfided. Therefore, the existing methods for preparing the deoxygenation catalyst need to be further improved, and the quality of the deoxygenation catalyst needs to be further improved.
Disclosure of Invention
The invention aims to overcome the defects that explosive toxic gases such as hydrogen, hydrogen sulfide and the like are used in the production process of the conventional synthesis gas deoxidation catalyst, and Pt and Mo cannot be completely vulcanized, and provides the deoxidation catalyst, a preparation method and application thereof.
Accordingly, in order to achieve the above objects, in one aspect, the present invention provides a method for preparing a deoxygenation catalyst, the method comprising the steps of:
(1) mixing MoS2Mixing with carrier to obtain mixture containing MoS2The vector of (1);
(2) to the MoS-containing2By introducing the active ingredient PtS into the carrierxObtaining a deoxidation catalyst precursor;
(3) and (3) sequentially carrying out molding and roasting treatment on the deoxidation catalyst precursor obtained in the step (2) to obtain the deoxidation catalyst.
In another aspect, the present invention provides a deoxygenation catalyst made by the method described above.
In a third aspect, the present invention provides a deoxygenation catalyst comprising a support and an active component supported on the support;
wherein the active components are molybdenum sulfide and platinum sulfide;
the content of the Mo element is more than 15 parts by weight and the content of the Pt element is 0.05-0.5 part by weight relative to 100 parts by weight of the deoxidation catalyst;
the BET specific surface area of the deoxidation catalyst is 80-300m2Per g, pore volume of 0.2-0.9cm3(iv)/g, crush strength greater than 50N/particle.
In a fourth aspect, the present invention provides the use of a deoxygenation catalyst as described above in the deoxygenation of synthesis gas and/or in the conversion of sulphur.
The method of the invention directly combines MoS2Mixing with carrier to prepare the product containing MoS2The MoS2Is not only an active component but also gamma-Al2O3Jointly used as a carrier to carry a noble metal active component PtSxThe method avoids the operation of using hydrogen and hydrogen sulfide in the production process of the existing synthesis gas deoxidation catalyst. The method can ensure that the active components Pt and Mo are in a completely vulcanized state, and obviously improves the performance of the deoxidation catalyst.
The content of molybdenum in the deoxidation catalyst in the invention can be up to 30 wt% under the preferable condition, for example, the deoxidation catalyst obtained in the embodiment 1 improves the content of the active component of the deoxidation catalyst, improves the deoxidation effect of the deoxidation catalyst, and the expected service life of the deoxidation catalyst is expected to be effectively prolonged.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
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 ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention provides a method for preparing a deoxygenation catalyst, the method comprising the steps of:
(1) mixing MoS2Mixing with carrier to obtain mixture containing MoS2The vector of (1);
(2) to the MoS-containing2By introducing the active ingredient PtS into the carrierxObtaining a deoxidation catalyst precursor;
(3) and (3) sequentially carrying out molding and roasting treatment on the deoxidation catalyst precursor obtained in the step (2) to obtain the deoxidation catalyst.
By adopting the method of the invention and through MoS2Introducing Mo element in the form of PtSxThe Pt element is introduced in the form of the catalyst, so that on one hand, the upper limit of the content of the Mo element in the prepared deoxidation catalyst can be improved, and the deoxidation efficiency of the deoxidation catalyst is improved; on the other hand, because the Mo element and the Pt element are added in the form of sulfides, the Mo element and the Pt element do not need to be reduced and vulcanized, and hydrogen sulfide do not need to be used, so that potential safety hazards are reduced.
According to the invention, the MoS2The amount of (A) can be selected within a wide range, such as the MoS2The amount of (b) may be such that the content of the Mo element in the prepared deoxygenation catalyst is 1 to 30% by weight. Preferably, the MoS2The amount of the Mo element is 9-30 wt% in the prepared deoxidation catalyst; for example, it may be 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 wt% or any value in between any two values. The inventors of the present invention found that an increase in the content of Mo element can improve the deoxidation effect of the deoxidation catalyst, and also leads to a decrease in the specific surface area of the deoxidation catalyst, thereby having a negative effect on the deoxidation effect of the deoxidation catalyst. Within the above Mo content range, the obtained deoxidation catalyst can obtain better deoxidation effect. More preferably, the MoS2The amount of the Mo element is 12-30 wt% in the prepared deoxidation catalyst.
Wherein, MoS2The average particle diameter of (b) can be selected within a wide range, preferably 10nm to 10 μm, and may be, for example, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1 μm, 2 μmAnd 4 μm, 5 μm, 6 μm, 8 μm, 10 μm, and any range of the compositions between any two values, more preferably 10 to 200nm, and still more preferably 10 to 100nm, the deoxidation effect of the obtained deoxidation catalyst is also improved.
According to the invention, the support may be one conventionally used in the art, for example, it may be selected from Al2O3Activated carbon, SiO2And a molecular sieve, preferably, the carrier is γ -Al2O3。
Wherein, the gamma-Al2O3The BET specific surface area of (A) can be selected within a wide range, and preferably, the gamma-Al2O3The BET specific surface area of (B) may be 150-300m2The number of the particles/g may be, for example, 150, 160, 180, 200, 220, 240, 260, 280, 300m2(iv)/g and any range of compositions between any two values, more preferably 200-300m2In the case of the catalyst,/g, the effect of the produced deoxidation catalyst is further improved.
Wherein, the gamma-Al2O3The average particle diameter of (b) is selected from a wide range, and is preferably 10nm to 10 μm, and for example, may be any range of 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1 μm, 2 μm, 4 μm, 5 μm, 6 μm, 8 μm, 10 μm, or any two values, more preferably 10 to 200nm, and still more preferably 10 to 100nm, the deoxidizing effect of the obtained deoxidizing catalyst is further improved.
In the present invention, only MoS is required2Mixing with carrier to obtain MoS-containing material2The method for mixing the carrier of (1) and the method for mixing uniformly are not particularly limited, and various methods commonly used in the art can be adopted, for example, the carrier and MoS can be mixed2Putting into a conical mixer for mixing.
According to the present invention, in step (2), the active component PtS may be reacted in a manner conventional in the artxIntroduction of MoS-containing2In the vector of (1). Preferably, PtS is introduced by means of impregnationxIntroduction ofContaining MoS2To obtain a deoxygenated catalyst precursor.
According to the invention, the PtSxWhere x is the molar ratio of S/Pt, x can be 3-20, for example, 3, 5, 8, 10, 12, 14, 16, 18, 20, and any range of compositions between any two values, preferably 5-10.
According to the invention, the PtSxCan be selected within a wide range, preferably the PtSxThe amount of (b) is such that the content of Pt element in the prepared deoxygenation catalyst is 0.05-0.5 wt%, and may be, for example, 0.05, 0.06, 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5 wt%, and any range of compositions between any two values. More preferably, the PtSxThe amount of the Pt element is 0.06-0.3 wt% of the prepared deoxidation catalyst.
According to a preferred embodiment of the invention, the MoS will be contained2Vector and PtSxThe aqueous solution is contacted to perform impregnation.
According to the invention, the PtSxThe method for preparing the aqueous solution is not particularly limited, and it is preferable to add an inorganic sulfide to a solution of a tetravalent platinum water-soluble compound to prepare PtSxAn aqueous solution.
Preferably, the PtS is not targetedxThe pH of the aqueous solution is adjusted.
Wherein, the tetravalent platinum water-soluble compound can be various compounds with tetravalent platinum valence which are imaginable to those skilled in the art, such as at least one selected from chloroplatinic acid, alkali metal salt of chloroplatinic acid and platinum tetrachloride; chloroplatinic acid is preferred.
Wherein the inorganic sulfur compound may be a sulfide salt or an aqueous solution thereof; preferably, the sulfide salt is selected from at least one of ammonium sulfide, sodium sulfide and potassium sulfide.
In a preferred embodiment of the present invention, PtSxThe aqueous solution is prepared by adding a certain amount of water and a solution of ammonium sulfide having a sulfur element content of 6-10 wt% to a solution of a tetravalent platinum water-soluble compoundAnd (3) making x be 3-20. Wherein the PtS is not subjected toxThe pH of the aqueous solution is adjusted.
According to the present invention, the impregnation method may be a conventional impregnation method in the art, and may be, for example, an excess impregnation method, an equal volume impregnation method or a multiple impregnation method, preferably an equal volume impregnation method.
According to the present invention, the deoxygenated catalyst precursor may be further subjected to a kneading treatment before being subjected to the shaping treatment, and the method and the apparatus for the kneading are not particularly required, and for example, a kneader may be used for the kneading.
According to the invention, no special requirements are imposed on the forming method and the formed shape, and for example, the forming method can be used for forming different shapes such as a sphere, a cylinder, a honeycomb, a clover, a sheet or a hollow shape by using a bar extruder, a ball rolling disc, a tablet press or other forming equipment.
In a preferred embodiment of the invention, the MoS-containing product obtained in step (1) is used2The carrier is added into a kneader and PtS is sprayedxThe aqueous solution was impregnated with the same volume, kneaded thoroughly, and then rolled into a spherical shape to prepare a spherical deoxygenated catalyst precursor.
In another preferred embodiment of the present invention, the MoS-containing product obtained in step (1) is used2Vector and PtSxAnd (3) fully kneading the water solution after isovolumetric impregnation, and extruding the product obtained after impregnation into strip-shaped small sections by using a strip extruding machine to obtain strip-shaped deoxidization catalyst precursor.
According to the present invention, the calcination conditions may be those conventional in the art, and preferably include calcination at 200-600 ℃ for 2-10h, and more preferably at 300-400 ℃ for 4-6h under nitrogen or inert atmosphere.
According to the invention, the method may also comprise ageing and drying treatments after said shaping and before firing.
Wherein the aging condition can be the conventional aging condition in the field, and preferably comprises the steps of placing the formed product in a closed manner for 12-72 hours, and further preferably 24-48 hours; the ambient environment of the placement is preferably at room temperature and pressure.
Wherein the drying conditions may be those conventional in the art, and preferably comprises drying the aged product at 80-150 deg.C for 5-12h, and more preferably at 120-140 deg.C for 8-10 h.
In a second aspect, the present invention provides a deoxygenation catalyst made by the method as described above.
In a third aspect, the present invention provides a deoxygenation catalyst comprising a support and an active component supported on the support; wherein the active components are molybdenum sulfide and platinum sulfide.
The content of the Mo element is more than 15 parts by weight, preferably 30 parts by weight or less, and may be, for example, 15.1, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 parts by weight or any value between any two values, based on 100 parts by weight of the deoxidation catalyst.
The content of the Pt element is 0.05 to 0.5 parts by weight, for example, may be in any range of 0.05, 0.06, 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5 and any combination thereof, and preferably 0.06 to 0.3 parts by weight, based on 100 parts by weight of the deoxidation catalyst.
Wherein the BET specific surface area of the deoxidation catalyst is 80-300m2The number of the particles/g can be, for example, 80, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300m2In the case of the catalyst having a composition in any range of values of the catalyst,/g, and any two values, a good catalytic effect can be obtained. More preferably 200-300m2When the amount is in the range of/g, the effect of the produced deoxygenation catalyst is further improved.
According to the invention, methods for determining BET specific surface area are described in GB/T19587-2017.
Wherein the pore volume of the deoxidation catalyst is 0.2-0.9cm3The/g may be, for example, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, and any value in between.
According to the present invention, the method for determining the pore volume of a deoxygenating catalyst is described in GB/T21650.1-2008.
Wherein the crush strength of the deoxygenation catalyst is greater than 50N per particle.
The method for determining the crush strength of a deoxygenating catalyst according to the present invention is found in ASTM D4179-11 (2017).
In a fourth aspect, the present invention provides the use of a deoxygenation catalyst as described above in the deoxygenation of synthesis gas or sulphur conversion.
According to the invention, the main constituents of the synthesis gas are CO and H2CO and H2In a molar ratio of 1-1.2: 1. Currently, methods for producing synthesis gas include a high-temperature coke and steam reforming method, a natural gas steam reforming method, a light naphtha reforming method, a heavy oil partial oxidation method, and the like. The synthesis gas produced by these processes contains trace amounts of impurities such as oxygen and COS.
In a preferred case, the deoxygenation catalyst of the present invention is capable of treating syngas with a trace oxygen content of 0.1 to 5000 ppm; and/or COS in an amount of 0-100 ppm.
According to the present invention, the conditions for the deoxidation or sulfur conversion using the deoxidation catalyst may be: the temperature is 160-190 ℃, the volume space velocity of the gas is 1000-8000h-1The pressure is 0.1-5 MPa; preferably, the temperature is 170--1The pressure is 1-2.5 MPa.
Examples
The following examples further illustrate the invention but are not intended to limit the invention thereto.
In the following examples and comparative examples, the evaluation method of the deoxygenation catalyst was as follows: 50ml of deoxygenation catalyst is loaded into a stainless steel reactor with the diameter of phi 25mm, and the temperature is 180 ℃, the pressure is 2.0MPa, and the reaction time is 5000h-1The synthesis gas has the following composition: h2 50.0％，CO 49.7％，O2 2000ppm，CO2 0.1％，COS 15ppm。
Detecting the Trace oxygen content in the reacted gas by using a Teledyne Ultra Trace 3000 Trace oxygen analyzer.
The obtained deoxygenation catalysts were evaluated in the following examples and comparative examples, wherein the BET specific surface area was measured in GB/T19587-2017, the pore volume was measured in GB/T21650.1-2008, and the crush strength was measured in ASTM D4179-11 (2017).
Preparation example 1
This preparation is illustrative of PtS according to the inventionxProcess for the preparation of an aqueous solution
(1) Preparation of chloroplatinic acid solution: a certain amount of sponge Pt is weighed, and a chloroplatinic acid aqueous solution with the Pt element content of 0.25 weight percent is prepared by using aqua regia solution.
(2)PtSxPreparation of an aqueous solution: adding a certain amount of water and an ammonium sulfide aqueous solution with the sulfur element content of 8 weight percent into the chloroplatinic acid aqueous solution obtained in the step (1) to obtain PtS with x of 3-20xAqueous solution, without pH adjustment.
Example 1
This example illustrates the preparation of the deoxygenation catalyst provided by the present invention.
1000g of a polymer having an average particle diameter of 10nm and a specific surface area of 300m2gamma-Al of/g2O3And 1000g of MoS having an average particle diameter of 10nm2Mixing in a conical mixer.
Adding PtS into the uniformly mixed carrierxThe aqueous solution (x is 8) was impregnated in an equal volume so that the Pt element was 0.1 parts by weight with respect to 100 parts by weight of the deoxygenation catalyst.
And fully kneading the impregnated materials, preparing strip-shaped small sections with the diameter phi of 3mm and the length of 5mm by using a strip extruding machine, then sealing and placing for 48 hours, then drying for 10 hours at 120 ℃, and finally roasting for 5 hours at 350 ℃ in a nitrogen atmosphere to prepare the deoxidation catalyst with the Mo element content of 30 weight percent and the Pt element content of 0.1 weight percent.
The BET specific surface area of the deoxygenation catalyst was determined to be 175m2Per g, pore volume of 0.45cm3(iv)/g, crushing strength of 65N/grain.
The deoxygenation effect of the deoxygenation catalyst is shown in table 1.
Example 2
This example illustrates the preparation of the deoxygenation catalyst provided by the present invention.
1000g of a polymer having an average particle diameter of 100nm and a specific surface area of 250m2gamma-Al of/g2O3And 350g of MoS having an average particle diameter of 100nm2Mixing in a conical mixer.
Adding PtS into the uniformly mixed carrierxThe aqueous solution (x is 5) was subjected to the equal volume impregnation so that the Pt element was 0.3 parts by weight with respect to 100 parts by weight of the deoxygenation catalyst.
And fully kneading the impregnated materials, preparing strip-shaped small sections with the diameter phi of 3mm and the length of 5mm by using a strip extruding machine, then sealing and placing for 24h, then drying for 8h at 140 ℃, and finally roasting for 4h at 400 ℃ in nitrogen atmosphere to prepare the deoxygenation catalyst with the Mo element content of 15.6 wt% and the Pt element content of 0.3 wt%.
The BET specific surface area of the deoxygenation catalyst was determined to be 160m2G, pore volume 0.52cm3(iv)/g, crush strength 102N/grain.
The deoxygenation effect of the deoxygenation catalyst is shown in table 1.
Example 3
This example illustrates the preparation of the deoxygenation catalyst provided by the present invention.
1000g of a polymer having an average particle diameter of 50nm and a specific surface area of 200m2gamma-Al of/g2O3And 250g of MoS having an average particle diameter of 50nm2Mixing in a conical mixer.
Adding PtS into the uniformly mixed carrierxThe aqueous solution (x is 10) was subjected to the equal volume impregnation so that the Pt element was 0.06 parts by weight with respect to 100 parts by weight of the deoxygenation catalyst.
And fully kneading the impregnated materials, preparing strip-shaped small sections with the diameter phi of 3mm and the length of 5mm by using a strip extruding machine, then sealing and placing for 48 hours, drying for 8 hours at 120 ℃, and finally roasting for 6 hours at 350 ℃ under nitrogen atmosphere to prepare the deoxidation catalyst with the Mo element content of 12 weight percent and the Pt element content of 0.06 weight percent.
The BET specific surface area of the deoxygenation catalyst was determined to be 170m2G, pore volume 0.54cm3Per g, crushingThe intensity was 118N/particle.
The deoxygenation effect of the deoxygenation catalyst is shown in table 1.
Example 4
This example illustrates the preparation of the deoxygenation catalyst provided by the present invention.
A deoxygenation catalyst was prepared according to the method of example 1, except that MoS2Has an average particle diameter of 200nm, and is prepared as a deoxidation catalyst with a Mo element content of 30 wt% and a Pt element content of 0.1 wt%.
The BET specific surface area of the deoxygenation catalyst was determined to be 168m2G, pore volume 0.42cm3(ii)/g, crushing strength of 60N/grain.
The deoxygenation effect of the deoxygenation catalyst is shown in table 1.
Example 5
This example illustrates the preparation of the deoxygenation catalyst provided by the present invention.
A deoxygenation catalyst was prepared according to the method of example 1, except that γ -Al2O3Has a specific surface area of 150m2The catalyst was prepared in the form of a deoxidation catalyst having a Mo element content of 30 wt.% and a Pt element content of 0.1 wt.%.
The BET specific surface area of the deoxygenation catalyst was determined to be 105m2G, pore volume 0.28cm3(iv)/g, crush strength 68N/grain.
The deoxygenation effect of the deoxygenation catalyst is shown in table 1.
Example 6
This example illustrates the preparation of the deoxygenation catalyst provided by the present invention.
A deoxygenation catalyst was prepared according to the method of example 1, except that γ -Al2O3Has an average particle diameter of 200nm, and is prepared as a deoxidation catalyst with a Mo element content of 30 wt% and a Pt element content of 0.1 wt%.
The BET specific surface area of the deoxygenation catalyst was determined to be 168m2Per g, pore volume 0.43cm3(iv)/g, crushing strength was 66N/grain.
The deoxygenation effect of the deoxygenation catalyst is shown in table 1.
Example 7
This example illustrates the preparation of the deoxygenation catalyst provided by the present invention.
A deoxygenation catalyst was prepared according to the method of example 1, except that MoS2And PtS8The amounts of the Mo element and the Pt element were varied, and a catalyst for deoxidation with a Mo element content of 9 wt% and a Pt element content of 0.1 wt% was prepared.
The BET specific surface area of the deoxygenation catalyst was determined to be 262m2G, pore volume 0.77cm3(iv)/g, crush strength was 115N/grain.
The deoxygenation effect of the deoxygenation catalyst is shown in table 1.
Example 8
This example illustrates the preparation of the deoxygenation catalyst provided by the present invention.
A deoxygenation catalyst was prepared according to the method of example 1, except that MoS2And PtS8The amounts of the Mo element and the Pt element were varied to prepare a deoxidation catalyst having a Mo element content of 27 wt% and a Pt element content of 0.1 wt%.
The BET specific surface area of the deoxygenation catalyst was determined to be 185m2G, pore volume 0.48cm3(iv)/g, crush strength 68N/grain.
The deoxygenation effect of the deoxygenation catalyst is shown in table 1.
Example 9
This example illustrates the preparation of the deoxygenation catalyst provided by the present invention.
A deoxygenation catalyst was prepared according to the method of example 1, except that MoS2And PtS8The amounts of the Mo element and the Pt element were varied, and a deoxygenation catalyst having a Mo element content of 7 wt% and a Pt element content of 0.06 wt% was prepared.
The BET specific surface area of the deoxygenation catalyst was determined to be 280m2Per g, pore volume 0.82cm3(ii)/g, crushing strength 125N/grain.
The deoxygenation effect of the deoxygenation catalyst is shown in table 1.
Comparative example 1
This comparative example serves to illustrate the preparation of a reference deoxygenation catalyst.
The deoxygenation catalyst was prepared according to the method of example 1 of patent CN1724155A, wherein the content of Mo element was 7 wt% and the content of Pt element was 0.06 wt%.
The BET specific surface area of the deoxygenation catalyst was determined to be 265m2G, pore volume 0.80cm3(iv)/g, crush strength 120N/grain.
The deoxidation effect of the obtained deoxidation catalyst is shown in table 1.
TABLE 1
Numbering Oxygen content (ppm) after deoxidation
Example 1 0.008
Example 2 0.012
Example 3 0.035
Example 4 0.011
Example 5 0.018
Example 6 0.011
Example 7 0.050
Example 8 0.009
Example 9 0.074
Comparative example 1 0.18
As can be seen from table 1, the deoxygenation catalyst prepared by the method of the present invention has a better deoxygenation effect than comparative example 1.
As can be seen by comparing example 1 with examples 4 and 6, the starting material MoS2And gamma-Al2O3The smaller the average particle size of the catalyst is, the better the deoxidation effect of the prepared deoxidation catalyst is; as can be seen by comparing example 1 with example 5, gamma-Al2O3The higher the specific surface area is, the better the deoxidation effect of the prepared deoxidation catalyst is; as can be seen from the comparison of example 1 with examples 7 to 9, the higher the Mo element content in the obtained deoxidizing catalyst, the better the deoxidizing effect of the deoxidizing catalyst.
The deoxidation catalyst of the invention directly prepares MoS in the preparation process2Mixing with carrier to prepare the product containing MoS2The MoS2Is not only an active component but also gamma-Al2O3Jointly used as a carrier to carry a noble metal active component PtSxThe method has the advantages of avoiding using explosive and toxic gases such as hydrogen, hydrogen sulfide and the like in the production process of the existing synthetic gas deoxidation catalyst. The method can ensure that the active components Pt and Mo are in a completely vulcanized state, and obviously improves the performance of the deoxidation catalyst.
The content of molybdenum element in the deoxidation catalyst prepared by the method can reach 30 wt% at most, and the active component is in a completely vulcanized state, so that the deoxidation effect is further improved, and the service life of the deoxidation catalyst can be expected to be effectively prolonged.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (11)

1. A method of preparing a deoxygenation catalyst, the method comprising the steps of:
(1) mixing MoS2Mixing with carrier to obtain mixture containing MoS2The vector of (1);
(2) to the MoS-containing2By introducing the active ingredient PtS into the carrierxObtaining a deoxidation catalyst precursor;
(3) and (3) sequentially carrying out molding and roasting treatment on the deoxidation catalyst precursor obtained in the step (2) to obtain the deoxidation catalyst.
2. The method of claim 1, wherein in step (1), the MoS2The amount of (b) is such that the content of the Mo element in the produced deoxidation catalyst is 1 to 30% by weight, preferably 9 to 30% by weight.
3. The method of claim 1 or 2, wherein the MoS is2The average particle diameter of (A) is 10nm-10 μm, preferably 10-200 nm.
4. The method of claim 1The carrier is selected from Al2O3Activated carbon, SiO2And a molecular sieve, preferably gamma-Al2O3；
Further preferably, the γ -Al2O3BET specific surface area of 150-300m2(ii)/g, the average particle diameter is in the range of 10nm to 10 μm.
5. The method according to claim 1, wherein in step (2), the PtS is impregnated by means of impregnationxIntroduction of said MoS-containing2In the vector of (1); wherein x is 3 to 20, preferably 5 to 10;
preferably, the PtSxThe amount of (b) is such that the content of Pt element in the prepared deoxygenation catalyst is 0.05 to 0.5 wt%, preferably 0.06 to 0.3 wt%.
6. The method of claim 5, wherein the method of impregnating comprises: will contain MoS2Vector and PtSxContacting the aqueous solution to perform impregnation;
preferably, the PtSxThe preparation method of the aqueous solution comprises the step of adding inorganic sulfide into a solution of a tetravalent platinum water-soluble compound to prepare PtSxAn aqueous solution;
preferably, the tetravalent platinum water-soluble compound is selected from at least one of chloroplatinic acid, an alkali metal salt of chloroplatinic acid, and platinum tetrachloride; and/or
The inorganic sulfur compound is a sulfide salt or an aqueous solution thereof; preferably, the sulfide salt is selected from at least one of ammonium sulfide, sodium sulfide and potassium sulfide.
7. The method according to claim 5 or 6, wherein the impregnation method is an excess impregnation method, an equal volume impregnation method or a multiple impregnation method, preferably an equal volume impregnation method.
8. The method as claimed in any one of claims 1 to 7, wherein, in the step (3), the roasting is carried out in a nitrogen or inert atmosphere, the roasting temperature is 200 ℃ and 600 ℃, and the roasting time is 2-10 h;
preferably, after the forming and before the firing, the method further comprises aging and drying treatments;
preferably, the aging is to hermetically place the molded product for 12-72 h;
preferably, the drying is to dry the aged product at 80-150 ℃ for 5-12 h.
9. A deoxygenation catalyst made by the method of any one of claims 1-8.
10. A deoxygenation catalyst, characterized in that the catalyst comprises a carrier and an active component supported on the carrier;
wherein the active components are Mo sulfide and Pt sulfide;
the content of the Mo element is more than 15 parts by weight and the content of the Pt element is 0.05-0.5 part by weight relative to 100 parts by weight of the deoxidation catalyst;
the BET specific surface area of the deoxidation catalyst is 80-300m2Per g, pore volume of 0.2-0.9cm3(iv)/g, crush strength greater than 50N/particle.
11. Use of a deoxygenation catalyst according to claim 9 or 10 for the deoxygenation of syngas and/or sulfur conversion.
CN201910731413.XA 2019-08-08 2019-08-08 Deoxygenation catalyst and preparation method and application thereof Pending CN112337487A (en)

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