CN111054366A - Organic sulfur conversion catalyst and its preparation method - Google Patents
Organic sulfur conversion catalyst and its preparation method Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 125000001741 organic sulfur group Chemical group 0.000 title claims abstract description 33
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 21
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 16
- 239000011733 molybdenum Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 239000011777 magnesium Substances 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 15
- 239000011609 ammonium molybdate Substances 0.000 claims description 15
- 229940010552 ammonium molybdate Drugs 0.000 claims description 15
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 15
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 10
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 10
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 10
- 239000001099 ammonium carbonate Substances 0.000 claims description 10
- 239000000969 carrier Substances 0.000 claims description 10
- 229940116318 copper carbonate Drugs 0.000 claims description 10
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 5
- 239000001095 magnesium carbonate Substances 0.000 claims description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 abstract description 13
- 230000023556 desulfurization Effects 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 7
- 230000003009 desulfurizing effect Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000007327 hydrogenolysis reaction Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000002860 competitive effect Effects 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 45
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Images
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-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/70—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
-
- B01J35/394—
-
- B01J35/399—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
Abstract
The invention relates to a novel organic sulfur conversion catalyst and a preparation method thereof. The technical scheme adopted by the invention is as follows: a novel organic sulfur conversion catalyst characterized by: based on the weight of the catalyst, the catalyst comprises 80-90% of active alumina carrier and 10-20% of active metal, wherein the specific surface area of the active alumina carrier is more than 400m2The structural pore diameter on the active alumina carrier is more than 12nm, and the active metal is the mixture of copper, magnesium and molybdenum. The invention has the advantages that: active alumina is used as a carrier, so that the diffusion resistance in the desulfurization process is reduced, and a multi-metal active component is adopted to highly disperse metal ions on the carrier through competitive adsorption, so that the uniform load type metal oxide desulfurizer is obtained. The activity and hydrogenolysis capacity of the active components are enhanced through the interaction among various metals, so that the purposes of low temperature, high space velocity and high conversion rate are achieved. The organic sulfur conversion rate is more than 90 percent, and the desulfurization precision can reach 0.02ppm by matching with a fine desulfurizing agent.
Description
Technical Field
The invention relates to a catalyst and a preparation method thereof, in particular to a novel organic sulfur conversion catalyst and a preparation method thereof.
Background
The existing desulfurizing agent is mainly used for desulfurizing by adopting a hydrolysis catalyst. Active alumina is adopted to load alkali metal K/Na, and COS is hydrolyzed into CO at the temperature of 60-80 DEG C2And H2S, and then removing H2S through a fine desulfurization catalyst to achieve the desulfurization effect. The existing desulfurizer has the following disadvantages: 1. only carbonyl sulfide (COS) can be converted, and the conversion effect cannot be generated compared with relatively complex organic sulfur (mercaptan, thioether and the like), so that the desulfurization precision is insufficient; 2. water needs to be injected, the temperature is raised to about 70 ℃, and the energy consumption is high; 3. after water injection, the components of the hydrolytic agent are lost, downstream blockage is caused, and blades of a compressor are damaged, so that the equipment is greatly damaged; 4. reversible reaction occurs at the time of start and stop, and the organic sulfur content increases. Therefore, a new technical solution should be provided to solve the above problems.
Disclosure of Invention
The purpose of the invention is: aiming at the defects, the novel organic sulfur conversion catalyst with low energy consumption and high desulfurization precision and the preparation method thereof are provided.
In order to achieve the purpose, the invention adopts the technical scheme that:
a novel organic sulfur conversion catalyst comprises 80-90% of active alumina carrier and 10-20% of active metal by taking the weight of the catalyst as a reference, wherein the specific surface area of the active alumina carrier is more than 400m2The structural aperture on the active alumina carrier is more than 12nm, and the active metal is a mixture of copper, magnesium and molybdenum
The preparation method of the novel organic sulfur conversion catalyst comprises the following steps:
1) preparation of the support
Selecting specific surface area greater than 300m2G, pore volume is more than 1.5cm3The gamma-Al is prepared by taking the pseudo-boehmite/g as a raw material and heating and dehydrating at the temperature of 400-2O3Then adding a pore-expanding agent polyacrylamide with the concentration of 10-20 wt%, then adding basic magnesium carbonate with the concentration of 2-5 wt%, stirring at normal temperature to uniformly mix the components, then preparing a spherical carrier by a forming disc, and roasting at the temperature of 700-900 ℃ to obtain the spherical carrier with the specific surface area of more than 400m2Active alumina carriers with the structural aperture larger than 12nm are selected as final carriers by screening;
2) preparation of active Metal component
2-1) preparation of metallic copper solution
Adding 200L of 25% ammonia water into 200L of deionized water, slowly adding 50kg of ammonium bicarbonate, stirring while adding to fully dissolve the ammonium bicarbonate, slowly adding 50kg of basic copper carbonate while stirring, and continuously stirring for 3-4 hours while adding to fully dissolve the basic copper carbonate to obtain a clear solution;
2-2) preparation of a molybdenum Metal solution
25kg of ammonium molybdate was weighed and dissolved in 400L of deionized water, and the solution was stirred while slowly adding the ammonium molybdate to dissolve the ammonium molybdate sufficiently to obtain a clear solution.
3) Second impregnation
3-1) weighing 200kg of the activated alumina carrier prepared in the step 1), soaking the activated alumina carrier in the copper solution prepared in the step 2-1) to ensure that the carrier is completely covered by the solution, soaking for 40 minutes, turning over the carrier in the soaking process to ensure that the carrier fully absorbs the copper solution, then draining for 30 minutes, and drying at the temperature of 120-140 ℃ for 10 hours to ensure that the water content is less than 5 percent;
3-2) soaking the dried carrier in the molybdenum solution prepared in the step 2-2) to enable the solution to completely cover the carrier, soaking for 40 minutes, turning over the carrier in the soaking process to enable the carrier to fully absorb the molybdenum solution, then draining for 30 minutes, and then drying at the temperature of 120-;
4) preparation of the finished product
And 3-2) roasting and activating the product subjected to secondary impregnation for 60 minutes in a rotary kiln at the temperature of 400-550 ℃, wherein in the roasting process of the rotary kiln, the material rolls in the rotary kiln to be heated uniformly, the active components are decomposed thoroughly, and finally the finished product of the organic sulfur conversion catalyst is obtained.
The organic sulfur conversion catalyst uses active alumina as a carrier, so that the diffusion resistance in the desulfurization process is reduced, a multi-metal active component (Cu-Mg-Mo) is adopted to highly disperse metal ions on the carrier through competitive adsorption to obtain a uniformly-loaded metal oxide desulfurizer, and the adsorption capacity of active sites on the surface of the catalyst on sulfides and the low-temperature hydrogenolysis capacity are improved by utilizing the multi-metal coordination effect, so that the organic sulfur conversion catalyst suitable for low temperature, high space velocity and high conversion rate is obtained. The activity and hydrogenolysis capacity of the active components are enhanced through the interaction among various metals, so that the purposes of low temperature, high space velocity and high conversion rate are achieved. The organic sulfur conversion rate is more than 90 percent, and the desulfurization precision can reach 0.02ppm by matching with a fine desulfurizing agent.
The reaction mechanism of the organic sulfur conversion catalyst of the present invention is:
the first step is to form a high-activity CuS active component in the desulfurization process, and the second step is to perform low-temperature hydrogenation conversion on COS under the action of CuS to form H2S; in the third step, the complex organic sulfur is converted into H2S under the catalysis of CuS. The reaction equation is as follows:
COS+CuO→CuS+CO2
H2S+CuO→CuS+H2O
COS+H2→H2S+CO2
RSH+H2→RH+H2S
R1SR2+2H2→R1H+R2H+H2S
C4H4S+4H2＝C4H10+H2S。
due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the organic sulfur conversion catalyst can be used at normal temperature, does not need water injection, and has high organic sulfur conversion rate which is more than 90 percent.
2. The organic sulfur conversion catalyst can reduce the total sulfur in the synthesis gas to below 0.02ppm by matching with a fine desulfurizing agent, completely meets the index requirement of a downstream main catalyst on sulfides, and solves the defects of the existing hydrolysis desulfurizing agent.
Drawings
FIG. 1 is an SEM image of a conventional impregnated desulfurization catalyst.
FIG. 2 is an SEM image of a desulfurization catalyst competitively impregnated with an auxiliary agent according to the present invention.
Detailed Description
The invention is further described with reference to the following figures and examples:
the first embodiment is as follows:
the novel organic sulfur conversion catalyst comprises 80% of active alumina carrier and 20% of active metal by weight of the catalyst, wherein the specific surface area of the active alumina carrier is more than 400m2The structural aperture on the active alumina carrier is more than 12nm, and the active metal is a mixture of copper, magnesium and molybdenum
The preparation method of the novel organic sulfur conversion catalyst comprises the following steps:
1) preparation of the support
Selecting specific surface area greater than 300m2G, pore volume is more than 1.5cm3The gamma-Al is prepared by taking the pseudo-boehmite of per gram as a raw material and heating and dehydrating at 400 DEG C2O3Then adding a pore-expanding agent polyacrylamide with the concentration of 10 wt%, then adding basic magnesium carbonate with the concentration of 2 wt%, stirring at normal temperature to uniformly mix the components, then preparing a spherical carrier by a forming disc, and roasting at 700 ℃ to obtain the spherical carrier with the specific surface area of more than 400m2Active alumina carriers with the structural aperture larger than 12nm are selected as final carriers by screening;
2) preparation of active Metal component
2-1) preparation of metallic copper solution
Adding 200L of 25% ammonia water into 200L of deionized water, slowly adding 50kg of ammonium bicarbonate, stirring while adding to fully dissolve the ammonium bicarbonate, slowly adding 50kg of basic copper carbonate while stirring, and continuously stirring for 3-4 hours while adding to fully dissolve the basic copper carbonate to obtain a clear solution;
2-2) preparation of a molybdenum Metal solution
25kg of ammonium molybdate was weighed and dissolved in 400L of deionized water, and the solution was stirred while slowly adding the ammonium molybdate to dissolve the ammonium molybdate sufficiently to obtain a clear solution.
3) Second impregnation
3-1) weighing 200kg of the activated alumina carrier prepared in the step 1), soaking the activated alumina carrier in the copper solution prepared in the step 2-1) to enable the carrier to be completely covered by the solution, soaking for 40 minutes, turning over the carrier in the soaking process to enable the carrier to fully absorb the copper solution, then draining for 30 minutes, and drying at 120 ℃ for 10 hours to enable the water content to be less than 5%;
3-2) soaking the dried carrier in the molybdenum solution prepared in the step 2-2) to enable the solution to completely cover the carrier, soaking for 40 minutes, turning over the carrier in the soaking process to enable the carrier to fully absorb the molybdenum solution, then draining for 30 minutes, and then drying at 120 ℃ for 10 hours to enable the moisture content of the carrier to be less than 5%;
4) preparation of the finished product
And 3-2) roasting and activating the product subjected to secondary impregnation for 60 minutes in a rotary kiln at the temperature of 400 ℃, rolling the material in the rotary kiln in the roasting process of the rotary kiln to ensure that the material is heated uniformly and active components are decomposed thoroughly, and finally obtaining the finished product of the organic sulfur conversion catalyst.
Example two
A novel organic sulfur conversion catalyst comprises 85% of active alumina carrier and 15% of active metal by weight of the catalyst, wherein the specific surface area of the active alumina carrier is more than 400m2The structural pore diameter of the active alumina carrier is larger than 12nm, and the active metal is a mixture of copper, magnesium and molybdenum.
The preparation method of the novel organic sulfur conversion catalyst comprises the following steps:
1) preparation of the support
Selecting specific surface area greater than 300m2G, pore volume is more than 1.5cm3The gamma-Al is prepared by taking the pseudo-boehmite of per gram as a raw material and heating and dehydrating at 450 DEG C2O3Then adding 15 wt% of pore-expanding agent polyacrylamide, adding 3 wt% of basic magnesium carbonate, stirring at normal temperature to mix them uniformly, then making them into spherical carrier by means of forming disk, roasting at 800 deg.C to obtain the invented product whose specific surface area is greater than 400m2Active alumina carriers with the structural aperture larger than 12nm are selected as final carriers by screening;
2) preparation of active Metal component
2-1) preparation of metallic copper solution
Adding 200L of 25% ammonia water into 200L of deionized water, slowly adding 50kg of ammonium bicarbonate, stirring while adding to fully dissolve the ammonium bicarbonate, slowly adding 50kg of basic copper carbonate while stirring, and continuously stirring for 3-4 hours while adding to fully dissolve the basic copper carbonate to obtain a clear solution;
2-2) preparation of a molybdenum Metal solution
25kg of ammonium molybdate was weighed and dissolved in 400L of deionized water, and the solution was stirred while slowly adding the ammonium molybdate to dissolve the ammonium molybdate sufficiently to obtain a clear solution.
3) Second impregnation
3-1) weighing 200kg of the activated alumina carrier prepared in the step 1), soaking the activated alumina carrier in the copper solution prepared in the step 2-1) to enable the carrier to be completely covered by the solution, soaking for 40 minutes, turning over the carrier in the soaking process to enable the carrier to fully absorb the copper solution, then draining for 30 minutes, and drying at 130 ℃ for 10 hours to enable the water content to be less than 5%;
3-2) soaking the dried carrier in the molybdenum solution prepared in the step 2-2) to enable the solution to completely cover the carrier, soaking for 40 minutes, turning over the carrier in the soaking process to enable the carrier to fully absorb the molybdenum solution, then draining for 30 minutes, and then drying at 130 ℃ for 10 hours to enable the moisture content of the carrier to be less than 5%;
4) preparation of the finished product
And 3-2) roasting and activating the product subjected to secondary impregnation for 60 minutes at 480 ℃, rolling the material in a rotary kiln in the roasting process of the rotary kiln to ensure that the material is heated uniformly and active components are decomposed thoroughly, and finally obtaining the finished product of the organic sulfur conversion catalyst.
EXAMPLE III
A novel organic sulfur conversion catalyst comprises 90% of active alumina carrier and 10% of active metal by weight of the catalyst, wherein the specific surface area of the active alumina carrier is more than 400m2The structural pore diameter of the active alumina carrier is larger than 12nm, and the active metal is a mixture of copper, magnesium and molybdenum.
The preparation method of the novel organic sulfur conversion catalyst comprises the following steps:
1) preparation of the support
Selecting specific surface area greater than 300m2G, pore volume is more than 1.5cm3The gamma-Al is prepared by taking pseudo-boehmite/g as a raw material and heating and dehydrating at 500 DEG C2O3Then adding a pore-expanding agent polyacrylamide with the concentration of 20 wt%, then adding basic magnesium carbonate with the concentration of 5 wt%, stirring at normal temperature to uniformly mix the components, then preparing a spherical carrier by a forming disc, and roasting at 900 ℃ to obtain the spherical carrier with the specific surface area of more than 400m2Active alumina carriers with the structural aperture larger than 12nm are selected as final carriers by screening;
2) preparation of active Metal component
2-1) preparation of metallic copper solution
Adding 200L of 25% ammonia water into 200L of deionized water, slowly adding 50kg of ammonium bicarbonate, stirring while adding to fully dissolve the ammonium bicarbonate, slowly adding 50kg of basic copper carbonate while stirring, and continuously stirring for 3-4 hours while adding to fully dissolve the basic copper carbonate to obtain a clear solution;
2-2) preparation of a molybdenum Metal solution
25kg of ammonium molybdate was weighed and dissolved in 400L of deionized water, and the solution was stirred while slowly adding the ammonium molybdate to dissolve the ammonium molybdate sufficiently to obtain a clear solution.
3) Second impregnation
3-1) weighing 200kg of the activated alumina carrier prepared in the step 1), soaking the activated alumina carrier in the copper solution prepared in the step 2-1) to enable the carrier to be completely covered by the solution, soaking for 40 minutes, turning over the carrier in the soaking process to enable the carrier to fully absorb the copper solution, then draining for 30 minutes, and drying at 140 ℃ for 10 hours to enable the water content to be less than 5%;
3-2) soaking the dried carrier in the molybdenum solution prepared in the step 2-2) to enable the solution to completely cover the carrier, soaking for 40 minutes, turning over the carrier in the soaking process to enable the carrier to fully absorb the molybdenum solution, then draining for 30 minutes, and then drying at 140 ℃ for 10 hours to enable the moisture content of the carrier to be less than 5%;
4) preparation of the finished product
And 3-2) roasting and activating the product subjected to secondary impregnation for 60 minutes at 550 ℃, rolling the material in a rotary kiln in the roasting process of the rotary kiln to ensure that the material is heated uniformly and active components are decomposed thoroughly, and finally obtaining the finished product of the organic sulfur conversion catalyst.
Example four
The following examples illustrate the practical use of the organosulfur conversion catalyst provided by the present invention. The organic sulfur conversion catalyst disclosed by the invention is successfully put into use in the project of synthesis gas fine desulfurization after low-temperature methanol washing by Shanxi' an coal-based synthetic oil company Limited (the operating conditions are shown in Table 1). After the product is used, the activity and the service cycle of the subsequent F-T synthetic catalyst are ensured. The catalyst is put into use without adding water body temperature, so that the energy consumption of the whole plant is reduced, and the energy consumption of more than 900 ten thousand yuan can be reduced one year and one month (about 50 tons of standard coal (7000 kcal/kg) is used for a 20-ton steam boiler every day, and 18250 tons of coal are consumed every year), so that a certain economic benefit is obtained.
Table 1, conditions of use conditions (Shanxi Lu an coal-based synthetic oil Co., Ltd. for refining desulfurization of synthesis gas after washing with methanol at low temperature)
EXAMPLE five
The following examples illustrate the comparison of the performance of the organosulfur conversion catalyst provided by the present invention with existing hydrolysis catalysts, with the results shown in table 2:
TABLE 2 comparison of the use of hydrolysis catalyst and conversion catalyst type KHA-1
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the true scope of the invention.
Claims (2)
1. A novel organic sulfur conversion catalyst characterized by: based on the weight of the catalyst, the catalyst comprises 80-90% of active alumina carrier and 10-20% of active metal, wherein the specific surface area of the active alumina carrier is more than 400m2The structural pore diameter of the active alumina carrier is larger than 12nm, and the active metal is a mixture of copper, magnesium and molybdenum.
2. A method for preparing a novel organic sulfur conversion catalyst according to claim 1, characterized in that: the method comprises the following steps:
1) preparation of the support
Selecting specific surface area greater than 300m2G, pore volume is more than 1.5cm3The gamma-Al is prepared by taking the pseudo-boehmite/g as a raw material and heating and dehydrating at the temperature of 400-2O3Then adding 10-20 wt% of polyacrylamide as pore-expanding agent, adding 2-5 wt% of basic magnesium carbonate, stirring at normal temperature to mix themMixing uniformly, then making into spherical carrier by molding disc, and roasting at 700-900 deg.C to obtain the product with specific surface area greater than 400m2Active alumina carriers with the structural aperture larger than 12nm are selected as final carriers by screening;
2) preparation of active Metal component
2-1) preparation of metallic copper solution
Adding 200L of 25% ammonia water into 200L of deionized water, slowly adding 50kg of ammonium bicarbonate, stirring while adding to fully dissolve the ammonium bicarbonate, slowly adding 50kg of basic copper carbonate while stirring, and continuously stirring for 3-4 hours while adding to fully dissolve the basic copper carbonate to obtain a clear solution;
2-2) preparation of a molybdenum Metal solution
25kg of ammonium molybdate was weighed and dissolved in 400L of deionized water, and the solution was stirred while slowly adding the ammonium molybdate to dissolve the ammonium molybdate sufficiently to obtain a clear solution.
3) Second impregnation
3-1) weighing 200kg of the activated alumina carrier prepared in the step 1), soaking the activated alumina carrier in the copper solution prepared in the step 2-1) to ensure that the carrier is completely covered by the solution, soaking for 40 minutes, turning over the carrier in the soaking process to ensure that the carrier fully absorbs the copper solution, then draining for 30 minutes, and drying at the temperature of 120-140 ℃ for 10 hours to ensure that the water content is less than 5 percent;
3-2) soaking the dried carrier in the molybdenum solution prepared in the step 2-2) to enable the solution to completely cover the carrier, soaking for 40 minutes, turning over the carrier in the soaking process to enable the carrier to fully absorb the molybdenum solution, then draining for 30 minutes, and then drying at the temperature of 120-;
4) preparation of the finished product
And 3-2) roasting and activating the product subjected to secondary impregnation for 60 minutes in a rotary kiln at the temperature of 400-550 ℃, wherein in the roasting process of the rotary kiln, the material rolls in the rotary kiln to be heated uniformly, the active components are decomposed thoroughly, and finally the finished product of the organic sulfur conversion catalyst is obtained.
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Cited By (2)
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|---|---|---|---|---|
| CN114804349A (en) * | 2022-04-24 | 2022-07-29 | 桂林电子科技大学 | Anaerobic ammonium oxidation sludge activator and preparation method thereof |
| CN117019209A (en) * | 2023-10-10 | 2023-11-10 | 杭州富阳奥玛德科技有限公司 | Blast furnace gas carbonyl sulfide hydrolysis catalyst carrier and preparation process thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105854577A (en) * | 2016-05-09 | 2016-08-17 | 中石化炼化工程（集团）股份有限公司 | Smoke desulfurizer and preparation method thereof |
| CN108525658A (en) * | 2017-03-03 | 2018-09-14 | 中国石油化工股份有限公司 | The method of the catalyst system and sulfur-bearing hydrocarbon oxidation sweetening of sulfur-bearing hydrocarbon oxidation sweetening |
-
2019
- 2019-11-26 CN CN201911171805.1A patent/CN111054366A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105854577A (en) * | 2016-05-09 | 2016-08-17 | 中石化炼化工程（集团）股份有限公司 | Smoke desulfurizer and preparation method thereof |
| CN108525658A (en) * | 2017-03-03 | 2018-09-14 | 中国石油化工股份有限公司 | The method of the catalyst system and sulfur-bearing hydrocarbon oxidation sweetening of sulfur-bearing hydrocarbon oxidation sweetening |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114804349A (en) * | 2022-04-24 | 2022-07-29 | 桂林电子科技大学 | Anaerobic ammonium oxidation sludge activator and preparation method thereof |
| CN117019209A (en) * | 2023-10-10 | 2023-11-10 | 杭州富阳奥玛德科技有限公司 | Blast furnace gas carbonyl sulfide hydrolysis catalyst carrier and preparation process thereof |
| CN117019209B (en) * | 2023-10-10 | 2024-03-05 | 杭州弘钰汇新材料有限公司 | Blast furnace gas carbonyl sulfide hydrolysis catalyst carrier and preparation process thereof |
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