CN106964363A - A kind of anti-arsenic CO sulfur-resistant transformation catalysts and preparation method - Google Patents

A kind of anti-arsenic CO sulfur-resistant transformation catalysts and preparation method Download PDF

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CN106964363A
CN106964363A CN201710244202.4A CN201710244202A CN106964363A CN 106964363 A CN106964363 A CN 106964363A CN 201710244202 A CN201710244202 A CN 201710244202A CN 106964363 A CN106964363 A CN 106964363A
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arsenic
carrier
sulfur
mgo
catalyst
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CN106964363B (en
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张新堂
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Shandong University of Science and Technology
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/882—Molybdenum and cobalt
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    • 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
    • B01J23/885—Molybdenum and 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
    • 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
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1076—Copper or zinc-based catalysts
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract

The invention discloses a kind of anti-arsenic CO sulfur-resistant transformation catalysts and preparation method, the catalyst is with Al2O3、MgO‑Al2O3Spinelle or the anti-arsenic CO sulphur-resistant conversion bifunctional catalysts of Cu (Mn) Co Mo systems that polynary inorganic oxide compound is carrier, the catalytic component contain CuO and/or MnO2, containing Co and/or Ni elements, and the catalytic component is also at least containing one kind in Mo, W element.The catalyst is used for the conversion process for converting gas processed through the gasify synthesis gas produced, carbon monoxide and water vapour containing the higher coal of arsenic, can be in 190 500 DEG C of temperature, sulfur content>Under conditions of 0.01%v/v, aqueous vapor mol ratio 0.1 1.6, different pressures（0‑10.0MPa）Conversion process in use, high mechanical strength adaptable to high-speed, arsenic resistance can it is good, service life is long.

Description

A kind of anti-arsenic CO sulfur-resistant transformation catalysts and preparation method
Technical field
The present invention relates to catalysis technical field, specially a kind of anti-arsenic CO sulfur-resistant transformation catalysts and preparation method.
Background technology
In coal chemical industry, petrochemical industry, the reaction of carbon monoxide and water vapour hydrogen making and carbon dioxide is extensive For producing ammonia synthesis gas, hydrogen and oxo-synthesis gas.This reaction, which is typically required for catalyst, to be carried out.Initially conventional urges Agent is Fe-Cr and Cu-Zn systems, and such catalyst is just active only under the conditions of without sulphur or low-sulfur.Twentieth century 60 The need for age is in order to adapt to using heavy oil, coal and decompression residuum as the higher synthesis gas of waste sulfur-bearing, Co-Mo systems have been invented resistance to Sulfur change catalyst.
Current Co-Mo sulfur-resistant transformation catalysts mainly have two major classes：(1) urged for non-alkali metal Co-Mo systems sulphur-resistant conversion Agent, its low temperature active is poor, and has certain limitation to the sulphur in process gas, serious less than limits value activity decay；(2) it is The Co-Mo systems sulfur-resistant transformation catalyst that alkali metal promotes, its low temperature active is good, requires wide to the sulphur in process gas, but in high temperature Or catalyst activity decline is serious under high water vapor partial pressure, and carrier structure is unstable.Above-mentioned two classes catalyst can by combination Using suitable for using heavy oil, decompression residuum as the higher synthesis gas of waste sulfur-bearing different sulfur resistant conversion process.It can also fit simultaneously For using coal as raw material, the synthesis gas treatment and purification technique produced using high-temperature coal gasification technology, such as coal water slurry gasification, SHELL The technologies such as coal gasification.
Because China's natural gas and petroleum resources are deficient, by chemical industry primary raw material of coal by long-term existence.In coal contain compared with High sulphur, and the existing forms of sulphur are complicated, and its carbon monoxide and water vapour transformationreation need the sulphur-resistant conversion catalysis of Co-Mo systems Agent.Arsenic and the common ore deposit of sulphur, general sulfur content of coal height, have higher arsenic content, arsenic is the poisonous substance of sulfur-resistant transformation catalyst simultaneously, Cause that the decline of catalyst shift activity is very fast, catalyst service life is shorter, and the replacement cycle is shorter, it has to frequently stop into The replacing of row catalyst, has had a strong impact on device production and economic benefit.Sulphur-resistant conversion is catalyzed in order to meet China's coal chemical industry The demand of agent, we have researched and developed anti-arsenic CO sulfur-resistant transformation catalysts.
The content of the invention
The technical problems to be solved by the invention be to provide a kind of service life length, raw material be easy to get, preparation technology it is simple Anti- arsenic CO sulfur-resistant transformation catalysts and preparation method thereof.
In order to solve the above technical problems, the technical scheme is that：A kind of anti-arsenic CO sulfur-resistant transformation catalysts, it is described to urge Agent is with Al2O3、MgO-Al2O3Spinelle or polynary inorganic oxide compound are anti-for Cu (Mn)-Co-Mo systems of carrier Arsenic-CO sulphur-resistant conversion bifunctional catalysts；The catalytic component contains CuO and/or MnO2, containing Co and/or Ni elements, and And the catalytic component is also at least containing one kind in Mo, W element.
Wherein, the CuO and/or MnO2Mass content in the catalyst be 1-10%.
It is wherein more excellent, the CuO and/or MnO2Mass content in the catalyst be 2-5%.
Wherein, Mo and/or W elements and CuO and/or MnO2Total moles compare 1：(0.10-2.5)；Co and/or Ni elements with CuO and/or MnO2Total moles compare 1：(0.10-2.5).
In addition present invention also offers a kind of method for preparing above-mentioned anti-arsenic CO sulfur-resistant transformation catalysts, preparation method includes Following steps：
1) Al is prepared2O3Carrier, MgO-Al2O3Spinel carrier or polynary inorganic oxide complexes carrier, wherein Al2O3Carrier is to use industrial boehmite, aluminium hydroxide etc. to be decomposed into the aluminum contained compound of aluminum oxide for raw material；MgO- Al2O3Spinel carrier, by MgO or Mg (OH)2And Al2O3-nH2O is well mixed；Or it is prepared into MgO- with Mg, Al compound Al2O3Spinelle material or the material containing Mg, Al；Polynary inorganic oxide compound is by MgO or Mg (OH)2In one kind With Al2O3-nH2O and zirconium dioxide, TiO2Or one kind or any several well mixed in ZnO；Backward mixed material in plus Enter the soluble copper salt containing auxiliary agent and/or manganese salt solution dipping is uniform, dry, pulverize；Then add-on type auxiliary agent, peptizing agent and Quality is dry material quality 30-40% water, mediates uniform shaping, is finally dried, is calcined；
2) under conditions of complexing agent presence, Mo and/or W soluble salt and Co and/or Ni soluble salt are configured to surely Fixed solution, and be well mixed；
3) carrier of the 1) roasting is added in the 2) stablizing solution being configured to, and uses incipient impregnation；
4) carrier drying 3) impregnated, roasting are obtained into the anti-arsenic CO sulfur-resistant transformation catalyst finished products.
Wherein, in 1), the Al containing copper and/or manganese is prepared2O3Carrier, MgO-Al2O3Spinel carrier is polynary inorganic During complex oxide carrier, drying temperature is 60-150 DEG C, drying time is that 2-8h, sintering temperature are 480-580 DEG C, roasting Time is 2-8h.
Wherein, auxiliary agent described in 1) be ethylene glycol, isopropanol, 1,2-PD, 1,3-PD, glycerine in one kind or It is several；The auxiliary agent and CuO and/or MnO2Total moles ratio (0-5)：1.
Wherein, shaping assistant described in 1) is sesbania powder, methylcellulose, sodium carboxymethylcellulose, stearic acid, polypropylene Acid amides or polyvinyl alcohol etc.；The peptizing agent is citric acid, nitric acid, acetic acid or oxalic acid etc.；2) complexing agent described in is that quality is dense Spend the ammoniacal liquor for 20-25%.
Wherein, in 3), incipient impregnation, dipping temperature is 10-60 DEG C, and dip time is 0.5-48h, the carrier impregnated Drying temperature is 100-150 DEG C, drying time be 2-8h, sintering temperature be 480-580 DEG C, roasting time be 2-8h.
The solution have the advantages that：Certainly the preparation method of the present invention, which may also be used for producing existing industrial cobalt molybdenum, urges Agent.The catalyst of the present invention is used to make through the synthesis gas produced that gasifies, carbon monoxide and water vapour conversion containing the higher coal of arsenic The conversion process of gas, can be in 190-500 DEG C of temperature, sulfur content>Under conditions of 0.01%v/v, aqueous vapor mol ratio 0.1-1.6, no Used in the conversion process of same pressure (0-10.0MPa), high mechanical strength adaptable to high-speed, arsenic resistance can be good, makes Use long lifespan.
Embodiment
With reference to embodiment, the present invention is expanded on further.It should be understood that these embodiments be merely to illustrate the present invention without For limiting the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, those skilled in the art can To be made various changes or modifications to the present invention, these equivalent form of values equally fall within the model that the application appended claims are limited Enclose.
Embodiment 1：
To containing Al2O363% Al2O3-nH2In O1000g, add shaping assistant sodium carboxymethylcellulose 30g and mix, then Plus the 45g of citric acid containing peptizing agent and the solution of appropriate water configuration, mediate uniform, progress shaping extrusion；The bar of extrusion is quiet 24h, 100 DEG C of dry 4h, 500 DEG C of roasting 3h are put, catalyst carrier a1 is made.It is cooled to room temperature measuring its water absorption rate：49%.
40g cobalt nitrates and 24g ammonium paramolybdates are weighed, is dissolved in the ammoniacal liquor that mass fraction is 25% concentration, is adjusted to 94mL and matches somebody with somebody Make stable cobalt molybdenum ammonia solution.
Then 200g catalyst carrier a1 are weighed, and are added into the cobalt molybdenum ammonia solution of above-mentioned preparation, are turned at 30 DEG C Dynamic dipping 12h；
After cobalt molybdenum ammonia solution is completely immersed in catalyst carrier a1,100 DEG C of dry 3h, 480 DEG C of roasting 2.5h are made and urged Agent C1.
Embodiment 2：
To containing Al2O363% Al2O3-nH2In O1000g, add shaping assistant sesbania powder 30g and mix, then add oxygen-containing Change copper 10g copper nitrate solution, then add the 45g of nitric acid containing peptizing agent and the solution of appropriate water configuration, mediate uniformly, be molded Extrusion；The bar of extrusion stands 36h, 100 DEG C of dry 3h, 520 DEG C of roasting 4h, and catalyst carrier a1 is made.It is cooled to room temperature Determine its water absorption rate：46%.
40g cobalt nitrates and 24g ammonium paramolybdates are weighed, is dissolved in the ammoniacal liquor that mass fraction is 25%, 94mL is adjusted to and prepares steady Fixed cobalt molybdenum ammonia solution.
Then 200g catalyst carrier a1 are weighed, and are added into the cobalt molybdenum ammonia solution of above-mentioned preparation, are stirred at 30 DEG C Impregnate 12h；
After cobalt molybdenum ammonia solution is completely immersed in catalyst carrier a1, catalysis is made in 100 DEG C of dry 3h, 480 DEG C of roasting 4h Agent C2.
Embodiment 3：
To containing Al2O363% Al2O3-nH2In O1000g, add shaping assistant methylcellulose 30g and mix, then add The copper nitrate solution of the 10g containing cupric oxide, ethylene glycol (alcohols and copper nitrate mol ratio 1 are added into the solution of copper nitrate:1), then Plus the 45g of acetic acid containing peptizing agent and the solution of appropriate water configuration, mediate uniform, progress shaping extrusion；The bar of extrusion is stood 36h, 100 DEG C of dry 3h, 520 DEG C of roasting 4h, is made catalyst carrier a1.It is cooled to room temperature measuring its water absorption rate：46%.
40g cobalt nitrates and 24g ammonium paramolybdates are weighed, is dissolved in the ammoniacal liquor that mass fraction is 25% concentration, is adjusted to 94mL and matches somebody with somebody Make stable cobalt molybdenum ammonia solution.
Then 200g catalyst carrier a1 are weighed, and are added into the cobalt molybdenum ammonia solution of above-mentioned preparation, are stirred at 30 DEG C Impregnate 12h；
After cobalt molybdenum ammonia solution is completely immersed in catalyst carrier a1, catalysis is made in 100 DEG C of dry 3h, 480 DEG C of roasting 4h Agent C3.
Embodiment 4：
To containing Al2O363% Al2O3-nH2In O1000g, add shaping assistant polyvinyl alcohol 30g and mix, then add and contain Cupric oxide 30g copper nitrate solution, ethylene glycol and propyl alcohol (alcohols and copper nitrate mol ratio 2 are added into the solution of copper nitrate:1, The mol ratio of ethylene glycol and propyl alcohol is 1:0.4), then add the solution of the 45g of citric acid containing peptizing agent and the configuration of appropriate water, mediate equal It is even, carry out shaping extrusion；The bar of extrusion stands 36h, 100 DEG C of dry 3h, 520 DEG C of roasting 4h, and catalyst carrier a1 is made. It is cooled to room temperature measuring its water absorption rate：46%.
40g cobalt nitrates and 24g ammonium paramolybdates are weighed, is dissolved in the ammoniacal liquor that mass fraction is 25% concentration, is adjusted to 94mL and matches somebody with somebody Make stable cobalt molybdenum ammonia solution.
Then 200g catalyst carrier a1 are weighed, and are added into the cobalt molybdenum ammonia solution of above-mentioned preparation, are stirred at 30 DEG C Impregnate 12h；
After cobalt molybdenum ammonia solution is completely immersed in catalyst carrier a1, catalysis is made in 100 DEG C of dry 3h, 480 DEG C of roasting 4h Agent C4.
Embodiment 5：
To containing Al2O363% Al2O3-nH2In O1000g, add shaping assistant polyacrylamide 30g and mix, then add The copper nitrate solution of the 50g containing cupric oxide, propyl alcohol and glycerine (alcohols and copper nitrate mol ratio 1.5 are added into the solution of copper nitrate: 1, the mol ratio of propyl alcohol and glycerine is 0.5:1), then add the solution of the 45g of nitric acid containing peptizing agent and the configuration of appropriate water, mediate equal It is even, carry out shaping extrusion；The bar of extrusion stands 36h, 100 DEG C of dry 3h, 520 DEG C of roasting 4h, and catalyst carrier a1 is made. It is cooled to room temperature measuring its water absorption rate：46%.
40g cobalt nitrates and 24g ammonium paramolybdates are weighed, is dissolved in the ammoniacal liquor that mass fraction is 25% concentration, is adjusted to 94mL and matches somebody with somebody Make stable cobalt molybdenum ammonia solution.
Then 200g catalyst carrier a1 are weighed, and are added into the cobalt molybdenum ammonia solution of above-mentioned preparation, are stirred at 30 DEG C Impregnate 12h；
After cobalt molybdenum ammonia solution is completely immersed in catalyst carrier a1, catalysis is made in 100 DEG C of dry 3h, 480 DEG C of roasting 4h Agent C5.
Embodiment 6：
To containing Al2O363% Al2O3-nH2In O1000g, add shaping assistant sodium carboxymethylcellulose 30g and mix, then Manganese oxide 10g copper nitrate solution is added, ethylene glycol (alcohols and copper nitrate mol ratio 1 are added into the solution of copper nitrate: 1), then add the solution of the 45g of oxalic acid containing peptizing agent and the configuration of appropriate water, mediate uniform, carry out shaping extrusion；The bar of extrusion 36h, 100 DEG C of dry 3h, 520 DEG C of roasting 4h are stood, catalyst carrier a1 is made.It is cooled to room temperature measuring its water absorption rate：46%.
40g cobalt nitrates and 24g ammonium paramolybdates are weighed, is dissolved in the ammoniacal liquor that mass fraction is 25% concentration, is adjusted to 94mL and matches somebody with somebody Make stable cobalt molybdenum ammonia solution.
Then 200g catalyst carrier a1 are weighed, and are added into the cobalt molybdenum ammonia solution of above-mentioned preparation, are stirred at 30 DEG C Impregnate 12h；
After cobalt molybdenum ammonia solution is completely immersed in catalyst carrier a1, catalysis is made in 100 DEG C of dry 3h, 480 DEG C of roasting 4h Agent C6.
Embodiment 7：
To containing Al2O363% Al2O3-nH2In O1000g, add shaping assistant stearic acid 30g and mix, then add oxygen-containing Change manganese 30g copper nitrate solution, ethylene glycol and propyl alcohol (alcohols and copper nitrate mol ratio 2 are added into the solution of copper nitrate:1, second The mol ratio of glycol and propyl alcohol is 1:0.4), then add the solution of the 45g of citric acid containing peptizing agent and the configuration of appropriate water, mediate equal It is even, carry out shaping extrusion；The bar of extrusion stands 36h, 100 DEG C of dry 3h, 520 DEG C of roasting 4h, and catalyst carrier a1 is made. It is cooled to room temperature measuring its water absorption rate：46%.
40g cobalt nitrates and 24g ammonium paramolybdates are weighed, is dissolved in the ammoniacal liquor that mass fraction is 25% concentration, is adjusted to 94mL and matches somebody with somebody Make stable cobalt molybdenum ammonia solution.
Then 200g catalyst carrier a1 are weighed, and are added into the cobalt molybdenum ammonia solution of above-mentioned preparation, are stirred at 30 DEG C Impregnate 12h；
After cobalt molybdenum ammonia solution is completely immersed in catalyst carrier a1, catalysis is made in 100 DEG C of dry 3h, 480 DEG C of roasting 4h Agent C7.
Embodiment 8：
To containing Al2O363% Al2O3-nH2In O1000g, add shaping assistant sesbania powder 30g and mix, then add oxygen-containing Change manganese 50g copper nitrate solution, propyl alcohol and glycerine (alcohols and copper nitrate mol ratio 1.5 are added into the solution of copper nitrate:1, third The mol ratio of alcohol and glycerine is 0.5:1), then add the solution of the 45g of nitric acid containing peptizing agent and the configuration of appropriate water, mediate uniform, enter Row shaping extrusion；The bar of extrusion stands 36h, 100 DEG C of dry 3h, 520 DEG C of roasting 4h, and catalyst carrier a1 is made.Cooling To its water absorption rate of room temperature measuring：46%.
40g cobalt nitrates and 24g ammonium paramolybdates are weighed, is dissolved in the ammoniacal liquor that mass fraction is 25% concentration, is adjusted to 94mL and matches somebody with somebody Make stable cobalt molybdenum ammonia solution.
Then 200g catalyst carrier a1 are weighed, and are added into the cobalt molybdenum ammonia solution of above-mentioned preparation, are stirred at 30 DEG C Impregnate 12h；
After cobalt molybdenum ammonia solution is completely immersed in catalyst carrier a1, catalysis is made in 100 DEG C of dry 3h, 480 DEG C of roasting 4h Agent C8.
Embodiment 9：
Light MgO 285g and containing Al2O363% Al2O3-nH2In O1400g, add shaping assistant sesbania powder 50g and mix, Then add the solution of the 76g of acetic acid containing peptizing agent and appropriate water configuration again, mediate uniform, progress shaping extrusion；The strip of extrusion Thing stands 48h, 110 DEG C of dry 5h, 540 DEG C of roasting 4h, and catalyst carrier a1 is made.It is cooled to room temperature measuring its water absorption rate： 47%.
40g cobalt nitrates and 24g ammonium paramolybdates are weighed, is dissolved in the ammoniacal liquor that mass fraction is 25% concentration, is adjusted to 94mL and matches somebody with somebody Make stable cobalt molybdenum ammonia solution.
Then 200g catalyst carrier a1 are weighed, and are added into the cobalt molybdenum ammonia solution of above-mentioned preparation, and stir dipping 24h；
After cobalt molybdenum ammonia solution is completely immersed in catalyst carrier a1,125 DEG C of dry 2.5h, 480 DEG C of roasting 6h are made and urged Agent C9.
Embodiment 10：
Light MgO 285g and containing Al2O363% Al2O3-nH2In O1400g, add shaping assistant polyvinyl alcohol 50g and mix It is even, manganese oxide 10g manganese nitrate solution is then added, then add the 76g of citric acid containing peptizing agent and the solution of appropriate water configuration, Mediate uniform, progress shaping extrusion；The bar of extrusion stands 48h, 100 DEG C of dry 6h, 540 DEG C of roasting 4h, and catalyst is made Carrier a1.It is cooled to room temperature measuring its water absorption rate：48%.
40g cobalt nitrates and 24g ammonium paramolybdates are weighed, is dissolved in the ammoniacal liquor that mass fraction is 25% concentration, is adjusted to 94mL and matches somebody with somebody Make stable cobalt molybdenum ammonia solution.
Then 200g catalyst carrier a1 are weighed, and are added into the cobalt molybdenum ammonia solution of above-mentioned preparation, and stir dipping 24h；
After cobalt molybdenum ammonia solution is completely immersed in catalyst carrier a1, catalysis is made in 105 DEG C of dry 3h, 520 DEG C of roasting 5h Agent C10.
Embodiment 11：
Light MgO 285g and Al2O363% Al2O3-nH2In O1400g, shaping assistant sodium carboxymethylcellulose 50g is added Mix, then add manganese oxide 30g manganese nitrate solution, ethylene glycol (ethylene glycol and nitric acid are added into the solution of manganese nitrate Manganese mol ratio 1.5:1), then add the solution of the 76g of oxalic acid containing peptizing agent and the configuration of appropriate water, mediate uniform, carry out shaping extrusion； The bar of extrusion stands 48h, 100 DEG C of dry 6h, 540 DEG C of roasting 4h, and catalyst carrier a1 is made.Be cooled to room temperature measuring its Water absorption rate：48%.
40g cobalt nitrates and 24g ammonium paramolybdates are weighed, is dissolved in the ammoniacal liquor that mass fraction is 25% concentration, is adjusted to 94mL and matches somebody with somebody Make stable cobalt molybdenum ammonia solution.
Then 200g catalyst carrier a1 are weighed, and are added into the cobalt molybdenum ammonia solution of above-mentioned preparation, and stir dipping 24h；
After cobalt molybdenum ammonia solution is completely immersed in catalyst carrier a1, catalysis is made in 105 DEG C of dry 3h, 520 DEG C of roasting 5h Agent C11.
Embodiment 12：
Light MgO 285g and Al2O363% Al2O3-nH2In O1400g, add shaping assistant stearic acid 50g and mix, so Manganese oxide 30g manganese nitrate solution is added afterwards, and ethylene glycol (ethylene glycol and manganese nitrate mol ratio are added into the solution of manganese nitrate 0.6:1), then add the solution of the 76g of citric acid containing peptizing agent and the configuration of appropriate water, mediate uniform, carry out shaping extrusion；Extrusion Bar stands 48h, 100 DEG C of dry 6h, 540 DEG C of roasting 4h, and catalyst carrier a1 is made.Being cooled to room temperature measuring, it absorbs water Rate：48%.
40g cobalt nitrates and 24g ammonium paramolybdates are weighed, is dissolved in the ammoniacal liquor that mass fraction is 25% concentration, is adjusted to 94mL and matches somebody with somebody Make stable cobalt molybdenum ammonia solution.
Then 200g catalyst carrier a1 are weighed, and are added into the cobalt molybdenum ammonia solution of above-mentioned preparation, and stir dipping 24h；
After cobalt molybdenum ammonia solution is completely immersed in catalyst carrier a1, catalysis is made in 105 DEG C of dry 3h, 520 DEG C of roasting 5h Agent C12.
Embodiment 13：
Light MgO 285g and Al2O363% Al2O3-nH2In O1400g, add shaping assistant sesbania powder 50g and mix, so Manganese oxide 50g manganese nitrate solution is added afterwards, and ethylene glycol and isopropanol (alcohols and manganese nitrate are added into the solution of manganese nitrate Mol ratio 1:1, the mol ratio of ethylene glycol and isopropanol is 1:0.8), then the 76g of citric acid containing peptizing agent and the configuration of appropriate water are added Solution, mediate uniform, carry out shaping extrusion；The bar of extrusion stands 48h, 100 DEG C of dry 6h, 540 DEG C of roasting 4h, is made Catalyst carrier a1.It is cooled to room temperature measuring its water absorption rate：48%.
40g cobalt nitrates and 24g ammonium paramolybdates are weighed, is dissolved in the ammoniacal liquor that mass fraction is 25% concentration, is adjusted to 94mL and matches somebody with somebody Make stable cobalt molybdenum ammonia solution.
Then 200g catalyst carrier a1 are weighed, and are added into the cobalt molybdenum ammonia solution of above-mentioned preparation, and stir dipping 24h；
After cobalt molybdenum ammonia solution is completely immersed in catalyst carrier a1, catalysis is made in 105 DEG C of dry 3h, 520 DEG C of roasting 5h Agent C13.
Embodiment 14：
Light MgO 285g and Al2O363% Al2O3-nH2In O1400g, add shaping assistant polyacrylamide 50g and mix It is even, the manganese nitrate solution of the 10g containing cupric oxide is then added, ethylene glycol (ethylene glycol and manganese nitrate are added into the solution of manganese nitrate Mol ratio 1.5:1), then add the solution of the 76g of citric acid containing peptizing agent and the configuration of appropriate water, mediate uniform, carry out shaping extrusion； The bar of extrusion stands 48h, 100 DEG C of dry 6h, 540 DEG C of roasting 4h, and catalyst carrier a1 is made.Be cooled to room temperature measuring its Water absorption rate：48%.
40g cobalt nitrates and 24g ammonium paramolybdates are weighed, is dissolved in the ammoniacal liquor that mass fraction is 25% concentration, is adjusted to 94mL and matches somebody with somebody Make stable cobalt molybdenum ammonia solution.
Then 200g catalyst carrier a1 are weighed, and are added into the cobalt molybdenum ammonia solution of above-mentioned preparation, and stir dipping 24h；
After cobalt molybdenum ammonia solution is completely immersed in catalyst carrier a1, catalysis is made in 105 DEG C of dry 3h, 520 DEG C of roasting 5h Agent C14.
Embodiment 15：
Light MgO 285g and Al2O363% Al2O3-nH2In O1400g, add shaping assistant sesbania powder 50g and mix, so The manganese nitrate solution of the 30g containing cupric oxide is added afterwards, and ethylene glycol (ethylene glycol and manganese nitrate mol ratio are added into the solution of manganese nitrate 0.6:1), then add the solution of the 76g of nitric acid containing peptizing agent and the configuration of appropriate water, mediate uniform, carry out shaping extrusion；The bar of extrusion Shape thing stands 48h, 100 DEG C of dry 6h, 540 DEG C of roasting 4h, and catalyst carrier a1 is made.It is cooled to room temperature measuring its water absorption rate： 48%.
40g cobalt nitrates and 24g ammonium paramolybdates are weighed, is dissolved in the ammoniacal liquor that mass fraction is 25% concentration, is adjusted to 94mL and matches somebody with somebody Make stable cobalt molybdenum ammonia solution.
Then 200g catalyst carrier a1 are weighed, and are added into the cobalt molybdenum ammonia solution of above-mentioned preparation, and stir dipping 24h；
After cobalt molybdenum ammonia solution is completely immersed in catalyst carrier a1, catalysis is made in 105 DEG C of dry 3h, 520 DEG C of roasting 5h Agent C15.
Embodiment 16：
Light MgO 285g and Al2O363% Al2O3-nH2In O1400g, add shaping assistant methylcellulose 50g and mix It is even, then add the manganese nitrate solution of the 50g containing cupric oxide, added into the solution of manganese nitrate ethylene glycol and isopropanol (alcohols with Manganese nitrate mol ratio 1:1, the mol ratio of ethylene glycol and isopropanol is 1:0.8), then the 76g of citric acid containing peptizing agent is added and appropriate The solution of water configuration, mediates uniform, progress shaping extrusion；The bar of extrusion stands 48h, 100 DEG C of dry 6h, 540 DEG C of roastings 4h, is made catalyst carrier a1.It is cooled to room temperature measuring its water absorption rate：48%.
40g cobalt nitrates and 24g ammonium paramolybdates are weighed, is dissolved in the ammoniacal liquor that mass fraction is 25% concentration, is adjusted to 94mL and matches somebody with somebody Make stable cobalt molybdenum ammonia solution.
Then 200g catalyst carrier a1 are weighed, and are added into the cobalt molybdenum ammonia solution of above-mentioned preparation, and stir dipping 24h；
After cobalt molybdenum ammonia solution is completely immersed in catalyst carrier a1, catalysis is made in 105 DEG C of dry 3h, 520 DEG C of roasting 5h Agent C16.
Performance test
The catalyst sample prepared in embodiment is divided into two, physical and chemical performance and conversion of the portion for fresh catalyst The measure of activity, another load diarsenic pentoxide carries out arsenic poisoning experiment, loads 0.5wt% diarsenic pentoxide, then surveys Determine the shift activity of catalyst, demarcate its arsenic resistance, be specifically shown in Table 1, table 2, table 3, table 4.
Sulfur-resistant transformation catalyst need to be used after vulcanization, 150-450 DEG C of curing temperature, preferable 200-300 DEG C of curing temperature, Cure time is determined by the sulphur concentration of vulcanization gas.
Catalyst activity test is carried out on pressurization evaluating apparatus.
Appreciation condition：
The activity of catalyst is represented with CO interconversion rates：
The feed gas volume composition of evaluation：CO45.7%CO20.0%H253.9%H2S0.4%.
The catalyst chemical of table 1 constitutes weight/mass percentage composition
The catalyst physical performance of table 2
The fresh catalyst activity determination test result of table 3
The load arsenic poisoning rear catalyst shift activity of table 4 is determined
On the activity rating device in laboratory, shift activity evaluation has been carried out to the sample after arsenic poisoning, by with it is new The shift activity measurement result of fresh sample compares, and anti-arsenic sulfur-resistant transformation catalyst of the invention loads 0.5wt% diarsenic pentoxide Shift activity and activity preservation rate show that the catalyst arsenic resistance of the present invention is better than apparently higher than conventional sulfur-resistant transformation catalyst afterwards Conventional sulfur-resistant transformation catalyst.
General principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its Equivalent thereof.All all fall within this hair without the Structural Transformation made by creative work from the present invention is to devise Within bright protection domain.

Claims (10)

1. a kind of anti-arsenic CO sulfur-resistant transformation catalysts, it is characterised in that the catalyst is with Al2O3、MgO-Al2O3Spinelle or Polynary inorganic oxide compound is anti-arsenic-CO sulphur-resistant conversion bifunctional catalysts for Cu (Mn)-Co-Mo of carrier；It is described Catalytic component contains CuO and/or MnO2, containing Co and/or Ni elements, and the catalytic component also at least contains Mo, W One kind in element.
2. anti-arsenic CO sulfur-resistant transformation catalysts as claimed in claim 1, it is characterised in that the CuO and/or MnO2Quality Content is 1-10% in the catalyst.
3. anti-arsenic CO sulfur-resistant transformation catalysts as claimed in claim 2, it is characterised in that the CuO and/or MnO2Quality Content is 2-5% in the catalyst.
4. anti-arsenic CO sulfur-resistant transformation catalysts as claimed in claim 1, it is characterised in that Mo and/or W elements and CuO and/or MnO2Total moles compare 1：（0.10-2.5）；Co and/or Ni elements and CuO and/or MnO2Total moles compare 1：（0.10-2.5）.
5. the anti-arsenic CO sulfur-resistant transformation catalysts as described in claim any one of 1-4, it is characterised in that preparation method include with Lower step：
1）Prepare Al2O3Carrier, MgO-Al2O3Spinel carrier or polynary inorganic oxide complexes carrier, wherein Al2O3Carry Body is to use industrial boehmite, aluminium hydroxide etc. to be decomposed into the aluminum contained compound of aluminum oxide for raw material；MgO-Al2O3It is sharp brilliant Stone carrier, by MgO or Mg (OH)2And Al2O3-nH2O is well mixed；Or it is prepared into MgO-Al with Mg, Al compound2O3It is sharp brilliant Stone material or the material containing Mg, Al；Polynary inorganic oxide compound is by MgO or Mg (OH)2In one kind and Al2O3- nH2O and zirconium dioxide, TiO2Or one kind or any several well mixed in ZnO；Backward mixed material in add containing helping Soluble copper salt and/or the manganese salt solution dipping of agent are uniform, dry, pulverize；Then add-on type auxiliary agent, peptizing agent and quality are dry Powder material quality 30-40% water, mediates uniform shaping, is finally dried, is calcined；
2）Under conditions of complexing agent presence, the soluble salt of Mo and/or W soluble salt and Co and/or Ni is configured to stabilization Solution, and be well mixed；
3）By 1）The carrier of the roasting adds 2）In the stablizing solution being configured to, and use incipient impregnation；
4）By 3）The carrier drying that has impregnated, roasting obtain the anti-arsenic CO sulfur-resistant transformation catalyst finished products.
6. anti-arsenic CO sulfur-resistant transformation catalysts as claimed in claim 5, it is characterised in that 1）In, prepare and contain copper and/or manganese Al2O3Carrier, MgO-Al2O3When spinel carrier or polynary inorganic oxide complexes carrier, drying temperature is 60-150 DEG C, drying time be 2-8h, sintering temperature be 480-580 DEG C, roasting time be 2-8h.
7. anti-arsenic CO sulfur-resistant transformation catalysts as claimed in claim 5, it is characterised in that 1）Described in auxiliary agent be ethylene glycol, One or more in isopropanol, 1,2- propane diols, 1,3- propane diols, glycerine；The auxiliary agent and CuO and/or MnO2Always rub You compare（0-5）：1.
8. anti-arsenic CO sulfur-resistant transformation catalysts as claimed in claim 5, it is characterised in that 1）Described in shaping assistant be sesbania Powder, methylcellulose, sodium carboxymethylcellulose, stearic acid, polyacrylamide or polyvinyl alcohol etc.；The peptizing agent is lemon Acid, nitric acid, acetic acid or oxalic acid etc.；2）Described in complexing agent be ammoniacal liquor that mass concentration is 20-25%.
9. anti-arsenic CO sulfur-resistant transformation catalysts as claimed in claim 5, it is characterised in that 3）In, incipient impregnation, dipping temperature Spend for 10-60 DEG C, dip time is 0.5-48h, the carrier drying temperature impregnated is 100-150 DEG C, drying time be 2-8h, Sintering temperature is 480-580 DEG C, roasting time is 2-8h.
10. a kind of method of the anti-arsenic CO sulfur-resistant transformation catalysts prepared described in claim any one of 1-9, it is characterised in that Including step：
1）Prepare Al2O3Carrier, MgO-Al2O3Spinel carrier or polynary inorganic oxide complexes carrier, wherein Al2O3Carry Body is to use industrial boehmite, aluminium hydroxide etc. to be decomposed into the aluminum contained compound of aluminum oxide for raw material；MgO-Al2O3It is sharp brilliant Stone carrier, by MgO or Mg (OH)2And Al2O3-nH2O is well mixed；Or it is prepared into MgO-Al with Mg, Al compound2O3It is sharp brilliant Stone material or the material containing Mg, Al；Polynary inorganic oxide compound is by MgO or Mg (OH)2In one kind and Al2O3- nH2O and zirconium dioxide, TiO2Or one kind or any several well mixed in ZnO；Backward mixed material in add containing helping Soluble copper salt and/or the manganese salt dipping of agent are uniform, dry, pulverize；Then add-on type auxiliary agent, peptizing agent and quality are dry powder thing Expect quality 30-40% water, mediate uniform shaping, be finally dried, be calcined；
2）Under conditions of complexing agent presence, the soluble salt of Mo and/or W soluble salt and Co and/or Ni is configured to stabilization Solution, and be well mixed；
3）By 1）The carrier of the roasting adds 2）In the stablizing solution being configured to, and use incipient impregnation；
4）By 3）The carrier drying that has impregnated, roasting obtain the anti-arsenic CO sulfur-resistant transformation catalyst finished products.
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