CN108043418B - Preparation method of low-cost high-stability sulfur-tolerant shift catalyst - Google Patents

Preparation method of low-cost high-stability sulfur-tolerant shift catalyst Download PDF

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CN108043418B
CN108043418B CN201711192201.6A CN201711192201A CN108043418B CN 108043418 B CN108043418 B CN 108043418B CN 201711192201 A CN201711192201 A CN 201711192201A CN 108043418 B CN108043418 B CN 108043418B
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sulfur
cobalt
temperature
shift catalyst
catalyst
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CN108043418A (en
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周志斌
周芳
程瑞
徐晓毅
肖辉亚
黄远军
陈劲松
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HUBEI SHUANGXIONG CATALYST CO Ltd
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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/06—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using steam
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts

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Abstract

The invention relates to a preparation method of a sulfur-tolerant shift catalyst with low cost and high stability, belonging to the technical field of catalysts. The preparation method utilizes waste Co-Mo-K/gamma-Al2O3Calcining sulfur-resistant conversion catalyst, natural cooling, pulverizing, hydrothermal reaction, and gamma-Al2O3All the cobalt and molybdenum are converted into boehmite (AlOOH), and the high-stability fresh cobalt and molybdenum sulfur-tolerant shift catalyst is prepared by utilizing the existing process for producing the active alumina carrier by a quick separation method. The method has the advantages that cobalt, molybdenum, potassium and alumina in the waste cobalt-molybdenum sulfur-tolerant shift catalyst are all utilized, the resource utilization rate reaches 100%, the production cost is greatly reduced, and the hydration resistance stability, the heat resistance stability, the strength and the activity of the catalyst are higher than those of the industrial K8-11 type cobalt-molybdenum sulfur-tolerant shift catalyst of the German BASF company. Effectively saves resources, improves the utilization rate of limited resources, thoroughly solves the problem of environmental pollution caused by waste cobalt-molybdenum sulfur-tolerant shift catalysts, and realizes social sustainable development.

Description

Preparation method of low-cost high-stability sulfur-tolerant shift catalyst
Technical Field
The invention relates to a preparation method of a sulfur-tolerant shift catalyst with low cost and high stability, belonging to the technical field of catalysts.
Background
Co-Mo series sulfur-resistant in current industrial applicationThere are two main classes of shift catalysts: one is low pressure<3.0MPa) low steam-gas ratio, adopts gamma-Al2O3The catalyst is mainly Co-Mo-K/gamma-Al as a carrier2O3(ii) a The other is used under the condition of high pressure (not less than 3.0MPa) and high steam-gas ratio, the catalyst mainly adopts Co-Mo/MgAl as a carrier2O4Or Co-Mo/Mg-Al-Ti. It is used in the hydrogen production industry for synthesizing ammonia, methanol and the like.
China is characterized by 'lack of oil, less gas and rich coal' in energy structure, and the dependence of petroleum resources reaches 65.4% in 2016, exceeding the safety warning line. The development of coal-based clean energy is an effective way for solving the problem of energy supply. The development of coal-based clean energy is surrounded by the modern coal chemical technologies such as coal-to-liquid, coal-to-natural gas, coal-to-olefin, coal-to-ethylene glycol and the like. The new modern coal chemical industry technology has the process requirement of adjusting the carbon-hydrogen ratio, namely, the transformation process, namely, the new projects have transformation processes, and the new projects all use cobalt-molybdenum sulfur-resistant transformation catalysts.
If 3 tons of CO cobalt molybdenum sulfur-tolerant shift catalyst are consumed per ten thousand tons of ammonia and 2 tons of CO cobalt molybdenum sulfur-tolerant shift catalyst are consumed per ten thousand tons of alcohol, according to reports of international nitrogen fertilizers and methanol in 2014, the national synthetic ammonia yield in 2013 is 6197.7 ten thousand tons, the methanol yield is 3585 ten thousand tons, the annual market consumption of synthetic ammonia and methanol on the cobalt molybdenum sulfur-tolerant shift catalyst is at least 6000 tons according to one service cycle in 4 years, and the annual consumption of the cobalt molybdenum sulfur-tolerant shift catalyst is nearly 4000 tons by adding novel modern coal chemical engineering projects (coal-to-oil, coal-to-natural gas, coal-to-olefin, coal-to-ethylene glycol and the like), namely 10000 tons of waste CO cobalt molybdenum sulfur-tolerant shift catalyst are generated in China each year.
With the stricter environmental protection requirements, how to dispose the waste cobalt-molybdenum sulfur-tolerant shift catalyst is urgent, the resource recycling of the waste cobalt-molybdenum sulfur-tolerant shift catalyst is not less than a correct and effective solution, and moreover, the main raw materials for producing the fresh cobalt-molybdenum sulfur-tolerant shift catalyst are: the equivalent lattices of cobalt salt, molybdenum salt and aluminum oxide are increased year by year, and the price is doubled in 2017 compared with the price in the past year, so that the waste cobalt-molybdenum sulfur-tolerant shift catalyst is recycled, the fresh high-stability cobalt-molybdenum sulfur-tolerant shift catalyst is prepared again, the production cost can be greatly reduced, the resources are effectively saved, the utilization rate of limited resources is improved, the problem of environmental pollution caused by the waste catalyst is solved, the social sustainable development is realized, and the contribution to the construction of a 'two-type' society is made.
Patent CN 103553104a discloses a method for recovering waste CO sulfur-tolerant shift catalyst, in particular to a method for recycling metal oxides in cobalt and molybdenum series waste CO sulfur-tolerant shift catalyst. The recovery method comprises the steps of crushing the waste CO sulfur-tolerant shift catalyst, roasting for the first time, adding alkali, roasting for the second time, and leaching with hot water. Dissolving the obtained residue with acid, adjusting pH with alkali, and removing Fe (OH)3Separating Al (OH)3Then the mixed solution containing the cobalt nitrate and the potassium nitrate is obtained. The mixed solution can be directly used for preparing a novel CO sulfur-tolerant shift catalyst. The pH value of the filtrate obtained by hot water leaching is adjusted step by acid, so that molybdic acid and potassium nitrate can be finally obtained, the metal in the waste CO sulfur-tolerant shift catalyst can be completely separated and recovered by the recovery method, the recovery rate of cobalt is over 85 percent, the recovery rate of molybdenum is over 90 percent, and the recovery rate is low. By-product Al (OH)3The purity is not enough, and the use value is not large. The byproduct potassium nitrate also needs to be concentrated, crystallized, washed and dried, the whole process flow is long, the use amount of acid and alkali is large, and the energy consumption is also large.
The patent CN 102950010A adopts alkaline aqueous solution of potassium to react with waste cobalt-molybdenum sulfur-tolerant shift catalyst, converts the molybdenum contained in the potassium into water-soluble powder material, and directly uses the water-soluble powder material as the raw material of active component for preparing sulfur-tolerant shift catalyst to prepare the cobalt-molybdenum sulfur-tolerant shift catalyst product, and the molybdenum recovery rate can reach 90%. The patent only utilizes molybdenum in the waste cobalt-molybdenum sulfur-tolerant shift catalyst.
The patent CN 103769166B relates to a method for recycling cobalt in a waste cobalt-molybdenum sulfur-tolerant shift catalyst, which is characterized in that the waste cobalt-molybdenum sulfur-tolerant shift catalyst is crushed, acid liquor is used for dissolving out the cobalt in the waste cobalt-molybdenum sulfur-tolerant shift catalyst, filtrate after filtration is put into a stirrer, aluminum nitrate, magnesium nitrate and sodium carbonate are used as coprecipitators to carry out precipitation reaction, and a precursor material containing cobalt is obtained by separation and washing through a centrifuge and is used for preparing the sulfur-tolerant shift catalyst. The patent only utilizes cobalt in the waste cobalt-molybdenum sulfur-tolerant shift catalyst.
Patent CN 1048196C relates to a regeneration method of cobalt-molybdenum series carbon monoxide sulfur-tolerant shift catalyst, which uses waste cobalt-molybdenum series carbon monoxide sulfur-tolerant shift catalyst as carrier, and uses soluble salts containing cobalt, molybdenum and alkali metal respectively to re-impregnate active component in ammonia water solution or aqueous solution to prepare sulfur-tolerant shift catalyst. The patent CN 1079035C discloses a regeneration method of a waste CO sulfur-tolerant shift catalyst, which comprises the steps of firstly crushing the waste sulfur-tolerant shift catalyst, then adding a solid peptizing agent such as pseudo-boehmite and the like and a liquid peptizing agent such as nitric acid and the like, roasting, then carrying out activation treatment by using an alkaline substance solution, a Co-Mo active component solution or a Co-Mo-alkali metal compound solution, and drying or roasting. The above patent only simply uses the waste catalyst directly or after crushing, actually uses the gamma-Al in the industrial waste cobalt molybdenum sulfur-tolerant shift catalyst2O3After three to five years of use, under certain conditions of temperature, pressure and water vapor, the gamma-Al2O3The phase structure is partially converted into an AlOOH phase, and if the waste catalyst is directly or simply crushed for use, the structural stability of the prepared fresh catalyst is inevitably deteriorated, so that the hydration resistance stability, the heat resistance stability, the strength stability and the activity stability of the fresh catalyst are deteriorated.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a sulfur-tolerant shift catalyst with low cost and high stability, which is characterized in that waste Co-Mo-K/gamma-Al is utilized2O3Calcining Co-Mo sulfur-tolerant shift catalyst at 500-550 deg.C for 2 hr, natural cooling, pulverizing to 80-100 meshes, hydrothermal reaction, gamma-Al2O3All the cobalt and molybdenum are converted into boehmite (AlOOH), and the high-stability fresh cobalt and molybdenum sulfur-tolerant shift catalyst is prepared by utilizing the existing process for producing the active alumina carrier by a quick separation method. The cobalt, molybdenum, potassium and alumina in the waste cobalt-molybdenum sulfur-tolerant shift catalyst can be fully utilized, and the resource utilization rateThe production cost is greatly reduced by 100 percent, and the hydration resistance stability, the heat resistance stability, the strength and the activity of the catalyst are higher than those of the industrial used K8-11 type cobalt-molybdenum sulfur-tolerant shift catalyst of the German BASF company. Effectively saves resources, improves the utilization rate of limited resources, thoroughly solves the problem of environmental pollution caused by waste cobalt-molybdenum sulfur-tolerant shift catalysts, and realizes social sustainable development.
The technological scheme of the existing fast-stripping method for producing the activated alumina carrier is shown in figure 1.
According to the figure 1, after being dried, the raw material (alpha-gibbsite) is crushed to 325 meshes in the crushing procedure, and the fine alpha-gibbsite stays in a high-temperature rapid dehydration device with hot gas at the temperature of 600-900 ℃ for 0.1-l second in highly turbulent hot gas flow for flash roasting to generate transition alumina; then, the fine powder is separated by a cyclone separator, and is added with water and an auxiliary agent to prepare an adhesive, raw balls with required size are prepared in a disc type granulation forming machine, and then the raw balls are soaked in hot water and continuously fed with steam to complete the hydration process. Finally, the active alumina carrier is prepared by high-temperature roasting.
The technical scheme adopted by the invention is as follows: a process for preparing the sulfur-resistant transform catalyst with low cost and high stability features use of waste Co-Mo-K/gamma-Al2O3Calcining Co-Mo sulfur-tolerant shift catalyst at 500-550 deg.C for 2 hr, natural cooling, pulverizing to 80-100 meshes, hydrothermal reaction, gamma-Al2O3All the thin boehmite (AlOOH) is converted into boehmite (AlOOH), after being dried, the boehmite (AlOOH) is crushed to 325 meshes in the crushing procedure, and the thin boehmite (AlOOH) stays in a high-temperature rapid dehydration device with hot gas at the temperature of 600-900 ℃ for 0.1-l second in highly turbulent hot gas flow for flash roasting to generate transition state alumina; then, a cyclone separator is used for separating the fine powder, and a magnesium acetate aqueous solution with the mass fraction of 60% and a cobalt acetate aqueous solution with the mass fraction of 50% are added into the fine powder according to the volume ratio of 3: the mixed aqueous solution prepared by the step 1 is used as an adhesive, raw balls with the diameter of 3-5 mm are prepared in a disc type granulation forming machine, or cylindrical strips with the diameter of 4mm are prepared in a strip extruding machine, then the raw balls are soaked in 10% potassium carbonate aqueous solution by mass percent for hydration, and finally the fresh sulfur-resistant shift catalyst is prepared by roasting at the temperature of 450-550 ℃ in an activation process. TheThe content of cobalt oxide (CoO mass fraction) of the catalyst is more than or equal to 3.0 percent, and molybdenum oxide (MoO)3Mass fraction) content is more than or equal to 7.0 percent.
The hydrothermal reaction conditions are as follows:
temperature: 300-320 ℃;
temperature rise rate: 1 ℃/min
Pressure: 10MPa to 14 MPa;
steam-gas ratio: 2.0 to 15.0
Gas medium: water vapor, nitrogen;
reaction time: 96-120 h.
The invention has the beneficial effects that: a process for preparing the sulfur-resistant transform catalyst with low cost and high stability features use of waste Co-Mo-K/gamma-Al2O3Calcining Co-Mo sulfur-tolerant shift catalyst at 500-550 deg.C for 2 hr, natural cooling, pulverizing to 80-100 meshes, hydrothermal reaction, gamma-Al2O3All the cobalt and molybdenum are converted into boehmite (AlOOH), and the high-stability fresh cobalt and molybdenum sulfur-tolerant shift catalyst is prepared by utilizing the existing process for producing the active alumina carrier by a quick separation method. The method has the advantages that cobalt, molybdenum, potassium and alumina in the waste cobalt-molybdenum sulfur-tolerant shift catalyst are all utilized, the resource utilization rate reaches 100%, the production cost is greatly reduced, and the hydration resistance stability, the heat resistance stability, the strength and the activity of the catalyst are higher than those of the industrial K8-11 type cobalt-molybdenum sulfur-tolerant shift catalyst of the German BASF company. Effectively saves resources, improves the utilization rate of limited resources, thoroughly solves the problem of environmental pollution caused by waste cobalt-molybdenum sulfur-tolerant shift catalysts, and realizes social sustainable development.
The method for evaluating the hydration resistance stability of the cobalt-molybdenum sulfur-tolerant shift catalyst comprises the following steps:
the catalyst is kept for a period of time under the conditions of certain temperature, water-vapor ratio, pressure and the like, and then the volume fraction of carbon monoxide in gas at the inlet and the outlet of the reactor is analyzed by a gas chromatograph, the conversion rate of carbon monoxide is calculated, and is compared with the conversion rate of carbon monoxide of the catalyst before water resistance, and the activity retention rate of the catalyst after high water-vapor ratio resistance represents the hydration resistance of the catalyst.
The schematic diagram of the device for testing the hydration stability resistance of the cobalt-molybdenum sulfur-tolerant shift catalyst is shown in figure 3.
The main performance parameters of the hydration resistance test device of the cobalt-molybdenum sulfur-tolerant shift catalyst are shown in table 1.
Table 1 test set-up key performance design parameters
Item Parameter(s)
Specification/mm of reaction tube in reactor φ38×3
The length/mm of isothermal zone of the reactor is more than or equal to 50
Maximum working pressure/MPa 10.0
Maximum use temperature/. degree.C 600
Parallelism (difference value)/% < less 2
Reproducibility (difference value)/% > is less than or equal to 3
If the sample is strip-shaped, the sample is processed into a sample with the length of 3.5 mm-4.0 mm; if spherical, they are processed into samples having a diameter of 4.0mm to 5.0mm [ sieved with test sieves having a pore size of 4.0mm and 5.0mm (according to the R40/30 series of GB/T6003.1) ]. 100mL of the full-size sample was densely packed in a 250mL measuring cylinder and weighed to obtain a bulk density, and then a sample having a mass of 30mL was weighed and prepared.
A layer of stainless steel sieve plate is arranged at the bottom of a reaction tube of the reactor, and ceramic balls with the particle size of 4-6 mm which are processed cleanly are filled into the reaction tube, tamped and filled to the position determined when the isothermal zone is measured. And then adding a layer of stainless steel sieve plate on the ceramic balls, carefully pouring the prepared catalyst sample into the reaction tube, lightly knocking the tube wall to ensure that the catalyst bed layer is tightly filled, measuring the filling height of the catalyst bed layer, then adding a layer of stainless steel sieve plate, filling a proper amount of ceramic balls with the granularity of 4-6 mm on the stainless steel sieve plate, lightly knocking the ceramic balls tightly, screwing down the screw cap of the reactor, and then connecting the reactor into a test system. Opening a raw material gas main valve, and introducing raw material gas into the system, wherein the raw material gas comprises (by volume fraction) carbon monoxide (45% -50%), carbon dioxide (3% -5%), hydrogen sulfide (0.1% -0.5%) and the balance of hydrogen. And the system inlet and outlet valves are closed when the pressure is stabilized under the activity measurement pressure, and if the pressure drops to less than 0.02MPa within 0.5h, the system is considered to be sealed. And opening an outlet valve of the system to exhaust after the leakage test meets the requirement, so that the system is reduced to normal pressure. The temperature thermocouple was inserted into the thermowell so that its hot end was located 5mm inside the gas inlet catalyst bed.
Introducing raw material gas into the reactor, wherein the space velocity of the raw material gas is 750h-1The system pressure is normal pressure. The temperature-raising vulcanization operation was as specified in Table 2. When the temperature of the reactor rises to 180 ℃, the total sulfur (as H) begins to be distributed into the feed gas2S) is 50g/Nm3～70g/Nm3And (3) stopping sulfur preparation until the temperature of the reactor is reduced from 420 ℃, and ending the vulcanization.
TABLE 2 vulcanization operating conditions
Temperature range/. degree.C Rate of temperature rise/(° c/h) Required time/h
Room temperature to 250 deg.c 60 4
250 0 6
250～350 50 2
350 0 4
350～420 50 1.5
420 0 2
420～350 Naturally cooling —
Determination of initial Activity
Heating the vaporizer and the heat preservation pipe to about 320 ℃, controlling and adjusting the system pressure to be 4.0MPa +/-0.02 MPa and the space velocity of the raw material gas to be 3000h-1±50h-1The volume ratio of the water vapor to the feed gas is 1.0 +/-0.02, and the temperature is 350 DEG CAnd +/-1 ℃, after stabilizing and ensuring 4 hours, beginning to analyze the volume fraction of the carbon monoxide in the gas at the inlet and the outlet of the reactor, calculating the conversion rate of the carbon monoxide, measuring the conversion rate of the carbon monoxide once every 1.5 to 2.0 hours, and finishing the initial activity test when the extreme difference value of the conversion rate of the carbon monoxide is not more than 1.0 percent for three times continuously.
Determination of Activity after Water resistance
Reducing the temperature of the reactor to 200 +/-1 ℃, changing the volume ratio of the water vapor to the feed gas to 2.0 +/-0.02, controlling and maintaining for 8 hours, then increasing the temperature of the reactor to 350 +/-1 ℃, changing the volume ratio of the water vapor to the feed gas to 1.0 +/-0.02, after stabilizing for 4 hours, beginning to analyze the volume fraction of the carbon monoxide in the gas at the inlet and the outlet of the reactor, calculating the conversion rate of the carbon monoxide, and then measuring once every 1.5 to 2.0 hours. When the extreme difference in the conversion of carbon monoxide is not more than 1.0% for three consecutive times, the post-water-resistance test can be ended. Parking
And closing a feed gas main valve, emptying the system for depressurization and simultaneously discharging condensed water in the condenser. When the system is reduced to normal pressure, the constant flow pump is closed, water injection is stopped, and finally the power supply of the system is cut off.
Processing of test data
The catalyst activity is calculated according to formula (1) as carbon monoxide conversion E:
Figure BDA0001481251870000051
in formula (1):
Figure BDA0001481251870000052
-the value of the volume fraction of carbon monoxide in the feed gas, expressed in%;
Figure BDA0001481251870000053
-the value of the volume fraction of carbon monoxide in the shifted gas, expressed in%.
The arithmetic mean of three consecutive measurements is taken as the measurement result, and the range of the three measurements should be not more than 1.0%.
Formula for calculating hydration resistance
Hydration resistance of the catalyst E0Calculated according to equation (2):
Figure BDA0001481251870000061
in formula (2):
E1-the value of the initial activity of the catalyst, expressed in%;
E2-the value of the activity of the catalyst after resistance to water, expressed in%.
The calculation result is expressed to one digit after the decimal point.
The method for evaluating the heat-resistant stability of the cobalt-molybdenum sulfur-tolerant shift catalyst comprises the following steps:
the catalyst is kept for a period of time under the conditions of certain temperature, water-vapor ratio, pressure and the like, and then the volume fraction of carbon monoxide in gas at the inlet and the outlet of the reactor is analyzed by a gas chromatograph, the conversion rate of carbon monoxide is calculated, and is compared with the conversion rate of carbon monoxide of the catalyst before heat resistance, and the heat resistance of the catalyst is represented by the activity retention rate of the catalyst after heat resistance.
The test method of the heat-resistant stability of the cobalt-molybdenum sulfur-tolerant shift catalyst is the same as the test method of the hydration-resistant stability of the cobalt-molybdenum sulfur-tolerant shift catalyst. Except that the activity after water resistance was changed to the activity after heat resistance.
The activity after heat resistance measurement conditions were:
the temperature of the reactor is raised to 530 +/-1 ℃, the volume ratio of the water vapor to the feed gas is changed to 1.0 +/-0.02, the reactor is controlled and maintained for 8 hours, the temperature of the reactor is lowered to 350 +/-1 ℃, the reactor is stabilized for 4 hours, the volume fraction of carbon monoxide in the gas at the inlet and the outlet of the reactor is analyzed, the conversion rate of the carbon monoxide is calculated, and then the carbon monoxide is measured every 1.5 to 2.0 hours. When the very poor value of the carbon monoxide conversion rate was not more than 1.0% in three consecutive times, the post heat resistance test could be ended.
Heat resistance calculation formula
Heat resistance of the catalyst F0Calculating according to the formula (3):
Figure BDA0001481251870000062
in formula (3):
F1-the value of the initial activity of the catalyst, expressed in%;
F2-the value of the activity of the catalyst after heat resistance, expressed in%.
The calculation result is expressed to one digit after the decimal point.
The method for measuring the strength of the cobalt-molybdenum sulfur-resistant transformation catalyst comprises the following steps:
the method is carried out according to the measurement of the crushing resistance of the HG/T2782-2011 fertilizer catalyst particles.
The method for measuring the content of cobalt and molybdenum in the cobalt-molybdenum sulfur-resistant transformation catalyst comprises the following steps:
the method is carried out according to the determination of the content of cobalt and molybdenum in the HG/T2781-2010 carbon monoxide sulfur-resistant shift catalyst.
The activity evaluation method of the cobalt-molybdenum sulfur-tolerant shift catalyst comprises the following steps:
the method is carried out according to a high-pressure activity test method in the HG/T4553-2013 carbon monoxide sulfur-resistant shift catalyst.
Wherein the activity evaluation conditions are as follows:
the particle size of the catalyst is as follows: processing the strips into samples with the length of 3.5 mm-4.0 mm or spherical shapes with the diameter of 4.0 mm-5.0 mm;
loading of the catalyst: 30 mL;
system pressure: (4.0 +/-0.02) MPa;
space velocity: (3000 +/-50) h-1；
Temperature for activity measurement: (300 + -1) deg.C;
steam-gas ratio: 1.0 +/-0.02.
Drawings
FIG. 1 is a flow chart of a prior art process for producing an activated alumina support by a rapid exfoliation method;
FIG. 2 is a flow diagram of a cobalt molybdenum sulfur tolerant shift catalyst production process of the present invention;
FIG. 3 is a schematic diagram of a device for testing the hydration stability resistance of a cobalt-molybdenum sulfur-tolerant shift catalyst.
1-1～1-2-mass flow meter; 1-3 to 1-4-wet gas flow meter; 2-CS2An evaporator; 3-gas mixing bottle; 4-1 to 4-2-reactors; 5-a vaporizer; 6-advection pump; 7-a metering tube; 8-1 to 8-2-condensers; 9-1 to 9-2-water sealed bottles; 10-gas chromatograph; 11-1 to 11-2-desulfurizers; 12-1 to 12-2, namely washing a bottle with alkali; 13-thermal insulation pipe
The specific implementation mode is as follows:
the present invention is illustrated below by specific examples, which are given for better illustration of the present invention, but the scope of the present invention is not limited by these examples.
Example 1
Waste Co-Mo-K/gamma-Al2O3The sulfur-resistant shift catalyst is analyzed by X-ray fluorescence and comprises the following components in percentage by mass (%): co (in CoO): 1.5%, Mo (in MoO)3Meter): 8.6%, K2O: 4.8%, S (in SO)2Meter): 9.2% of Al2O3: 75.9 percent. The waste cobalt-molybdenum sulfur-tolerant shift catalyst is roasted for 2 hours at the temperature of 500-550 ℃, naturally cooled and crushed into 100 meshes. Taking 100kg of the crushed materials, placing the crushed materials in a 500L pressure container with the highest use pressure of 15.0MPa and the highest use temperature of 350 ℃ and blowing by nitrogen (more than or equal to 99.9 percent in volume fraction) in advance, then adding 50kg of deionized water, sealing and heating, and controlling the temperature rise speed: controlling the temperature at 300 +/-1 ℃ at 1 ℃/min, charging nitrogen when the pressure is increased to 8.0MPa, keeping the pressure at 10.0 +/-0.1 MPa, continuously controlling the temperature at 300 +/-1 ℃ and keeping the temperature for 120h under the conditions. Then reducing the temperature to normal pressure and normal temperature, taking out, drying, crushing to 325 meshes in a crushing process, and flash roasting the fine boehmite (AlOOH) and hot gas at 600-900 ℃ in a high-temperature rapid dehydration device for 0.1-l second in a highly turbulent hot gas flow to generate transition alumina; then, a cyclone separator is used for separating the fine powder, and a magnesium acetate aqueous solution with the mass fraction of 60% and a cobalt acetate aqueous solution with the mass fraction of 50% are added into the fine powder according to the volume ratio of 3: 1 as adhesive, in a disc type granulating and forming machine, making into green balls with diameter of 3-5 mm, and soaking in 10% carbonHydrating in potassium aqua and final activating at 450-550 deg.c to obtain fresh Co-Mo sulfur-tolerant shift catalyst C1.
Example 2
Waste Co-Mo-K/gamma-Al2O3The sulfur-resistant shift catalyst is analyzed by X-ray fluorescence and comprises the following components in percentage by mass (%): co (in CoO): 1.5%, Mo (in MoO)3Meter): 8.6%, K2O: 4.8%, S (in SO)2Meter): 9.2% of Al2O3: 75.9 percent. The waste cobalt-molybdenum sulfur-tolerant shift catalyst is roasted for 2 hours at the temperature of 500-550 ℃, naturally cooled and crushed into 100 meshes. Taking 100kg of the crushed materials, placing the crushed materials in a 500L pressure container with the highest use pressure of 15.0MPa and the highest use temperature of 350 ℃ and blowing by nitrogen (more than or equal to 99.9 percent in volume fraction) in advance, then adding 50kg of deionized water, sealing and heating, and controlling the temperature rise speed: controlling the temperature at 300 +/-1 ℃ at 1 ℃/min, charging nitrogen when the pressure is increased to 8.0MPa, keeping the pressure at 12.0 +/-0.1 MPa, continuously controlling the temperature at 300 +/-1 ℃ and keeping the temperature for 96h under the conditions. Then reducing the temperature to normal pressure and normal temperature, taking out, drying, crushing to 325 meshes in a crushing process, and flash roasting the fine boehmite (AlOOH) and hot gas at 600-900 ℃ in a high-temperature rapid dehydration device for 0.1-l second in a highly turbulent hot gas flow to generate transition alumina; then, a cyclone separator is used for separating the fine powder, and a magnesium acetate aqueous solution with the mass fraction of 60% and a cobalt acetate aqueous solution with the mass fraction of 50% are added into the fine powder according to the volume ratio of 3: the mixed aqueous solution prepared by the step 1 is used as an adhesive, raw balls with the diameter of 3mm to 5mm are prepared in a disc type granulation forming machine, then the raw balls are soaked in 10 percent of potassium carbonate aqueous solution by mass percent for hydration, and finally the fresh cobalt-molybdenum sulfur-tolerant shift catalyst C2 is prepared by roasting at the temperature of 450 ℃ to 550 ℃ in the activation procedure.
Example 3
Waste Co-Mo-K/gamma-Al2O3The sulfur-resistant shift catalyst is analyzed by X-ray fluorescence and comprises the following components in percentage by mass (%): co (in CoO): 1.5%, Mo (in MoO)3Meter): 8.6%, K2O: 4.8%, S (in SO)2Meter): 9.2% of Al2O3: 75.9 percent. Will be provided withThe waste cobalt-molybdenum sulfur-tolerant shift catalyst is roasted for 2 hours at the temperature of 500-550 ℃, naturally cooled and crushed into 100 meshes. Taking 100kg of the crushed materials, placing the crushed materials in a 500L pressure container with the highest use pressure of 15.0MPa and the highest use temperature of 350 ℃ and blowing by nitrogen (more than or equal to 99.9 percent in volume fraction) in advance, then adding 50kg of deionized water, sealing and heating, and controlling the temperature rise speed: controlling the temperature at 320 +/-1 ℃ at 1 ℃/min, charging nitrogen when the pressure is increased to 10.0MPa, keeping the pressure at 12.0 +/-0.1 MPa, continuously controlling the temperature at 320 +/-1 ℃ and keeping the time for 120h under the conditions. Then reducing the temperature to normal pressure and normal temperature, taking out, drying, crushing to 325 meshes in a crushing process, and performing flash roasting on the fine boehmite (AlOOH) and hot gas at the temperature of 600-900 ℃ in a high-temperature rapid dehydration device for 0.1-l second in a highly turbulent hot gas flow to generate transition-state alumina; then, a cyclone separator is used for separating the fine powder, and a magnesium acetate aqueous solution with the mass fraction of 60% and a cobalt acetate aqueous solution with the mass fraction of 50% are added into the fine powder according to the volume ratio of 3: the mixed aqueous solution prepared by the step 1 is used as an adhesive, raw balls with the diameter of 3mm to 5mm are prepared in a disc type granulation forming machine, then the raw balls are soaked in 10 percent of potassium carbonate aqueous solution by mass percent for hydration, and finally the fresh cobalt-molybdenum sulfur-tolerant shift catalyst C3 is prepared by roasting at the temperature of 450 ℃ to 550 ℃ in the activation procedure.
Example 4
Waste Co-Mo-K/gamma-Al2O3The sulfur-resistant shift catalyst is analyzed by X-ray fluorescence and comprises the following components in percentage by mass (%): co (in CoO): 1.5%, Mo (in MoO)3Meter): 8.6%, K2O: 4.8%, S (in SO)2Meter): 9.2% of Al2O3: 75.9 percent. The waste cobalt-molybdenum sulfur-tolerant shift catalyst is roasted for 2 hours at the temperature of 500-550 ℃, naturally cooled and crushed into 100 meshes. Taking 100kg of the crushed materials, placing the crushed materials in a 500L pressure container with the highest use pressure of 15.0MPa and the highest use temperature of 350 ℃ and blowing by nitrogen (more than or equal to 99.9 percent in volume fraction) in advance, then adding 50kg of deionized water, sealing and heating, and controlling the temperature rise speed: controlling the temperature at 320 +/-1 ℃ at 1 ℃/min, charging nitrogen when the pressure is increased to 10.0MPa, keeping the pressure at 14.0 +/-0.1 MPa, and continuously controlling the temperature at 320 +/-1 ℃, wherein the strip is prepared by the steps ofThe under-condition maintenance time is 96 h. Then reducing the temperature to normal pressure and normal temperature, taking out, drying, crushing to 325 meshes in a crushing process, and flash roasting the fine boehmite (AlOOH) and hot gas at 600-900 ℃ in a high-temperature rapid dehydration device for 0.1-l second in a highly turbulent hot gas flow to generate transition alumina; then, a cyclone separator is used for separating the fine powder, and a magnesium acetate aqueous solution with the mass fraction of 60% and a cobalt acetate aqueous solution with the mass fraction of 50% are added into the fine powder according to the volume ratio of 3: the mixed aqueous solution prepared by the step 1 is used as an adhesive, raw balls with the diameter of 3mm to 5mm are prepared in a disc type granulation forming machine, then the raw balls are soaked in 10 percent of potassium carbonate aqueous solution by mass percent for hydration, and finally the fresh cobalt-molybdenum sulfur-tolerant shift catalyst C4 is prepared by roasting at the temperature of 450 ℃ to 550 ℃ in the activation procedure.
Example 5
Waste Co-Mo-K/gamma-Al2O3The sulfur-resistant shift catalyst is analyzed by X-ray fluorescence and comprises the following components in percentage by mass (%): co (in CoO): 1.5%, Mo (in MoO)3Meter): 8.6%, K2O: 4.8%, S (in SO)2Meter): 9.2% of Al2O3: 75.9 percent. The waste cobalt-molybdenum sulfur-tolerant shift catalyst is roasted for 2 hours at the temperature of 500-550 ℃, naturally cooled and crushed into 100 meshes. Taking 100kg of the crushed materials, placing the crushed materials in a 500L pressure container with the highest use pressure of 15.0MPa and the highest use temperature of 350 ℃ and blowing by nitrogen (more than or equal to 99.9 percent in volume fraction) in advance, then adding 50kg of deionized water, sealing and heating, and controlling the temperature rise speed: controlling the temperature at 300 +/-1 ℃ at 1 ℃/min, charging nitrogen when the pressure is increased to 8.0MPa, keeping the pressure at 10.0 +/-0.1 MPa, continuously controlling the temperature at 300 +/-1 ℃ and keeping the temperature for 120h under the conditions. Then reducing the temperature to normal pressure and normal temperature, taking out, drying, crushing to 325 meshes in a crushing process, and flash roasting the fine boehmite (AlOOH) and hot gas at 600-900 ℃ in a high-temperature rapid dehydration device for 0.1-l second in a highly turbulent hot gas flow to generate transition alumina; then, a cyclone separator is used for separating the fine powder, and a magnesium acetate aqueous solution with the mass fraction of 60% and a cobalt acetate aqueous solution with the mass fraction of 50% are added into the fine powder according to the volume ratio of 3: 1 the mixed aqueous solution prepared is used as adhesive and is made into a phi 4mm circle in a strip extruding machineThe catalyst is in a column shape and a strip shape, and then is soaked in potassium carbonate aqueous solution with the mass fraction of 10 percent for hydration, and finally the catalyst is roasted at 450-550 ℃ in the activation procedure to prepare the fresh cobalt-molybdenum sulfur-tolerant shift catalyst C5.
Example 6
Waste Co-Mo-K/gamma-Al2O3The sulfur-resistant shift catalyst is analyzed by X-ray fluorescence and comprises the following components in percentage by mass (%): co (in CoO): 1.5%, Mo (in MoO)3Meter): 8.6%, K2O: 4.8%, S (in SO)2Meter): 9.2% of Al2O3: 75.9 percent. The waste cobalt-molybdenum sulfur-tolerant shift catalyst is roasted for 2 hours at the temperature of 500-550 ℃, naturally cooled and crushed into 100 meshes. Taking 100kg of the crushed materials, placing the crushed materials in a 500L pressure container with the highest use pressure of 15.0MPa and the highest use temperature of 350 ℃ and blowing by nitrogen (more than or equal to 99.9 percent in volume fraction) in advance, then adding 50kg of deionized water, sealing and heating, and controlling the temperature rise speed: controlling the temperature at 300 +/-1 ℃ at 1 ℃/min, charging nitrogen when the pressure is increased to 8.0MPa, keeping the pressure at 12.0 +/-0.1 MPa, continuously controlling the temperature at 300 +/-1 ℃ and keeping the temperature for 96h under the conditions. Then reducing the temperature to normal pressure and normal temperature, taking out, drying, crushing to 325 meshes in a crushing process, and flash roasting the fine boehmite (AlOOH) and hot gas at 600-900 ℃ in a high-temperature rapid dehydration device for 0.1-l second in a highly turbulent hot gas flow to generate transition alumina; then, a cyclone separator is used for separating the fine powder, and a magnesium acetate aqueous solution with the mass fraction of 60% and a cobalt acetate aqueous solution with the mass fraction of 50% are added into the fine powder according to the volume ratio of 3: the mixed aqueous solution prepared by the step 1 is used as an adhesive, is made into a phi 4mm cylindrical strip shape in a strip extruding machine, is soaked in a potassium carbonate aqueous solution with the mass fraction of 10 percent for hydration, and is finally calcined at the temperature of 450-550 ℃ in an activation procedure to prepare the fresh cobalt-molybdenum sulfur-tolerant shift catalyst C6.
Example 7
Waste Co-Mo-K/gamma-Al2O3The sulfur-resistant shift catalyst is analyzed by X-ray fluorescence and comprises the following components in percentage by mass (%): co (in CoO): 1.5%, Mo (in MoO)3Meter): 8.6%, K2O: 4.8%, S (in SO)2Meter): 9.2% of Al2O3: 75.9 percent. The waste cobalt-molybdenum sulfur-tolerant shift catalyst is roasted for 2 hours at the temperature of 500-550 ℃, naturally cooled and crushed into 100 meshes. Taking 100kg of the crushed materials, placing the crushed materials in a 500L pressure container with the highest use pressure of 15.0MPa and the highest use temperature of 350 ℃ and blowing by nitrogen (more than or equal to 99.9 percent in volume fraction) in advance, then adding 50kg of deionized water, sealing and heating, and controlling the temperature rise speed: controlling the temperature at 320 +/-1 ℃ at 1 ℃/min, charging nitrogen when the pressure is increased to 10.0MPa, keeping the pressure at 12.0 +/-0.1 MPa, continuously controlling the temperature at 320 +/-1 ℃ and keeping the time for 120h under the conditions. Then reducing the temperature to normal pressure and normal temperature, taking out, drying, crushing to 325 meshes in a crushing process, and flash roasting the fine boehmite (AlOOH) and hot gas at 600-900 ℃ in a high-temperature rapid dehydration device for 0.1-l second in a highly turbulent hot gas flow to generate transition alumina; then, a cyclone separator is used for separating the fine powder, and a magnesium acetate aqueous solution with the mass fraction of 60% and a cobalt acetate aqueous solution with the mass fraction of 50% are added into the fine powder according to the volume ratio of 3: the mixed aqueous solution prepared by the step 1 is used as an adhesive, is made into a phi 4mm cylindrical strip shape in a strip extruding machine, is soaked in a potassium carbonate aqueous solution with the mass fraction of 10 percent for hydration, and is finally calcined at the temperature of 450-550 ℃ in an activation procedure to prepare the fresh cobalt-molybdenum sulfur-tolerant shift catalyst C7.
Example 8
Waste Co-Mo-K/gamma-Al2O3The sulfur-resistant shift catalyst is analyzed by X-ray fluorescence and comprises the following components in percentage by mass (%): co (in CoO): 1.5%, Mo (in MoO)3Meter): 8.6%, K2O: 4.8%, S (in SO)2Meter): 9.2% of Al2O3: 75.9 percent. The waste cobalt-molybdenum sulfur-tolerant shift catalyst is roasted for 2 hours at the temperature of 500-550 ℃, naturally cooled and crushed into 100 meshes. Taking 100kg of the crushed materials, placing the crushed materials in a 500L pressure container with the highest use pressure of 15.0MPa and the highest use temperature of 350 ℃ and blowing by nitrogen (more than or equal to 99.9 percent in volume fraction) in advance, then adding 50kg of deionized water, sealing and heating, and controlling the temperature rise speed: controlling the temperature at 320 +/-1 deg.C at 1 deg.C/min, charging nitrogen when the pressure is increased to 10.0MPa, maintaining the pressure at 14.0 +/-0.1 MPa, and continuing the heating processControlling the temperature to be 320 +/-1 ℃ and maintaining the temperature for 96h under the conditions. Then reducing the temperature to normal pressure and normal temperature, taking out, drying, crushing to 325 meshes in a crushing process, and flash roasting the fine boehmite (AlOOH) and hot gas at 600-900 ℃ in a high-temperature rapid dehydration device for 0.1-l second in a highly turbulent hot gas flow to generate transition alumina; then, a cyclone separator is used for separating the fine powder, and a magnesium acetate aqueous solution with the mass fraction of 60% and a cobalt acetate aqueous solution with the mass fraction of 50% are added into the fine powder according to the volume ratio of 3: the mixed aqueous solution prepared by the step 1 is used as an adhesive, is made into a phi 4mm cylindrical strip shape in a strip extruding machine, is soaked in a potassium carbonate aqueous solution with the mass fraction of 10 percent for hydration, and is finally calcined at the temperature of 450-550 ℃ in an activation procedure to prepare the fresh cobalt-molybdenum sulfur-tolerant shift catalyst C8.
In examples 1 to 8, the performance of the commercially available K8-11 cobalt-molybdenum sulfur-tolerant shift catalyst was measured by the method for measuring the cobalt-molybdenum content of the cobalt-molybdenum sulfur-tolerant shift catalyst; a method for measuring the strength of the cobalt-molybdenum sulfur-resistant transformation catalyst; a method for evaluating the hydration resistance stability of a cobalt-molybdenum sulfur-tolerant shift catalyst; a method for evaluating the heat-resistant stability of a cobalt-molybdenum sulfur-tolerant shift catalyst; the activity of the cobalt-molybdenum sulfur-tolerant shift catalyst is measured by an evaluation method. The results are shown in Table 3.
TABLE 3 measurement results of Co-Mo content, strength, hydration resistance, heat resistance and activity of Co-Mo sulfur-tolerant shift catalyst
Figure BDA0001481251870000111
Note: the K8-11 type cobalt molybdenum sulfur-tolerant shift catalyst is a product used in industry by BASF company in Germany.
From the results of the performance evaluation of the catalysts in Table 3, it can be seen that the strength, hydration resistance, heat resistance and activity of the cobalt-molybdenum sulfur-tolerant shift catalyst prepared by the present invention are superior to those of the cobalt-molybdenum sulfur-tolerant shift catalyst K8-11, BASF corporation, Germany.

Claims (2)

1. A process for preparing the sulfur-resistant transform catalyst with low cost and high stability features use of waste Co-Mo-K/gamma-Al2O3Calcining Co-Mo sulfur-tolerant shift catalyst at 500-550 deg.C for 2 hr, natural cooling, pulverizing to 80-100 meshes, hydrothermal reaction, gamma-Al2O3All the thin boehmite (AlOOH) is converted into boehmite (AlOOH), after being dried, the boehmite (AlOOH) is crushed to 325 meshes in the crushing procedure, and the thin boehmite (AlOOH) stays in a high-temperature rapid dehydration device with hot gas at the temperature of 600-900 ℃ for 0.1-l second in highly turbulent hot gas flow for flash roasting to generate transition state alumina; then, a cyclone separator is used for separating the fine powder, and a magnesium acetate aqueous solution with the mass fraction of 60% and a cobalt acetate aqueous solution with the mass fraction of 50% are added into the fine powder according to the volume ratio of 3: the mixed aqueous solution prepared by the step 1 is used as an adhesive, raw balls with the diameter of 3-5 mm are prepared in a disc type granulation forming machine, or cylindrical strips with the diameter of 4mm are prepared in a strip extruding machine, then the raw balls are soaked in 10% potassium carbonate aqueous solution by mass percent for hydration, and finally the fresh sulfur-resistant shift catalyst is prepared by roasting at the temperature of 450-550 ℃ in an activation process.
2. The method of claim 1, wherein the hydrothermal reaction is carried out at a temperature of 300-320 ℃; the temperature rising speed is 1 ℃/min; the pressure is 10MPa to 14 MPa; the steam-gas ratio is 2.0-15.0; the gas medium is water vapor and nitrogen; the reaction time is 96-120 h.
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